US3529922A - Process for dyeing nitrogen-containing textile fibres - Google Patents

Description

United States Patent m 3,529,922 PROCESS FOR DYEING NITROGEN-CONTAINING TEXTILE FIBRES Alfred Berger and Heinz Abel, Reinach, Basel-Land, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a company of Switzerland No Drawing. Filed Sept. 2, 1966, Ser. No. 576,865 Claims priority, applicagior; S/vgtzerland, Sept. 9, 1965,

Int. Cl. C09b 67700; D06p 3/14, 5/06 US. Cl. 854 9 Claims ABSTRACT OF THE DISCLOSURE The invention relates to a process for dyeing nitrogencontaining textile fibres with wool dyestuffs in the presence of a combination of levelling agents substantially consisting of (a) quaternary ammonium compounds and (b) acid esters of at least dibasic oxygen acids and their corresponding alkali metal, ammonium and amine salts, of polyglycol compounds.

It has been found that nitrogenous textile fibres can be dyed in an advantageous manner with wool dyestuffs in the presence of (a) quaternary ammonium compounds of polyglycol compounds of the formula (b) of acid esters, derived from at least dibasic oxygen acids, of polyglycol compounds I I CHCH-O ta-J1me) where R and R each represents an aliphatic hydrocarbon residue containing 12 to 24 carbon atoms, A represents an anion, Q the residue obtained when the anion is elimiated from a quaternating agent of the formula AQ; X represents the residue obtained on eliminating a hydroxyl group from an at least dibasic oxygen acid; t'=1 or 2, and p, q, p and q are Whole numbers, the sums (p+q) and (p+q) each being at least 4 and at most 200 and at least a substantial portion of the groups -(IJH-CHO corresponding to the formula CH CH O and any possible further C H-( 3H-O groups corresponding to the formula r -CHCHO where one Z represents a hydrogen atom and the other Z an alkyl or phenyl group.

For the present process there are required at least one quaternary compound and at least one acid ester of the composition defined above, which are derived from identical or different polyglycol compounds, both these polyglycol compounds answering to the above definition. The aliphatic hydrocarbon residues containing 12 to 24 carbon atoms may be saturated or unsaturated, branched or preferably linear. Advantageously, they contain 16 to 3,529,922- Patented Sept. 22, 1970 and octadecenylamine. Furthermore, there may be mentioned monoalkyl-alkylenediamines Whose alkyl radical contains 12 to 24 and the alkylene radical 2 to 3 carbon atoms. These alkyl radicals may be of the same composition as mentioned with the rnonoamines referred to above. By reacting such amines with alkenoxy compounds of low or high molecular weight there are obtained in known manner polyglycol compounds. Suitable alkenoxy compounds are, for example, low-molecular compounds such as ethylene oxide, propylene oxide, or butylene oxide, or compounds of higher molecular Weight such as decene-oxide, olefine oxides containing 16 to 18 carbon atoms or styrene oxide. The amine may be reacted with a unitary alkylene oxide or With a mixture of different alkylene oxides. By virtue of its ready accessibility propylene oxide in admixture with ethylene oxide is preferred to the other alkylene oxides. At least a substantial portion of the resulting groups should be ethenoxy groups. Thus, except when ethylene oxide exclusively is added on to the amine, it is of advantage to use for every mol of amine only 1 to 3 mols of propylene oxide or styrene oxide and at least 3 mols of ethylene oxide. In general it is advantageous to add on to the amine a total not exceeding 60 to 70 alkenoxy groups.

Advantageously, both the quaternary ammonium compounds and the acid esters are derived from polyglycol compounds of the formula oHPom-o H M Where R represents an aliphatic, preferably linear, hydrocarbon residue containing 12 to 24 carbon atoms; m and s each is 1 or 2; and p, q and r are Whole numbers, the sum p+q+r(m-l) being at least 4.

Quaternation of the amine-alkylene oxide adducts, preferably those of the Formula. 1, gives rise to the compounds (a) and esterification to the compounds (b). Both these reactions may be carried out in known manner. The esterification is advantageously performed with functional derivatives of at least dibasic oxygen acids under conditions such that at least one acid ester group preferably in the form of an alkali, ammonium or amine saltis introduced. Polybasic organic acids suitable for formation of the acid esters are organic polycarboxylic acids or carboxylic acid-sulphonic acids, for example maleic or succinic acid-sulphonic acid, or poly'basic inorganic oxygen acids such as phosphoric acid or preferably sulphuric acid, or functional derivatives of these acids such as their anhydrides, halides or amides. It is advantageous to manufacture the acid sulphuric acid esters in the form of their ammonium salts directly by heating the starting materials with amidosulphonic acid in the presence of urea.

For quaternation the starting polyglycol compounds are reacted in known manner with a conventional alkylating or aralkylating agent such as dimethylsulphate, ethylbromide, benzylchloride, chloracetamide, ethylene-chlorohydrin, ethylene-bromohydrin, epichlorohydrin or epibromohydrin.

The acid esters (b) must contain at least one ester group per molecule. In other respects, there may be used compounds of which only some or 11 hydroxyl groups present are esterified. In the case of the compounds (a) most or all of the tertiary nitrogen atoms should be quaternated. The effect of the products is, however, hardly impaired when a monoamino-polyglycol compound is quaternated only to 85 to 90% or when in a diamino-polyglycol compound only one of the two nitrogen atoms is quaternated.

Depending on the constitution of the dyestuffs it may be advantageous when the compounds (a) and (b) have a higher or lower content of alkenoxy groups and the compounds (a) have been reacted with certain quaternating agents.

As will be realized from the foregoing it is advantageous to use in the present process quaternary ammonium compounds of the formula (2) (CHzCHzO) D-H A9 (|Q,\(C H2CH20) H and acid esters of the formula omomo rr OH on if p 2 2 it} H which may be prepared by the addition of ethylene chlorohydrin to the reaction product of arachidylamine and ethylene oxide.

The present process my be used for dyeing nitrogenous fibres in any desired stage of their processing, which are suitable for dyeing with wool dyestuffs in the usual manner, for example polyamide fibres from E-caprolactam or adipic acid and hexamethylenediamine. Particularly suitable are natural fibres such as silk or above all wool.

According to the present process wool yarn may be dyed with any desired wool dyestuff by one of the conventional methods. The dyestuffs may belong, for eX- ample, to the following types:

(A) Acid wool dyestuffs including dyestuffs, especially anthraquinone and azo dyestuffs that contain at least one acid group imparting solubility in water, preferably a sulphonic acid group, but which contain no metal in complex union and no reactive groups.

(B) lrl-chromium complex dyestuffs containing sulphonic acid groups, that is to say chromium compounds 4 in the complex formation, preferably a sulphonic acid group.

(D) 1:2-chromium or i-cobalt dyestuff complexes whose complex molecule contains a single acid group imparting solubility in water which does not participate in the complex formation, preferably a sulphonic acid group.

(B) 1: 2-chromium or -cobalt dyestuff complexes that are free from acid groups imparting solubility in water that do not participate in the complex formation. These dyestuffs contain as a rule a sulphonamide group which may be substituted on the nitrogen atom or a methylsulphone group.

(F) Reactive dyestuffs which, in contradistinction to the above types of dyestuffs, contain at least one group or substituent capable of reacting with the nitrogenous fibre. In other respects these dyestuffs may belong to widely disparate types; they may be, for example, stilbene, perinone, peridicarboxylic acid imide, nitro, triphenylmethane or phthalocyanine dyestuffs or above all acid anthraquinone or azo dyestuffs, including both metal-free and metallizable and metalliferous monoazo or polyazo dyestuffs containing groupings or substituents capable of reacting with the nitrogenous fibres. The dyestuffs contain at least one, but generally 2 or more, acid groups imparting solubility in water. Particularly good results are in general achieved with dyestuffs that contain 3 sulphonic acid groups.

From among the reactive groups or substituents of the reactive dyestuffs referred to above there may be mentioned, for example, the ethyleneimide group, epoxy groups, the vinyl grouping in a vinylsulphone group or in the acrylic acid residue, and above all those labile substituents which are easy to eliminate with entrainment of the bond electron pair.

As labile substituents that can be eliminated with entrainment of the electron pair of the bond there may be mentioned, for example, aliphatically bound phosphoric acid ester or sulphuric acid ester groups, sulphonylfluoride groups, aliphatically bound sulphonyloxy groups and above all halogen atoms, especially a mobile chlorine atom. These labile substituents advantageously occupy the 'y or ii-position of an aliphatic residue bound with the dyestuff molecule directly or through an amino, sulphone or sulphonamide group. In the case of reactive dyestuffs that contain as labile substituent a halogen atom, these mobile halogen atoms may also be in an aliphatic acyl radical (for example in the B-position of a propionyl residue) or preferably in a heterocycle; in this last-mentioned case there may be used dyestuffs containing a monohalogenated heterocycle, for example a monochlorinated 1,3,5-triazine residue, such as the 1,3,5-triazine residue of the formula where X is an alkyl, aryl, aralkyl, alkylmercapto or arylmercapto radical, especially a possibly substituted amino group or a preferably substituted hydroxy group, as well as dyestuffs that contain a dichlorotriazine or a dichloropyrimidine residue. Further suitable are reactive dyestuffs containing u-bromoor a-chloroacrylamino groups, 2,3- dichloroquinoxalinoyl, dihalogenophthalazine, dichloropyridazone, 2-chlorothiazole, propionylsulphone residues or residues of the formulae Quaternary compounds (a) and acid esters (b) whose molecule contains 6 to 9 alkenoxy groups, especially ethenoxy groups, are particularly suitable when used in the present process in combination with dyestuffs as defined sub B and/ or F, and also with those sub C. The quaternary ammonium compounds (a) preferably contain a halogen as the anion so that, for example, said quaternating compounds are obtained by reaction of a tertiary amine with chloracetamide, ethylene-chlorohydrin, ethylene-bromohydrin, epichlorohydrin or epibromohydrin.

When the quaternary compounds (21) and the acid esters (b) contain at least 15, for example 20 to 35, alkenoxy groups such as ethenoxy groups, they are particularly suitable for use in dyeing with dyestuffs sub A, B or E, and also sub D, especially when the quaternary nitrogen atoms are linked to dimethylsulphate.

The proportions of substances to be added to the dyebaths to be used in the present dyeing process may vary within relatively wide limits. The amount of dyestuff depends on the desired tinctorial strength, taking into consideration the nature of the material to be dyed. It is advantageous to choose the quantity of the polyglycol compounds (a) and b) as a whole, that is to say a+b, referred to the weight of the fibre] from the range of 0.2 to 3%.

The ratio of quaternary compound (a) to acid ester (b) should be from 3:1 to 1:3 or preferably from 2:1 to 1:2. It is advantageous to use equimolecular proportions of (a) and (b).

Otherwise, the known dyeing methods conventionally employed for the selected type of dyestuif may be used. As a rule, it is advantageous to dye wool in an acid medium, that is to say at a pH value from 1.7 to 6, which is adjusted by adding acetic, formic or sulphuric acid. It is also advantageous to add sodium sulphate to the dyebath. Dyeing is performed at an elevated temperature, for example by starting the dyeing process proper at 50 to 80 C., heating the bath to the boil and continuing and completing the dyeing process at the boil. More especially when rapidly depositing dyestuifs and reactive dyestuffs are used it may be advantageous to introduce the material to be dyed into the bath containing the polyglycol compounds (a) and (b) and the further ingredients at room temperature or at a moderately raised temperature, whereupon the material to be dyed is heated, and at an elevated temperature, for example, at 50 to 80 C., an aqueous solution of the dyestuff is added to the dyebath. When dyeing wool with dyestuffs containing sulphonic acid groups by the present process it is, incidentally, not necessary to maintain the dyebath with the material being dyed at the boil during the whole of the dyeing process but it suflices to maintain a temperature not exceeding 85 C., advantageously from 75 to 85 C.

The quaternary ammonium compound (a) and the acid ester (b) may be added to the dyebath separately. Alternatively, a stable dyeing preparation ready for use may be manufactured by mixing the two components as such, or aqueous solutions thereof, at a suitable ratio, for example of 1:3 to 3:1, which preparations contain (a) quaternary ammonium compounds of polyglycol compounds and (b) acid esters of polyglycol compounds, derived from at least dibasic oxygen acids;

the compounds (a) and (b) have the compositions defined above.

In the present process the two polyglycol compounds produce on textile fibres, especially on wool in any stage of processing, a good levelling effect. This is a true combination eifect, since, when the quaternary compound (a) is used in combination with the acid ester (b), there are achieved effects which as a whole cannot be achieved with either component by itself. It is a substantial advantage of the combination that it can be used for a wide range of types of dyestuffs. Furthermore, various disadvantages which impede or restrict the use of known wool levelling agents do not occur in this process. While it is possible to achieve with such known levelling agents likewise level dyeings with the use of favourable plant, there generally occur disturbing eifects when dyeing unwoven wool, such as loose wool or wool slubbings or piecegoods, especially when dyeing wool yarn in apparatus by the so-called suspension method with wool dyestuffs. Thus, in addition to the irksome appearance of viscible scum, air bubbles are very tenaciously retained on the :fibre surface, and this prevents the even penetration of the material being dyed, and the material tends to rise to the surface of the bath. Especially when dyeing crosswound bobbins this causes deformation of the bobbins.

Furthermore, the known levelling agents increase the adhesion between fibre and fibre so that a more or less pronounced sticking together of the yarns occurs, and as a result channels are formed in the material and the dyeing turns out uneven. The known levelling agents have the further disadvantage that adducts from dyestuif and levelling agent on being heated below the boiling temperature undergo dehydration and settle out in droplet form (the so-called turbidity point) which are mechanically retained by the material. This phenomenon, called the draining effect, may result in dyeings that are instable towards abrasion and uneven.

While it has already been proposed to remedy these disadvantageous properties of the known levelling agents by incorporation of special combination preparations, for example mixtures of parafiin oil, emulsifier and antifoaming agent, the'use of such preparations renders the dyeing process more complicated and expensive.

Finally, it is also known to use as levelling agents for wool compounds, obtained by treating esterifiable polyglycol compounds, whose molecule contains at least one basic nitrogen atom, a lipophilic residue and a polyglycol chain of at least 4 ethoxy groups, with sulphating or phosphating agents and quaternating at least one tertiary nitrogen atom with dimethylsulphate. The known compounds of this composition can, however, be used only to a limited extent as levelling agents for wool dyestuffs, and moreover they cause deformation of crosswound bobbins.

Unexpectedly, the combinations to be used in the present invention display on dyeing unwoven wool none of the aforementioned disadvantages of the known levelling agents developed for this purpose, they satisfy all requirements of the dyeing practice and render superfluous the use of dyeing assistants which render the dyeing process more complicated and expensive. Finally, the present process may also be successfully applied to cleaning and at the same time dyeing greasy wool, for example wool in the yolk.

Parts and percentages in the following manufacturing instructions and examples are by weight unless otherwise indicated.

Manufacturing instruction I (a) 1190 parts (1 mol) of an adduct from 20 mols of ethylene oxide and 1 mol of a commercial fatty amine (tallow fatty amine) which contains 35% of hexadecylamine, 25% of octadecylamine and of octadecenylamine are heated to 55 to 80 C. while being stirred. Within 15 minutes 126 parts of dimethylsulphate are added and the whole is heated for 1 hour at 75 to 80 C., then dissolved in 1316 parts of water, to yield a solution of strength of the quaternation product.

(b) 1620 parts (1 mol) of an adduct from 30 mols of ethylene oxide and 1 mol of a commercial fatty amine consisting of about 10% of stearylamine, of arachidylamine and 35% of behenylamine, are heated to to C. While stirring; there are added within 15 minutes 200 parts of urea and then within 30 minutes 320 parts of amidosulphonic acid and the batch is esterified for 6 hours at to C. and then dissolved in 1480 parts of water, to yield a solution of about 50% strength containing the ammonium salt of the acid sulphuric acid' ester of the adduct.

7 1 part of the quaternation product described under (a) and 1 part of the esterifiable product sub (b) are mixed together: Levelling agent 1.

Manufacturing instruction II (a) 5 80 parts (1 mol) of an adduct from about 7 mols of ethylene oxide with 1 mol of a commercial fatty amine consisting of 35% of hexadecylamine, 25% of octadecylamine and 45% of octadecenylamine are heated to 60 to 65 C. In the source of 30 minutes 145 parts of chloracetamide are stirred in and the batch is heated for 12 hours at 95 to 100 C. and then dissolved in 622 parts of water, to yield a solution of about 50% strength which contains the quaternation product.

(b) 580 parts (1 mol) of the aliphatic amine-ethylene oxide adduct described above su-b (a) are heated to 60 to 65 C. Within minutes 107 parts of urea and then within 30 minutes 107 parts of amidosulphonic acid are added and the batch is esterified within 6 hours at 95 to 100 C. Then the reaction mixture is dissolved in 560 parts of water; it forms a solution of about 50% strength containing the ammonium salt of the acid sulphuric acid ester.

1 part of the quaternation product described sub (a) is then mixed with 1 part of the esterified product sub (1)): Levelling agent 11.

Manufacturing instruction HI 144 parts each of the adduct from 8 mols of ethylene oxide with 1 mol of a commercial alkylpropylenediamine of the formula RNH(CH NH [where R represents the hydrocarbon corresponding to soybean fatty amine], are

(a) quaternated for 10 hours at 95 to 100 C. with 50 parts of chloracetamide,

(b) esterified with 22.4 parts of amidosulphonic acid in the presence of 22.4 parts of urea for 6 hours at 100 to 105 C., whereupon the reaction product is dissolved with heating in 137 parts of water.

1 part of the quaternation product obtained as described under (a) is dissolved with heating in 1 part of water and then mixed at about 40 C. With 2 parts of the solution of about 50% strength of the esterified product obtained according to (b): Levelling agent III.

Manufacturing instruction IV (a) 926 parts (1 mol) of an adduct from 14 mols of ethylene oxide and 1 mol of a commercial fatty amine containing about 10% of stearylamine, 55% or arachidylamine and 35% of behenylamine are mixed at 60 C. with 150 parts of epichlorohydrin and then quaternated for 16 hours at 100 to 105 C.

(b) 476 parts (1 mol) of an adduct from 1 mol of tal low faty amine with 4 mols of ethylene oxide are esterified in the presence of 107 parts of urea with 116 parts of amidosulphonic acid for 16 hours at 100 to 105 C. On addition of 440 parts of water a solution of 50% strength is obtained which contains the ammonium salt of the acid sulphuric acid ester.

14 parts of the quaternation production obtained as described under (a) are dissolved at 60 to 70 C. in 13 parts of water, cooled to 40 C. and mixed with 8 parts of the esterified product obtained according to (b): Levelling agent IV.

Manufacturing instruction V 580 parts (1 mol) of the adduct, used in manufacturing instruction Ila, from 1 mol of tallow fatty amine and 7 mols of ethylene oxide are mixed within 30 minutes at 80 C. with 108 parts of maleic anhydride, and the mixture is kept for 30 minutes at 100 C. and then for 30 minutes at 120 C. After cooling to 100 C., a solution of 200 parts of sodium sulphite in 720 parts of Water is added and the batch is heated for another hour at 95 to 100 C., to yield a solution of 50% strength which contains the sodium salt of the sulphosuccinic acid ester of the ethylene oxide-fatty amine product.

1 part of the resulting product is mixed at about 40 C. with 1 part of the quaternation product obtained according to manufacturing instruction IIa: Levelling agent V.

Manufacturing instruction VI 1410 parts (1 mol) of an adduct obtained by adding 1 mol of styrene oxide, 1 mol of propylene oxide and thenu 21 mols of ethylene oxide on to 1 mol of tallow fatty amine is quaternated with 360 parts of dimethylsulphate for 6 hours at 100 to 105 C. under nitrogen. 1 part of the resulting product is dissolved at 60 C. in 1 part of water and then mixed with 3 parts of the product prepared according to manufacturing instruction Ib: Levelling agent VI.

Manufacturing instruction VII 2620 part (1 mol) of an adduct from 50 mols of ethylene oxide with 1 mol of stearylamine and 2 mols of butylene oxide are mixed at 60 C. with 200 parts of urea and 320 parts of amidosulphonic acid and esterified for 6 hours at 100 to 105 C. The reaction product is then dissolved in 2480 parts of water, to yield a solution of about 50% strength which contains the ammonium salt of the acid sulphuric acid ester of the adduct. 5 parts of the resulting product are mixed with 2 parts of the product prepared according to manufacturing instruction Ia: Levelling agent VII.

Manufacturing instruction VIII 4410 parts (1 mol) of an adduct from 1 mol of a commercial laurylpropylenediamine, 2 mols of a commercial olefine oxide containing a total of 16 to 18 carbon atoms, and 160 mols of ethylene ovide are quaternated under nitrogen with 440 parts of dimethylsulphate for 12 hours at to C. 8 parts of the resulting product are then dissolved with heating in 8 parts of water and then mixed at about 40 C. with 5 parts of the product prepared according to manufacturing instruction Ib: Levelling agent VIII.

Manufacturing instruction IX 7770 parts (1 mol) of an adduct from 1 mol of a commercial laurylpropylenediamine, 2 mols of dodecene oxide and 160 mols of ethylene oxide are quaternized under nitrogen with 950 parts of dimethylsulphate for 12 hours at 100 to C. 8 parts of the resulting product are dissolved with heating in 8 parts of water and then mixed at about 40 C. with 9 parts of the esterified product prepared according to manufacturing instruction Ib: Levelling agent IX.

Manufacturing instruction X (a) 580 parts (1 mol) of the adduct, used in manufacturing instruction IIa, from 1 mol of tallow fatty amine with 7 mols of ethylene oxide are quaternated with 196 parts of epichlorohydrin for 12 hours at 100 to 105 C. and then dissolved in 658 parts of water.

(b) 580 parts (1 mol) of the fatty amine-ethylene oxide adduct described under (a) above are esterified for 6 hours at 100 to 105 C. with 116 parts of amidosulphonic acid in the presence of 107 parts of urea. The reaction product is dissolved in 551 parts of water to furnish a preparation of about 50% strength which contains the ammonium salt of the acid sulphuric acid ester of the adduct.

The preparation of about 50% strength, obtained as described under (a) which contains the quaternation product, is mixed at about 40 C. with the product obtained under (b): Levelling agent X.

Manufacturing instruction XI 580 parts (1 mol) of an adduct from 1 mol of tallow fatty amine and 7 mols of ethylene oxide are quaternated with 120 parts of ethylene-chlorohydrin for 24 hours at 9 120 to 125 C. and then dissolved with heating in 620 parts of water.

The resulting preparation, which is of 50% strength, is mixed at about 40 C., with the product obtained according to manufacturing instruction Xb: Levelling agent XI.

Manufacturing instruction XII 580 parts (1 mol) of an adduct from 1 mol of tallow fatty amine with 7 mols of ethylene oxide are quaternated with 188 parts of ethylene-bromohydrin for 24 hours at 105 to 110 C. and then dissolved with heating in 642 parts of water.

The resulting product, which is of 50% strength, is mixed at about 40 C. with the product obtained according to manufacturing instruction Xb: Levelling agent XII.

Manufacturing instruction XIII (a) 162 parts (1 mol) of the adduct, described in manufacturing instruction Ib, from 1 mol of fatty amine and 30 mols of ethylene oxide are quaternated under nitrogen with 21 parts of dimethylsulphate for 6 hours at 95 to 100 C. On dissolving the reaction product in 180 parts of water a preparation of about 50% strength is obtained.

(b) A solution, prepared at to C., of 28 parts of chlorosulphonic acid in 140 parts of anhydrous pyridine is mixed at 5 C. with 119 parts (1 mol) of the adduct from 1 mol of tallow fatty amine and 20 mols of ethylene oxide; the batch is heated for 3 hours at 40 to 45 C. and then neutralized at 20 to 30 C. with sodium hydroxide solution of 30% strength then suctioned and the filter cake rinsed with pyridine. The filtrate is freed from its volatile constituents by distillation on a boiling waterbath and under reduced pressure, and the residue is dissolved in 420 parts of water, to yield a solution of about 25% strength which contains the sodium salt of the acid sulphuric acid ester.

3 parts of the quaternation product obtained under (a) are mixed with 4 parts of the esterified product obtained under (b), to form a preparation of about 35% strength: Levelling agent XIII.

Manufacturing instruction XIV A mixture of 27.6 parts of urea phosphate and 31.6 parts of urea is slowly heated to 155 C. and then for 30 minutes at 155 to 160 C., allowed to cool to 110 C., then 64.8 parts of the adduct, described in manufacturing instruction Ib, from 1 mol of fatty amine and 30 mols of ethylene oxide are added and the whole is heated under nitrogen for 2 hours at 145 to 150 C. After cooling the flask contains 107 parts of a hard substance which is dissolved in 166 parts of hot water, to yield a solution of about 25% strength which contains the ammonium salt of the acid phosphoric acid ester of the fatty amine-ethylene oxide adduct.

4 parts of the preparation are mixed at 50 to 60 C. with 1 part of the quaternation product prepared according to manufacturing instruction Ia, to yield a preparation of about 30% strength: Levelling agent XIV.

Manufacturing instruction XV 1190 parts (1 mol) of an adduct from 1 mol of tallow fatty amine and 20 mols of ethylene oxide are quaternated for 24 hours at 110 to 115 C. With 126 parts of benzylchloride.

1 part of the resulting product is dissolved in 1 part of warm water and mixed at about 40 C. with 3 parts of the esterified product obtained according to manufacturing instruction Ib: Levelling agent XV.

Manufacturing instruction XVI 1190 parts (1 mol) of an adduct from 1 mol of tallow fatty amine and 20 mols of. ethylene oxide are dissolved in 400 parts of absolute alcohol and stirred with 400 parts of methylbromide for 8 hours at 5 to 10 C. and then for 20 hours at 20 to 25 C. The liquid constituents are distilled off under vacuum on the waterbath, to leave 1286 parts of the quaternation product.

1 part of the resulting product is dissolved at 60 C. in 1 part of water and then mixed with 3 parts of the esterified product obtained according to manufacturing instruction Ib: Levelling agent XV I.

Manufacturing instruction XVII (a) 2510 parts (1 mol) of an adduct from 1 mol of tallow fatty amine and 50 mols of ethylene oxide are quaternated with 440 parts of dimethylsulphate under nitrogen for 6 hours at to C.

(b) 1010 parts (1 mol) of an adduct from 1 mol of tallow fatty amine and 16 mols of ethylene oxide are esterified with 320 parts of amidosulphonic acid in the presence of 200 parts of urea for 6 hours at 100 to 105 C., and the reaction product is then dissolved in 880 parts of water.

30 parts of the quaternation product described under (a) above are dissolved at 60 C. in 28 parts of water and then mixed at about 40 C. with 20 parts of the esterified product obtained as described under (b): Levelling agent XVII.

Manufacturing instruction XVIII 7770 parts (1 mol) of an adduct from 1 mol of a commercial laurylpropylenediamine, 2 mols of dodecene oxide and 160 mols of ethylene oxide are quaternated under nitrogen with 950 parts of dimethylsulphate for 12 hours at 100 to C.

3 parts of the resulting product are dissolved with heating in 3 parts of water and then at 40 C. mixed with 8 parts of the esterified product described in the first paragraph of manufacturing instruction VII: Levelling agent XVIII.

Example 1 100 kilograms of Wool yarn on crosswound bobbins are wetted for 10 minutes in 1500 litres of water at 50 C. in a dyeing apparatus for crosswound bobbins. There are then added: 2 kg. of acetic acid of 80% strength, 10 kg. of crystalline sodium sulphate, 1 kg. of levelling agent I and 0.5 kg. of the 1:2-cobalt complex of the dyestuif of the formula The temperature is raised within 60 minutes to the boil and the whole is boiled for one hour; the yarn is then rinsed, the bobbins are freed from theirwater content and dried. An even, yellow dyeing is obtained. The crosswound bobbins have not been deformed. When the levelling agent I is replaced by an equal quantity of levelling agent XVIII, similar results are obtained.

Instead of the above-mentioned 1:2-metal complex dyestuif there may be used the dyestuffs of the following formulae, either by themselves or in admixture with 1:2-metal complex dyestuffs:

yellow ll 12 (7) HZN Example 3 100 kilograms of wool yarn on crosswound bobbins are wetted in 1000 litres of Water containing 1 kg. of levelling agent II at 50 C. for minutes in a vat for dyeing crosswound bobbins. 2 kilograms of acetic acid of 80% strength, 10 kg. of crystalline sodium sulphate SOKH and 1 kg. of one of the dyestufis of the following formublue o N-O-NH-OC-OHa N Example 2 (l HN- -NIIO/ \CHNO 100 kilograms of wool yarn are wetted in 2000 litres So H of water and 6 kg. of sulphuric acid of 98% strength 0 for 10 minutes at 50 C. in a hank dyeing vat. There are then added: 10 kg. of crystalline sodium sulphate,

1 kg of levemng agent of the lzl'chmmmm The temperature is raised to the boil within 40 minutes complex of the dyestufi of t e formula and the yarn is boiled for 60 minutes, then rinsed, and

( HO 8 OH the crosswound bobbins are freed from their Water con- 3 tent and dried. The wool is dyed a fast and level shade,

and the bobbins have not been deformed.

C OZN -O Example 4 0 100 kilograms of wool slubbings on bobbins are packed of the chromium complex dyestufi of the into a slubbing dyeing machine. In the liquor tank a bath (10) H0 is prepared from:

2 Q 1500 litres of water HOaS- -N=N-O 2 kg. of glacial acetic acid 5 kg. of sodium sulphate 1 1 kg. of levelling agent XII H3 2 kg. of the dyestuif of the formula and 0.7 kg. of the 1:1-chromium complex dyestufi of the formula (11) E038 HO NH--COCH..O

HO HO I I I {Q N==N NBC 0 0H201 HOaS N=N g g B038 The whole is heated within 20 minutes to 80 C. and dyeing is performed for one hour at 80 C. The yarn is then rinsed. To neutralize the sulphuric acid left on the yarn it may be after-treated with an aqueous sodium acetate solution for 20 minutes at room temperature.

Finally, the evenly dyed, brown yarn is centrifuged and The bath is then heated to 50 C. and pumped into the dried. dyeing machine. The temperature is then raised to the boil 13 Within 45 minutes and the slubbings are dyed at the boil for 60 minutes.

The pH value of the bath is then raised to 8.5 by adding ammonia, the steam is turned off and the bath is allowed to circulate for 15 minutes. Finally, the slubbings are rinsed clean' and dried. They are dyed a fast level red shade. The bobbin carrying the slubbings was not deformed. Similar results are obtained with levelling agents X, XI, IV, H1 or V, or When the above dyestuif is replaced by one of the following:

(I? NH:

sour

NEG-302E NHGOCHzOHzCl blue H038 H0 (3H3 N\ H3coo-N=N N('J (5431 N N HOaS O 1 red ({H 11:36 (3Ha Ha? HOSIS 03H HOaS 3 e1 I 11111 NHoodHoH2o1 NHONHCOOHCHzOl O t H a SIOaH H? YN---N H038 NC OCHCHzBr (311a ILr EN 0 0 CIJHG HzBr Br orange red 01 Hots HO 11111-0: H

I N o=o n (:1

H038 SOaH red SOaH

OzQHzCHzOSOaH blue 14 Example 5 200 kilograms of wool yarn on a goods carrier are introduced into a hank dyeing vat which contains a liquor prepared from:

4000 litres of water 4 kg. of glacial acetic acid 10 kg. of sodium sulphate 2 kg. of levelling agent II 3 kg. of the dyestuff of the formula HCOCH=CH2 scarlet Example 6 100 kilograms of yarn, consisting of 92% of Wool and 8% unshrunk polyvinylchloride staple fibre, are wetted in a hank dyeing machine in 2000 litres of water at 50 C. containing 0.5 kg. of levelling agent X. The following are then added: 6 kg. of sulphuric acid of 98% strength 5 kg. of sodium sulphate 0.7 kg. of the lzl-chromium complex dyestuif containing the dyestuff component of the formula CH3 HO HOOO N SOaH N=NO i C=N HOaS 0.7 kg. of the lzl-chromium complex dyestuff containing the dyestulf component of the formula OH HO I 3 CH3 0.7 kg. of the lzl-chromium complex dyestuff containing the dyestuif component of the formula HO SOaH Within 60 minutes the bath is raised to C. and the yarn is dyed for 60 minutes at 80 C. The yarn is then rinsed and in the last rinse buffered by adding 6% of sodiumacetate. A level, fast, brown dyeing is obtained. During the dyeing process no channels form in the yarn; it remains lofty and voluminous. Dyeing at 80 C. causes the mixed yarn to shrink only little so that subsequent steaming leaves a voluminous product.

15 Instead of levelling agent X there may be used the products mentioned in Example 4, and also levelling agent II or XV IH.

Example 7 100 kilograms of wool slubbings are packed into a machine for dyeing slubbings. In the liquor tank a bath is prepared from:

1200 litres of water 1.5 kg. of acetic acid of 80% strength 0.4 kg. of levelling agent III 0.3 kg. of a condensation product from 1 mol of a commercial mixture of higher fatty amines containing 16 to 22 carbon atoms, and 70 mols of ethylene oxide 10 kg. of the dyestuif of the formula N02 This liquor is heated to 80 C. and pumped into the dyeing machine. Dyeing is performed at 80 C. After 30 minutes 1 kg. of acetic acid of 80% strength is added and after another 15 minutes 1 kg. of formic acid of 85% strength. 15 minutes later the dyebath is substantially exhausted, and 1.5 kg. of potassium bichromate and 30 minutes later ammonia solution of 3% strength are added. The temperature is still 80 C. Finally, the material is thoroughly rinsed, treated in a back-washing machine and dried, whereupon it displays a fast, level, black shade. The slubbing material has not undergone any deformation and has retained its original shape.

Example 8 100 kilograms of nylon 6 spun yarn on conical crosswound bobbins are wetted in a machine for dyeing crosswound bobbins in 2000 litres of water at 50 C. Then the following are added:

1.2 kg. of glacial acetic acid 5 kg. of sodium sulphate 2 kg. of levelling agent VI 1 kg. of the 1:2-chromium complex dyestuif containing two molecules of the dyestuif component of the formula HO H 01 H2N.SO2

The temperature is raised to the boil within 60 minutes, and the yarn is dyed for 60 minutes at the boil, then rinsed and dried, whereupon it displays a level, fast, blue shade. During the dyeing process the bobbins have undergone no deformation.

Similar results are obtained with the levelling agents XIII, XVI and XVIII.

Example 9 200 kilograms of wool yarn in hank form are wetted in a hank dyeing machine in 3000 litres of water at C. Then the following are added.

2 kg. of glacial acetic acid 5 kg. of sodium sulphate 4 kg. of levelling agent XVII 2 kg. of the 1:2-cobalt complex containing two molecules of the dyestuif component of the formula NHCH(OHa)z 0.5 kg. of the dyestufl of the formula SOaH 0.5 kg. of the dyestufr of the formula HOaS 0311 Within 40 minutes the dyebath is heated to the boil and the yarn is dyed for minutes at the boil, then rinsed and dried; it displays a level claret shade. The yarn is lofty and voluminous. Similar results are achieved with levelling agents X IH, XIV, VI, VII, VIII, IX, XV and XVI.

Example 10 kilograms of woolen pieces are wetted in a winch vat in 4000 litres of water at 40 C. Then the following are added:

2 kg. of glacial acetic acid 1 kg. of levelling agent VIII 0.5 kg. of the 1:2-chromium complex dyestufl containing two molecules of the dyestuif component of the formula H INS O Dyestufi complex Metal:

Co- OH Shade Yellow;

TABLE-Contin ued Dyestufi complex Shade Metal:

Cr H Red;

N N- C I C =N HgN S 02''- I I 3O C1 C0 OH HzN Blue.

OaN

O H S OzNHCH2H-CH Co- Cl Brown.

HO OH OH I I C--N N=N plus N=NO I I O =N S 02 EN S 02 I I I 3 0 C 0 CH 0 o HO Green.

OH HzN OH I I C-CH -N=N plus N=NC /CH 0 O NH CHzC H 2N- I C4H9 CHaNHS O2 O2NHCH(CH3)2 Cr OH H? OH HO Grey:

N=N plus HlII -N=N C O NH I HN I I CH3 I i CHsNHSOz (I NHz I O C 3 CH What is claimed is: consisting of dimethylsulfate, eth'ylbromide, benzylchlo- 1. Process for dyeing nitrogenous textile fibers with wool dyestuffs which consists in dyeing the fibers with dyeing preparations containing a levelling agent substantially consisting of mixtures of (a) quaternary ammonium compounds and (b) acid esters of at least dibasic oxygen acids or their alkali, ammonium or amine salts, both of polyglycol compounds, each corresponding to the formula wherein R represents an aliphatic hydrocarbon atom with 12 to 24 carbon atoms, Z is a member selected from the group consisting of a hydrogen atom, an alkyl group with 1 to 16 carbon atoms and a phenyl group, wherein at least one Z is a hydrogen atom, m and a each is 1 or 2, p, q and r are whole numbers, the sum p+q+r(m-1) being at least 4 and at the most 200; the quaternated products being obtained by reacting the polyglycol compounds With quaternating agents selected from the group ride, chloracetamide, ethylenechlorohydrin, ethylenebromohydrin, epichlorohydrin and epibromohydrin; the esterified products being obtained. by reacting the polyglycol compounds with at least dibasic acids or their functional derivatives such as their anhydrides, halides or amides selected from the group consisting of sulfuric acid, phosphoric acid, chlorosulphonic acid, amidosulphonic acid and maleic anhydride; the ratio of quaternary compound (a) to acid ester (b) being in the range 3:1 to 1:3.

2. Process according to claim 1 wherein the quaternary ammonium compounds (a) correspond to the formula A it oHz-OH2-o- 1-I A represents an anion, Q is the radical obtained on elimiobtained on eliminating a hydroxyl group, I is 1 or 2,

19 p, q, and p, q, are whole numbers wherein the sum (p+q) and (p'+q) each is at least 4.

3. Process according to claim 2 wherein the quaternating agent of compound (a) is a member selected from the group consisting of dimethylsulfate, chloroacetamide, epichlorohydrin, epibromohydrin, ethylene chlorohydrin, ethylene bromohydrin benzylchloride and methylbromide and the acid ester radical belongs to an acid selected from the group consisting of sulfuric acid, sulfosuccinic acid and phosphoric acid or a water soluble salt of such acids.

4. Process according to claim 1 wherein wool dyestutfs selected from the group consisting of acid wool dyes, 1: l-chromium complex dyes containing sulfonic acid groups, 1:2-chromium or cobalt complex dyes containing at least one free acid group imparting solubility in water; 1:2-chromium or cobalt complex dyes containing sulfonamide or alkylsulfone groups and reactive dyestuffs.

5. Process according to claim 1 wherein the polyglycol compound contains 6 to 35 ethenoxy groups.

6. Process according to claim 1 wherein Wool is dyed with water-soluble wool dyes selected from the group con sisting of lzl-chromium complex dyes containing sulfonic acid groups, 1:2-chromium or cobalt complex dyes containing at least two free acid water-solubilizing groups and reactive dyes in the presence of (a) quaternary ammonium compounds obtained by quaternating with a compound selected from the group consisting of chloroacetamide, ethylene chlorohydrin, ethylene bromohydrin, epichlorohydrin and epibromohydrin and (b) the ammonium salt of the sulfuric acid ester of polyglycol compounds containing 6 to 9 alkenoxy groups.

7. Process according to claim 1 wherein wool is dyed with water-soluble wool dyes selected from the group consisting of acid wool dyes 1:1-chromium complex dyes containing sulfonic acid groups, 1:2-chromium or cobalt complex dyes containing one sulfonic acid group, and 1:2- chromium or cobalt complex dyes containing sulfonamide or methylsulfone groups in the presence of (a) quaternary ammonium compounds obtained by quaternating with dimethylsulfate and (b) the ammonium salt of the sulfuric acid ester of polyglycol compounds containing 20 to 35 alkenoxy groups.

8. Dyeing assistant suitable for carrying out the dyeing process according to claim 1 which dyeing assistant substantially consists of a mixture of (a) quaternary ammonium compounds and (b) acid esters of at least dibasic oxygen acids or their alkali, ammonium or amine salts, both of polyglycol compounds, each corresponding to the formula (H-CH-Oh-H I g I I Z -1 Z Z wherein R represents an aliphatic hydrocarbon atom with 12 to 24 carbon atoms, Z is a member selected from the group consisting of a hydrogen atom, an alkyl group with 1 to 16 carbon atoms and a phenyl group, wherein at least one Z is a hydrogen atom, m and s each is 1 or 2, p, q and r are whole numbers, the sum p+q+r(m1) being at least 4 and at the most 200; the quaternated products being obtained by reacting the polyglycol compounds with quaternating agents selected from the group consisting of dimethylsulfate, ethylbromide, benzylchloride, chloracetamide, ethylene-chlorohydrin, ethylenebromohydrin, epichlorohydrin and epibromohydrin; the esterified products being obtained by reacting the polyglycol compounds with at least dibasic acids or their functional derivatives such as their anhydrides, halides or amides selected from the group consisting of sulfuric acid, phosphoric acid, chlorosulphonic acid, amidosulphonic acid and maleic anhydride; the ratio of quaternary compound (a) to acid ester (b) being in the range 3:1 to 1:3.

9. Dyeing assistant according to claim 8 wherein the ratio of components azb is 2:1 to 1:2.

References Cited UNITED STATES PATENTS 3,211,514 10/1965 Casty et al. 8-54 3,097,040 7/1963 Casty 854 3,307,901 3/1967 Bindler et al. 884

NORMAN G. TORCHIN, Primary Examiner J. E. CALLAGHAN, Assistant Examiner US. Cl. X.R. 884, 172

CASE BTTl/E zgig s UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 529,922 Dated September 22, 1970 Inventor(s) ALFRED BERGER ET AL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 19, line 2, after "and" delete "(p' q)" and insert Signed and sealed this 24th day of August 1971.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Pat ents