US3334960A

US3334960A - Process for coloring nitrogen-containing fibrous material

Info

Publication number: US3334960A
Application number: US519521A
Authority: US
Inventors: Abel Heinz
Original assignee: Ciba AG
Current assignee: BASF Schweiz AG
Priority date: 1962-11-27
Filing date: 1966-01-10
Publication date: 1967-08-08
Anticipated expiration: 1984-08-08
Also published as: GB997513A; DE1287554B; CH454082A; AT249621B; FR1383151A; NL300987A; ES293882A1; BE640414A; CH1391262A4

Description

United States Patent Office 3,334,960 7 Patented Aug. 8, 1967 PROCESS FOR COLORING NITROGEN-CONTAIN- ING FIBROUS MATERIAL Heinz Abel, Reinach, Basel-Land, Switzerland, assignor to Ciba Limited, Basel, Switzerland No Drawing. Filed Jan. 10, 1966, Ser. No. 519,521 Claims priority, application Switzerland, Nov. 27, 1962, 13,912/ 62; Jan. 11, 1965, 366/65 Claims. (Cl. 8-54) This is a continuation-in-part of our application Ser. No. 326,240 filed Nov. 26, 1963, now abandoned. It relates to a process for coloring nitrogen-containing fibrous material.

It has been found that fibrous materials containing nitrogen can.be colored, i.e. dyed or printed at 'room higher fatty amines containing, for example 10 to 22 temperature with dyestuffs that are soluble or only disganic carboxylic acid to the preparations. Though it is possible to use alternatively inorganic acids, for example phosphoric acid, organic aliphatic monocarboxylic and dicarboxylic acids, above all those of low molecular binations such, for

carbon atoms.

Among the cationic assistants particularly good results have been obtained with those which owe their solubility in water exclusively to groupings containing a basic nitrogen atom. These compounds are predominantly amine Y salts or quaternary ammonium salts of cyclic or openchain. tertiary amines or of reaction products 'ofalkyloamides of higher fatty acids with 'alkanolamines. Accordingly, there may be used, for example,' cetyl trimethyl ammonium bromide, cetyl pyridinium' bromide, a quaternary salt of the reaction product of stearic acid methylolamide with triethanolamin e, ,orfa quaternary salt of bis-lauryltetramethylethylenediamine. In some cases a particularly, advantageous lev lling lfect may be achieved with com' assistants. Particularly suitable cornassistants, the .componentsof such combinations having the structure defined above. Y

The. surface active.coacervating agents may be nonionic or anionic andmust be capable of causing the dye preparation tocoacerv'ate. The term coacervation describes the deinixing of a, colloidal solution of a hydrophilic colloid to formtwo liquid phases. The phase having a higher contentof colloidin this case the phase containing a larger share of auxiliaryis called the coacervate, whereas the, phase having a lower content of colweight are particularly suitable. Inter alia, good results m are obtained by using monochloroacetic or nitric acid. Likewise good results are achieved with tartaric, propionic,

glycollic and lactic acid. Particularly good results are obtained with acetic acid and especially with formic acid; these two acids are advantageously used in as concentrated a form as possible. The amount of acid to be added 'may vary within rather wide limits, for example from 4 to 30% calculated on the weight of the dye preparation, though an amount of the order of 10 to 20% is preferred.

A wide variety of fibrous materials containing nitrogen can be dyed or printed by the. present process, including both natural and synthetic materials. Among the natural materials there may be mentioned leathers, pelts (for example sheepskins), hairs, for example human hair, hairs of goats, rabbits or hares, feathers, sisal (which contains proteinic substances embedded in cellulose) and above all wool. Suitable synthetic materials are primarily those from polyaprylonitrile, polyamide (for example condensation products of hexamethylenediamine and adipic acid), polycondensates of w-aminoundecanoic acid especially of e-caprolactam. It will be readily understood that mixtures containing the afore-mentioned materials may likewise be dyed or printed.

. Thedye preparation must contain at least one surfaceactive ""assistant. These assistants act as levelling, dispersingfor wetting agents, may have coacervating power and may be of the non-ionic or cationic kind or even of the anionic type if they have coacervating power. These surface-active agents may be used either alone or in mixtures with one another.

Thenon-ionic assistants are adducts of ethylene oxide withi'compounds containing at least one reactive hydrogeniatom, that is to say with compounds that contain primary or secondary amino groups or hydroxyl groups,

which groups may be linked with a carbonyl group. Thus, the compounds concerned are polyglycol ethers of hydroxy compounds, for example of alkylphenols, such as an octylphenol or nonylphenol, or of higher aliphatic alcohols, such as lauryl, cetyl or octadecyl alcohol, or of loidin this case the phase containing less auxiliaryis called the equilibrium liquid. Thus, in a coacervated system the two phases contain the same solvent. It is another. characteristic ofa coacervated system that a small amount of colloid is capable, of taking up a relatively large amount. of solvent, in the present case water. As a rule the amount of solvent taken up is, a multiple of the amount of coacer-; vating agent used. The two co-existing liquid phases should be present in the form of an emulsion. If necessary, a rather stable emulsion in which the two phases are well I distributed can be prepared by adding a thickener.

"Auxiliariescapable of satisfying these conditions may belong to a wide variety of compounds. Particularly suitable for the present process are the reaction products obtained from higher fatty acids and hydroxyalkylamines.

Ethylene oxide adducts of such reaction products are likewise suitable. Such products can be prepared, without additional use of ethylene. oxide, from higher fatty acids, preferably those-which contain about 12 carbon atoms 1 such as caprylic, stearic, oleic or especially coconut oil fatty acids, and'hydroxyalkyl amines, such as triethanolamine, dihydroxyethylenediamine and preferably diethanol amine. The reaction is so conducted as to produce a molar ratio of hydroxyalkylamine-fatty acid greater than I 1, for example 2:1. Such compounds have been described in US. Patent No. 2,089,212. If ethylene oxide condensation products of these compounds are required, the molecular proportion of fatty acid to ethylene oxide should be 1:2 to 1:15. The sequence in which the three reactants are reacted is immaterial.

Apart from the reaction products of fatty acids with hydroxyalkylamines there may also be used those from fatty acids with N-substituted or unsubstituted aminoacids or their salts. Such a compound is, for example, the

' lauric acid sarcoside-monoethanolamine salt.

alcohols, alkylphenols, higher alkylmercaptans or higher:

aliphatic amines. This type of auxiliaries should prefer-;

ho's'e oftwo disparate non-ionic assistants v I p a V j as adductsof-ethylene oxide with; higheraliphatic, alcohols-or with alkylphenols with ethyl-. ene oxide adducts of higher aliphatic amines. If desired, there maybe used combinations of non-ionic and cationic.

ably contain at most 8 mols of ethylene oxide in the polyglycol ether chain. They correspond to the formula where R represents a hydrophobic radical, X represents a hydrogen atom or an acid solubilizing group and n is a whole number not greater than 8. Special mention in this connection is deserved by the group of compounds of the formula where n and X have the above meanings and R represents an aliphatic, cycloaliphatic or aliphatic-aromatic radical, preferably a hydrocarbon radical with 10 to 22 carbon atoms. Such radicals are derived from alcohols, such as lauryl, tridecyl, oleyl, octadecyl or hydroabiethyl alcohol, from carboxylic acids such as lauric acid or coconut oil fatty acid, and especially from alkylphenols such as octylphenol or nonylphenol.

These assistants are obtained when the aforementioned alcohols, acids or alkylphenols are reacted with e.g. l to mols of ethylene oxide, preferably with 1 to 3 mols of ethylene oxide and the resulting reaction product is, if desired or required, etherified with a halogencarboxylic or hydroxycarboxylic acid, for example with chloroacetic acid; or is converted into an acid ester with the aid of an organic dicarboxylic acid such as maleic, malonic or succinic acid, or preferably with an inorganic polybasic acid, such as orthophosphoric acid or especially sulfuric acid.

Particularly valuable compounds in this group are those of the formula where m is a whole number, at least 7, p is a number from 1 to 5, preferably from 1, 2 or 3, and Z represents an acid water-solubilizing group, preferably the radical of a polybasic inorganic acid. It is also possible to use mixtures of assistants of the above formulae, especially those in which the {-CH CH O) radicals are non-uniform so that the average value of n or p no longer represents a whole number, and may be, for example, about 1.5. It is of special advantage to use for the manufacture of the aqueous preparations, instead of the acid ethers or esters, their alkali metal, ammonium or amine salts.

The amounts of coacervating agents to be used may vary within wide limits. Since the amount at which coacervation occurs differs according to the auxiliary used, it is not possible to state generally applicable limiting quantities, but it is a definite advantage if the coacervate formed constitutes at least of the total volume of the dye preparation. The amount of coacervate formed can be measured by sedimentation in a measuring cylinder or according to a microscopic method.

The dyestuffs to be used in the present process are at least dispersible in water, that means that they are water-soluble or only dispersible in water. These dyestuffs may contain reactive groups capable of entering a covalent bond with the fibrous material or they may be. free from such groups.

Among the water-soluble dyestufis preference is given to those which owe their solubility in water to the presence of acid groups, such as carboxylic acid groups, and especially of sulfonic acid groups. In other respects, the dyestuffs may belong to a wide variety of types, for example to the oxazine, triphenylmethane, xanthene, nitro, acridone or phthalocyanine dyestuffs, and above all to the metallized and metal-free monoazo or polyazo dyestuffs or to the anthraquinone dyestuffs.

The term reactive dyestuffs-which otherwise may belong to the groups mentioned above-includes dyestuffs that are capable of forming a chemical, that is to say covalent, bond with the material to be dyed or printed. As groupings capable of imparting this property to the dyestuff there may be mentioned epoxide groups, ethyleneimino groups, isocyanate groups, isothiocyanate groups, carbamic acid aryl ester groups, the propiolic acid amide grouping, arylamino groups; groupings that contain a mobile substituent and are easy to split with entrainment of the bond electron pair, for example sulfohalide groups, aliphatically bound sulfuric acid ester groups and aliphatically bound sulfonyloxy groups and halogen atoms, more especially an aliphatically bound chlorine atom; above all the vinylacyl groups, such, for example, as the vinylsulfone groups and especially the carboxyvinyl group. These mobile substituents are advantageously in position v or [3 of an aliphatic radical which is bound with the dyestuff molecule directly or through an amino, sulfone or sulfonic acid amide group; in the case of those relevant dyestuffs which contain as mobile substituents halogen atoms, these mobile halogen atoms may also be present in an aliphatic acyl radical, for example in an acetyl radical, or in positions 5 or out? of a propionyl or acryl radical or in a'heterocyclic radical, for example in a pyrimidine, pyridazine or triazine ring. The dyestuffs contain advantageously a grouping of the formula in which X represents a nitrogen bridge and Z a hydrogen atom, a possibly substituted amino group, an etherified hydroxyl or mercapto group or a halogen atom or an alkyl, aryl or aralkyl group and A represents a hydrogen or halogen atom. The halogen atoms are, for example, bromine atoms, or preferably chlorine atoms.

It is also possible to use dyestuffs containing diphenoxytriazine groups or those which contain a grouping of the formula where R stands for an ortho-arylene radical.

Further suitable reactive groupings are the following radicals: Trichloropyridazine, dichloroquinoxaline, dichlorobutene, halogenated pyridazone, sulfonyldichloropropylamide, allylsulfone, allylsulfide, 2-halogenobenzthioazole-carbarnide and ,B-sulfatopropionic acid. amide. Especially favourable results are obtained with reactive dyestuffs that are derived from azo dyestuffs and contain as the reactive group at least one acrylamide or a-halogenoacrylamide group, that is to say an ethylenically unsaturated group, or a group convertible thereinto, for example an azfl-dihalogenopropionyl group.

The term dyestuffs dispersible in water refers to those which are insoluble in water but are capable of forming in the finely ground state, at least with the aid of a dispersant, very fine aqueous suspensions. In the form of these suspensions the dyestuffs produce very durable dyeings, more especially on synthetic fibers and pelts. It is advantageous to use so-called disperse dyestuffs, which may be free from metal or contain =metal bound in complex union.

Preferred azo dyestuffs are those which contain sulfonic acid groups and have affinity for wool, for example from an acetic acid or sulfuric acid bath. Likewise, very good results are obtained with acid azo-chromium complex dyestuffs containing one atomic production of chromium for every dyestuff molecule. However, not only metallized dyestuffs are suitable but also those which are subjected to metallization only in the course of the dyeing process. In this connection particularly valuable results have been obtained with ortho: orthd-dihydroxyazo dyestuffs and with dyestuffs containing ortho-hydroxycarboxy groupings which are conventionally formed in acid dyeba-ths with metal donors, more especially potassium bichromate, at an elevated temperature. Particularly favorable results are obtained with azo metal complexes containing one atomic proportion of metal for every two dyestuff molecules in the case where coacervating surfaceactive assistants are used. Especially suitable metal atoms in this connection are chromium and cobalt. These 1:2- metal complexes may be free from the afore-mentioned acid water-solubilizing groups and contain in their place alkylsulfone or sulfonamide groups.

The present process is suitable for coloring fibrous ma terials containing nitrogen at room temperature. The impregnation with the aqueous preparation can be carried out on a padder, or the fibrous material can be printed, preferably by the slubbing printing method. Best results have been obtained in vigoureux printing.

After the dye preparation has been applied according to the present process to the material to be dyed or printed, the latter is stored for a varying period of time at room temperature, during which it must be ensured that the material does not dry even partially. Consequently, the material must be stored in a closed system, for example in a closed vessel, or it must be Wrapped in a plastic foil or in a rubber blanket. For the present purpose room temperature signifies the temperature in the room concerned or a temperature that varies only insignificantly therefrom and it is immaterial whether this temperature is high or low. It is taken to be on an average about 20 C.; if it is higher, the storing period is correspondingly shorter, when it is lower, the storing period is correspondingly extended. The minimum storing period is 1-0 minutes, but it can be advantageously extended, for example up to 24 to 48 hours, especially in the case of medium strong to dark shades.

After having been stored, the material is washed in order to remove any acid residues from the dyed or printed material. The washing operation may be performed with hot or preferably cold washing liquors which, for the purpose of neutralizing the excess acid, contain an alkali metal compound, such, for example, as sodium carbonate or sodium hydroxide or preferably ammonia.

As further constituents the dye preparations may contain thickening agents, provided they are compatible with acids. There are suitable, above all, starch ethers, carboxyalkyl celluloses, especially carboxymethyl cellulose, etherified carbubic acids or compounds having similar effects.

In manufacturing the dye preparations there may be further added a solution promoter, that is to say, as is commonly known, a substance that renders compounds that are practically insoluble in a certain solvent soluble in that particular solvent. As such compounds there are preferably used in the present process derivatives of ethyleneglycol. Particularly suitable for this purpose are polyethyleneglycols of widely varying molecular weights and monomeric glycols etherified with lower alcohols (for example those containing 1 to 4 carbon atoms), more especially ethyleneglycol monoethyl ether.

Furthermore, it has proved advantageous to add an antifoaming agent to the dye preparation, especially when coacervating agents are used; particularly good results have been obtained with silicone based antifoaming agents. 7

Notwithstanding the relatively 'high acid concentrations the fibers are not damaged when treated according to the present process. This is why it offers the advantage that 6 dyeings of considerable tinctorinal strength can be achieved without using external hearing and more especially also on materials that are sensitive to heat.

Unless otherwise indicated, parts and percentages in the following example are by weight.

Example 1 Pure wool gabardine piecegoods are impregnated in the triangular interspace between the rollers of a horizontal padder with the following preparation and then squeezed to a weight increase of 70%:

10 parts of the dyestutf of the formula 5 parts of a reaction product of 100 parts of commercial oleylamine and 113 parts of ethylene oxide 2 parts of an adduct of 8 mols of ethylene oxide with 1 mole of para-tertiary octylphenol 100 parts of a 5% aqueous thickening of etherified carubic acids 200 parts of formic acid 683 parts of water 1000 parts The padded material is stored for 6 hours at room temperature while being protected from drying by being wrapped in a polyethylene foil. After storing, the material is rinsed in a conventional washing machine for 15 minutes with cold water and then until neutral with addition of 2 parts of 25% ammonia solution per 1000 parts of water, then once more rinsed in cold water and finally dried. The resulting vivid red dyeing has good properties of wet fastness.

Similarly good results are obtained when the above continuation of assistants is replaced by one of the following combinations (a) 5 parts of the adduct of 35 mols of ethylene oxide with 1 mol of octadecyl alcohol 5 parts of cetyl pyridinium bromide wherein the second component may be replaced by 5 parts of cetyl trimethyl ammonium bromide or 5 parts of the dibromide of bis-lauryl tetramethylenediamine (b) 3 parts of the acetate of a condensation product of 1 mol of stearic acid methylolamide and 1 mol of triethanolamine 2 parts of an adduct of 8 mols of ethylene oxide with 1 mol of para-tertiary octylphenol or by the separate assistants (c) 5 parts of the reaction product of parts of commercial oleylamine and 113 parts of ethylene oxide (d) 5 parts of the adduct of 8 mols of ethylene oxide with 1 mol of para-tertiary octylphenol.

The replacement of formic acid by thioglycollic acid, acetic acid or acrylic acid gives similarly good results.

The Wool gabardine piecegoods can be replaced by slubbings, loose wool, human hair, feathers, wool felts, ladies dress materials or other woollen fabrics of any quality and state of processing.

Without imparing the results the storing time can be reduced down to 3 hours or extended up to 24 hours.

1: 1 METAL COMPLEXES Metal Dyestufi Color HO H038 OH i 3 Cr N=N-O I I Red.

OH H2N Cr O2NGN=N Green.

OaH

1103s OH HO Cr N=N Blue.

S OaH OH HO S0311 Cr HOaS-%N=N Blue.

Example 3 HOBS H0 Wool' muslin is chlorinated and then impregnated with 0:8 N= ON=N the following padding liquor: p

' CH: HOZS NH 5 parts of the dyestufi of the formula 5 I I 40 CH8 HOaS l IH O CH3 solrr' 11d HOaS NCO-CH=CH1 10 parts of the dyestufl of the formula HN-COCH=CH2 I? NH,

- SOaH 3 parts of the acetate of a condensation product of 1 mol of stearic acid methylolamide and 1 mol of triethanolamine H 2 parts of an adduct of 8 mols of ethylene oxide with 0 NHONHCOCH v 1 mol of para-tertiary octylphenol 100 parts of a 5% aqueous thickening of ethenfied 5 parts of the dyestufi of the formula carub1c acids 150 parts of 85% formic acid H 0 740 pans of water SOSH I 1000 parts I I 0H3 The padded material is reeled, wrapped up so as to NH exclude all air and so stored for 20 minutes at room tem- H perature, then thoroughly rinsed in flowing water and finally treated for another 20 minutes in a bath contain- N N ing per 1000 parts of water 2 parts of sodium carbonate. O 5 l' The resulting orange-red dyeing-is of medium tinctorial 1 strength and has good wet fastness properties. CH3 N 3 parts of a reaction product of 100 parts of com- Example 4 10 parts of the dyestuff of the formula mercial oleylamine and 113 parts of ethylene oxide 5 parts of an adduct of 8 mols of ethylene oxide with 1 mol of para-tertiary octylphenol 200 parts of a 5% aqueous thickening of ethen'fied carubic acids 11 150 parts of 85% formic acid 617 parts of water 1000 parts The impregnated fabric is reeled, wrapped in a polyethylene foil and so stored for 10 hours at room temperature, then washed in a bath containing per 1000 parts of water 6 parts of 25% ammonia solution, thoroughly rinsed and finally dried.

A clear green/red melange effect is obtained, the wool being dyed green and the cotton red.

Equally good results are obtained when the above assistant combination is replaced by 10 parts of dinaphthylmethanesulfonic acid and 50 parts of the reaction product of 1 mol of coconut oil fatty acid with 2 mols of diethanolamine.

When the above dyestufi combination is replaced by 20 parts of the dyestufi of the formula 1103s HO H03sQN=N N=N drr, Hogs r trr i CH3 H038 NH MON: H

H038 110 and parts of the dyestuff of the formula 1 G01 SOaH a red tone-in-tone dyeing is obtained.

With a combination of 25 parts of the dyestuff of the formula 2 parts of an adduct of 8 mols of ethylene oxide with 1 mol of para-tertiary octylphenol 100 parts of a 5% aqueous thickening of etherified carubic acids 200 parts of 85% formic acid 683 parts of water 1000 parts The impregnated skin is stored for 5 hours, and is prevented from drying by being wrapped in a polyethylene foil. After this storing the skin is thoroughly rinsed in a bath containing per 1000 parts of water 3 parts of 25% ammonia solution, then washed neutral, once more rinsed and finally dried.

The skin is dyed a full yellow shade. Chrome-tanned leather can be dyed in a similar manner.

Example 6 A fabric of which the fibers consist predominantly of a copolymer of acrylonitrile and vinyl acetate is impregnated on a two-roller padder and then expressed to a weight increase of about 70%. The padding liquor consists of:

10 parts of the dyestuif ofthe formula 1000 parts NH-O-O on:

and 10 parts of the dyestuff of the formula HOaS SOaH A sheep skin is impregnated with the following padding liquor by padding or brushing:

10 parts of the 1:1-chromium complex dyestuff containing per 1 atom of chromium 1 molecule of the dyestufi' of the formula 5 parts of a reaction product of 100 parts of commercial oleylamine and 113 parts of ethylene oxide The impregnated fabric is wrapped in a polyethylene foil and stored for 10 hours at room temperature, then washed neutral in a full-width washing machine in a bath containing per 1000 parts of water 8 parts of 25% ammonia solution, thoroughly rinsed and then dried.

A vivid yellow dyeing is obtained. Instead of the dyestufr' used above there may be used the following dyestuff 1130 CH; C

/CHa CHz-CHa-Cl HaC Cl red amine is impregnated on a two-roller padder with the following liquor:

10 parts of the dyestuif of the formula 2 parts of an adduct of 8 mols of ethylene oxide with 1 mol of para-tertiary octylphenol 10 parts of et-herified carubic acids 200 parts of 85% formic acid 778 parts of water 1000 parts The impregnated fabric is wrapped in a polyethylene foil and stored for 10 hours at room temperature while being gently rotated. The fabric is then thoroughly rinsed in a full-width washing machine and finally dried.

A strong yellow shade is obtained. Similar results are obtained with continuous fiber fabrics from e-capro- 'lactam, or staple fiber fabrics from hexamethylene diamine adipate or from e-caprolactam.

Example 8 A mixed fabric consisting of equal parts of wool and polyamide fibers (obtained by polycondensation of adipic acid and hexamethylene diamine) is impregnated on a two-roller padder With a liquor of the following composition: 7

parts of the dyestufi of the formula 5 parts of the dyestuff of the formula parts of an adduct of 8 mols of ethylene oxide with 1 mol of para-tertiary octylphenol 5 parts of etherified carubic acids 200 parts of 85% formic acid 775 parts .of water 1000 parts The impregnated fabric is stored for 14 hours at room temperature while being gently rotated, then washed neutral in a full-width washing machine in a bathcontaining per-1000 parts of water 8 parts of ammonia solution, thoroughly rinsed and then dried.

The mixed fabric is dyed a tone-in-tone orangered.

When the dyestulf combination used above is replaced by the following combination:

10 parts of the dyestulf of the formula lTIH-CH:

10 parts of the lzl-chromium complex dyestulf con- 14 taining per atom of chromium 1 molecule of the dyestulf of the formula a clear blue-red two-tone efliect is obtained, the wool being dyed red and the polyamide fiber blue.

Example 9 A fabric of real silk is impregnated on a padder and expressed to a weight increase of 70%. The padding liquor has the following composition:

10 parts of the dyestuif of the formula no 'NH-COOH3 OH; I G

HOaS 803B 5 parts of a reaction product of '100 parts of commercial oleylamine and 113 parts of ethylene oxide 2 parts of an adduct of 8 mols of ethylene oxide with 1 mol of para-tertiary octylphenol. 300 parts of a 5% aqueous thickening of etherified carubic acids 200 parts of formic acid 483 parts of water '15 I: l-copper complex containing for every atom of chromiurn 1 molecule of the dyestufi of the formula HO3IS OH H? SOaH O- red Example Pure wool gabardine piecegoods are impregnated on a horizontal two-roller padder and then expressed to a weight increase of 70%. The padding liquor used consists of:

20 parts of the dyestufi? of the formula H30 01 01 CH:

parts of a commercial starch ether 200 parts of 85% formic acid parts of preparation from- 65 parts of water 60 parts of an adduct of 8 mols of ethlylene oxide with 1 mol of para-tertiary octylphenol parts of a reaction product from 100 parts of commercial oleylamine and 113 parts of ethylene oxide 10 parts of potassium bichromate 735 parts of water 1000 parts The impregnated material is wrapped in a polyethylene foil, stored for 24 hours at room temperature, then neutralised in an ammoniacal bath and thoroughly rinsed. A vivid blue dyeing is obtained which has good wet fastness properties.

Similar, good results are obtained with the following dyestufiis A pure woollen, non-woven garment felt is impregnated on a two-roll padder at room temperature with the follow- 16 ing preparation and then squeezed to a weight increase of 10 parts of the metal complex dyestufl? containing 1 atom of cobalt for each mol of the following 2 dyestuffs:

40 parts of a reaction product from 1 mol of coconut oil fatty acid with 2 mols of diethanolamine,

100 parts of a 5% aqueous thickening of etherified carubic acids,

200 parts of formic acid of strength and 650 parts water.

The padded felt is reeled, wrapped airtight in a polyethylene film and stored for 48 hours at room tempera ture. After having been so stored the felt is thoroughly rinsed with cold water on a full-width washing machine and then dried. The resulting strong brown shade has good properties of fastness.

Similar results are obtained with any dyestufi enumerated in the tables of Example 2 or with the following dyestuffs:

1:2-ME TAL COMPLEXES Metal dyestufl molecules color 01' N=N(fi-CCH Orange red.

HOO\ /N N I NH:

OH HaN 0r ON= 0 and Green.

OzH

OH HaN Co OaNO-N=N-@ Green.

| NO: SOsH OH HO\ Or H0 8 N=NC\ Orange red.

/C=N 3O and \ Brown.

-HO3S 0r Hogs 'N=NC I Red.

(|)H HO v Cr HOaS-8N=N8 Blue.

Similar good results are obtained when the garment felt is replaced by worsted tops and the padder is replaced byv Similar good results are also obtained when only 100 a Vigoureux printing machine.

,75 parts of formic acid are used.

Example 12 Pure woollen ladies dress material is impregnated on a two-roll padder with the following preparation and then squeezed to a weight increase of 80% parts of the dyestuff of the formula 40 parts of a reaction product from 1 mol of coconut oil fatty acid and 2 mols of diethanolamine 100 parts of a 5% aqueous thickener of etherified carubic acids 2 parts of a silicone based anti-foaming agent 200 parts of formic acid of 85% strength, and

653 parts of water.

OH I

I -on HOaS the fabric is stored and then reeled on a winch and thoroughly rinsed, then treated for 30 minutes in a boiling 1% aqueous bath of potassium dichromate (referred to the dry weight of the goods) and the dyeing is finished off by rinsing, a fast grey shade is obtained.

Instead of the woollen fabric a sheepskin can be dyed, and in this case the impregnation is advantageously performed by brushing. In otherwise identical manner a perfect dyeing results which may require a slight after-tanning depending on the tanning method original used.

Example 13 A so-called stretch fabric for ski clothes, whose weft consists of wool and the warp of crimped continuous polyamide filaments from a hexamethylenediamine adipate condensate, is impregnated on a 3-rol1 padder with the following preparation and then squeezed to a weight increase of 100%:

parts of the dyestuif of the formula SOaH 40 parts of a 63% solution of the diethanolamine salt of coconut oil fatty acid, coconut oil fatty acid-polyethyleneglycol ester with 6-8 mols of ethylene oxide sodium tetralinsulphonate in aqueous isopropanol 100 parts of a 5% aqueous thickener from etherified carubic acids 2 parts of a silicone based anti-foaming agent 200 parts of formic acid of 85 strength and 648 parts of water.

20 The padded material is reeled, wrapped airtight in a rubber blanket and stored for 24 hours at room temperature. The fabric is then rinsed in cold water, washed for 20 minutes in a cold bath containing in 1000 parts of, 5 water 1 part of ammonia and 0.5 part of the reaction product of 1 mol of coconut oil fatty acid with 2 mols of diethanolamine and finally once more rinsed. A deep blue tone-in-tone dyeing is obtained.

Similar results are obtained when the following dyestuffs are used:

I l N O a S 03131 yellow o NH- CHa S'O3H blue HaO-C O-NH N=N 8 0 H red Equally good results are also obtained when the parts of the auxiliary combination described above are replaced by an equal quantity of one of the following auxiliaries (a) Reaction product of 1 mol of coconut oil fatty acid with 2 mols of diethanolamine;

(b) Condensation product of 1 mol of para-tertiary nonylphenol with 5-6 mols of ethylene oxide;

'(c) Mixture of'equal parts of cocon'ut'oil fatty acid diethanolamine salt and coconut oil fatty acid-polyethyleneglycol ester with 6-8 mols of ethylene oxide;

(d) Lauric acid sarcoside-monoethanolamine salt, or

(e) 44% aqueous solution of the ammonium salt of the acid sulphuric acid ester of the condensation product from 1 mol of para-tertiary nonylphenol with 2 mols of ethylene oxide.

When instead of the wool/polyamide mixed weave a knitwear article from wool and basically modified polypropylene fibres is treated, similar .good results are achieved.

Example 14 A carpet having a jute backing and a pile of textured polyarnide from e-caprolactam is impregnated by immersing it twice on a 3-roll padder in the following preparation:

20 parts of the dyestuif of the formula I CHI The impregnated carpet is squeezed'to a weight increase 7 of rolled up, wrapped airtight and stored for 24 21 hours at room temperature while being slowly rotated.

The carpet is then thoroughly rinsedin cold water and washed for 15 minutes in a bath maintained at 30 C. which contains for every 1000 parts of water 1 part of sodium carbonate and 1 part of heptadecenyl benzimidazole sulphonate.

Finally, the carpet is once more rinsed and then dried. It is dyed a strong yellow shade, while the jute backing is only faintly dyed.

Similar results are obtained with the auxiliaries used in Examples 1 to 4 .and the following dyestuffs:

HrN

& l HgC-CH-N SOaH red I l IO S 0 H yellow 0 N H2 H 1] 0 NH CH S 0 H blue Metal complex dyestuff containing 1 atom of chromium for every 2 mols of the dyestutf of the formula Ho H0 31 ON=N reddish S O 2 C H: 1 blue Metal complex dyestuff containing 1 atom of cobalt for every 2 mols of dyestufr of the formula OH HO N 02 violet What is claimed is:

1. In a process for coloring fibrous materials containing nitrogen at room temperature with dyestuffs that are at least dispersible in water in the presence of at least one surfactant selected from the group consisting of nonionic ethylene oxide condensation products,cationic compounds containing a quaternary nitrogen atom and nonionic and anionic coacervating agent, the improvement which comprises bringing the material to be colored into contact with an aqueous preparation consisting substantially of 4 to 30%, calculated on the total weight of the preparation and 100% strength acid, of an aliphatic carboxylic acid with at most 5 carbon atoms then storing the material so treated for at least minutes during which time the material is prevented from drying whereupon it is finished off by being washed.

2. In a process for coloring according to claim 1 the improvement which comprises applying to the fibrous material an aqueous preparation containing an aliphatic carboxylic acid selected from the group consisting of formic acid and acetic acid.

3. In a process for coloring according to claim 1 the improvement which comprises applying to the fibrous material an aqueous preparation containing a combination of two non-ionic surfactants one of which is a condensation product of ethylene oxide with a fatty amine containing 10 to 22 carbon atoms and the other is a condensation product of ethylene oxide with an aryl phenol containing 6 to 12 carbon atoms in the alkyl radical.

4. 'In a process for coloring according to claim 1 the improvement which comprises applying to the fibrous material an aqueous preparation of a two-phase system produced by a coacervating surfactant that is a reaction product of a higher fatty acid with hydroxyalkyl amines.

5. In a process for coloring according to claim 1 the improvement which comprises applying to the fibrous material an aqueous preparation of a two-phase system produced by a coacervating surfactant of the formula wherein R is a hydrophobic radical, X represents a member selected from the group consisting of hydrogen and an acid solubilizing group and n is a whole number from 1 to 8.

6. In a process for coloring according to claim 1 the improvement which comprises applying to the fibrous material an aqueous preparation consisting of a coacervated two-phase system wherein the coacervate constitutes at least 10% by volume of the whole preparation.

7. In a process for coloring according to claim 1 the improvement which comprises applying to wool an aqueous preparation containing at least one water-soluble 1:1- metal complex azo dyestutf and a combination of two non-ionic surfactants one of which is a condensation product of ethylene oxide with a fatty amine containing 10 to 22 carbon atoms and the other is a condensation product of ethylene oxide with an alkyl phenol containing 6 to 12 carbon atoms in the alkyl radical.

8. In a process for coloring according to claim 1 the improvement which comprises applying to wool an aqueous preparation containing at least one Water-soluble metal-free acid wool dyestutf and a combination of two non-ionic surfactants one of which is a condensation product of ethylene oxide with a fatty amine containing 10 to 22 carbon atoms and the other is a condensation product of ethylene oxide with an alkyl phenol containing 6 to 12 carbon atoms in the alkyl radical.

9. 'In a process for coloring according to claim 1 the improvement which comprises applying to wool an aqueous preparation of a coacervated two-phase system wherein the two-phase system is formed by a coacervating surfactant selected from the group consisting of a reaction product of a higher fatty acid with hydroxyalkyl amines and a compound of the formula wherein R is a hydrophobic radical, X represents a member selected from the group consisting of hydrogen and an acid solubilizing group and n is a whole number from 1 to 8 and contains at least one dyestufl? selected from the group consisting of a water-soluble 1:1-metal complex azo dyestufi and a water-soluble metal-free acid wool dyestutf.

10. In a process for coloring according to claim 1 the improvement which comprises applying to wool an aqueous preparation of a coacervated two-phase system wherein the two-phase system is formed by a coacervating surfactant selected from the group consisting of a reaction product of a higher fatty acid with hydroxyalkyl amines and a compound of the formula wherein R is a hydrophobic radical, X represents a member selected from the group consisting of hydrogen and an acid solubilizing group and n is a whole number from 1 to 8 and contains at least one water-soluble 1:2-meta1 complex azo dyestufi.

References Cited UNITED FOREIGN PATENTS 4/1962 Australia.

OTHER REFERENCES STATES PATENTS 5 B. Kramrisch: Review of Textile Progress, v01. 12, h k X 1960, pp.

g f Casty: Amer. Dyestuff Reporter, Dec. 12, 1960, pp. Wegmann et a1. 8-1.23

ggf 5 -25 10 NORMAN G. TORCHIN, Primary Examiner.

Boedeker fit a1. 8-54 X T. I. HERBERT, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,334,960 August 8, 1967 Heinz Abel It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 21, line 62, for "agent" read agents column 22, line 7, for "aryl" read alkyl Signed and sealed this 6th day of August 1968 (SEAL) Attest:

EDWARD J. BRENNER Edward M. Fletcher, Jr.

Commissioner of Patents Attesting Officer

Claims

1. IN A PROCESS FOR COLORING FIBROUS MATERIAL CONTAINING NITROGEN AT ROOM TEMPERATURE WITH DYESTUFFS THAT ARE AT LEAST DISPERSIBLE IN WATER IN THE PRESENCE OF AT LEAST ONE SURFACTANT SELECTED FROM THE GROUP CONSISTING OF NONIONIC ETHYLENE OXIDE CONDENSATION PRODUCTS, CATIONIC COMPOUNDS CONTAINING A QUATERNARY NITROGEN ATOM AND NINIONIC AND ANIONIC COACERVATING AGENT, THE IMPROVEMENT WHICH COMPRISES BRINGING THE MATERIAL TO BE COLORED INTO CONTACT WITH AN AQUEOUS PREPARATION CONSISTING SUBSTANTIALLY OF 4 TO 30%, CALCULATED ON THE TOTAL WEIGHT OF THE PREPARATION AND 100% STRENGTH ACID, OF AN ALIPHATIC CARBOXYLIC ACID WITH A MOST 5 CARBON ATOMS THEN STORING THE MATERIAL SO TREATED FOR AT LEAST 10 MINUTES DURING WHICH TIME THE MATERIAL IS PREVENTED FROM DRYING WHEREUP IT IS FINISHED OFF BY BEING WASHED.