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hid-97,03? , United States Patent 0 ” ICC Patented July 9, 1963 1 2 ?bers than can be dyed with acid dyestulfs in the usual 3,097,039 manner, for example silk, polyamide fibers of Z-capro lactam or of adipic acid and hexamethylene diamine. Arthur Buehler, Rheinfelden, and Richard Casty, Kaiser Particularly advantageous results are obtained by the augst, Switzerland, assignors to Qiba Limited, Basel, 5 present process in dyeing wool, if desired blended with Switzerland No Drawing Filed Man 28, 1960’ Ser_ No. 17,795 other nitrogenous or nitrogen-free ?bers. When ap Claims priority, application Switzerland Apr. 10, 1959 plwd to polyamlde ?bers the present Process is Particu PROCESS FGlR DYEING NITROGENOUS FBERS 5 Claims. (Cl. 8--43) larly advantageous since these ?bers are dyed an identical tint, and as a rule also in identical depth, as wool, where Hitherto only two classes of metalliferous dyestuffs 10 as in the after-chroming process the tint of the unchromed have achieved any practical importance [for dyeing nitrog- dyestuff is generally retained on polyamide ?bers. eIlOllS ‘?bers, more ‘especially W001, namely, 0n the One The dyestuifs used are 1:2-chromium or 1:2-cobal-t hand, the 1:1-chrornium complexes of monoazo dyestulfs complex compounds of azo-dyestulfs, for example disazo containing sulfonic acid groups and, on the other hand, the dyestu?s or more especially monoazo dyestuffs, that is to 1:2-chromium and 1:2-cobalt complexes of azo dyestuffs, 15 say complexes in which two molecules of one azo dye primarily monoazo dyestuffs, in ‘which the complex molstuff or one molecule each of two different azo dyestuffs ecule (hereinafter called “the complex” for short), conare bound in complex union to one atom of chromium tains in the two azo dyestu? molecules which participate or cobalt respectively. The complex may contain, for in the complex formation and may be identical or ditferexample, a disazo dyestufr’ ‘ and a monoazo dyestuff or out, together at most a single sulfonic acid group or pref- 20 preferably two identical or different monoazo dyestuff erably no free sulfonic acid group at all nor a free molecules. Furthermore, the complex must contain at carboxyl group, that is to say one that does not particileast two acid groups imparting solubility in water such pate in the complex formation, but does contain as a groups being, for the present purpose, free carboxyl rule sulfonamide groups or substituents having a similar groups (-—COO-cation) or more especially free sulfonic action, such as sulfone groups or sulfonic acid ester 25 acid groups (—SO3-cation); such carboxyl groups as groups. participate in the formation of the complex do not count On the other hand, 1:2-complexes whose molecule conas solubilizing groups since, in this kind of linkage, they tains more than one acid group imparting solubility in no longer produce solubility in water. The groups im water, for example those containing two or more sulfonic parting solubility in Water may take up any desired posi acid groups, have hitherto been found practically useless 30 tions in the complex. As a rule it is of advantage when as a rule. Both from a strongly acidic and a weakly the complex contains at least one sulfonic acid group. acidic bath they produce on Wool extremely non~uniform When the complex contains a total of two solubilizing and skittery dyeings as well as weak and ?at tints. groups, and the complex-forming metal is referred to by Useful to very valuable dyeings of any desired tinctorial Me and the two dyestuffs by F1 and F2 respectively there strength and satisfactory levelness and good fastness 35 are the following possibilities available shown sche properties can be obtained by producing the aforemenmatically in the table below: 2 ~——OOOH One dye contains 2solubilizing groups, one dye contains no solubilizing groups. C O OH /Fl (21) Me \Fg Both dyes contain one solubilizing group each. 1 —COOH+1 -—SO3H 0 O OH /Fi COOH (0) Me \Fz Fi-—COOH (b) Me tioned complexes on the ?ber or in some cases during S 03H /Fi 80311 (9) Me \Fa Ill-C0011 (d) Me Fz-COOH 2 ——SO3H SOaH Fr-s03H (f) Me F2—SO3H Fa—-SO:H Of special advantage are the dyestuffs mentioned under the dyeing operation from metal-free dyestuffs and suit(e) and (f) above-among other reasons because of their able metal-yielding agents. It is, therefore, easy to underready accessibility-—which contain in the molecule of stand that this dyeing method, the afterchroming method 55 the dyestuff complex two sulfonic acid groups, or quite or the single-bath chroming method, is still widely pracgenerally dyestuffs that contain in the molecule of the ticed although it involves considerable disadvantages complex at least two sulfonic acid groups. Special men and dii?culties in its performance and, substantial damage tiori deserve those dyestutfs in which, as in the complexes to the wool cannot be avoided. mentioned above under (1‘), two monoazo dyestutl mole~ By the present process it is ROW possible to produce 60 cules, each of which contains at least one sulfonic acid on nitrogenous ?bers, more especially wool, with the 1:2group, are bound in complex union to one atom of chro complexes of the aforementioned kind-which otherwise mium or cobalt. are unsuitable for this purpose-in a very simple manner Apart from the obvious ‘differences between F1 and F2 perfectly level dyeings of any desired tinctorial strength. in the above cases (a), (c), (d) and (e), the dyestuffs In the present process for dyeing nitrogenous ?bers that 65 F1 and F2 may in all cases have the same or a different are suitable for dyeing with acid dyestuffs the ?bers are constitution. In other respects the position of the solubi dyed in an aqueous vbath in the presence of a cationlizing groups in the dyestuffs F1 and F2 is as desired; active compound with dyestuffs consisting substantially they may be present in the radical of the diazo or cou of 1:2-chromium or 1:2-cobalt complex compounds of pling component, and if desired 2, 3 or 4 solubilizing azo dyes Whose metal complex molecule contains at least 70 groups may be present in one and the same radical. Ex cessive massing of solubilizing groups, more especially of two acid groups imparting solubility in Water. The present process is suitable for dyeing nitrogenous sulfonic acid groups, is as a rule less advantageous, more 3,097,039 3 especially when a relatively low molecular Weight is in volved, because this may impair the wet fastness of the dyeings. The presenceof, for example, two, three or four sulfonic acid groups in the complex has proved es pecially advantageous. "The metal complex ‘forming groups in the monoazo dyestuffs are preferably ortho:0rtho’-dihydroxyazo group 4 other suitable method, such as addition of certain water miscible organic solvents. The dyeing according to ‘the present process is per formed in the presence of a cation-active compound, ad vantageously one that owes its solubility in water ex clusively to groupings containing basic nitrogen atoms and advantageously at least one aliphatic radical of at least ings or ortho-hydroxy-ortho’-carboxyazo groupings. Other 8 connected carbon atoms. Particularly suitable are complex forming groups, such as ortho-hydroxy-ortho' quarternary ammonium compounds. carboxymethoxy groupings ‘or ortho—hyd-roxy~ortho' 10 Among the last-mentioned compounds may be named aminoazo groupings are likewise admissible. more especially the compounds of the formula In other respects the azo dyestuffs required for the manufacture of the metal complexes may be manufac tured in known manner ‘from known diazo and coupling components. Incidentally, a large number of such azo 15 dyestuifs have been known as chroming dyestuffs for a in which R1 represents a preferably unbranched aliphatic long time past. For the manufacture of such azo ‘dye hydrocarbon radical containing at least 12, preferably stuffs there are suitable, for example, ortho-hydroxy 16 to 20, carbon atoms; R2, R3 and R4 represent lower amines or ortho-carboxyamines of the benzene and hydrocarbon radicals, such as ethyl or methyl groups, or naphthalene series, and as coupling components hydroxy 20 two or three of these radicals together with the nitrogen benzenes, hydroxynaphthalenes, 2:4-dihydroxyquinolines, atom represent a hetero ring; and X represents an anion, pyrazolones and acetoacetyla-mino benzenes capable of for example a halogen atom such as bromine or chlorine, coupling in vicinal position to a hydroxyl ‘group (or an or a met-hosulfate group. enolizable keto group). The statement that two or three of the radicals R2, R3 In this connection the following components may be 25 and R4 together with the nitrogen atom form a hetero mentioned: (1) Diazo components free from groups imparting solu bility in water (including ortho-arninocarboxy'lic acids not containing a further solubilizing group) (2) Diazo components containing solubilizing groups (3) Coupling components free from solubilizing groups (4) Coupling components containing solubilizing groups ring is intended to mean that such a ring is composed either of the nitrogen atom and two of these radicals ‘attached to ‘the nitrogen atom by a simple bond and also to each other, a third radical being present in the form 30 of a lower alkyl group; or that the whole grouping -—N / R2 The 1:2-complexes to be used in the present process can likewise be manufactured in the conventional and 35 consists of a hetero ring, the nitrogen atom being linked as such known manner from metal~free monoazo dye through a double bond to R2/R3 and through a single stuffs, advantageously by a method known for the manu ‘bond to R4, and R2/R3 and R4 are likewise linked to facture of 1:2-metal complexes free from groups im each other as is the case, for example, with the pyn'dine parting solubility in water. For the manufacture of sym metrical complexes, in which‘ the metal atom is bound ‘to 40 ring. As examples of compounds of the Formula 1 may be two identical tdyes'tuff molecules, it is advantageous to 19R, treat dyestuif in such manner and with such metal-yield ing ta'gerits-ésuch as alkali chromesalicylate, chromium mentioned cetyl trimethyl ammonium bromide, cetyl pyri dinium bromide and tetradecyl pyridinium bromide. Likewise suitable cation-active compounds are salts, if acetate, sodium-cobalt tartrate, cobalt acetate or cobalt sulfate-as give direct rise to the desired complex. To 45 desired quaternary ammonium salts of basic condensa tion products from alkylolamides of higher fatty acids and these methods belongs the chroming with alkali metal bi alkanolamines such, for example, as the ‘acetate of the chromate in the presence of a reducing agent. condensation product from 1 mol of stearic acid methylol To manufacture asymmetrical complexes it is in gen amide and 1 mol of triethanolamine. eral advisable to use another method which leads to Furthermore there may be used in the present process unitary products and not to mixtures containing a sub as cation-active compounds monoquaternary ammonium stantial portion of symmetrical by-products, some of which salts containing at least one aralkyl radical or cycloalkyl contain no 'solubilizing group at all and are there-fore radical or the atomic grouping of the formula undesirable. In such a case it is advantageous to prepare the lzl-chromium complex from one of the two dyestuffs from which the asymmetrical lz2-complex is synthesized, 55 preferably that dyestu?f which contains solubilizingagroups (unless both dyestuffs contain solubilizinggroups), and in which R1 ‘and R2 represent alkyl radicals which may be substituted or may be interrupted by hetero atoms, the ‘with the other, metal-free dyestuif. 1It should also be alkylene radical connecting the two nitrogen atoms con mentioned that the 1; l-complexes as Well as the 1:2 60 taining, if desired, substituents. Particularly suitable com complexes of ortho:ortho’-dihydroxyazo dyestuffs can be pounds are those of the formula made not only from the ortho:ortho'-dihydroxyazo dye (5) R2 stuffs themselves but also from the appropriate ortho-hy the lzl-chromium complex so formed is then reacted droxy-ortho'-alkoxyazo dyestuffs. Accordingly ‘there may be used for the ‘direct manufacture of Lil-complexes more especially for the manufacture of lcl-complexes which are subsequently'to be made into l:2~complexes— the appropriate ortho-alkoxydiazo compounds, more es R1—l€\.?£R3 halogene \R4 in which R1 represents a preferably straight-chain alkyl radical containing 12 to 18‘ carbon atoms; R2 and R3 rep resent alkyl radicals containing one or two carbon atoms, and R4 represents a benzyl or cyclohexyl radical which 70 may be further substituted. As relevant examples may Under certain conditions the working up of the 1:2 be mentioned dimethylbenzyl laurylammonium chloride, complexes may cause certain difficulties, since these com dimethylbenzyl-stearylamrnonium chloride, dihydroxy pounds are readily soluble in water. A complex which ethyl benzyl lauryl ammonium chloride and dimethyl cy for this reason does not lend itself to salting out can be clohexyl lauryl ammonium bromide. isolated by evaporating the reaction mixture or by an Finally, there may be mentioned as cation-active com pecially the'methoxy compounds, instead of the ortho hydroxydiazo compounds. 3,097,039 5 least two quaternary nitrogen atoms and at least one, or preferably two, higher aliphatic hydrocarbon radicals. process it is not necessary to raise the temperature closely or wholly to the boiling point of the dyebath. As a rule, practically equally good results are obtained when the These salts correspond, for example, to the general for mula (4) R5 R2 I l [ 6 C., the dyebath is then raised to the boil, and dyeing is continued and completed at the boil. It has, however, been observed that even when dyeing wool by the present pounds also quaternary ammonium salts that contain at process is performed well below the boil, for example at @ 69 a temperature between 80 and 90° C. (x9) To ensure that the nitrogenous compound can act from the onset, the 10 material to be dyed can be immersed in the bath which contains the acid, if desired sodium sulfate, as well as the in which R and R1 each represents a higher aliphatic hy assistant or assistants (i.e. the cation-active compound drocarbon radical; R2 to R6 represent alkyl, cycloalkyl or and if desired the non-ionic dispersant) at room tempera aralky radicals which may be further substituted; Z rep ture or at most at a moderately raised temperature, resents an alkylene radical which may be further substia whereupon the dyebath is heated and when it is hot an tuted or may be interrupted by hetero atoms or functional aqueous solution of the dyestuff is added. groups; Z1 and Z2 are lower alkylene radicals; n=1 or 2; If desired dyeing can be carried out continuously, for and X represents an anion. Relevant examples are the example by ?rst padding the material to be dyed with a compounds of the following formulae cold, neutral dyestuff solution and then subjecting it to 20 a short after-treatment in a hot acid bath. The present process is also very suitable for melange printing on worsted slubbings. The printing pastes re quired for this purpose contain, in addition to at least one dyestu? and one assistant of the speci?ed composition, a 25 thickener such as tragaoanth or British @1111 and it should also contain an acid, for example acetic acid. They may CH3 OH OH 9369 CH3 (019) CH: 2 Ha also contain further additives conventionally present in In general, it is of advantage when the dyebath con printing pastes, for example oil of turpentine, hydrotropic tains a non-ionic dispersant in addition to the cation 35 active compounds. Particularly suitable dispersants are polyglycol ethers of hydroxy compounds, for example of; alkylphenols such as para-nonylphenol or para-tertiary octylphenol or preferably of higher aliphatic alcohols, such as lauryl, cetyl, or octadecyl alcohol; advantageously they are produced by an additive reaction of 10 to 50 mols of ethylene oxide with 1 mol of the selected alcohol. There may also be used polyglycol ethers derived from substances such as urea and/ or agents that prevent reduc tion, such as sodium nitrobenzene sulfonate. In other respects the procedure known in melange printing may be followed. The printed material is steamed, for example under atmospheric pressure, for 40 to 120 minutes, advantageously with ‘at least one inter ruption. The melange prints obtained in this manner are dis tinguished by good exhaustion of the dyestu? and very compounds other than hydroxy compounds, ‘for example from amides of higher fatty acids or from alkylmercaptans 45 good properties of fastness. The Wet fastness, more especially the potting fastness with a higher alkyl radical. of the dyeings obtained by the present process, can in The present process gives valuable results both in dye some cases be considerably increased insofar as migration ing proper and in printing. When dyeing from an aque-: (bleeding out) is concerned by raising the pH value of ous bath the amounts of the substances to be added to the dyebaths used in the present process may vary within 50 the dyebath above 6, for example by adding ammonia, after the ?bers have absorbed the desired amount of dye relatively wide limits. The amount of dyestuff depend-, of course on the desired tinctorial strength. There may also be used mixtures of complexes of the composition stu? from an acid bath, that is to say at a pH value below 6. In dyeing mixtures of nitrogeneous ?bers and cellu speci?ed above, as well as dyestuffs of a different com-_ position in a minor amount, that is to say 11p to about 55 lose ?bers, for example so-called half-wool, the increased pH value is particularly advantageous since it enables the 20% of the total amount of dyestuil used, more especially dyeing to be performed in 2 stages in a single bath: First, so-called shading dyestuffs. The amount of cation~active the Wool share of the ?ber mixture is dyed as described compound added is advantageously about 0.25% to 2% above, the cellulose share remaining practically undyed. of the weight of the wool. The amount of nonaionic dis persant used is advantageously of the same order as that 60 After raising the pH value, for example with the aid of ammonia, sodium sulfate and then a direct dyeing cotton of the cation-active compound. dyestuff are added, advantageously without further heat Furthermore it is found advantageous to dye in an acidic ing. It is of advantage to use dyestuffs that dye wool at to at most neutral medium so that the pH value of the dye— most only very slightly in the neighborhood of 100° C. bath ranges from about 3 to 7, preferably from 4 to 6. This pH value can be advantageously adjusted by adding 65 The material is then dyed until also the cellulose ?ber displays the desired tint, for example for 1/a hour, and acetic acid or an ammonium salt or a mixture of these the material is then ?nished in the conventional manner. substances. There are used, for example, 3 to 8 parts of acetic acid of 40% strength, or 2 to 5 parts of ammonium To improve the wet fastness of the cellulose ?ber share sulfate or ammonium acetate, per 100‘ parts of ?ber ma it may be of advantage to perform a known after-treat terial. It is also of advantage to add to the dyebath an 70 ment with an agent capable of improving the wet fast alkali metal salt, for example sodium sulfate. As is the general practice in dyeing nitrogenous ?bers, more especially wool, the present process is performed at ness, for example a condensation product of dicyandia mide and formaldehyde. Instead of adding the dyestuif and the cation-active an elevated temperature, for example in the following compound separately to the dyebath used in the present 75 manner: the actual dyeing is begun at about 50 to 80° 3,097,039 7 & , process, these two substances-and if desired further Manufacture of the Dyestu? substances, more especially the non-ionic dispersant 41.6 parts of the monoazo dyestuff prepared by coupling tdiazotized 1—amino-2—hydroxynaphthalene-4-sulfonic acid can be made up into stable preparations ready for use. These preparations likewise form an object of the present invention and are characterized in that they contain as dyestu? predominantly 1:2-chromium or 1:2-cobalt com— plex compounds of monazo dyestu?s in which the mole cule of the metal complex contains at least two acid with 2-hydroxynaphthalene are dissolved in 1000 parts. of water and mixed With 100 parts by volume of a sodium chromsalicylate solution containing 2.85% of chromium. Re?uxing for several hours completes the metalliza-tion. The chromium complex is salted out with sodium chloride, ?ltered oil and dried. groups imparting solubility in water, as well as a cation active compound and, if desired, a non-ionic dispersant. 10 These preparations can be made by mixing the dye stu? complex with the cation-active compound and, if desired, the dispersant, or by evaporating or atomizing EXAMPLE 2 The process described in Example 1 is carried out with the use of the chromium complex described below. This a solution of suspension which contains the dyestuff and the assistant or assistants. 15 procedure yields a level, red dyeing, Whereas when the same procedure is followed, except that the assistants Unless otherwise indicated, parts and percentages in mentioned are omitted, a more yellowish, skittery ‘dyeing the following examples are by weight: is obtained. EXAMPLE 1 The chromium complex is prepared in the following manner: 100 parts of knitting wool are immersed at 50 to 80° 20 A solution of 51.0 parts of the dyestu'?? prepared by C. in a dyebath containing 3000 parts of water, 10 parts of crystalline sodium sulfate, 6 parts of acetic acid coupling diazotized 4-chloro-2-amino-l-hydroxybenzene é-sulfonic acid with 1~phenyl-3-methyl-5-pyraZolone-4' of 40% strength, 1 part of cetyl trimethyl ammonium sulfonic acid in 750 parts of water is rendered just slightly bromide, 2 parts of the adduct from 1 mol of octadecyl alcohol and 35 mols of ethylene oxide, and 2 parts of 25 alkaline to phenolphthalein with sodium hydroxide. 93 parts by volume of a sodium chromsalicylate solution con the dyestu? described below. In the course of 1/2 hour taining 2.85% of chromium are added, and the mixture the bath is raised to the boil and the wool is then dyed is stirred under re?ux until the parent dyestu? can no for one hour at the boil, rinsed and dried. A level blue longer be detected. The deep-red solution is neutralized dyeing is obtained. When the cetyl trimethyl ammonium bromide is omitted, a very skittery, slightly greyish, prac 30 with acetic acid and evaporated to dryness. tically useless dyeing is obtained. When instead of the EXAMPLE 3 dyestuit described below the 1:2-chromium complex is used which has been obtained in identical manner from The process described in Example 1 is performed but instead of the chrorniferous dyestuffs used in that example the monoazo dyestuif of diazotized 1-amino-2-hydroXy naphthalene-4-sulfonic acid and l-hydroxynaphthalene, a 35 one of the undermentioned 1:2-metal complexes obtain able in the conventional manner is used, whereby level level blue dyeing is likewise obtained. After immersion dyeings are likewise obtained. of the Wool the temperature of the dyebath can. then be ‘ In the 1:2-complexes listed in Table A, 'two molecules raised only to 85° C. instead of the boil and dyeing can of the same dyestutf are bound in complex union to'o'ne be continued at this temperature for one hour. 40 atom of metal. TABLE A Metal Dyestuff . ‘Tint on wool ' HOaS 1____ Or ____ _. no OH é ®—N=N~O< I 01 ' HO3S ' >Red. C=N' I CHa HO OH l % 2.“. O0 ____ _. ®—N=N—C \ | 01 ' C: I 'Brown red. CH3 3____ OH I Or ____ _. H? /\ 7 _OH , Grey. _N:N___ o1 HOsS/V (prepared by coupling diazotized 4-ehloro-2-amino-l-i hygroxybenzene with 2:8-dihydroxynaphthalene-6~sulfonic 301 HO 1 OH 4..-- Cr ____ __ H038 —N=N—C / Pink. $21“ CH3 3,097,039 11 12 EXAMPLE 4 The acetate of the composition mentioned above can be replaced by the compound ‘of the formula A dyebath is prepared from 5000 parts of water, 3 parts of acetic acid of 40% strength, 4 parts of the adduct from 1 mol of octadecyl alcohol and 35 mols of ethylene oxide, 2 parts of the acetate of the condensation product from 1 mol of stearic acid methylolamide and 1 mol of triethanolamine, and 2 parts of the 1:2-cobalt complex of the dyestuif of the formula 11038 OH HO 10 A dyebath is vprepared which contains in 3000 parts of water, 2 parts of cetyl trimethyl ammonium bromide, 1 part of the adduct from 1 mol of octadecyl alcohol with 35 mols of ethylene oxide, 3 parts of acetic acid of 40% strength, and 3 parts of the dyestuff No. 3 in 15 Table A. 100 parts of a polyamide fabric-are immersed in the re 100 parts of a mixture of ?bers containing 80% of wool and 20% of 'polyamide staple ?ber are im mersed at 50° in the dyebath which is then raised to the boil and dyeing at the boil is performed for 1 hour. A sulting dyebath at about 50° C., the bath is raised to 95° C., and dyeing is performed for 1 hour at 95° C. level grey dyeing is obtained. The fabric is then rinsed and dried. A level, strong, 20 EXAMPLE 9 violet dyeing is obtained. In an identical manner a ?abric of blended ?bers of vThe process described in Examples 1 to 3 is performed wool and polyamide can be dyed. instead of with the ethylene oxide adduct described in those examples, with an adduct from 1 mol of nonyl EXAMPLE 5 25 phenol with 9 mols of ethylene oxide, or an adduct from 30 parts of the adduct from 35 mols of ethylene oxide 1 mol of castor oil with 40 mol-s of ethylene oxide, or an adduct from 1 mol of tertiary dodecylmercaptan with with 1 mol of octadecyl alcohol, and 40 parts of dextrin 8 to 10 mols of ethylene oxide. are stirred with 400 parts of water for 15 minutes at 70° What is claimed is: C. :and the clear solution is treated por-tionwise with 10 parts of the lz2-chromium complex prepared as described 30 1. A process for dyeing wool, which comprises dyeing at the end of Example 1. A solution of 6.5 parts of the wool in an aqueous bath in the presence of a cation cetyl trimethyl ammonium bromide in 50 parts of water active quaternary ammonium compound of the formula is then vigorously stirred The mixture, which is now-opaque but free from sediment, is stirred on for 30 minutes at 70° C. and then ‘evaporated to dryness under 35 'vacuum. The residue is gound and there are obtained about 85parts of a, deep-violet readily water-soluble dye preparation which dyes wool, from an acetic acid bath Without any additives, level blue tints. in which R1 represents an aliphatic hydrocarbon radical In an identical manner dye preparations of the follow 40 containing 12 to 20 carbon atoms, R2, R3 ‘and ‘R4 each ing compositions can be made: represent a lower alkyl radical and X represents an anion, and in the presence of a polyglycol ether of a higher (a) aliphatic ‘alcohol with a dyestuif consisting’ essentially of a 1:2-metal complex compound which compound is 10 parts of ethylene oxide adduct (seeabove) 45 selected from the group consisting of chromium and 16 parts of dextrin cobalt compounds and contains in the molecule of the 5.5 parts of cetyl trimethyl ammonium bromide metal complex at least two sulfonic acid groups. 5.8 parts of dyestuff No. l in Table A 2. A process for dyeing wool, which comprises dyeing '(b) 10 parts of ethylene oxide adduct (see above) 18 parts of dextrin 5 .5 parts of cetyl trimethyl ammonium bromide 8.7 parts of dyestutf No. 3 in Table A EXAMPLE 6 the wool in an ‘aqueous bath in the presence of cetyl tri 50 methyl ammonium bromide and the adduct from 1 mol of octadecyl alcohol and 35 mols of ethylene oxide, with a dyestuif consisting essentially of a 1:2-metal complex compound which compound is selected ‘from the group consisting of chromium and cobalt compounds and con 55 tains in the molecule of the metal complex at least two sulfonic said groups. 100 parts ‘of wool are pretreated wat the boil for 30 3. Process for dyeing wool comprising dyeing said minutes in a ‘bath containing 2 parts of cetyl trimethyl wool in an aqueous bath in the presence of cation active quaternary ammonium compound of the formula densation product from 1 mol of stearic acid methylol 60 amide and 1 mol of trie-thanolamine. The wool is then dyed in a fresh bath containing 0.5 part of the dyestu? N0. 3 in Table A and 2 parts of acetic acid of 40% strength in 3000 parts of water. A level grey dyeing is obtained. 65 EXAMPLE 7 wherein R1 is aliphatic hydrocarbon of 12 to 20 carbons, R2, R3 and R4 are lower alkyl, and X is anion, and in 100 parts of wool are dyed as described in Example 1 the presence of non-ionic dispersant selected from the in a bath prepared from 3000 parts'of water, 2 par-tsof the acetate of the condensation product from 1 mol of 70 group consisting of polyglycol ether of ( 1) hydroxy com pounds, (2) higher fatty acid amides and (3) higher stearic acid methylolamide and 1 mol of triethanolarniue, alkyl mercaptans, with dyestulfs consisting essentially of 1 plant of the adduct from 1 mol of 'octadecyl alcohol a 1:2-metal complex compound which compound is with 35 molstof ethylene oxide, v3 parts of acetic acid of selected from the group consisting of chromium and 40% strength, and 1 part of the dyestu? No. 3 in Table cobalt compounds and contains in the molecule of the A. 'A'level ‘grey dyeing‘is obtained. 75 metal complex at least two sulfonic acid groups. ammonium bromide or 2 parts of the acetate of the con 3,097,039 13 4. A dyestuff preparation which comprises a cation active quaternary ammonium compound of the formula 314 References Cited in the ?le of this patent UNITED STATES PATENTS 1,970,578 2,153,701 in which R1 is aliphatic hydrocarbon containing 12 to 20 carbons, R2, R3 and R4 are each lower alkyl and X is an anion, a non-ionic dispersant selected from the group consisting of polyglycol ethers of (1) hydroxy com 10 pounds, (2) higher fatty acid amides and (3) higher alkyl mercaptans, and a dyestuff consisting of chromium and cobalt compounds and contains in the molecule of the metal complex at least two ‘sulfonic 'acid groups. 5. Dyestuff preparation of claim 4 wherein the non 15 ionic dispersant is polyglycol ether of .a higher ‘aliphatic alcohol. 2,674,515 2,763,530 2,890,094 2,900,218 3,903,325 2,933,489 2,973,351 3,007,912 Schoeller et al. _______ __ Aug. 21, Straub et a1. _________ _.. Apr. 11, Widmer et a1. _________ __ Apr. 6, Schuetz et al. _________ __ Sept. 18, 1934 1939 1954 1956 Tucker _______________ __ June 9, 1959 Gray ________________ __ Aug. 18, Geigy _______________ __ Sept. 8, Biedermann et a1. _____ __ Apr. 19, Montmollin et al _______ __ Feb. 28, Betta et a1. ___________ __ Nov. 7, 1959 1959 1960 1961 1961 OTHER REFERENCES Goldsmith: Chemical Industries, March 1943, pp. 326-3 28 .