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Publication numberUS3391985 A
Publication typeGrant
Publication dateJul 9, 1968
Filing dateNov 2, 1964
Priority dateFeb 8, 1963
Also published asDE1290913B
Publication numberUS 3391985 A, US 3391985A, US-A-3391985, US3391985 A, US3391985A
InventorsZurbuchen Jacques, Rauchle Ernst Adolf, Bindler Jakob
Original AssigneeGeigy Ag J R
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for pad-dyeing and printing wool and synthetic textile fibers in carrier compositions
US 3391985 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,391,985 PROCES FORPAD-DYEING AND PRINTING WOOL AND SYNTHETIC TEXTILE FIBERS IN CARRIER COMPOSITIONS Jacques Zurbuchen, Basel-Stadt, and Ernst Adolf Rauchle,

Pratteln, Switzerland, and Jakob Bindler, Pratteln, Switzeriand, by Efin Bindler, legal representative, St. Blaise, Switzerland, assignors to J. R. Geigy A.G., Basel, Switzerland No Drawing. Continuation-impart of application Ser. No. 333,261, Dec. 23, 1963. This application Nov. 2, 1964, Ser. No. 409,349 Claims priority, application Switzerland, Feb. 8, 1963, 1,594/63; May 21, 1963, 6,325/63; July 22, 1964, 9,566/64; July 24, 1964, 9,705/64 15 Claims. (Cl. 8-55) This application is a continuation-in-part of our pending application Ser. No. 333,261, filed Dec. 23, 1963, now abandoned.

This invention relates to a process for the continuous pad-dyeing of natural and synthetic polyamide and other textile fibers, as well as pad liquors and novel carriers suitable for use in this process.

It is known that polyamide fibers can be pad-dyed by continuous processes. A known process of this type comprises impregnating wool with an aqueous, thickened solution of acid wool dyestuffs (pad liquor) at temperatures below the drawing temperature of these dyestuffs, then drying the goods and fixing the dyestuif by passing the goods through a hot acid bath (so-called acid shock), and rinsing. As this process has proved to have serious disadvantages, for instance, by producing uneven dyeings, it has not gained practical importance.

As a further development of this process, it has already been suggested to add carriers to the impregnation liquor. As such, the condensation products of fatty acids having 8 to 14 carbon atoms or mixtures of such acids and 2 equivalents of dialkanolamine have proved to be the best. Such condensation products are obtained by the process described in U.S. Patent 2,089,212.

However, the use of these improved impregnating liquors still has a number of drawbacks, the main one being that they are not stable. After a few hours, without any apparent exterior cause, they often separate irreversibly into two phases, one poor in auxiliaries and the other rich therein, the latter containing the main amount of dyestuif. This phase separation in the impregnating liquor makes the uniform dyeing, particularly of large batches, more difiicult. In order to prevent phase separation in the dye liquor it is necessary to calculate carefully the ratio of dyestuif, electrolyte and auxiliaries to each other which makes the constancy of performance of the process considerably more diflicult and adversely affects its eifective range of application.

In order to prevent this undesirable phase separation in the dye liquor, it has also been proposed to introduce into the liquor used for padding wool and the like polyamides soluble salts of saturated aliphatic monocarboxylic acids having 8 to 14 carbon atoms, or polyglycol ethers of alkanols having 8 to 14 carbon atoms or of fatty acids having 4 to 12 ether groups, or by using the condensation products of fatty acids and dialkanolamine mentioned above according to U.S. Patent 2,089,212 together with non-foaming, anion-active dispersing agents such as tetrahydronaphthalene sulfonic acid. However, the stable pad-liquors thus obtained require a pH above 5.0 and preferably a neutral to alkaline pH range in order to remain homogeneous. This is disadvantageous for the dyeing of polyamide fibers and particularly of wool, and undesirable because it excludes the use of certain commercially valuable wool dyestuffs which require after-chrom- 'ice ing in a pH range below 5.0 such as Eriochrome Black It is, therefore, the main object of this invention to provide a continuous process for the pad-dyeing of natural polyamide fibers, especially wool or synthetic polyamide fibers, in a wide pH range embracing also acid pH values as low as 2.

The process according to the invention comprises:

(I) impregnating the said polyamide fibers with an aqueous pad-liquor which contains, as essential constituents, an amount of 5 to grams, and preferably 20 to 40 grams, per liter of liquor, of a dyestutf carrier according to the invention as defined in detail below; noncationic dyestulf capable of drawing on the above-listed fibers from a pad liquor of a. pH ranging from 2 to 10; and, optionally, as a clarifying agent, especially isopropa- 1101 or a ,B-alkoxy-ethanol of a total of from 3 to 8 carbon atoms, such as B-methoxyethanol, B-ethoxyethanol or fihexoxyethanol, or mixtures of isopropanol and the aforesaid alkoxy-ethanols, said impregnation being carried out at a temperature below the drawing temperature of the respective dyestuifs being used and at a pH of about 2 to 10, and

(II) fixing the dyestuif in the treated goods by a heat treatment in a humid medium, preferably without intermediate drying, by treating the goods with hot steam and/or passing them through a hot acid bath.

According to the invention, the above-mentioned dyestuif carrier, upon the composition of which the successful dyeing according to the invention depends, consists essentially of a mixture of (A) an unsulfated amide or a mixture of unsulfated amides of a substantially saturated aliphatic monocarboxylic, i.e., fatty acid from 10 to 14 carbon atoms in the lipophilic radical, which fatty acid may also be substituted by higher alkyl-phenoxy wherein the higher alkyl moiety has from 8 to 12 and preferably 9 carbon atoms, or of a mixture of such fatty acids of from 8 to 14 carbon atoms which mixture of acids has preferably an average number of more than 10, and preferably 12 carbon atoms, amidified with primary or sec ondary amines containing at least one hydroxy-lower alkyl group which may be etherified; more specifically, unsulfonated amides defined under (A) supra, which can be used in the pad liquors according to the invention are derived from, for example, caprylic, pelargonic, capric, lauric or myristic acid, or, preferably, from the acid mixture of fatty acids obtained from coconut oil, or from lower fatty acids substituted by alkylphenoxy radicals, in particular alkylphenoxy-acetic acids, wherein the alkyl moiety has from 8 to 12 and preferably 9 carbon atoms, e.g., octylor nonyl-phenoxy-acetic acid, and the following aliphatic amines:

(a) from monoand di-hydroxy-alkylamines such as ,B-hydroxyethylamine, 'y-hydroxypropylamine, ,8,'ydihydroxy-mono-propylamine;

(b) from bis-(hydroxyalkyl)-amines preferably of a total of from 4 to 6 carbon atoms such as bis-(flhydroxyethyl) amine, bis ('y hydroxypropyl)- amine, bisa-methyl-fi-hydroxyethyl) -amine;

(c) from N-alkyl-N-(hydroxyalkyl)-amines, preferably N-methyl-N-w-hydroxyalkylamines of from 3 to 4 carbon atoms, or the corresponding N-ethylsubstituted amines of from 4 to 5 carbon atoms such as N-methylor N-ethyl-N-(,B-hydroxyethyD- amine, or N-methylor N-ethyl-N-(y-hydroxypropyl)-amine;

(d) from amino-lower alkyl ethers, especially mono- (w-alkoxy-alkyD-amines of a total of from 3 to 5 carbon atoms, at least two of which pertain to the 3 alkyl moiety, such as B-methoxyor fi-ethoxyethylamine or v-methoxyor 'y-ethoxypropylamine;

(B) sulfated, surface-active organic polyglycol ether or a soluble salt thereof, which polyglycol ether is the condensation product of an alkanol or a higher alkyl phenol with ethylene oxide or propylene oxide in molar ratios ranging from 1 to 20, the terminal hydroxy group of which condensation product has been sulfated, such sulfated polyglycol ether being more in particular (i) a sulfated condensation product of an alkancl of 8 to 14 carbon atoms, with ethylene oxide condensed with each other in a molar ratio of from 1:1 to 1:20, and preferably from 1:2 to 1:5,

(ii) a sulfated condensation product of alkylphenol, the alkyl moiety of which has from 8 to 12 carbon atoms, with ethylene oxide, in a molar ratio of from 1:1 to 1:20, and preferably 1:2 to 1:3, e.g., sulfated glycol ethers of octyl phenol or nonyl phenol, or

(iii) an alkali metal, ammonium lower alkylammonium or w-hydroxy-lower alkylammonium salt of (i) Or (ii).

The ratio of acid amides (A) to the sulfated polyglycol ethers (B) ranges from about 2:1 to 1:2, and preferably 3:2 to 1:15, and, when the above-mentioned clarifying agent is present in order to ensure homogeneity of the carrier mixture for a period of several months and even a year or more, the proportions by weight of (A) to (B) also range from about 2:1 to 1:2, and preferably 3:2 to 1:15, and the content of said clarifying agent ranges from 4 to 20% by weight, calculated on the total weight of said mixture.

Of course, the pad liquors can also be prepared, shortly prior to use, from the individual constituents (A) and (B) of the above-described carrier mixture in the proportions given, in which case the addition of component (C), the clarifying agent is superfluous. In this case, the amide (A) is heated to render the same readily flowing and is added with stirring to an aqueous solution of the constituent (B).

The addition of isopropanol assists flowability of the carrier mixture, but does not affect the color depth of the dyeing obtained in the process according to the invention.

As components (A) in the mixtures the bis-(hydroxyalkyl)-amides, mainly those having hydroxyalkyl radicals containing two or three carbon atoms are preferred, such as bis-(fi-hydroxyethyl)-amides or bis-('y-hydroxypropyl) amides of the fatty acids described above, because they produce good color yields.

The amides described under (A) above are obtained by reacting the esters of suitable fatty acids with lower alkanols, e.g., reacting the fatty acid methyl or ethyl ester with the desired amine in the presence of sodium or potassium alcoholate, for example, by one of the processes described in British Patent N0. 631,367.

Sulfated polyglycol ethers of lauryl alcohol having, in particular, 2 to 3 ether oxygen atoms are preferred as components (B), as these compounds produce particularly level dyeings of good color strength.

The sulfated surface-active polyglycol ether compounds defined under (B) are generally used in the form of their soluble salts; in particular the alkali metal or ammonium salts, but also the alkyl and hydroxyalkyl ammonium salts can be used.

In the dyestutf carriers which are more pronouncedly acid in nature, and particularly in the pad liquors obtained therewith which have a strongly acid pH of 2 to 5, these salts are usually saponified so that the respective free polyglycol ether sulfuric acids, are present therein.

The above-described, sulfated surface-active polyglycol ethers used in preparing the carrier mixture are produced in a conventional manner by first condensing a suitable alkanol or alkylphenol falling under the definition given hereinbefore, with the corresponding number of ethylene oxide moles in the presence of a suitable alkaline catalyst such as sodium ethylate or caustic soda, and subsequent sulfation with chlorosulfonic acid and, finally, neutralization with a suitable cation donor to form the desired salts of the respective sulfated polyglycol ether. Details of the method for producing these compounds are to be found in British Patent 463,624, granted to I. G. Farbenindustrie in 1937, and elsewhere.

Lower when used in this specification in connection with an aliphatic radical means that such radical has from 1 to maximally 4 carbon atoms.

According to one aspect of the invention the dyestuff carrier, the composition of which is an important and critical feature in the process of the invention, consists essentially of a mixture of an unsulfonated amide as defined under (A), supra, and (C) a sulfated amide of an aliphatic monocarboxylic acid, which is optionally substituted and has at least one lipophilic radical, with primary or secondary amines having at least one lower hydroxyalkyl group, and more particularly, sulfated fatty acid mono-B-hydroxyethyl-amides the fatty acid radicals of which have 8 to 14, preferably. 12 carbon atoms (including the COOH group), in particular sulfated coconut oil fatty acid mono-B-hydroxyethyl-amide or sulfated higher alkylphenoxy-substituted fatty acid amides of the above definition, in particular alkylphenoxy acetic acid mono-B-hydroxyethyl-amides or, preferably, alkylphenoxy acetic acid bis-,B-hydroxyethyl amides the alkyl radical of which has 8 to 12, preferably 9 carbon atoms, for example, sulfated nonylp'henoxy acetic acid bis-flhydroxyethylamide, the weight ratio of the sulfated compounds to the non-sulfated compounds being in the range of 5:1 :to 1:5, and preferably from 2:1 to 1:2.

The admixture of such a carrier mixture to an aqueous dyestutf solution or pad liquor allows continuous padding, in particular in the pH-range of 7 to 2.

The sulfated compounds defined under (C) are usually employed in the form of their soluble salts, in particular their alkaline, ammonium, lower alkyl or hydroxy-alkylammonium salts, in the latter case the dior tri-(flhydroxyethyl-amine -salts.

The same stabilizing agents improving the homogeneity and storabili-ty of pad liquors can also be used throughout the instant disclosure in the same proportions as given hereinbefore.

The above-mentioned dyestuif carrier can also consist essentially of an unsulfated amide as defined under (A), supra and (D) a sulfated (alkylphenyl)-(2,3-dihydroxypropyl)-ether the alkyl radical of which has 8 to 12, preferably 9 carbon atoms or a mixture of the sulfated amide mentioned under (C) with a sulfated ether as defined under (D) or of the soluble salts of these sulfated compounds, respectively.

What has been stated hereinbefore with regard to the proportions of carrier components and operating conditions, stabilization of pad liquors, etc., applies equally here.

Sulfated ('alkylphenyl) (2,3-dihydroxypropyl)ethers usable according to the invention are primarily sulfated (nonylphenyl) 2,3-dihydroxypropyl) -ether.

Such ethers are obtained by the reaction of glycol chlorohydrin or l-chloro-2,3-dihydroxy-propane with the corresponding alkylphenols and sulfating the resulting dihydroxy compounds by methods known per se.

Organic fibers which are dyed according to the invention are, among others, polyester fibers such as cellulose dito tri-acet-ate, especially, however, also high-molecular esters of aromatic polycarboxylic acids with polyfunctional alcohols, e.g., polyterephthalic acid glycol esters, or polyurethanes, as well as polymeric and copolyrneric acrylonitrile and methacrylonitrile, polyolefine, chiefly however, synthetic and natural polyarnide fibers such as nylon, Wool or silk.

The capability of the dyestuffs, used in the process of the invention, of drawing on the goods made from the aforesaid fibers can be readily determined by simple routine tests, with which any dyer is familiar.

The process of the invention yields uniform dyeings also with material of great yardage.

The drawing temperature of the dyestuffs used, i.e., the temperature at which the dycstuff draws within about a minute upon the fiber, is usually about 70 C. or more. Impregnating according to the invention has to be effected below this drawing temperature.

Non-cationic dyestuffs capable of drawing on fibers falling under the above-described group under the conditions given, are monoand poly-, preferably dis, azo dyestuffs, namely metal-free, metallizable and heavymetal-containing, in particular chromiurn-, cobalt, nickeland copper complex azo dyes which comprise also the formazane dyes, furthermore, anthraquinone, nitro and methine dyes, acid triphenylmethane and xanthone dyes, naphthazarine dyes and quinophthalone dyes, and also copper phthalocyanine dyes.

To these dyestuffs, there pertain, on the one hand, dyestuffs which are soluble in neutral, acid, or basic medium, within the pH range specified above, and, on the other hand, dyestuffs which are dispersible in water.

As far as the various above-listed textile fibers are concerned, suitable dyestuffs for natural and synthetic polyamide fibers are the so-called acid wool dyes which comprise the above-listed azo, anthraquinone, triphenylmethane and xanthone dyes, and, in particular, also those containing fiber-reactive groups, i.e., so-calied reactive wool and cotton dyes, derived from azo, anthraquinone or phthalocyanine dyes.

Finally, in addition to or instead of dyestuff, the impregnating liquor used in the invention can also contain bactericidal and fungicidal compounds as well as agents which protect against insects, i.e., moth-proofing agents such as the compounds of the formulas SOSH and

which are of the type of known commercial products such as Mitin and Eulan.

For these fibers, and, chiefly for wool, the water-soluble so-called acid wool dyestuffs, particularly also heavymetal-containing, i.e., chromium-, cobaltor copper-containing, azo dyestuffs, including formazane dyestuffs, especially metallized monoazo dyestuffs which contain one metal atom to two molecules of azo dyestuffs are preferred. Chrome dyestuffs are also suitable for these fibers, particularly chromable azo dyestuffs, which latter are used with chromium (III) salts or soluble chromates, preferably in acid medium.

For polyester, polyacrylonitrile and especially modified, in particular vinyl-pyridine-modified copolymers of acrylonitrile and methacrylonitrile fibers as well as polyolefine, in particular polypropylene fibers, there are suitable for use according to the invention azo, anthraquinone, nitro and methine dyestuffs free from water-solubilizing groups, naphthazarine and quinophthalone dyes, while polyurethane fibers as well as synthetic polyamide fibers such as the various types of nylon can be dyed satisfactorily with the aforesaid water-soluble dyestuffs, and also with disperse dyes of the group listed above.

As thickeners, those products which are conventional in textile printing are used, e.g., carob bean flour, galactomannan, tragacanth, dextrin, British gum or-in alkaline medium-also the water-soluble salts of alginic acid. Cellulose derivatives such as methyl cellulose or soluble salts of carboxymethyl cellulose can also be used.

The thickeners must not cause the formation of precipitates in the pad liquor under the conditions of the above-described dyeing method.

Insofar as suitable apparatus is available, the organic fibers to be dyed according to the invention can be in any form desired. For example, they can be in the form of flocks, slubbing, yarn or fabrics. The material to be dyed can also be in the form of mixed fibers which can cousst, for example, of poly-amide fibers and incrusted cellulose fibers, or in the form of blended fabrics, particularly from wool and polyester fibers such as cellulose acetate, cellulose triacetate and, particularly, polyterephthalic acid glycol ester fibers. In these mixtures, only the polyamide (e.g., the wool) or also the polyamide and polyester components can be dyed simultaneously with dyestuffs suitable therefor.

The fibers are impregnated, for example, by printing, in which case wool can be previously chlorinated, as is conventionally the case prior to printing thereon, or the fibers can be impregnated by coating or spraying, preferably, however, by padding. The impregnating solution (pad liquor) according to the invention is advantageously prepared by mixing warm aqueous dycstuff solutions or dispersions of suitable concentration, which contain thickeners, with the desired amount of carrier mixture according to the invention, as defined herebefore, as well as, optionally, other additives. The polyamide fibers are impregnated advantageously at 30 to 70 C. and then equeezed out to the desired content of impregnating liquor which is about 40 to 130%, and preferably 50 to 100%, of the weight of the fiber (400 grams to 1,300 grams per kilogram of goods).

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

Subsequently to the aforesaid steaming, the dyestufi" is preferably fixed on the fibers by treatment in a hot acid bath by known methods (acid shock). The acid content is advantageously about 9 to 10 grams per liter. Preferably, the goods are introduced into the acid bath at to 98 C. To adjust the acid pH value of the bath, inorganic and organic acids are suitable, e.g., sulfuric, phosphoric or hydrochloric acid or formic or acetic acid. Organic acids are preferred, in particular formic acid. In some cases it is useful to add water-soluble salts, preferably water-soluble calcium salts to the acid bath. Development can also be performed by continued steaming as well as, in the case of polyamide and polyacrylonitrile fibers, with hot dilute acid.

The fixed goods are then advantageously rinsed, e.g., with cold or warm water which can contain the auxiliaries usual in the dyeing industry, e.g., formic acid or acetic acid or also wetting or detergent substances.

Pad liquors suitable for carrying out the padding process according to the invention can also be prepared from pre-mixed pastes which contain as the essential ingredients:

(a) 8 to 35%, and preferably 10 to 20% by weight of a suitable dyestulf as defined hereinbefore,

(b) 5 to 25% by weight of a dyestuff carrier mixture according to this invention, the aforesaid percentages being calculated on the total weight of the paste, the balance consisting of (c) water, and, furthermore, optionally,

(cl) depending on the nature of the dyestuff, acid or alkaline agents such as, in particular, acetic acid, formic cid, sulfuric acid, phosphoric acid, sodium or potassium carbonate or bicarbonate, sodium or potassium acetate, or sodium or potassium hydroxide, in amounts sufficient to adjust the pH of the paste to a value most compatible with the dyestuif and with the maintenance of a satisfactory homogeneity of the paste, and, optionally of,

(e) Thickener in sufiicient amount to impart to the paste a viscosity in the range of from 1 to 50, and preferably 10 to 40, poises.

A homogeneity-enchancing and/ or preserving agent such as isopropanol or one of the other compounds mentioned hereinbefore of the here-employed carriers according to the invention, is especially present in the paste in those cases where the latter is prepared from carriers listed above which contain such ingredient.

Pad liquors for use in the method according to the invention are prepared from these pastes by diluting the latter with water, preferably in such proportions that 1 kg. of pad liquor is obtained from every 100 to 400 kg. of paste, depending on the desired depth of shade of the resulting dyeings.

The use of such pastes in the preparation of pad liquors represents a considerable advantage over the conventional preparation from the individual constituents, and, usually, the dyestuffs are present in the pad liquors thus prepared from pastes according to the invention, in a fine and particularly uniform distribution, especially independent of the amount of pad liquor being prepared, which is not easily achieved and not as easily reproducible by preparation of the pad liquors by other methods.

The process according to the invention for the dyeing of organic fibers has remarkable advantages over similar known processes. The main advantage consists in the pH range which stretches very far and deep into the acid region at which dyeing can be performed, so that the most favorable dyeing conditions can be chosen without the pH of the liquor being taken into consideration. Thus, for example, because of the possibility of dyeing in the acid range also, certain chromable dyestuffs such as Eriochrome Black T can be used with chromium (III) salts.

This has not been possible previously. Another advantage of the process according to the invention is that the pad liquors are homogeneous under the conditions of the above-described dyeing method and remain so for a long time, as mentioned hereinbefore.

While known pad liquors, especially those consisting of two phase emulsions, which form a so-called coacervate suffer easily phase separation within a relatively short time, require special adjuvants such as alginates to postpone this separation, and, once such separation has occurred, yield spotty, unlevel dyeings, the pad liquors according to the invention need no such stabilizing adjuvants and remain stable since they are one-phase systems They thus do not require such careful adjustment of the proportions of the ingredients, are simpler to prepare, and do not require special stabilizing adjuvants but can be used with satisfactory results, after standing for weeks or even months.

Dyeings obtained with the pad liquors according to the invention show good dyestuff yields and particularly good fixability of the dyestutf on the fibers after padding, without any special further adjuvants. In particular, dyed fibers and filaments padded according to the process of the invention are, to our knowledge, the first that permit: successful fixation of the fiber by steaming directly following padding. When steaming, for instance, fibers or slubbing, these goods are given a fluffy texture blowing up the space occupied by the padded goods by just the right amount, namely about three to seven times the original volume, but not further so that no entanglement of the fibers occurs which might disturb passage of the material through the steaming apparatus, whereby a rapidly fixable material is obtained. The desirable blow-up of the texture practically never occurs if the mixed carriers according to the invention in the pad liquors used in the above-described process are replaced by the individual components of these mixed carriers, c.g., the sulfutcd polyglycol ether alone, or the fatty acid amide component alone. Known mixed carriers, on the other hand, lead to excessive blow-up, entanglement of the fibers in the material and the above-mentioned disturbances in the steaming operation.

Use of either component alone, in lieu of the highly critical mixtures of the two components as defined above also leads to other draw-backs, such as dependence on, for instance, wool of specific origin, while wool blends from different origin can be dyed evenly in the same bath with the pad liquors used in this invention. Another drawback of pad liquors containing as carriers only one of the two components of the mixed carrier employed according to the invention, is the formation, during fixation by steaming, of the socalled sandwich etfect mentioned hereinbefore, which imparts a greyish hue to the finished dyeings.

As a further advantage, dyeing with pad liquors hereemployed permits much shorter steaming times, for instance, depending on the nature and concentration of the dyestuffs, only 20 minutes, where, with the same dyestuff in the same concentration, use of a known carrier would require 40 minutes of steaming.

Carrier as used in this specification and the appended claims means a color transfer agent which assists in carrying the dyestulf from a pad liquor or ink on to and into the fiber to be printed.

The following non-limitative examples serve to illustrate the invention further. The temperatures given therein are in degrees centigrade. Where not otherwise 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 (1111.) CL means Color Index, Second Edition, 1956, published by The Society of Dyers and Colourists, Bradford, England, and The American Association of Textile Chemists and Colorists, Lowell, Mass, U.S.A.

EXAMPLE 1 40 parts of the commercial form of the chromium complex compound of the monoazo dyestuff Z-aminophenol 4-methylsulfonee1-phenyl-3-methyl-pyrazolone (molar ratio of dyestuff: chromium is 2:1)containing about 50% of sodium sulfate as diluting agentare dissolved in a 60-warm mixture of 300 parts of an aqueous 2.5%-solution of carob bean flour and 30 parts of a carrier mixture consisting of the sodium salt of sulfated lauryl alcohol diglycol ether coconut oil fatty acid, N,N-bis-(B-hydroxyethyD-amide and isopropanol in a weight ratio of 9:9:2, and 250 parts of water. The resulting solution is diluted to 900 parts with warm water (60 C.) and the pH is adjusted to about 2.5 with formic acid. The temperature of the mixture should then be about 50. This solution is then diluted with water to 1000 parts. Wool flannel is impregnated at 50 With this liquor, squeezed out to a liquor content of about 100% calculated on the dry weight of the fibers and steamed with saturated steam for 15 minutes at 98. The goods are then washed first with a solution containing 1 gram (g.) per liter of nonylphenolpolyglycol ether condensation product (molar ratio about 1:12), then rinsed with water and then washed with an aqueous solution containing 2 milliliters (ml.), per liter, of formic acid and again rinsed with water.

A level, well penetrated orange wool dyeing is obtained which has no so-called sandwich efiect.

By using in the above example, instead of the dyestuff mentioned, similar chromium-containing monoazo dyestuffs of the type containing 2 dyestuff molecules per chromium atom (2:1 complexes) which contain no sulfonic acid groups but which are substituted by lower alkylsulfonyl groups or which contain sulfonic acid amide groups which may be substituted at the nitrogen atom by alkyl groups, for example, the chromium-containing dyestutf: 2-aminophenol-S-sulfonic acid an1ide l-phenyl-3- methyl-pyrazolone, the chromium-containing dyestuff mixture: 2-amino-5-nitrophenol Z-hydroxynaphthalene, 2 amino 5 nitrophenol l hydroxynaphthalene 3,6- bis-sulfonic acid methylamide (dyestuff:chromium=2:1) or the chromium-containing monoazo dyestuff: 2-aminophenol 4 methylsulfone l acetylamino 7 hydroxynaphthalene (dyestutf:chromium=2:l), while otherwise the procedure given in the above example is followed, equally well penetrated and level red, navy blue or grey colored wool flannel dyeings, respectively, are obtained.

By using, instead of the carrier mixture given in the above Example 1, parts of a carrier mixture prepared by mixing with each other: 9 parts of the ammonium salt of sulfated lauryl alcohol triglycol ether 9 parts of coconut oil fatty acid-N,N-bis-(hydroxyethyl)- amide, and 2 parts of isopropanol and following the procedure given in the example, paragraph one, equally well penetrated and level dyeings are obtained.

Also diand tri-ethanolamine salts of sulfated lauryltriglycol ether can be used instead of the ammonium salt.

EXAMPLE 2 Woolen slubbing is padded with the liquor described in the first part of Example 1, the pH of which, however, has been adjusted to 4 with acetic acid instead of formic acid, and the procedure given in the first part of Example 1 is followed.

Equally well penetrated and level orange, red, navy blue or grey dyed woolen slubbing is obtained.

Turquoise dyeings of similarly good qualities are obtained by repeating Example 2, but using, instead of the 40 parts of dyestufi used therein, 20 parts of the corn mercially available dyestufi Solophenyl Turquoise Blue GL (C1. Direct Blue 86), and otherwise following the same method as given in Example 2.

Similar satisfactory results are obtained when carrying out the procedure given in the first paragraph of Example 1 with a carrier mixture free from isopropanol.

EXAMPLE 3 By repeating the above Example 2, but using, instead of the last-mentioned dyestuffs, 20 g. of the copper complex of the dyestufl of the formula COOH produced as described in Example 2 of the US. Patent 2,839,521 to Schetty, issued June 17, 1958, wool slubbings of very fast, light brown shades are obtained.

EXAMPLE 4 By repeating the above Example 2, but using, instead of the last-mentioned dyestufl 18 g. of the commercial dyestuff Reacton Brilliant Red BGL (Color Index, 2nd Edition, Reactive Red 20) wool slubbings of particularly brilliant red shades are obtained.

EXAMPLE 5 W001 flannel is impregnated at 60 with pad liquor prepared as described in the first part of Example 1 and squeezed out to a liquor content of about 100%. The padded fabric is introduced into a 98-warm aqueous bath which contains 8 cc./liter of 85% formic acid, and is left in this bath for 5 minutes. The wool flannel so dyed is then washed with a 45-warm aqueous solution of 0.5 g./ liter of nonylphenol polyglycol ether for 5 minutes, whereupon it is rinsed with cold water. The resulting orange dyeing is well penetrated and has no sandwich effect.

By using, instead of the carrier mixture used in Example 1, 40 parts of a mixture consisting of 24 parts of the potassium salt of sulfated myristal alcohol pentaglycol ether [C H -(OC H -OSO K], 12 parts of coconut oil fatty acid, N,N-bis-(hydroxyethyl)amide, and 4 parts isopropanol and following the procedure, otherwise, as given in the example, then equally well penetrated and level dyeings are obtained.

Instead of the potassium salt of sulfated myristal alcohol pentaglycol ether, also the potassium or sodium salt of sulfated octylphenol diglycol ether [CSHITQ (O CzHr) 2-0 S 03K] can be used.

EXAMPLE 6 Woolen slubbing is impregnated at 40 on a pad mangle with an impregnating liquor which contains the dyestutf Acid Red 133 (Color Index, 2nd Edition) instead of the azo dyestuff mentioned in the first part of Example 1 and which is otherwise prepared as described in Example 1. The slubbing is squeezed out to 100% content. The goods are then steamed under slight excess pressure for 15 minutes at 98. They are then washed first with a solution containing 1 g. per liter of nonylphenol polyglycol ether, then rinsed with water, then washed with an aqueous solution containing 2 ml. per liter of aqueous 85%-formic acid and, optionally, rinsed with water.

A level and well-penetrated red woolen slubbing is obtained which has no sandwich effect.

By using, instead of the aforesaid Acid Red 133, the disazo dyestuff coupling in an acid medium according to the formula or the chromium-containing (chromium to dyestuif ratio 1:1) dyestufi Neolan Yellow 8 GE (Acid Yellow 101 of the Color Index, 2nd Edition), and otherwise following the procedure given in the above example then equally well penetrated and level red or yellow colored material, respectively, is obtained.

EXAMPLE 7 parts of Eriochrome Black T (Mordant Black 11 of the Color Index, 2nd Edition) and 5 parts of aqueous 25%-ammonia solution are dissolved in hot water, 100 parts of an aqueous 2.5 %-carob bean flour solution and 30 parts of a mixture produced by mixing with each other 13.5 parts of the sodium salt of sulfated lauryl alcohol ether [C12H25(OC2H4)2-OS3N3.], parts of coconut oil fatty acid N,N-bis-(fihydroxyethyl)amide, 1.5 parts of fi-methoxy-methanol, and 1.5 parts of isopropanol, which 30 parts have been dissolved in 500 parts of .'arm water, are added to the solution.

A mixture consisting of 20 parts of chromium fluoride (CrF and 50 parts of an aqueous 20% solution of chromium acetate which has been previously boiled is added to the solution obtained, the resulting solution is rought to 900 parts with warm water and 20 ml. of aqueous formic acid are added to the solution which is then made up to 1000 ml. with water. The temperature of the ready solution should be about 50.

Woolen slubbing is impregnated at 50 with this liquor,

1 1 squeezed out to a liquor content of about 100% and steamed with saturated steam for 30 minutes at 98.

The slubbing is then rinsed in a first bath in a backwashing machine at 40 and then treated for 15 to 30 seconds in a second back-washing machine bath in an aqueous solution containing 10 g./liter of sodium bichromate, and 8 mL/liter of aqueous 85%-formic acid, at a temperature of 70.

The slubbing is then rinsed in further back-washing machine baths with water of about 40.

Slubbing dyed evenly black is obtained which can be readily combed and spun.

EXAMPLE 8 Grained silk is impregnated at 40 with an impregnating liquor produced according to the first part of Example 1, squeezed out to a liquor content of 80% and introduced into a 98 warm aqueous bath which contains 8 cc./liter of 85 %-formic acid. It is kept in this bath for 5 minutes. The grained silk is then washed with a 45-Warm aqueous solution of 0.5 g./liter of nonylphenol polyglycol ether and then rinsed with cold water.

In this way, a well-penetrated orange-colored grained silk is obtained which is very level without a sandwich efiect.

Corresponding yellow dyeings on grained silk of equally good penetration and evenness are obtained if, in the above example, instead of the dyestuff mentioned, the dyestuff Neolan Yellow 8 GE (Acid Yellow 101 of Color Index, 2nd Edition) is used and the procedure given in the example is followed.

EXAMPLE 9 37.5 parts of the chromium-containing monoazo dyestuff 2-carboxy-l-aminobenzene-e l-phenyl-S-methyl-pyrazolone (dyestuilzchromium is 2:1) and 14.0 parts of the chromium-containing monoazo dyestufl 2-aminophenol- 4-sulfonic acid methylamide l-carbethoxyamino 7 hydroxynaphthaiene (dyestuifzchromium=2zl) are dissolved in an 80-warm mixture of 200 parts of an aqueous 2.5%-sodium alginate solution and 10 parts of a mixture of the ammonium salt of sulfated nonylphenol triglycol ether Plain-woven nylon fabric is impregnated at 40 with an impregnating liquor produced according to the first paragraph of Example 9 which only contains, however, two thirds of the amount of dyestuif given in that example. The fabric is then squeezed out to a liquor content of 50% calculated on the weight of the fibers, introduced into a 98-warm aqueous bath containing 4 ml. per liter of aqueous 85 %-formic acid and treated in this bath for 4 minutes. The fabric is then rinsed first with Warm and then cold water; it is well and evenly dyed olive.

EXAMPLE 11 A plain-woven fabric made from poly-e-aminocaprolactam (nylon 66) is padded at 40 with an impregnating liquor produced according to Example 8. The fabric is squeezed out to a liquor content of 50% calculated on the weight of the fibers and then dried under thermofixing conditions for seconds at 190.

The Perlon fabric thus treated is introduced into a 98- Warm aqueous bath which contains 4 ml. per liter of aqueous 85%-formic acid, and is boiled in this bath for 4 minutes. It is then rinsed with warm and cold water.

An olive Perlon dyeing is obtained which is level and well-penetrated.

EXAMPLE 12 2.5 parts of the cobalt-containing monoazo dyestuti: 2-aminophe-nol-4-sulfonic acid methylamide+ 1-phenyl-3- methyl-S-pyrazolone (dyestufi:cobalt==2:l) and 0.5 part of the chromium-containing monoazo dyestutf:2-amino-4- nitrophen0l 1-phenol-3-methyl-5 pyrazolone (dye'stuif: chromium=2:1) are dissolved in an 80-warm mixture of 300 parts of an aqueous 2.5%-carob bean flour solution and 25 parts of a mixture of: the sodium salt of sulfated lauryl alcohol diglycol ether, coconut oil fatty acid-N,N bis (hydroxyethyl)-amide, and fi-ethoxy-ethanol, the weight ratio of the three components being 9:912.

The solution is adjusted to a pH of 4 with aqueous 80%-acetic acid, and diluted up to :1000 parts. Woolen slubbing is impregnated at 40 with this liquor, squeezed out to a liquor content of about 100% (calculated on the weight of the fibers) and steamed for 15 minutes at 98 with saturated steam.

The goods are then washed with a solution containing 1 g./liter of n-onylphenol polyglycol ether and 1 ml./liter of concentrated ammonia solution, then rinsed with water, washed with aqueous solution containing 2 ml./liter of aqueous 85%-formic acid and again rinsed with water.

The orange-yellow slubbing so obtained is well penetrated and very level. The touch of the goods is very loose and voluminous and the material can be readily combed and spun.

EXAMPLE 1 3 40 parts of the commercial, chromium-containing monoazo dyestuff Z-aminophenol 4 methylsulfonee l-acetylamino-7-hydroxynaphthalene (dyestutf chromium =2: 1) are dissolved in a -warm mixture of 300 parts of an aqueous 2.5%-sodium alginate solution and 30 parts of a mixture of: sodium salt of sulfated lauryl alcohol diglycol ether, coconut oil fatty aci-d-N,N-bis-(hydroxyethyl)- amide, and fl-hexoxy-ethanol, in a weight ratio of 9:9:2, which mixture is dissolved in 200 parts of water.

The solution obtained is made up to 1000 parts with water. The temperature of the solution should be 60.

Wool flannel is impregnated with this liquor at 60 and squeezed out to a liquor content of about The padded fabric is introduced into a 98-Warm aqueous bath which contains 8 ml./liter of aqueous %-formic acid, and is kept in this bath for 5 minutes.

The grey-colored wool flannel is then Washed with a 45-warm aqueous solution of 0.5 g./ liter of nonylphenol polyglycol ether and then rinsed with cold Water. A wellpenetrated grey Wool flannel of level shade Without a sandwich effect is obtained.

By using, in the above example, instead of the dyestuff mentioned, the cobalt-containing monoazo dyestuft' 2- amino-4-chloro-phenol 2 hydroxynaphthalene-6-sulfonic acid methylamide (dyestutf:coba]t=2:l) or the chromium-containing monoazo dyestufi 2 amino 4 chlorophenol+1 hydroxynaphthalene 3 sulfonic acid amide (dyestuff:chromium=2: 1) and otherwise following the procedure given above in the example, a ruby or blue colored wool flannel, respectively, is obtained. The dyeing is equally well penetrated and level.

EXAMPLE 14 40 parts of the commercial form of the dyestufif 'EriochromeCyanine R (Acid Blue 13 of Color Index, 2nd

of an aqueous 2.5 %-sodium alginate solution, 30 parts of [CsHirO-(O mrnn-osomm] coconut oil fatty acid-N,N-bis-((fi-hydroxyethyD-amide, and isopropanol, (weight ratio 9:922) which mixture is dissolved in 200 parts of water, as well as 10 parts of potassium chromate, dissolved in 250 parts of water.

The pH of the resulting solution is adjusted, if necessary, to 7.5 to 8, with acetic acid and brought up to 1000 parts with water. The temperature should be 50.

Wool flannel is padded with this liquor at 60 and squeezed out to a liquor content of about 100%. The padded fabric is then steamed with saturated steam for 30 minutes. The resulting blue-colored wool flannel is then washed with a 45 -warm aqueous solution of 0.5 g./liter of nonylphenol polyglycol ether, treated in an acid bath which contains ml./liter of 85%-formic acid for 15 to 30 seconds at 70 and then rinsed with 50-warm water. A well-penetrated, very level blue wool flannel is obtained which is free from a sandwich effect.

By using, in the above example, instead of the dyestufr mentioned, Eriochrome Yellow G (Cl. 25,100) or Eriochrome Red G (Cl. 18,750), and otherwise fOllOWing the procedure given in the example, correspondingly yellowor red-colored wool flannel, respectively, is obtained. The dyeings are equally well-penetrated and level.

EXAMPLE 15 By using, instead of the pad liquors described in Example 14, similar liquors, the pH of which has been adjusted to 3.5 to 4 with aqueous 80%-acetic acid and which contain, instead of sodium alginate, methyl cellulose and, instead of potassium chromate, 30 parts of chromium fluoride as agent afiording chromium, and Wool flannel is padded therewith at 50, squeezed out to a liquor take up of about 100% calculated on the weight of the goods and steamed with saturated steam for 30 minutes at 90, then blue, yellow or red-colored wool flannel, respectively, is obtained.

The dyeings have equally good penetration and evenness. If the steaming time is raised from 30 to 45 or 60 minutes, then dyeings of somewhat more color strength are obtained.

EXAMPLE 16 A fabric consisting of 45 parts of wool and 55 parts of polyglycol terephthalate fiber is impregnated and steamed in accordance with the first part of Example 1. The Wool portion is dyed orange while the polyester portion remains practically undyed.

EXAMPLE 17 A mixed fabric of wool and cellulose triacetate (weight ratio 1:1) is impregnated and steamed as described in the first part of Example 1. The wool portion is dyed orange, while the triacetate portion remains practically undyed.

EXAMPLE 18 11 parts of the chromium-containing monoazo dyestutf 2-aminophenol-4-sulfonic acid N,N dimethylamide 1- (3'-chlorophenyl)-3-methyl-5-pyrazolone, 1 part of the chromium-containing monoazo dyestuif 2-amino-4-methylsulfonyl-benzene carboxylic acid- 1 phenyl-3-methyl-5- pyrazolone and 0.5 part of the mixed chromium-containing dyestuff 2-amino-4-methylsulfonyl-benzene l-methylsulfonylamino-7-hydroxynaphthalene 1-(4'-chlorophenyl)-3-methylpyrazolone (the overall molar ratio of dyestufizchromium being 2:1) are dissolved in a 50-warm mixture of 300 parts of an aqueous 2.5 %-carob bean flour solution and 30 parts of a carrier mixture consisting of: di-(B-hydroxyethyD-amino salt of sulfated nonylphenol triglycol ether l e 1sC Carin-o s og-Nuncirnou) i1 14- coconut oil fatty acid-N,N-bis-(hydroxyethyl)-amide, and isopropanol, in a weight ratio of 9:9:2, which mixture has been dissolved in 250 parts of water.

10 parts of moth-proofing agent of the formula previously dissolved in 100 parts of warm water are added to this solution, the whole is diluted with warm water to 900 parts, then about 20 ml. of aqueous %-formic acid are added, and the whole is made up to 1000 parts with water.

The pH of the solution ready for use should be about 3.5 and the temperature should be about 50.

Woolen slubbing is padded with this liquor at 50, squeezed out to a liquor content of about calculated on the weight of the goods, and steamed with saturated steam for 15 minutes at 98". The goods are then washed with a solution containing 1 g./liter of nonylphenol polyglycol ether, rinsed with water, washed with an aqueous solution containing 2 nil/liter of aqueous 85%formic acid and again rinsed with water. Thereby, a level and well-penetrated moth-proof wool dyeing is obtained which shows no sandwich effect.

By using, instead of the moth-proofing agent of the above example, a compound of the formula and otherwise following the above-described procedure, a level orange-colored slubbing is obtained which has similar good properties to those described hereinbefore.

EXAMPLE 19 20 parts of the commercial form of the dyestutf Setacyl Yellow 2 GN (Disperse Yellow '3 of Color Index, 2nd edition) are dissolved in a 60-Warm mixture of 200 parts of an aqueous 2.5%sodium alginate solution and 35 parts of a carrier mixture consisting of: the tri-(B-hydroxyethyD-amine salt of sulfated octylphenol diglycol ether coconut oil fatty acid-N,N-bis-(fl-hydroxyethyD-amide, and isopropanol, in a weight ratio of 9:9:2, which carrier has been dissolved in 250 parts of water.

The solution obtained is brought up to about 1000 parts with warm water, whereby the pH should be at about 7 to 8 and, if necessary, this is adjusted with a small amount of acetic acid.

Polyacrylonitrile ('Orlon) fibers are impregnated at 30 with this solution, squeezed out at about 50%, cal culated on the weight of the goods, and steamed with saturated steam for 30 minutes at 98. The goods are then washed with a solution containing 1 g./liter of nonylphenol polyglycol ether and rinsed with cold water. A yellow-colored slubbing is obtained.

By using, instead of the 20 parts of the dyestuff given, the same amount of the commercial form of the dyestutf Setacyl Brilliant Red P-BL (C1. Disperse Red 55, Gallay-proofs) and otherwise following the same procedure as given above in this example, red-colored Orlon slubbing is obtained.

Instead of Orlon, Leacryl or Acrylan Regular can be padded with the same padding liquors in the same manner as described above.

15 EXAMPLE 20 Polyglycol terephthalate slubbing is padded with a liquor produced according to Example 19 at 50 and squeezed out to a liquor content of 60%, calculated on the weight of the goods.

The slubbing is steamed for 30 minutes at 98 with saturated steam, then washed with a solution containing 1 g./liter of nonylphenol polyglycol ether and rinsed with warm and cold water. A level yellow or red-colored polyester slubbing is obtained.

If, in the above padding liquors, 5 parts of p-phenylphenol are added, and otherwise the procedure given in the example is followed, then yellow or redeolored slubbing of greater color strength is obtained.

EXAMPLE 21 A pad liquor is prepared as described in Example 19 by repeating the same procedure, but using, in lieu of the dyestuif used therein, 20 parts of the dyestuff of the formula This dyestuif is produced as described in Example 1 of patent application Serial No. 237,755, filed Nov. 14, 1962, but using instead of 17.8 parts of dichloroaniline, an equimolar amount of 1=amino-2-bromo-4-nitrobenzene, and otherwise following the same procedure.

' To the resulting pad liquors there are added 5 parts of the sodium salt of o-phenylphenol and 5 parts of diammonium phosphate.

Polyglycol terephthalate yarn is then padded with the resulting liquor and squeezed out to a liquor content of 50% calculated on the Weight of the yarn.

The yarn is then steamed for 30 minutes at 90 with saturated steam, then washed with a solution containing 1 g./liter of nonylphenol polyglycol ether and rinsed with warm and cold water. A level greenish-blue polyester yarn is obtained, which is fast to washing and light.

EXAMPLE 22 360 parts of "a press cake of Eriochrome Black A (Color Index, 2nd Edition, Mordant Black 1) are introduced in batches into a vessel equipped with a turbomixer of the Homo-Rex type manufactured by Broglie & Co., Basel, Switzerland, having a preferred operational speed in the range of about 3,000 to 5,000 r.p.m., which vessel has been charged with 360 parts of water, and the contents are stirred for one hour at a speed of about 4,000 r.p.m.

In another vessel, a solution is prepared by mixing 120 parts of a carrier mixture consisting of sodium lauryloxy-ethoxyethyl sulfate (sodium salt of sulfat lauryl alcohol diglycol ether), coconut oil fatty acid N,N-bis-'(,8-hydroxyethyl)-amide and isopropanol, in a weight ratio of 9:9:2, 150 parts of water, and 10 parts of aqueous 80%-acetic acid, whereby the pH of the paste is adjusted to a value below 5.

This solution is added slowly to the contents of the first vessel while continuing stirring which is terminated minutes after the addition of the solution from the second vessel is complete.

A completely homogeneous, brown paste ready for use is obtained. 7

A pad liquor is prepared from 300 parts of the above paste by stirring the same with 350 parts of 60-warm water and parts of an aqueous 2.5% carob bean flour solution. To the resulting liquor there is added a mixture of 20 parts of chromium trifluoride (Cland 50 parts of an aqueous 20%-chromium acetate solution which has previously been boiled.

The solution is brought to 900 parts with 60-warm water and 20 cc. of aqueous 85%-formic acid are added to the solution which is then made up to 1000 cc. with water. The temperature of the pad liquor ready for use is then approximately 50.

Woolen slubbing is padded with this liquor in strict accordance with the method described in Example 7, with identically satisfactory results.

EXAMPLE 23 (l) parts of myristic acid n-('y-ethoxypropyl)- amide are liquefied by heating and are added slowly to 170 parts of bis-('y-hydroxy-propyl)ammonium salt of sulfated laurylphenolhexaglycol ether [bis-(' -hydroxypropyl)-ammonium laurylphenol hexa oxy-ethyl sulfate] in a turbomixer with stirring at about 4,000 r.p.m., for one hour. The completely homogenized mixture is then dissolved with 2,000 parts of 60-warm water.

(I 20 parts of the commercial dyestuif Cibazet Blue 46 (Color Index, 2nd Edition, Disperse Blue 16) are dissolved in 200 parts of hot water (50) and 230 parts of the carrier solution prepared as described under part I of this example are added with stirring to the dyestufi' solution. While continuing stirring, 200 parts of an aqueous 2.5%-carob bean flour solution are added slowly to the resulting mixture during about 5 minutes. The liquid is I then diluted with water of 50, the pH of the liquor is adjusted to approximately 6 by adding dilute aqueous acetic acid, and further water is added to make up 1000 parts of liquor.

(III) Perlon (nylon 66) fabric is impregnated with the pad liquor thus obtained, and then squeezed to leave 60% of liquor, calculated on the weight of the fabric, on the latter. The moist fabric is then directly steamed in saturated steam for 15 minutes.

A blue dyeing of good color depth is obtained.

Similarly good results are obtained when using in the preparation of the pad liquor according to this example, an aqueous 7%-galactomannan (condensation product of the polysaccharides in a molar ratio of about 1:1) solution in lieu of the carob bean solution described above.

Cellulose acetate or triacetate fabrics, or fabrics made of polyvinylalcohol of the Kuralon type (manufactured by Kurashiki Rayon K.K., Japan) or fabrics of polyurethane, of the Lycra-Spandex type of fibers (manufactured by E. I. du Pont de Nemours, Wilmington, Del.) are paddyed in the same manner as described above for Perlon, and similarly good quality blue dyeings are obtained.

EXAMPLE 24 (I) A carrier mixture according to the invention is prepared in the same manner as described in Part I of Example 23, but using, instead of 130 parts of the myristic amide and 170 parts of the sulfated laurylphenol hexaglycol ether salt used therein: parts of capric acid N-ethyl-N-y-hydroxy-propyl-amide, and 200 parts of N- methyl N 'yhydroxy-propylamrnonium p-octylphenyldeca-oxyethyl-sulfate, respectively.

(II) 20 parts of commercially available lrgalan Brown 2R1 (Color Index, 2nd Edition, Acid Brown 45) are dissolved in hot water (70) and the solution is slowly added during 5 minutes with stirring to 235 parts of the carrier mixture prepared as described above in Part I of this example. While continuing to stir, 300 parts of an aqueous 2.5%-carob bean flour solution are added with stirring to the resulting mixture. The liquor thus obtained is diluted with water of about 50 to make up 900 parts, its pH is then adjusted to about 5.5 to 6 by adding an adequate amount of dilute acetic, and water is then added to make up 1000 parts of a pad liquor ready for use.

(III) A fabric of polypropylene modified by basic groups, of the Meraklon D type (manufactured by Polymer Industrie Chimiche, S.p.a., Milan, Italy) is impregnated on the pad with the above-described pad liquor having a temperature of about 50 to 55, and is then squeezed to leave a liquor content of 60 to 70% by weight on the fabric (calculated on the weight of the fabric prior to impregnation).

The fabric is then steamed for 40 minutes in an atmosphere of saturated steam at 98. The steamed fabric is then washed in a bath containing 1 gram of nonylphenol polyglycol ether per liter of water, and finally rinsed with water, and dried.

A brown dyeing of good color depth and good quality is obtained.

Similarly, satisfactory brown dyeings are obtained by pad-dyeing polyurethane fabrics of the Lycra type (manufactured by E. I. du Pont de Nemours, Wilmington, Del.), 21 vinylpyridine-modified polyacrylonitrile fabric of the Acrilan regular type (manufactured by The Chemstrand Corporation, Decatur, Ala.), or a polyethylene fabric of the Curlin type (manufactured by Courtaulds, Ltd., London, England) according to the method described in this example.

EXAMPLE 25 (I) A carrier mixture is prepared as follows:

80 parts of capric acid N-(w-hydroxybutyD-amide are liquefied by heating and then added slowly into a turbomixer charged with 100 parts of potassium nonyloxy- (ethoxy) -ethyl sulfate (potassium salt of sulfated octyl alcohol decaglycol ether), and the resulting mixture is stirred at 4,000 rpm. for one hour.

To the resulting, fully homogenized mixture, there are added 20 parts of B-hexoxyethanol and 2500 parts of 60 warm Water, whereby a clear dyestulr' carrier mixture is obtained.

(III) A thickened dyestutf solution is prepared from 218 parts of the above carrier mixture solution and 205 parts of an aqueous solution of 5 parts of the commercial dyestuff Irgalan Yellow (Color Index, 2nd Edition, Acid Yellow 129), proceeding in the same manner as described in part H of the preceding example.

Similar good yellow dyeings are obtained on the fabrics used in Part III of Example 24, by proceeding in the same manner as described therein.

Similarly satisfactory results are obtained when using, in lieu of the carob bean flour solution used in Example 24, Part II, the same amount of an aqueous 2%-carboxymethyl cellulose solution.

EXAMPLE 26 Example 25 is repeated, but instead of 8 parts of the capric acid amide used therein, 12 parts of N,N-bis-(fihydroxypropyl)-lauramide are used as the first component, and, instead of the parts of the potassium salt of sulfated octylpolyglycol ether used therein, 14 parts of the potassium salt of sulfated myristyl alcohol tetraglycol ether C H (OC H -OSO K] are used as the second component of the carrier mixture according to the invention, and otherwise following strictly the same procedure as in the preceding example.

This dyestufi carrier solution is employed in Parts II and III of Example 24 in lieu of the carrier used therein. Similarly good results are obtained.

EXAMPLE 27 18 thalene-G-sulfonic acid, 6 g. of the dyestulf of the formula CH CHQNHG O CHr-Cl and 13 g. of the chromium-complex of the monoazo dyestulf 2 amino phenol 4 methyl sulfone- 1-phenyl-3- methylpyrazolone (molar ratio of dyestufi to chromium=2:1) are pasted with 60 g. of cold water. 750 g. of hot water are added while stirring and the whole is heated to boiling. Then 10 g. of crystal gum thickening agent pasted with ethanol for better solubility, are added while stirring. After the thickening agent has formed a clear solution, the solution is cooled to about 50, and 30 g. of a carrier mixture are added which mixture consist of 9 parts of nonylphenoxy-acetic acid bis-fi-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diethyleneglycol ether and 2 parts of isopropanol. 160 g. of an aqueous solution consisting of 40 g. of formic acid and 120 g. of water are added to this solution.

The pad liquor thus obtained is used to impregnate woolen slubbing at 50; the slubbing is then squeezed on a pad mangle to a liquor content of about calculated on the dry weight of the goods. The slubbing is then steamed for 30 minutes in saturated steam at 100- 102. After steaming, the goods are washed with about 40 warm water, and subsequently, at 40, with an aqueous solution containing 1 gram per liter of nonylphenol polyglycol ether. Then it is rinsed and dried. A bordeauxcolored slubbing is obtained which has no sandwich effect.

Equally good dyeings without a sandwich effect are obtained when the carrier mixture used in the example is replaced by equivalent amounts of one of the following mixtures, the procedure being otherwise the same as described:

(b) 9 parts of nonylphenoxy acetic acid-bis-fl-hydroxyethyl amide, 9 parts of the ammonium salt of sulfated lauryl alcohol triglycol ether and 2 parts of isopropanol, or

(c) 9 parts of nonylphenoxy acetic acid bis-fi-hydroxyethyl amide, 9 parts of the di-p-hydroxyethyl amine salt of sulfated lauryl alcohol triglycol ether and 2 parts of isopropanol, or

(d) 9 parts of nonylphenoxy acetic acid bis-fi-hydroxyethyl amide, 9 parts of the tri-[i-hydroxyethyl amine salt of sulfated lauryl alcohol triglycol ether and 2 parts of isopropanol, or

(e) 12 parts of nonylphenoxy acetic acid bis-B-hydroxyethyl amide, 24 parts of the potassium salt of sulfated myristyl alcohol pentaglycol ether and 4 parts of isopropanol, or

(f) 12 parts of nonylphenoxy acetic acid bis-fi-hydroxyethyl amide, 24 parts of the sodium or potassium salt of sulfated octylphenol diglycol ether and 4 parts of isopropanol, or

(g) 13.5 parts of nonylphenoxy acetic acid bis-fi-hydroxyethyl amide, 13.5 parts of the sodium salt of sulfated lauryl alcohol diglycol ether, 1.5 parts of isopropanol and 1.5 parts of fi-methoxy-ethanol, or

(h) 18 parts of nonylphenoxy acetic acid bis-,S-hydroxyethyl amide, 9 parts of the ammonium salt of sulfated nonylphenol triglycol ether and 3 parts of isopropanol, or

(i) 12 parts of nonylphenoxy acetic acid bis-fi-hydroxyethyl amide, and 14 parts of the potassium salt of sulfated myristyl alcohol tetraglycol ether, or

(k) 15 parts of nonylphenoxy acetic acid-fi-hydroxyethyl amide and 20 parts of the N-methyl-N-(y-hydroxypropyl)-amine salt of sulfated octylphenol decaglycol ether, or

(1) 9 parts of octylphenoxy acetic acid bis-jS-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol, or

(m) 9 parts of nonylphenoxy acetic acid mono-fl-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol, or

(n) 12 parts of nonylphenoxy acetic acid bis-,B-hydroxyethyl amide, 12 parts of the potassium salt of sulfated myristyl alcohol pentaglycol ether and 12 parts of the ammonium salt of sulfated nonylphenoxy acetic acid bis-fi-hydroxyethyl amide, or

(o) 15 parts of nonylphenoxy acetic acid-B-hydroxyethyl amide and parts of the N-methyl-N-(y-hydroxypropyl)-amine salt of sulfated octylphenol decaglycol ether and 10 parts of the sodium salt of sulfated coconut oil fatty acid mono-fl-hydroxyethyl amide.

EXAMPLE 28 35 g. of the dyestuff 1-amino-6-nitro-2-hydroxynaphthalene-4-sulfonic acid 2-hydroxynaphthalene are pasted with 60 g. of cold water and dissolved in 770 g. of hot water by heating to the boiling temperature. 50 g. of an aqueous acetic acid solution consisting of 10 g. of 80% acetic acid and 40 g. of water are slowly added to this solution. Then, 14 g. of galactomannan thickening agent pasted with a small amount of ethanol for better solubility, are added while stirring. Upon dissolution of the thickening agent, the mixture is cooled to about 50, and 35 g. of a carrier mixture are added consisting of 9 parts of nonylphenoxy acetic acid bis-fi-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol. 20 g. of 85% formic acid as well as a dispersion consisting of 80 g. of water and 40 g. of chromium fluoride are added to this solution.

This pad liquor is used to impregnate woolen slubbing at 50 which is squeezed on a pad mangle to a liquor content of about 105% calculated on the dry weight of the goods. The slubbing is then steamed at 100 to 102 with saturated steam. After steaming, the goods are washed with about 40 warm water and subsequently, at 40, with an aqueous solution containing 1 g./liter of nonylphenol polyglycol ether; then it is rinsed and dried.

In this manner a' black dyeing is obtained which has no sandwich etfect.

When the carrier mixture used in the example is replaced by one of the mixtures of letters (b) to (o) of Example 27 the procedure being otherwise the same as before, a black dyeing is also obtained which is free from a sandwich effect.

Similar satisfactory results are achieved by carrying out the procedure of this example with a carrier mixture free from isopropanol.

EXAMPLE 29 Then 10 g. of formic acid and 30 g. of water are added to this solution.

This pad liquor is used to impregnate woolen slubbing at 50 which is squeezed on a pad mangle to a liquor content of about 110% calculated on the dry weight of the goods. The slubbing is then steamed for 15 minutes in saturated steam at to 102. After steaming it is washed in about 40 warm water and then, at 40, in an aqueous solution containing 1 g./liter of nonylphenol polyglycol ether, whereupon it is rinsed and dried. A yellow dyeing is obtained which has no sandwich effect.

When the carrier mixture used in the example is replaced by one of the mixtures of letters (c) to (o) of Example 27 or by the carrier mixture used in Example 27 under (a), the procedure being otherwise the same as in Example 29, yellow dyeings are obtained which are free from any sandwich effect.

EXAMPLE 30 (a) 16 g. of the dyestuff sulfanilic acid 1-hydroxy[(3'- trichloropyrimidylamino) benzoylamino] naphthalene- 3,6-disulfonic acid are pasted with 40 g. of water and dissolved with further heating in 890 g. of hot water. 10 g. of galactomannan as thickening agent pasted with a small amount of ethanol for better solubility, are added to this solution while stirring. After dissolution of the thickening agent, the solution is cooled to 50, and 30 g. of a carrier mixture are added consisting of 9 parts of nonylphenoxy acetic acid bis-fl-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol. Then 10 g. of 85 formic acid and 30 g. of water are added to this solution.

The pad liquor thus obtained is used to impregnate woolen slubbing at 50 which is squeezed on a pad mangle to a liquor content of about 100% calculated on the dry weight of the goods. The slubbing is then steamed for 15 minutes in saturated steam at 100 to 102. After steaming, it is washed with about 40 warm water and then, at 40, with an aqueous solution containing 1 g./liter of nonylphenol polyglycol ether, whereupon it is rinsed and dried. A red dyeing is obtained which has no sandwich effect.

EXAMPLE 31 13 g. of the 1:2 chromium-complex of the dyestuff 2-aminophenol-4-methyl-sulfone 1 acetylamino 7 hydroxy-naphthalene are pasted with 60 g. of cold water and dissolved with further heating in 890 g. of hot water.

10 g. of galactomannan thickening agent (Solvitose OFA) pasted with a small amount of ethanol for better solubility, are added to this solution while stirring. After dissolution of the thickening agent, the solution is cooled to 50, and then 30 g. of a carrier mixture are added consisting of 9 parts of nonylphenoxy acetic acid bis-flhydroxy-ethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol.

10 g. of 80% acetic acid and 10 g. of water are added to this solution.

The pad liquor thus obtained is used to impregnate woolen slubbing at 50 which is squeezed on a pad mangle to a liquor content of about 105% calculated on the dry weight of the goods. The slubbing is then steamed for 15 minutes in saturated steam at 100 to 102". After steaming, it is washed with about 40 warm water and then, at 40, with an aqueous solution containing 1 g./liter of nonylphenol polyglycol ether, whereupon it is rinsed and dried. A grey dyeing is obtained which has no sandwich elfect.

Dyeings of a similar quality are obtained when the carrier mixture mentioned above is replaced by one of the mixtures of letters (b) to (o) of Example 27, the procedure being otherwise the same as in Example 31.

21 EXAMPLE 32 13 g. of the chromium-complex of the dyestufi used in Example 31 are pasted with 60 g. of cold water and dissolved with further heating in 890 g. of hot water.

10 g. of galactomannan as thickening agent pasted with a small amount of ethanol for better solubility, are added to this solution while stirring. After dissolution of the thickening agent the solution is cooled to 50, and then 30 g. of a carrier mixture are added consisting of 9 parts of nonylphenoxy acetic acid bis-fi-hydroxy-ethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol.

10 g. of 80% acetic acid and 10 g. of water are added to this solution.

The pad liquor thus obtained is used to impregnate woolen slubbing at 50 which is squeezed on -a pad mangle to a liquor content of about 105% calculated on the dry weight of the goods. The slubbing is then steamed for 10 minutes in saturated steam at 100 to 102. Then it is treated for 5 minutes in an aqueous bath of 95 containing 6 g./liter of 85% formic acid.

The slubbing treated in this way is washed with 40 warm water, then, at 40, in an aqueous bath containing 1 g./liter of nonylphenol polyglycol ether, and then rinsed and dried. A grey dyeing is obtained which has no sandwich effect.

When the carrier mixture used in the example is replaced by one of the mixtures of letters (b) to (o) of Example 27, the procedure being otherwise the same as described in the example, grey dyeings are obtained which are free from sandwich effect.

EXAMPLE 33 37.5 g. of the 1:2 chromium-complex of the monoazo dyestuff Z-carboxy 1 aminobenzene l phenyl 3- methyl-S-pyrazolone and 5.0 g. of the 1:2-chromiumcomplex of the monoazo dyestutf 2-aminophenol-4-sulfonic acid N methyl amide- 1 carbethoxyamino 7- hydroxy-naphthalene are dissolved in an 80-warm mixture of 200 g. of a 2.5% aqueous galactomannan-solution, 270 g. of water and 30 g. of a carrier mixture consisting of 9 par-ts of nonylphenoxy-acetic acid bis-flhydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol. The resulting solution is adjusted to a pH- value of 7 and diluted with cold water to 1000 parts. The temperature should be about 40.

This pad liquor is used to impregnate nylon toi-le which is squeezed to a liquor content of 50% of the fiber weight, steamed for 8 minutes at a temperature of 130, and rinsed first in hot and then in cold water.

A well-penetrated and very level olive dyeing is obtained.

EXAMPLE 34 A fabric consisting of 45 g. of wool and 55 g. of a blended fabric of 50% wool and 50% Polyethylene glycol terephthalate fiber is impregnated and steamed analogous to the manner described in Example 31. The woolen fibers of the fabric are dyed grey while the polyester portion remains practically undyed.

EXAMPLE 3 5 A blended fabric consisting of 50% wool and 50% cellulose triacetate is impregnated and steamed analogous to the manner described in Example 31. The woolen fibers of the fabric are dyed grey while the triacetate portion remains practically undyed.

EXAMPLE 36 7 g. of the 1:2 chromium-complex of the dyestutf 2- aminophenol 4 methyl-sulfone l acety1amino-7-hydroxynaphthalene are pasted with 60 g. of cold water and dissolved with further heating in 690 g. of hot Water.

10 g. of a thickening agent galactomannan pasted with a small amount of ethanol for better solubility, are added to this solution while stirring. After dissolution of the thickening agent, the solution is cooled to 50, and 30 g. of a carrier mixture are added consisting of 9 parts of nonylphenoxy acetic acid bis-fl-hydroxyethyl amide, 9 parts of the di-B-hydroxyethyl amine salt of sulfated lauryl alcohol triglycol ether and 2 parts of isopropanol.

10 g. of the moth deterrent of the formula SOsH NHCONH -o1 pre-dissolved in 100 g. of warm water are added to this solution. The whole is diluted with Warm water to 990 g., and finally 10 g. of acetic acid are added.

The pad liquor thus obtained is used to impregnate woolen slubbing at 50 which is squeezed on a pad mangle to a liquor content of about 105% calculated on the dry weight of the goods. The slubbing is then steamed for 15 minutes in saturated steam at to 102. After steaming, it is washed with about 40 warm water and then, at 40, with an aqueous solution containing 1 g./liter of nonylphenol polyglycol ether, whereupon it is rinsed and dried.

A greydyeing is obtained which does not show a sandwich effect and is well protected against damage by moths.

EXAMPLE 37 11 g. of the dyestufi of the formula HO (T I i NBC 0 CH CH3 are dispersed in an 80 warm mixture of 200 g. of a 2.5% aqueous sodium alginate solution and 35 g. of a carrier mixture consisting of 9 parts of nonylphenoxy acetic acid bis-,B-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol. The resulting solution is diluted with warm water to about 1000 g.; the pH-value should be about 7.

This solution is used to impregnate at 30 slubbing consisting of Orlon type polyacrylonitrile fiber which is squeezed to a liquor content of about 100% calculated on the dry weight of the fibers and steamed for 30 minutes in saturated steam at 98. Then it is washed with an aqueous solution containing 1 g./liter of nonylphenol polyglycol ether and rinsed with cold and warm water. A yellow dyeing is obtained.

When the 10 g. of the dyestuif mentioned are replaced by the same amount of the dyestufi l-amino-Z-methoxy- 4-hydroxyanthraquinone, the procedure being otherwise the same as described in the example, an Orlon slubbing is obtained which is dyed red.

The same pad liquors and the same methods as for Orlon can be used for the dyeing of Leacrylor Acrilantype polyacrylonitrile fibers.

EXAMPLE 3 8 Polyethylene glycol terephthalate slubbing is impregnated at 30 with a pad liquor prepared according to Example 27 and is squeezed to a liquor content of 80%.

The slubbing is steamed for 30 minutes in saturated steam at 98, then it is washed with an aqueous solution containing 1 g./liter of nonylphenol polyglycol ether and rinsed with warm and cold water. A level yellow or red dyeing, respectively, is obtained.

When the above pad liquor is mixed with 5 g. of ophenylphenol, the procedure being otherwise the same as 23 described in the example, a yellow or red dyeing, respectively, is obtained which has higher color strength.

EXAMPLE 39 360 g. of the dyestufi. 1-amino-6-nitro-2-hydroxynaphthalene-4-sulfonic acid- 2-hydroxynaphthalene in the form of a press cake are introduced in portions while stirring into a boiler fitted with a turbo-mixer and containing 360 g. of water. The mixture is stirred for one hour. 120 g. of a carrier mixture consisting of 9 parts of nonylphenoxy acetic acid bis-B-hydroxyethyl amide, 9 parts of the sodium salt of sulfated lauryl alcohol diglycol ether and 2 parts of isopropanol are mixed with 10 g. of 80% acetic acid in a second mixing vessel. This homogeneous mixture is poured slowly while stirring continuously into the dyestuff suspension, and the whole is stirred for another minutes until a homogeneous brown dyeing preparation is obtained which is ready for use.

A pad liquor is prepared by stirring 300 g. of this dyeing preparation with 350 g. of 60 warm water and 100 g. of a 2.5% aqueous carob bean flour thickener solution. The resulting solution is mixed with 40 g. of chromium trifiuoride and g. of 85% formic acid, and the liquor is then diluted With warm water to 1 liter. This liquor is used to impregnate woolen slubbing in the manner described in Example 18.

A level black dyeing is obtained, and the slubbing can be well combed and spun. The dyeing has good fastness to washing and light.

EXAMPLE 40 (a) 22 g. of the diazo dyestuff 2,2'-diamino-4,4'-di- 'd chlorodiphenyl sulfide 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 6 g. of the dyestuff of the formula CH: CH2NHC O GHz-Cl and 13 g. of the chromium-complex of the monoazo dyestutf 2-amino-phenyl 4 methyl sulfone 1-phenyl-3- methylpyrazolone (molar ratio of dyestuff to chromium =2z1) are pasted with 60 g. of cold water. 750 g. of hot water are added while stirring and the whole is heated to boiling. The 10 g. of crystal gum thickening agent pasted with ethanol for better solubility, are added while stirring. After the thickening agent has formed a clear solution, the solution is cooled to about 50, and 30 g. of a carrier mixture are added which consists of 16 parts of coconut oil fatty acid bis-fi-hydroxyethyl amide, 8 parts of the sodium salt of sulfated nonylphenoxy acetic acid bisfl-hydroxyethyl amide, 8 parts of water and 3 parts of isopropanol.

This solution is combined as in Example 27, with 160 g. of an aqueous solution consisting of 40 g. of 85% formic acid and 120 g. of water.

Woolen slubbing is dyed in the same manner as in Example 27.

Equally good dyeings without a sandwich effect are obtained by using instead of the carrier mixture employed in Example 40(a), equivalent parts of one of the following mixtures the procedure being otherwise the same as above:

(b) 16 parts of coconut oil fatty acid bis-B-hydroxyethyl amide, 16 parts of water and 6- parts of isopropanol,

(c) 16 parts of coconut oil fatty acid bis-B-hydroxyethyl amide, 32 parts of the sodium salt of sulfated nonylphenoxy acetic acid bis-)S-hydroxyethyl amide, 32 parts of water and 12 parts of isopropanol, or

(d) 152 parts of coconut oil fatty acid bis-B-hydroxyethyl amide, 58 parts of the sodium salt of sulfated coconut oil fatty acid mono-p-hydroxyethyl amide, 95 parts of water and 34 parts of isopropanol, or

(e) 24 parts of coconut oil fatty acid bis-p-hydroxypropyl amide, 10 parts of the sodium salt of sulfated (nonylphenyl)-(2,3-dihydroxypropyl)-ether, 14 parts of water and 8 parts of isopropanol, or

(f) 136 parts of coconut oil fatty acid bis-B-hydroxyethyl amide, 38 parts of the ammonium salt of sulfated nonylphenoxy acetic acid mono-fl-hydroxyethyl amide, 68 parts of water and 30 parts of isopropanol, or

(g) 16 parts of coconut oil fatty acid bis-fi-hydroxyethyl amide, 8 parts of the sodium salt of sulfated nonylphenoxy acetic acid b'is-B-hydroxyethyl amide and 8 parts of water, or

(h) 16 parts of coconut oil fatty acid bis-,B-hydroxyethyl amide, 8 parts of the ammonium salt of sulfated nonylphenoxy acetic acid bis-fi-hydroxyethyl amide and 8 parts of potassium salt of sulfated myristyl alcohol pentaglycol ether.

EXAMPLE 41 (a) Example 28 is repeated, but in lieu of the 35 g. of the carrier employed therein, 35 g. of a carrier mixture are added which consists of 16 parts of coconut oil fatty acid bis-fl-hydroxyethyl amide, 8 parts of the sodium salt of sulfated nonylphenoxy acetic acid bis-fi-hydroxyethyl amide, 8 parts of water and 30 parts of isopropanol. 20 g. of formic acid as well as a dispersion comprising -80 g. of Water and 40 g. of chromium fluoride are added to this solution.

Padding is then carried out'as described in Example 28.

A black slubbing is obtained which has no sandwich effect.

A similar black dyeing without sandwich effect is obtained by using instead of the carrier mixture employed in Example 41(a) above, one of the following mixtures the procedure being otherwise the same as before:

(b) 153 parts of coconut oil fatty acid bis-fi-hydroxyethyl amide, 58 parts of the sodium salt of sulfated coconut oil fatty acid mono-B-hydroxyethyl amide, parts of water and 34 parts of isopropanol, or

(c) 24 parts of coconut oil fatty acid bis-fi-hydroxypropyl amide, 10 parts of the sodium salt of sulfated (nonylphenyl)-(2,3-dihydroxypropyl)-ether, 14 parts of water and 8 parts of isopropanol, or

(d) 136 parts of the ammonium salt of sulfated nonylphenoxy acetic acid mono-fi-hydroxyethyl amide, 68 parts of water and 30 parts of isopropanol.

Equally satisfactory results are obtained bycarrying out the procedure of the example with a carrier mixture which does not contain isopropanol.

EXAMPLE 42 (a) Example 29 is repeated but instead of the carrier used therein, 30 g. of a carrier mixture are added consisting of 153 parts of coconut oil fatty acid bis-fi-hydroxyethyl amide, 58 parts of the sodium salt of sulfated coconut oil fatty acid mono-fl-hydroxyethyl amide, 95 parts of water and 34 parts of isopropanol. 10 g. of 85% formic acid and 30 g. of water are added to this solution. Padding is then carried out as described in Example 29. A yellow dyed slubbing is obtained which has no sandwich effect.

A yellow dyeing without a sandwich effect is also obtained when the carrier mixture employed in the example is replaced by one of the following mixtures the procedure being otherwise the same as before:

(b) 240 parts of coconut oil fatty acid bis-fi-hydroxypropyl amide, parts of the sodium salt of sulfated (nonylphenyl)-(2,3-dihydroxypropyl)-ether, parts of water and 80 parts of isopropanol.

(c) 136 parts of coconut oil fatty acid bis-,B-hydroxyethyl amide, 68 parts of the ammonium salt of sulfated nonylphenoxy acetic acid mono-Bhydroxyethyl amide, 68 parts of water and 30 parts of isopropanol.

When the steaming period is extended from 15 to 30 or 45 minutes, dyeings of a somewhat higher strength are obtained.

EXAMPLE 43 (a) Example 30 is repeated but instead of the carrier mixture used therein 30 g. of a carrier mixture are added which consists of 160 parts of coconut oil fatty acid bis-,8- hydroxyethyl amide, 80 parts of the sodium salt of sulfated nonylphenoxy acetic acid bis-B-hydroxyethyl amide, 80 parts of water and 30 parts of isopropanol. 10 g. of 85% formic acid and 30 g. of water are added to this solution.

Woolen slubbing is then padded in the manner described in Example 30.

A red dyeing is obtained which has no sandwic effect.

A turquoise-blue dyeing is obtained when using instead of the 16 g. of the above dyestuff, g. of sodium-copper phthalocyanin disulfonate, the procedure being otherwise the same as in the above example.

When the carrier mixture employed in the example is replaced by one of the following mixtures the procedure being otherwise the same as before, a red or a turquoise dyeing, respectively, is obtained which has no sandwic effect:

(b) 153 parts of coconut oil fatty acid bis-fi-hydroxyethyl amide, 58 parts of the sodium salt of sulfated coconut oil fatty acid mono-B-hydroxyethyl amide, 95 parts of water and 34 parts of isopropanol, or 240 parts of coconut oil fatty acid bis-fi-hydroxypropyl amide, 100 parts of the sodium salt of sulfated (nonylphenyl)-(2,3-dihydroxypropyl)-ether, 140 parts of water and 80 parts of isopropanol, or 136 parts of coconut oil fatty acid bis-fi-hydroxyethyl amide, 68 parts of the ammonium salt of sulfated nonylphenoxy acetic acid mono-p-hydroxyethyl amide, 68 parts of water and 30 parts of isopropanol.

EXAMPLE 44 (a) Example 31 is repeated but instead of the carrier mixture used therein 30 g. of a carrier mixture are added consisting of 160 parts of coconut oily fatty acid bis-fihydroxyethyl amide, 80 parts of the sodium salt of sulfated nonylphenoxy acetic acid bis-B-hydroxyethyl amide, 80 parts of water and 30 parts of isopropanol.

Then g. of 80% acetic acid and 10 g. of Water are added to this solution.

Woolen slubbing is then padded in the manner described in Example 31.

A grey dyeing is obtained which has no sandwich effect.

Dyeings of similar quality are obtained when the carrier mixture mentioned is replaced by one of the following mixtures, the procedure being otherwise the same as above:

(b) 153 parts of coconut oil fatty acid bis-fl-hydroxyethyl amide, 58 parts of the sodium salt of sulfated coconut oil fatty acid mono-B-hydroxyethyl amide, 95 parts of water and 34 parts of isopropanol, or

(c) 240 parts of coconut oil fatty acid bis-B-hydroxypropyl amide, 100 parts of the sodium salt of sulfated (nonylphenyl)-(2,3-dihydroxypropy1)-ether, 140 parts of water and 80 parts of isopropanol, or 136 parts of coconut oil fatty acid bis-B-hydroxyethyl amide, 68 parts of the ammonium salt of sulfated nonylphenoxy acetic acid mono-B-hydroxyethyl amide, 68 parts of water and parts of isopropanol.

EXAMPLE 45 Example 32 is repeated but instead of the carrier mixture used therein, 30 g. of a carrier mixture are added consisting of 160 parts of coconut oil fatty acid bis-)3- hydroxyethyl amide, 80 parts of the sodium salt of sulfated nonylphenoxy acetic acid bis-B-hydroxyethyl amide, 80 parts of water and 30 parts of isopropanol. 10 g. of

% acetic acid and 10 g. of water are added to this solution.

Woolen slubbing is treated further with this pad liquor as described in Example 32.

A grey dyeing is obtained which has no sandwich effect.

A grey dyeing without sandwich effect is also obtained when the carrier mixture employed in this example is replaced by one of the following mixtures, the procedure being otherwise the same as before:

(b) 153 parts of coconut oil fatty acid bis-B-hydroxyethyl amide, 58 parts of the sodium salt of sulfated coconut oil fatty acid mono-B-hydroxyethyl amide, parts of water and 34 parts of isopropanol, or

(c) 240 parts of coconut oil fatty acid bis-fi-hydroxypropyl amide, parts of the sodium salt of sulfated (nonylphenyl)-(2,3-dihydroxypropyl)-ether, parts of water and 80 parts of isopropanol, or

(d) 136 parts of coconut oil fatty acid bis-,B-hydroxyethyl amide, 68 parts of the ammonium salt of sulfated nonylphenoxy acetic acid mono-B-hydroxyethyl amide, 68 parts of water and 30 parts of isopropanol.

EXAMPLE 46 5.6 g. of the 1:2 chromium-containing monoazo dyestutf 2 carboxy-l-aminobenzene-e1-phenyl-3-methyl-5- pyrazolone and 5.0 g. of the 1:2 chromium-containing monoazo dyestutf 2-aminophenol-4-sulfonic acid-N-methyl amide 1-carbethoxyamino-7-hydroxynaphthalene are dissolved in an 80 warm mixture of 200 g. of a 2.5% aqueous galactomannan solution and 30 g. of a carrier mixture consisting of parts of coconut oil fatty acid bis-fl-hydroxyethyl amide, 80 parts of sulfated nonylphenoxy acetic acid bis-B-hydroxyethyl-amide, 30 parts of isopropanol and 350 parts of water. The resulting solution is adjusted to a pH-value of 7 and diluted with cold Water to 1000 parts. The temperature should be about 40.

This liquor is used to impregnate nylon toile which is squeezed to a liquor content of 50% of the fiber weight, steamed for 8 minutes at a temperature of 130 and then rinsed first in hot and then in cold Water.

A well-penetrated and level orange dyeing is obtained.

EXAMPLE 47 A fabric consisting of 45 g. of wool and 55 g. of polyethylene glycol terephthalate is impregnated and steamed in the manner described in Example 44. The woolen fibers of the fabric are dyed grey while the polyester portion remains practically undyed.

EXAMPLE 48 A blended fabric consisting of 50% of wool and 50% of cellulose triacetate is impregnated and steamed as described irr Example 4-4. The woolen fibers of the fabric are dyed grey while the triacetate portion remains practically undyed.

EXAMPLE 49 Example 36 is repeated but instead of the carrier mixture used therein, 30 g. of a carrier mixture are added consisting of 153 parts of coconut oil fatty acid bis-13- hydroxyethyl amide, 58 parts of sulfated coconut oil fatty acid mono-B-hydroxyethyl amide, 95 parts of water and 34 parts of isopropanol. 10 g. of the moth deterrent used I in Example 36 are added in the same manner.

27 EXAMPLE 5o 10 g. of the dyestutf of the formula are dispersed in an 80 warm mixture of 200 g. of a 2.5% aqueous sodium alginate solution and 35 g. of a carrier mixture consisting of 160 parts of coconut oil fatty acid bis-B-hydroxyethyl amide, 80 parts of sulfated nonylphenoxy acetic acid bis-,S-hydroxyethyl amide, 80 parts of water and 30 par-ts of isopropanol.

The resulting solution is diluted with warm water to about 1000 g.; the pH value should be about 7.

Orlon-type polyacrylonitrile fiber slubbing is impregnated in the same manner as described in Example 37.

A yellow dyeing is obtained.

When the 10 g. of the dyestuff mentioned are replaced by equivalent amounts of the dyestufr" l-amino-Z-methoxy- 4-hydroxy-anthraquinone the procedure being otherwise the same as described in the example, a red dyeing on Orlon is obtained. 7

The same pad liquors and the same methods used for Orlon can be used for dyeing Leacryl-or-Acrilan-type polyacrylonitrile fibers.

EXAMPLE 51 Polyethylene glycol terephthalate slubbing is impregnated with a pad liquor as prepared in Example 50, and is squeezed to a liquor content of 80%.

The slubbing is steamed for 30 minutes with saturated steam at 98, washed with an aqueous solution containing 1 g./liter of nonylphenol polyglycol ether and rinsed with warm and cold Water.

A level yellow or red dyeing, respectively, is obtained.

When the above pad liquor is mixed with g. of ophenylphenol and the same procedure is used as above, a more intensive yellow or red dyeing, respectively, is obtained.

EXAMPLE 52 Example 39 is repeated, but instead of the carrier used therein, 120 g. of a carrier mixture consisting of 16 parts of coconut oil fatty acid bis-B-hydroxyethyl amide, 8 parts of sulfated nonylphenoxy acetic acid ibis-fi-hydroxyethyl amide, 8 parts of water, and 3 parts of isopropanol, which 120 g. of carrier have been mixed together with 10 g. of 80% acetic acid in a separate mixing vessel, are added under continuous stirring to the dyestufi suspension, and the whole is stirred for another minutes. In this manner, a homogeneous brown dyeing preparation is obtained which is ready for use.

The pad liquor is obtained by diluting 300 g. of the above dyeing preparation with 350 g. of warm water at 60 and 100 g. of an aqueous 2.5% carob bean flour thickening solution. The resulting solution is mixed with 40 g. of chromium trifiuoride and g. of 85% formic acid, and the liquor is diluted to 1 liter with Warm water. This liquor is used to impregnate woolen slubbing in the manner described in Example 41.

A level black dyed slubbing is obtained which can be well combed and spun. The dyeing has good fastness to washing and light.

We claim:

1. A process for pad dyeing textile fibers selected from the group consisting of polyamide, polyester, polyacrylonitrile, polyurethane, polyethylene and polypropylene-type fibers, comprising (A) impregnating said fibers at a temperature of about to 70 C. with an aqueous pad liquor having a pH ranging from 2 to 10, which pad liquor contains as essential ingredients a non-cationic dyestufi capable of drawing on said fibers from a pad liquor of a pH in the aforesaid range, a thickener and a carrier mixture consisting essentially of (a) an unsulfated amide of substantially entirely saturated fatty acid of 8 to 14 carbon atoms substituted by from 0 to 1 higher alkyl-phenoxy radical wherein the higher alkyl moiety has from 8 to not more than 12 carbon atoms, amidified with a member selected from the group consisting of (a) monoto di-hydroxyalky-lamine offrom 2 to 4 carbon atoms, having one hydroxy group in w-position,

(B) bis-(w-hydroxyalkyD-amine of a total of from 4 to 6 carbon atoms,

('7) N-methyl-N-w-hydroxyalkylamine of a total of from 3 to 4 carbon atoms,

(6) N-ethyl-N-w-hydroxyalkylamine of a total of from 4 to 5 carbon atoms, and

(e) mono-(w-alkoXy-alkyl)-amine of a total of from 3 to 5 carbon atoms, at least two of which pertain to the alkyl moiety;

(b) a member selected from the group consisting (i) a sulfated condensation product of an alkanol of 8 to 14 carbon atoms with ethylene oxide, condensed with each other in a molar ratio of from 1:1 to 1:20,

(ii) a sulfated condensation product of alkylphenol, the alkyl moiety of which has from 8 to 12 carbon atoms, with ethylene oxide, in a molar ratio of from 1:1 to 1:20, and

(iii) the alkali metal, ammonium, lower alkylammonium and w-hydroxy-lower alkylammonium salts of (i) and (ii), and

(iv) a sulfated amide of a substantially entirely saturated fatty acid of 8 to 14 carbon atoms substituted by from 0 to 1 higher alkyl-phenoxy radical wherein the higher alkyl moiety has from 8 to not more than 12 carbon atoms;

(v) a sulfated(higher alkylphenyl)-(2,3-dihydroxypropyl) -ether the higher alkyl radical of which has from 8 to 12 carbon atoms,

(0) a member selected from the group consisting of isopropanol and a fi-alkoxy-ethanol of a total of from 3 to 8 carbon atoms,

the proportions by weight of (a) to (b) ranging from about 2:1 to 1:2, and the content of (c) ranging from 0 to 20% by weight, calculated on the total weight of said mixture, the content of said carrier mixture in said pad liquor ranging from about 5 to grams per liter of liquor;

(B) removing from the impregnated fibers pad liquor in excess of about 40 to calculated on the weight of the unirnpregnated fibers, and

(C) heat-treating the resulting humid fibers, thereby fixing the dyestuif on the fibers.

2. A process for pad-dyeing polyamide fibers compris- (A) impregnating said fibers at a temperature of about 30 to 70 C. with an aqueous pad liquor of a pH ranging from 2 to 10, which pad liquor contains as essential ingredients non-cationic dyes-tufl capable of drawing on said fibers from a pad liquor of a pH in the aforesaid range, a thickener and a carrier mixture consisting essentially of (a) an amide of substantially entirely saturated fatty acid of 8 to 14 carbon atoms amidified with bis-(w-hydroxyalkyl)-amine of a total of from 4 to 6 carbon atoms,

(b) an alkali metal salt of a sulfated condensation product of an alkanol of 8 to 14 carbon atoms, in a molar ratio of from 1:1 to 1:20,

with ethylene oxide condensed with each other (c) a member selected from the group consisting of isopropanol and a ,B-alkoxyethano'l of a total of from 3 to 8 carbon atoms, the proportions by weight of (a) to (b) ranging from about 2:1 to 1:2, and the content of (c) ranging from to 20% by weight, calculated on the total weight of said mixture, the content of said carrier mixture in said pad liquor ranging from about 20 to 40 grams per liter of liquor;

(B) squeezing the impregnated fibers to leave therein liquor amounting to about 40 to 130%, calculated on the weight of the unimpregnated fibers, and

(C) heat-treating the squeezed fibers in a humid medium, thereby fixing the dyestuff on the fibers.

3. A process as defined in claim 1, wherein the textile fibers are polyamide fibers.

4. A process as defined in claim 1, wherein the textile fibers are polyurethane fibers.

5. A process as claimed in claim 1 wherein the component under (b) is a sulfated condensation product of alkylphenol the alkyl moiety of which contains from 8 to 12 carbon atoms, with ethylene oxide the molar ratio of alkylphenol to ethylene oxide being from 1:1 to 1:20.

6. A process as described in claim 1 wherein the component under (b) is a sulfated condensation product of an alkanol of from 8 to 14 carbon atoms with ethylene oxide the molar ratio of alkanol to ethylene oxide being from 1:1 to 1:20.

7. A process as defined in claim 6, wherein said padliquor contains a dyestuff carrier consisting essentially of (a) coconut oil fatty acid N,N-'bis-(fl-hydroxyethyl)- amide,

(b) the sodium salt of sulphated lauryl alcohol diglycol ether, and

(c) isopropanol, the proportions by weight of (a) to (b) ranging from about 2:1 to 1:2, and the content of (c) ranging from 4 to 20% by weight calculated on the weight of said mixture.

8. A process as defined in claim 6, wherein said padliquor contains a dyestutf carrier consisting essentially of (a) a coconut oil fatty acid N,N-bit-(w-hydroxyalkyhamide,

(b) sodium salt of sulphated lauryl alcohol diglycol ether, and

(c) a mixture of isopropanol and fi-alkoxy-methanol of from 3 to 8 carbon atoms, of a weight ratio of 1:4 to 4:1;

the proportions by weight of (a) to (b)) ranging from about 2:1 to 1:2, and the content of (c) ranging from 4 to 20% by weight calculated on the weight of said mixture.

9. A process as claimed in claim 1 wherein the component under (b) is an alkali metal, ammonium, lower alkylammonium or w-hydroxy-lower alkylammonium salt of a sulfated condensation product of alkanol of from 8 to 14 carbon atoms with ethylene oxide the molar ratio of alkanol to ethylene oxide being from 1:1 to 1:20.

10. A process as defined in claim 9, wherein said padliquor contains a dyestufi' carrier consisting essentially of (a) coconut oil fatty acid N,N-bis-(5-hydroxyethyl)- amide,

( b) N,N di-ethanol-ammonium salt of sulphated lauryl alcohol diglycol ether, and

(c) a mixture of isopropanol and fi-alkoxy-methanol of from 3 to 8 carbon atoms, of a weight ratio of 1:4 to 4: 1; the proportions by weight of (a) to b) ranging from about 2:1 to 1:2, and the content of (c) ranging from 4 to 20% by weight calculated on the weight of said mixture.

11. A process as defined in claim 9, wherein said padliquor contains a dyestuff carrier consisting essentially of (a) a coconut oil fatty acid N,N-bis-(w-hydroxyalkyD- amide of a total of from 4 to 6 carbon atoms, and

(b) an alkali metal salt of sulphated lauryl alcohol monot-o pentaglycol ether, the proportion of (a) to (b) ranging from about 2:1 to 1:2.

12. A process as claimed in claim 1 wherein the component under b) is an alkali metal, ammonium, lower alkyl-ammonium or w-hydroxy lower alkylammonium salt of a sulfated condensation product of alkylphenol the alkyl moiety of which has from 8 to 12 carbon atoms, with ethylene oxide, the molar ratio of alkylphenol to ethylene oxide being from 1:1 to 1:20.

13. A. process as defined in claim 12, wherein said pad-liquor contains a dyestuff carrier consisting essentially of (a) an alkali metal salt of sulphated alkylphenol diglycol ether, alkyl having 8 to 12 carbon atoms,

(b) coconut oil fatty acid N,N-bis-(fi-hydroxyethyl)- amide, and

(c) isopropanol, the proportions by weight of (a) to (b) ranging from about 2:1 to 1:2, and the content of (c) ranging from 4 to 20% by weight calculated on the weight of said mixture.

14. A process as defined in claim 12, wherein said pad-liquor contains a dyestutf carrier consisting essentially of (a) the ammonium salt of sulphated nonylphenol triglycol ether,

(b) lauric acid N,N-=bis-(fi hydroxyethylyamide, and

(c) isopropanol, the proportions by weight of (a) to ('b) ranging from about 2:1 to 1:2, and the content of (c) ranging from 4 to 20% by weight calculated on the weight of said mixture.

15. A process for printing woolen material comprising (A) printing textile material made from unchlorinated wool at a temperature of about 15 to 55 C. with a printing mixture having a pH ranging from 2 to 10, which mixture contains as essential ingredients, apart from water, a dyestutf capable of drawing on said fibers from a medium of a pH in the aforesaid range, and a thickener, a dyestuff carrier mixture consisting essentially of (a) an unsulfated amide of substantially entirely saturated fatty acid of 8 to 14 carbon atoms substituted by from 0 to 1 higher alkyl-phenoxy radical wherein the higher alkyl moiety has from 8 to not more than 12 carbon atoms, amidified with a member selected from the group consisting of v (a) mono-w-hydroxyalkylamine of from 2 to 4 carbon atoms, (5) bis-(w-hydroxyalkyl)-amine of a total of from 4 to 6 carbon atoms, (7) N-methyl-N-w-hydroxyalkylamine of a total of from 3 to 4 carbon atoms, (6) N-ethyl-N-w-hydroxyalkylamine of a total of from 4 to 5 carbon atoms, and (e) mono-(w-alkoxy-alkyl)-amine of a total of from 3 to 5 carbon atoms, at least two of which pertain to the alkyl moiety; (1)) a member selected from the group consisting (i) a sulfated condensation product of an alkanol of 8 to 14 carbon atoms with ethylene oxide, condensed with each other in a molar ratio of from 1:1 to 1:20, (ii) a sulfated condensation product of alkylphenol, the alkyl moiety of which has from 8 to 12 carbon atoms, with ethylene oxide, in a molar ratio of from 1:1 to 1:20, and (iii) the alkali metal, ammonium, lower al- 31 kylammoniurn and w-hydroxy-lower alkylammonium salts of (i) and (ii),

(iv) a sulfated amide of a substantially entirely saturated fatty acid of '8 to 14 carbon atoms substituted by from Otto 1 higher alkyl-phenoxy radical wherein the higher alkyl moiety has from 8 to not more than 12 carbon atoms,

(v) a sulfated (higher alkylphenyl) (2,3-dihydroxypropyl)-ether the higher alkyl radical of which has from 8 to 12 carbon atoms,

(c) a member selected from the group consist ing of isopropanol and a fi-alkoxy-ethanol of a total of from 3 to 8 carbon atoms, the proportions by weight of (a) to (b) ranging from about 2:1 to 1:2, and the content of (c) ranging from '0 to 20% 'by weight, calculated on the total weight of said mixture, the content of said carrier mixture in said pad liquor ranging from about 5 to 100 grams per liter of liquor, and

(B) heat-treating the printed fibers in a humid medium,

thereby fixing the dyestuif on the fibers.

UNITED" STATES PATENTS Kritchevsky 8- 8 X Richardson 252-152 Preston 252;-11'7 Vitale et a1. 252 1 52 Casty et a1 8+-93 Casty 8 '54 Casty 8.54 Kritchevsky 8-- 90 Kritchevsky 8,90 'Katz 88 6; X Musser et a1. 8-83 Hirsbrunner et a1. '8 55 Weinstein et a1. 89 4 OTHER REFERENCES NORMAN G. TORCHIN, Primary Examiner.

J. HERBERT, Assistant Examiner.

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US3469930 *May 3, 1966Sep 30, 1969Ici LtdWool dyeing process
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Classifications
U.S. Classification8/501, 8/904, 8/609, 8/572, 8/907, 8/540, 8/908, 8/920
International ClassificationD06P1/649, D06B3/16, D06P1/613, D06B17/02, D06P1/62
Cooperative ClassificationD06B2700/095, Y10S8/907, D06P1/649, Y10S8/92, D06P1/613, D06P1/6496, D06P1/627, D06B17/02, D06P1/628, Y10S8/904, D06P1/6131, Y10S8/908, D06P1/6135, D06B3/16
European ClassificationD06B3/16, D06P1/62D, D06P1/649K2, D06P1/613B, D06B17/02, D06P1/62B4, D06P1/613B4, D06P1/649, D06P1/613