DK142244B - Method of dyeing nitrogenous textile fibers with wool dyes. - Google Patents

Description

1422U

The present invention relates to a process for dyeing nitrogen-containing textile fibers with wool dyes in the presence of quaternary ammonium compounds of polyalkylene glycol compounds and acidic esters of polyalkylene glycol compounds derived from polybasic oxyacids.

From the specification of GB Patent No. 808,647, a method for staining nitrogen-containing fibers with water-soluble, metal-containing azo dyes or acidic wool dyes in slightly acidic medium is known. The dye baths contain 10 water-soluble polyalkylene glycol compounds which contain quaternary nitrogen atoms or may be esterified with orthophosphoric acid, in addition an organic acid, a buffer salt and an alkali metal sulfate. The esterified polyalkylene glycol compounds are acid phosphoric acid esters of fatty alcohol ethylene oxide addition products. These can be used alone or in admixture with others, e.g. quaternary ammonium compounds. '

These quaternary compounds are reaction products of a fatty amine, ethylene oxide and dimethyl sulfate.

Further, from the disclosure of Swedish Patent Nos. 187-478, a method for dyeing nitrogen-containing fibers with wool-reactive dyes containing at least 2 sulfonic acid groups is known in the presence of nitrogen-containing polyethylene glycol compounds. Also acidic esters of these polyethylene glycol ethers can be used as well as the corresponding 25 quaternary ammonium compounds, however, used singly.

It has been found that for dyeing nitrogenous textile fibers with wool dyes in the presence of quaternary ammonium compounds of polyalkylene glycol compounds (a) and 30 acid esters of polyalkylene glycol compounds derived from multi-basic oxygen fatty acids and certain esterified fatty amine alkyl amine products, -aminalkylenoxidadditionsprodukter. This auxiliary mixture is particularly suitable as an equalizer in staining 2

U22M

of nitrogen-containing textile materials and gives excellent results. Using this auxiliary combination, the equalizing effect obtained with the same amount of use is substantially greater than the effect obtained with an auxiliary breath of an anionic fatty alcohol ethylene oxide addition product and a quaternary fatty amine ethylene oxide addition product used as described in the above GB. Patent No. 808,647, or with an optionally quaternized or esterified, nitrogen-containing polyalkylene glycol compound used as described in the above-mentioned Swedish Patent No. 187,478.

Accordingly, the process of the invention is characterized in that both the quaternary ammonium compounds and the acidic esters of the molecule contain a nitrogen-linked aliphatic hydrocarbon group having 12-24 C atoms rg to nitrogen bonded - (- CH-CH-O -) ^ - groups where k is an entirely positive number, in which in the molecule there are in total at least 4 -CH-CH-Q groups, of which a substantial part or all have the formula -CH 2 -CB ^ -O- f 20 while any other has the formula

Z Z

-CH-CH-O- wherein one Z represents hydrogen and the other Z represents an alkyl or phenyl group.

The present process requires at least one quaternary ammonium compound and at least one acidic ester of the composition specified which are derived from the same or different polyalkylene glycol compounds, both polyalkylene glycol compounds meeting the above definition. The aliphatic carbohydrate groups having 12 to 24 C atoms may be saturated or unsaturated, branched or unbranched. They advantageously contain 16-22 C atoms.

As basic elements may be used uniformly high molecular weight alkyl amines or also mixtures obtained by transferring natural fatty acid mixtures, e.g. tallow fatty acid, to the corresponding amines. As amines, for example, mention may be made of dodecylamine, hexadecylamine, octadeoylamine, arachidylamine [Η ^ Ο-ζΟ ^^^ - ΝΗ ^ Ι, behenylamine [H ^ C-CCH ^^ NHg] ° B octadecenylamine. Also mentioned are monoalkylalkylene diamines whose alkyl groups contain 12-24 and whose alkylene groups contain 2-5 C atoms. The alkyl groups can here have the same composition as in the monoamines mentioned.

By reacting such amines with low or high molecular weight alkenoxy compounds, polyalkylene glycol compounds are known in the known manner. Suitable alkenoxy compounds are e.g. low molecular weight compounds such as ethylene oxide, propylene oxide, butylene oxide or higher molecular weight such as dedecene oxide, olefin oxide having 16-18 C atoms or also styrene oxide. The reaction with the amines can either take place with a single alkylene oxide or with a mixture of different alkylene oxides. Due to the ease of availability, propylene oxide in mixtures with ethylene oxide is preferred over the other alkylene oxides. At least one substantial portion of the thus-obtained CH-CH-O groups thus obtained must be etheneoxy groups. Thus, when ethylene oxide is not exclusively added to the amines, only 1-3 moles of propylene oxide or styrene oxide and at least 3 moles of ethylene oxide are preferably used. mol amine. In general, it is advisable not to add more than a total of 60-70 alkenoxy groups to the amines.

Conveniently, both the quaternary ammonium compounds and the acidic esters of polyalkylene glycol compounds of the formula are derived.

JCH2-CK2-0 + -V-H

R - N-CH2 - fCH2) s - N (I)

- (CH2-CH2-0-4p-H H

J m-1 wherein R is an aliphatic, preferably unbranched carbohydride group having 12-24 C atoms, m and s both are an integer of no more than 2 and p, q and r are integers, whereby the sum p + q + rCm-1) is at least 4.

By quaternizing the amine-alkylene oxide preparation products, preferably those of formula (I), compounds (a) and esterification compounds (b) are obtained. Both reactions can be carried out in a conventional manner. The boron ester is conveniently carried out with functional derivatives of 10 multi-base oxygen acids under such conditions that at least one acidic ester group is introduced, preferably in the form of an alkali metal, ammonium or amine salt. As polybasic organic acids for the formation of the acidic esters, one can use organic polycarboxylic acids or carboxylic acid sulfonic acids, e.g. maleic or succinic sulfonic acid, or multi-basic inorganic oxygen acids, such as phosphoric acid or preferably sulfuric acid, or functional derivatives of these acids such as anhydrides, halides or amides.

The acidic sulfuric acid esters are advantageously prepared directly in the form of their ammonium salts by heating the starting materials in the presence of urea with amido sulfonic acid.

For the quaternization, conventional alkylation or arylalkylating agents such as dimethyl sulfate, ethyl bromide, benzyl chloride, chloroacetamide, ethyl- can be reacted in the known manner.

25 enchlorohydrin, ethylene bromohydrin, epichlorohydrin or epibromohydrin, with the starting polyalkylene glycol compounds in the usual manner. In the acidic esters (b) there must be at least one ester group in the molecule. Incidentally, some or all of the hydroxyl ester compounds present can be used partially or advantageously. For compounds (a), the tertiary nitrogen atoms should be extensive until fully quaternized. However, the effect of the products is hardly affected, even if a monoaminopolyalkylene glycol compound 5 Η 2244 is quaternized only up to 85-90% or if not both of the nitrogen atoms in a diaminopolyalkylene glycol compound are quaternized.

Depending on the constitution of the dyes, it may be advantageous that compounds (a) and (b) exhibit a higher or lower content of alkenoxy groups and that compounds (a) have been reacted with certain quaternizing agents.

As can be seen, the process of the present invention advantageously employs quaternary ammonium compounds of the formula

R (CH2 -Ctio-O-J-H

\ / 2 2 T

I UD

A I (CH2-CH2-0 - ^ - H

Q

and acidic esters of formula R '- (III) wherein E and S1 represent aliphatic hydrocarbon groups having 12-24 C atoms, A an anion, Q the group obtained by separating the anion from a quaternizing agent of formula AQ, X the separation of an HO group obtained from a polybasic oxygen group, t 'is an integer of no more than 2 and p, q, p' and q 'are integers, with the sum of p + q and p' + q 'each must be at least 4 and preferably not more than 60.

142244 6

According to the present method, it is possible to dye such nitrous-containing fibers which are present in any processing state and which can be dyed with wool dyes in the usual manner, e.g. polyamide fibers of 5 caprolactam or of adipic acid and hexamethylenediamine. In particular, natural fibers, such as silk and, above all, wool.

Wool yarn can thereby be dyed with any wool dye according to the most common methods. The dyes can f.

10 items belong to the following classes: A. Acid wool dyes. By this is meant such dyes, especially anthraquinones and azo dyes, which contain at least one acidic group which provides water solubility, preferably a sulfonic acid group, but no complexly bound metal and no reactive groups.

B. Sulfonic acid group containing 1: 1 chromium complex dyes, i.e. complex chromium compounds of dyes, especially monoazo dyes in which 1 atom of chromium complex is attached to a dye molecule and which in the molecule 20 has at least one sulfonic acid group.

C. 1: 2-Chromium or cobalt complex dyes, which contain in the complex molecule at least two acidic groups which provide water solubility and which do not participate in the complex bond, preferably a sulfonic acid group.

D. 1: 2-Chromium or cobalt complex dyes which contain in the complex molecule a single group which provides water solubility and which do not participate in the complex bond, preferably a sulfonic acid group.

E. Erie 1: 2-chromium or cobalt complex dyes with 30 acidic groups which provide water solubility and do not participate in the complex bond. These dyes usually contain an optionally substituted sulfonic acid amide group or a methyl sulfone group optionally substituted by the nitrogen atom.

F. Reactive dyes. Unlike the previously mentioned dye classes, these contain at least one reactive group or the reactive substituent with the nitrogenous fibers. Incidentally, they may belong to the most diverse dye classes, e.g. consideration is given to still life dyes, perinone dyes, 10 peridicarboxylic acid imide dyes, nitro dyes, triphenylmethane dyes, phthalocyanines, especially however the acidic anthraquinone and azo dyes, and here both metal-free and metallizable and metal-containing mono-substituents, which contain or substitute polyazo dyes, as fibers. The dyes contain at least one, as a rule, however, 2 or more acidic groups which provide water solubility, and generally good results are obtained with dyes containing 3 sulfonic acid groups of 20.

Among the said reactive groups or substituents of the reaction dyes, e.g. mention is made of the ethylene-imide group, epoxy groups, the vinyl grouping in a vinylsulfone group or in an acrylic acid residue, and especially such labile substituents which can be readily cleaved with the inclusion of the bonding electron pair.

As labile substituents which can be cleaved off with the inclusion of the bonding electron pair, e.g. mention is made of aliphatic bonded phosphorus or sulfuric acid ester groups, sulfonic acid fluoride groups, aliphatic bonded sulfonyloxy groups, and most importantly halogen atoms, especially a moving chlorine atom.

Conveniently, these labile substituents are in the α or β position of an aliphatic group which is directly or above an amino, sulfonic or sulfonic acid amide group attached to 8

14224A

the dye molecule; by the reaction dyes containing halogen atoms as labile substituents, these exchangeable halogen atoms may also be in an aliphatic acyl group (e.g., in the β position of a propionyl group) or preferably in a heterocyclic ring, whereby in the latter cases such dyes are considered which have a monohalogenated heterocyclic ring, e.g. a monochlorinated 1,3,5-triazine group such as the 1,3,5-triazine group of formula Λ 10 -CO-Cl in i,% N (IV)

X

wherein X represents an alkyl, aryl, arylalkyl, alkylmercapto or arylmercapto group, especially, however, an optionally substituted amino group or a preferably substituted hydroxy group, as well as dyes having a dichlorotriazine group or dyes having a dichloropyrimide group.

In addition, reactive dyes with α-bromo or chloro acrylamino groups having 2,3-dichloroquinoxa-alinoyl, dihalogen phthalazine, dichloropyridazone, 2-chloro-thiazole, propionic acid sulfone groups or groups of the formulas -CH 2 -HH-OC -alkyl-halogen, -CH 2 -MI-OC-alkenyl halogen or -Iffl-SO 2 CH 3 -CH 3 -O-SO 2 H.

Quaternary compounds (a) and acidic esters (b) containing in the molecule every 6-9 alkenoxy groups, especially ethhenoxy groups, are particularly suitable when used with the dyes of B in the present process.

or f or both, further with those of C. Thus, the quaternary ammonium compounds (a) preferably contain a halogen as anion, e.g. in that the quaternary nitrogen atoms are attached to chloroacetamide, ethylene-chlorohydrin, ethylene bromohydrin, epichlorohydrin or epibromohydrin.

142244 9

Contains the quaternary compounds (a) and the acidic esters (h) at least 15, e.g. 20-35, alkenoxy groups such as ethene oxy groups, are particularly suitable for dyeing with dyes according to A, B and E, furthermore according to D, especially when the 5 quaternary nitrogen atoms are attached to dimethyl sulfate.

The amounts of the substances to be added to the dye baths in the present color process can fluctuate between relatively wide limits. The amount of the dyes depends on the desired color strength, taking into account the nature of the dye. It is recommended to select the amount of the polyalkylene glycol compounds (a) and (b) (total, i.e.

(a) + (b), calculated on the basis of the fiber weight) between 0.2 and 3%.

The ratio of quaternary compound (a) to acidic ester (b) should be between 3: 1 and 1: 3, but better between 2: 1 and 1: 2. Advantageously, one works at a molar ratio of 1: 1.

In addition, one can dye according to conventional methods known per se which are adapted to the dye class chosen.

As a rule, it is appropriate to dye wool in acidic medium, ie. at pH values between 1.7-6, which are adjusted by the addition of acetic acid, formic acid or sulfuric acid. It is also recommended to add sodium sulfate to the dye bath. One works at elevated temperature, e.g.

25 so that the actual color process begins at 50-80 ° C, warms to the boiling point and completes and ends the process at this temperature. Particularly for rapidly drawing dyes and for reactive dyes, it may be advantageous to add the dye to the bath containing the polyalkylene glycol compound (a) and (b) as well as the other additives, at room temperature or slightly higher temperature and heat the dye and add the dye as a aqueous solution in the heat, e.g. at 50-80 ° C. Moreover, when dyeing wool with sulfonic acid group-containing dyes according to the present process, one does not need to heat to the boiling point throughout the dyeing process, but can operate at temperatures not exceeding 85 ° C, preferably at 75-85 ° C.

The quaternary ammonium compound (a) and the acidic ester (b) can be individually added to the dye baths. However, one can also mix the two components or their aqueous solutions in suitable proportions, e.g.

1: 5 to 3 ^ 1 »produce durable color aids that are 10 ready for use.

In the present method, a good leveling effect is obtained on the textile fibers, especially on wool of any processing step, by means of the two polyalkylene glycol compounds. This is a true combination effect, in that the joint use of the quaternary compound (a) and the acidic ester (b) results in effects which together cannot be achieved with any of the individual components alone. A major advantage of the combination lies in its wide application width with respect to various dye classes. Furthermore, there are none of the various disadvantages which hinder or restrict the use of known equalizing agents for dyeing wool. However, with known equalizing agents, uniform colorings can also be obtained under favorable apparatus conditions. However, when dyeing unspun wool, such as loose wool or woolen comb or from piece goods, especially when dyeing woolen yarn in appliances according to the so-called hanging system, wool dyes usually have various disturbing effects. Thus, in addition to the annoying presence of visible foam, air blisters are also held very stiff to the fiber surface, thereby interfering with the uniform penetration of the dye, and the material tends to rise to the surface of the bath. This is especially true when staining cross-55 coils results in a deformation of the material.

142244 11

Furthermore, the adhesion of the individual fibers to each other is also increased by the known equalizers so that a greater or less same adhesion of the gamut occurs, which leads to channel formation in the dye and thus to unevenness. The known leveling agents also have the disadvantage that addition barriers of dye and leveling agent are separated into small droplets by heating below the boiling point due to dehydration (so-called pluming point), which are mechanically held by the material. The appearance of this, referred to as "draining effect", can lead to non-tearing and uneven staining. 'i; - Λ i

Admittedly, it has been proposed to avoid these drawbacks of the known equalizers by the addition of particular combination compositions such as e.g. mixtures of paraffin oil, emulsifiers and antifoam agents. The use of such preparations is complicated and expensive; the color process, however.

Finally, it is also known as welding agents to use compounds prepared by the action of sulfating or phosphating agents on esterifiable polyalkylene glycol compounds containing in the molecule at least one basic nitrogen atom, a lipophilic group and a polyethylene glycol chain of at least 4 ethoxy groups, and Addition of at least one tertiary nitrogen atom with dimethyl sulfate. However, these known compounds of this composition are only limitedly useful as equalizing agents for wool dyes and also cause a deformation of cross coils. : 30 It is surprising that the combinations used in the process of the invention do not cause any of the above-mentioned disadvantages of the known equalizers. The combinations used in the process of the invention satisfy all practical requirements and thus obviate the simultaneous use of adjuvants which complicate and expensive the dyeing process.

In the following Preparation Examples I-XVIII and Examples 1-10, parts denote weight parts and percent weight percent, where otherwise not stated.

Preparation Example I

a) II90 parts (1 mole) of the commercially available commercially available fat mole (tallow fatty amine) containing 35 ° / ° hexadecylamine, 25% octadecylamine and 10 45% octadecenylamine, and 20 moles of ethylene oxide are heated with stirring to 55-6 ° C. 126 parts of dimethyl sulfate are added over 15 minutes and the temperature is maintained for one hour at 75-80 ° C. Then, in 1316 parts, Water is dissolved and a 50% solution of the quaternization product is obtained.

b) 1620 parts (1 mole) of the additive product of 1 mole of commercially available fatty amine which contains ca.

10% stearylamine, 55% arachidylamine and 55% behenylamine, and of 30 moles of ethylene oxide are heated to 60-65 ° C. Under 20 stirring, 200 parts of urea are added over 15 minutes and then 320 parts of amidosulfonic acid added and esterified for 6 hours at 95-100 ° C. The solution is then dissolved in 1480 parts of water to give an approx. 50% solution containing the ammonium salt 25 of the acid sulfuric acid ester of the adduct.

By mixing 1 part of the quaternization product described under (a) and 1 part of the esterification product described under (b), equalizer I is obtained.

Preparation Example II

A) 580 parts (1 mole) of the addition product of 1 mole of a commercially available fatamine containing 35% hexadecylamine, 25% octadecylamine and 45% octadecenylamine, and ca. 7 moles of ethylene oxide are heated to 60-65 ° C. With U2244 13 stirring, 145 parts of ehloroacetamide are added over 30 minutes and then the temperature is maintained at 95-100 ° C for 12 hours. The solution is then dissolved in 622 parts of water and an approx. 50% solution containing the quaternization product.

b) 580 parts (1 mole) of the fatty ethylene oxide addition product described above under (a) is heated to 60-65 ° C. Within 15 minutes, 107 parts of urea and 107 parts of amido-sulfonic acid are added in 30 minutes and esterified for 6 hours at 95-100 ° C.

Then dissolve in 560 parts of water and give an approx. 50% solution containing the ammonium salt of the acid sulfuric acid ester.

By mixing 1 part of the quaternary product described under a) with 1 part of the esterified product described in b), equalizer II is obtained.

Preparation Example III

144 parts of the addition product of 1 mole of a commercially available alkylpropylenediamine of the formula Ε-ΝΞ- (CH 2), wherein E means the so-called fatty amine hydrocarbon, 1 * hydride, and of 8 moles of ethylene oxide are treated with a) respectively. 50 parts ehloroacetamide for 10 hours at 95-100 ° C for quaternization and b) 22.4 parts amidosulfonic acid in the presence of 22.4 parts 25 urea for 6 hours at 100-105 ° C under esterification, whereupon the reaction product dissolves hot in 137 parts water.

part of the quaternization product obtained under (a) is dissolved hot in 1 part of water and then mixed at ca. 40 ° C with 2 parts of the approx. 50% solution of the esterified product to give leveling agent III.

14 U224 *

Preparation Example IV

a) To 926 parts (1 mole) of the addition product of 1 mole of a fatty amine present in the product containing about 1090 stearylamine, 55% arachidylamine and 55% behenylamine, and 5 of 14 moles of ethylene oxide are added at 60 ° C to 150 parts of epichlorohydrin and quaternized at 100-105 ° C for 16 hours.

b) 476 parts (1 mole) of the addition product of 1 mole of tallow fatamine and of 4 moles of ethylene oxide are esterified in the presence of 107 parts of urea with 116 parts of amidosulfonic acid for 10 16 hours at 100-105 ° C. After the addition of 440 parts of water, a 50% solution containing the ammonium salt of the acid sulfuric acid ester is obtained. 14 parts of the quaternization product obtained in (a) are dissolved at 60-70 ° C in 13 parts of water, cooled to 40 ° C and 15 are mixed with 8 parts of the esterified product obtained in h) to give equalizer IT.

Preparation Example 7

To 380 parts (1 mole) of the addition product used in Preparation Example 11a of 1 mole of tallow fatty amine and of 7 moles of 20 ethylene oxide are added at 80 ° C to 108 parts of maleic anhydride over 30 minutes * The temperature is maintained at 100 ° G for 30 minutes. 30 minutes at 120 ° C. After cooling to 100 ° C, a solution of 200 parts of sodium sulfite in 720 parts of water is added and further maintained at 95-100 ° C for one hour. A 50% solution is obtained which contains the sodium salt of the sulphuric acid ester of the fatty-ethylene oxide addition product. 1 part of the resulting product is mixed with 1 part of the quaternization product prepared according to Example IIa at ca. 40 ° C to give equalizer 7.

Preparation Example 71 1410 parts (1 mole) of an addition product prepared by the addition of 1 mole of styrene oxide, 1 mole of propylene oxide and then of 21 moles of ethylene oxide to 1 mole of saturated fatty amine are quaternized with 360 parts of dimethyl sulfate under nitrogen.

U22U

gene for 6 hours at 100-105 ° C. 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 of Preparation Example 11b Ib to give equalizer VI.

5 Cream Position Example VII

To 2620 parts (1 mole) of an addition product of 1 mole of stearylamine, 2 moles of butylene oxide and of 50 moles of ethylene oxide are added at 60 ° C 200 parts of urea and 520 parts of amidosulfonic acid and esterified for 6 hours at 100-100 $ ° C. Then the reaction product is dissolved in 2480 parts of water and a ca. 50% solution containing the ammonium salt of the acid sulfuric acid ester of the addition product. Five parts of the resulting product are mixed with 2 parts of the product prepared according to Example 1a to give 15 equalizer VII.

Cream Position Example VIII

4410 parts (1 mole) of an addition product of 1 mole of a technical laurylpropylenediamine, 2 moles of a commercial olefin oxide having a total of 16-18 G atoms and 20 of 80 moles of ethylene oxide are quaternized under nitrogen with 440 parts of dimethyl sulfate in 12 hours at 95-100 ° C. Eight portions of the resulting product dissolve hot in 8 parts of water and then mix at ca. 40 ° C with 5 parts of the product of Preparation Example Ib to give 25 equalizer VIII.

Cream Position Example IX

7770 parts (1 mole) of an addition product of 1 mole of a technical laurylpropylenediamine, 2 moles of dodecene oxide and 160 moles of ethylene oxide are quaternized under nitrogen with 950 parts of dimethyl sulfate for 12 hours at 100-105 ° C. Eight portions of the resulting product are dissolved hot in 8 parts of water and then mixed with 9 parts of the esterified product obtained according to Example Example 1b at ca. 40 ° C to give leveling agent IX.

16 1422 * 4

Preparation Example X

a) 580 parts (1 mole) of the addition product used in Preparation Example 11a of 1 mole of tallow fatty amine and of 7 moles of ethylene oxide are quaternized with 196 parts of epichlorohydrin for 12 hours at 100-105 ° C and then dissolved in 658 parts of water.

h) 580 parts (1 mole) of the fatamine-ethylene oxide addition product described above under a) is esterified for 6 hours at 100-105 ° C in the presence of 107 parts of urea with 116 parts of amido sulfonic acid. The product is dissolved in 551 parts of water and an approx. 50% mixture; which contains the ammonium salt of the acid sulfuric acid ester of the addition product.

Mix at approx. 40 ° C, obtained according to (a), approx.

15% mixture containing the quaternization product with the product obtained according to b) to give equalizer X.

Preparation Example XI

580 parts (1 mole) of the addition product of 1 mole of tallow fat-20 amine and 7 moles of ethylene oxide are quaternized with 120 parts of ethylene chlorohydrin for 24 hours at 120-125 ° C and then dissolved hot in 620 parts of water. The resulting 50% mixture is mixed at approx. 40 ° C with the product obtained according to Example Xb to give equalizing agent XI.

Preparation Example XII

580 parts (1 mole) of the addition product of 1 mole of tallow fatamine and .7 moles of ethylene oxide are quaternized with 188 parts of ethylene-bromohydrin for 24 hours at 105-110 ° C and then dissolved hot in 642 parts of water. The resulting 50% mixture is mixed at ca. 40 ° C with the product of Example Xb obtained to give equalizer XII.

Preparation Example XIII

a) 162 parts (1 mole) of the addition product described in Preparation Example 1b of 1 mole of fatamine and 30 moles of ethylene oxide are quaternized with 21 parts of dimethyl sulfate for 6 hours at 95-100 ° C under nitrogen. The product is then dissolved in 180 parts of water to give a solution of about 50%.

B) to a solution prepared at 0 ° C; 28 parts of chlorosulfonic acid in 140 parts of anhydrous pyridine are added at 5 ° C 119 parts (1 mole) of the addition product of 1 mole of tallow fatamine and 20 moles of ethylene oxide, then the temperature is maintained for 3 hours at 40-45 ° C. with 10 30% sodium hydroxide solution at 20-30 ° C. Filters are then filtered by suction and post-washing with pyridine. The filtrate is liberated by distillation on a boiling water bath and under vacuum for the volatiles, and the residue is dissolved in 420 parts of water. You get an approx. 25% solution containing the sodium salt of the acid sulfuric acid ester.

3 parts of the quaternization product described in (a) and 4 parts of the esterified product described in (b) are mixed to give an approx. 3S & a mixture, which is designated equalizer XIII.

Preparation Example XIV

27.6 parts of urea phosphate and 31 »6 parts of urea are slowly heated to 155 ° C? and the temperature is maintained for 30 minutes at 155-160 ° C. It is allowed to cool to 10 ° G, then 23 64.8 parts of the addition product described in Preparative Example 1b of 1 mole fatamine and 30 mole ethylene oxide are added and the temperature is maintained for 2 hours, at 145-150 ° C under nitrogen. After cooling, in the flask, 107 parts of a hard mass remain, which are dissolved in 166 parts of warm water. You get 30 approx. 25% solution containing the ammonium salt of the acid phosphoric acid ester of the fatty-ethylene oxide addition product.

4 parts of the product are mixed at 50-60 ° C with 1 part of the quaternization product prepared according to Example 1a to give an approx. 30% mixture, which is designated equalizer XIV.

cream position example XV

II90 parts (1 mole) of an addition product of 1 mole of tallow fat amine and 20 moles of ethylene oxide are quaternized with 126 parts of 5 benzyl chloride for 24 hours at 110-115 ° C. 1 part of the resulting product dissolves hot in 1 part water and mix at ca.

4 ° C with 3 parts of the esterified product obtained according to Example Example 1 to give equalizer XV.

10 Cream Position Example XVI

II90 parts (1 mole) of an addition product of 1 mole of sebaceous fat amine and of 20 moles of ethylene oxide are dissolved in 400 parts of absolute ethanol and stirred with 400 parts of methyl bromide for 8 hours at 5-10 ° C and then for 20 hours at 20 ° C. 25 ° G. The volatiles are then distilled off under reduced pressure on the water bath, leaving 1286 parts of the quaternization 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 Preparation Example Ib to give equalizer XVI.

cream position example XVII

a) 2500 parts (1 mole) of an addition product of 1 mole of tallow grafted amine and of 50 moles of ethylene oxide are quaternized with 25,440 parts of dimethyl sulfate under nitrogen for 6 hours at 100-105 ° C.

b) 1010 parts (1 mole) of an addition product of 1 mole of tallow fat amine and 16 moles of ethylene oxide are esterified in the presence of 200 parts of urea with 320 parts of amido sulfonic acid for 30 hours at 10 DEG-105 DEG C. and the reaction product is then dissolved in 880 parts of water.

19

U22AA

30 parts of the quaternization product described in (a) are dissolved at 60 ° C in 28 parts of water and then mixed at ca. 40 ° C with 20 parts of the esterified product described in (b) to give leveling agent XVII.

Preparation Example XVIII

7770 parts (1 mole) of the addition product of 1 mole of one technical 1 aurypropyl endiamine, 2 moles of dodecene oxide and 160 moles of ethylene oxide are quaternized under nitrogen with 950 parts of dimethyl sulfate for 12 hours at 100-105 ° C. Three parts of the resulting product are dissolved hot in 3 parts of water and then mixed at 40 ° C with 8 parts of the esterified product prepared according to Preparation Example VII Section 1 to give equalizer XVIII.

The process of the invention is illustrated by the following 13 examples.

Example 1 In a cross coil dye apparatus, 100 kg of wool yarn in the form of cross coils are moistened in 1500 liters of water at 50 ° C for 10 minutes, then 2 kg of 80% acetic acid, 10 kg of crystalline sodium sulfate, 1 kg of leveling agent I and 0.5 kg are added. 20 of the 1: 2-cobalt complex compound of the dye of formula

HQ

° H J-C

/ S-NiJf-C * -S ',, y = s ν-Μ - <\ Γ> (T) h2h-so2 8 η During - 60 minutes, raise the temperature to the boiling point and cook for one hour. then rinses and water 25 is removed from the cross coils which are dried. A uniform yellow color is obtained. The cross coils are not deformed. Replaced = equalizer I with the same amount of equalizer XVIII, similar results are obtained.

U2244 Instead of the specified 1: 2 metal complex dye, the dyes of the following formulas can be used separately, in admixture with each other or in admixture with the 1: 2 metal complex dyes: -f N-f V-SO Η (VI)

Cl N — N-C ^ "I ^ === - ^ H J Sul

H2K

~: f <f ^ V ~ C1 S ° 3H red 0 ™ ΑΛΛ_303η (Till) o In blue M - </ —MH-OC- CH ^

Example 2 In a string dyeing apparatus, 100 kg of wool yarn is moistened in 2000 liters of 10 water and 6 kg of 98% sulfuric acid for 10 minutes at 50 ° C. Then, 10 kg of crystalline sodium sulfate, 1 kg of leveling agent II, 1.5 kg of the 1: 1-chromium complex compound of the dye of the formula 142.2 are added.

HO ^ S OH

J-C-g- "- X" "3 (II) Y * 8 ^ 13 — HN— ^ \ 02n i \ = e / 1.0 kg of the 1: 1 chromium complex dye of formula OH H9

_I yO -— N ~ A V

H03- ^ y —— is j (Xj

'hJ

and 0.7_kg of 1: 1 chromium complex dye of the formula H0 <1> which is heated for 20 minutes to 80 ° C and stained for one hour at 80 ° C. Then rinse. To neutralize the sulfuric acid remaining on the wool, it can be post-treated with an aqueous sodium acetate solution at room temperature for 20 minutes.

10 Finally, centrifuge and dry the uniform brown colored yarn.

Example 5 In a cross coil dye apparatus, 100 kg of wool yarn in the form of cross coils are moistened in 1000 liters of water, to which is added 15 1 kg of leveling agent II, at 50 ° C for 10 minutes. Then 2 kg of 80% acetic acid is added, 10 kg of crystalline sodium sulfate and 1 kg of a dye of any of the following formulas

ho3 -nh-AN: -HN- ^ "X-SC ^ H

- '"f H °?% Ί A A ίχιι)

Cl N = N— {r \ sV

I il r'cid

H03S / ^^ Nn ^ N'S03H

| ° 3H H03S- NH-C ^^ C-HW- ^ X-SC> 3H

H C-CO-HN-A> —W = N — I I J ['i X = X. \ c / so3h h6 ^ (XIII) scarlet

HN-C nC-HN-CH ~ -CHO-OH

HO I II 2 2> -, I A \ A (XIV)

H03S - <^ V-N = N- ^ γ X I

; 1 µl Cl red

H03S ^^ Nv ^ NS03H

In f2

Yfy (XV) o W-A A — M— (f ^ \ j — Μ— A V bla

A = A I K X — A

I n /

SCLH

3 I

Cl 142244 23

The temperature is raised to a boiling point over 40 minutes and boiled for 60 minutes. Then rinse and the cross coils are dewatered and dried. The wool is uniform and true colored and the coils are not deformed.

Example 4 In a camgam color apparatus, 100 kg of wool camgam is packed in the form of winds. Prepare the following bath in the add-on container: 150 liters of water 10 2 kg glacial acetic acid 5 kg sodium sulfate

1 kg equalizer XII

2 kg of dye of formula HO NH-COCH 2 -O-0-N

In Io3H

15 It is heated to 50 ° C and then pumped into the color apparatus.

The temperature is raised to a boiling point in 45 minutes and stained at this temperature for 60 minutes.

By adding ammonia, the pH is then raised to 8.5 and allowed to circulate for 15 minutes after closing the vapor supply. Finally, rinse and dry there. An even true red color is obtained. The camgam winds do not deform.

Similar results are obtained with the equalizers X, 142, 24 XI, IV, III, V, or when the above-mentioned dye is replaced by one of the following dyes: o m2 to allow o m- <Z> -S03h ehgoch2ch2ci

HO, S HO

3 1 λ f * λ H ^ CCQ - * / U-Cl 3 FO S_I 1 I in IL BT red

Cl

OH H, C GEL H-C

1 _1 L

^^ -m- -hhcoch = ch2 'j HO, .S SO ^ H scarlet

WITH

o HO., S Cl t> O HH- V, -HHC0CHCH2C1 O Mi - </ V, -] mC0CHCH2Cl Γ Cl

HO, S O

U22U

25

SO-jH HO

1 in 9-N === N- orange red E ^ W ~ f ° fc ¥ r CHxBr HHC0 (jHCH2Br 5

br

Cl Æ-Cv HOzS HO HH-C * f JH red

I Λ Λ I I

^ X V Cl Cl Γι) ill ΗΟ, δτ'νΝί ^ ΈΟ, Η 5 5 O NH0 1 yr blue O HH- ^ so2ch2ch2oso3h

Example 5 5 200 kg of wool yarn is fed with a material conveyor into a string dyeing apparatus, in which are the following prepared baths: 4000 liters of water 4 kg of glacial acetic acid 10 10 kg of sodium sulfate

2 kg equalizer II

3 kg of dye of formula

U22U

26 1 f2

S03 H

so2ch2ch2oso3h

The initial temperature is 40 ° C. Over 40 minutes, warm to the boiling point and stain for 20 minutes at this temperature. Then rinse and dry there. The 5 results in a true even blue staining of the wool yarn. The gamut is open and voluminous and does not stick together, similar results give all the dyes from Example 4.

Example 6 In a string dyeing apparatus, 100 kg of yarn consisting of 92% wool and 8% non-shriveled polyvinyl chloride staple fibers are wetted in 2000 liters of water at 50 ° G with the addition of 0.5 kg of equalizer X. Then 6 kg of 98% are added. sulfuric acid 5 kg sodium sulfate 0.7 kg l: 1-chromium complex dye with the dye component of the formula HO? H3

HOOC J I

~ = 1, / - γ <ΙΙ> _303η

H03S hJ

0.7 kg l: 1-cb, rum complex dye with the dye component of formula 142244 27

HAY

OH | .-- _ \ Λ-N- <f3I \ HO ^ S- ^ V-N = N-CT j ^ '^ _r in CH3 0.7 kg l: l-chromium complex8 dye with the dye component of the formula

OH HO SO3H

% - »sssdi — Cu 8 Cu 5 Raise the temperature over 60 minutes to 80 ° C and color for 60 minutes at this temperature. Then, rinse the color goods and buffer in the last rinse bath by adding a 6% sodium acetate solution. You get an even real tan. During staining, no channel formation occurs in the material and the gamut remains open and voluminous.

By. the staining at 80 ° C only slightly shrinks the mixing gamut so that a subsequent swelling of yarn was obtained.

Instead of equalizer X, the products mentioned in Example 4 as well as equalizers 15 II and XVIII can also be used.

Example 7 In a comb yarn apparatus, 100 kg of wool comb yam are packed. In the addition vessel, prepare the following baths: 1200 liters of water 20 1.5 kg of 80% acetic acid

0.4 kg leveling agent III

0.5 kg of the condensation product of 1 mole of a commercially available fatty amine mixture of fatty amines with 16-22 C atoms. and 70 moles of ethylene oxide 10 kg of the dye of formula

OH HO

HO 3 S-S

As soon as the bath is heated to 80 ° C, it is pumped into the color apparatus. Stain at 80 ° C. After 30 minutes, 1 kg of 80% acetic acid is added and after another 15 minutes 1 kg of 85% formic acid. After 15 minutes 10 the bath is mostly depleted. Add 1.5 kg of potassium bichromate and after 30 minutes 3% of ammonia water. The temperature is still 80 ° C. Finally, rinse thoroughly, shake and dry. You get a true even black color. The net is not deformed, but has retained its original shape.

Example 8 In a cross coil apparatus, 100 kg of nylon 6 spongam in the form of tapered cross coils are moistened in 2000 liters of water at 50 ° C.

Then the addition of 20 1.2 kg of glacial acetic acid followed 5 kg of sodium sulfate

2 kg equalizer VI

1 kg of the 1: 2 chromium complex dye with two molecules of the dye component of the formula HO HO Cl

Jv — N — N— h2w.s ° 2—

Cl 29 1422ΑΛ

The tenure is raised to a boiling point in 60 minutes and the gamut is boiled for 60 minutes. Then rinse and dry there. You get an even true blue tint. The coils do not deform during staining.

5 similar results are obtained with equalizers XIII, XVI and XVIII.

Example 9 In a string dyeing apparatus, 200 kg of woolen yarn in the form of fat is wetted with 3000 liters of water at 5 ° C. with two 15 molecules of the dye component

of formula OH HO

S0? ^ In 2 NHCH (CH 3) 2 0.5 kg of dye of formula

HQN

21 '

Cl- ^ V-N = N-V

- [HO- S \ 0 ^

SO-H

<0> -01 0.5 kg of dye of formula 30 U2244

Hi * - <0 Η |

HO ^ -L Jl J-SO3H

The temperature is brought to a boil for 40 minutes at the boiling point and the gamut is boiling for 60 minutes. Then rinse and dry there. You get an even burgundy staining of the wool.

5 The yarn is open and voluminous. Similar results are obtained with the equalization mediums: XXII, XIV, VI, VII, VIII, IX, XV and XVI.

Example 1Q

In a reel container, 100 kg of wool pieces are wetted with 4000 liters of 10 water at 4 ° C. Then comes the addition of 2 kg of glacial vinegar

1 kg equalizer VIII

0.5 kg of the 1: 2-chromium complex dye with two molecules of the dye component of the formula OH HO Cl H2 H2QQ2-lSJ · k / N /

Cl

The temperature is raised to the boiling point in 45 minutes and the wool pieces are stained, boiling for 50 minutes. Then rinse and dry there. You get an even blue tint. During the staining, the pieces do not swim on the surface but are still in the liquid. similar results are also obtained with the equalizing agents mentioned in Example 9 and with the 1: 2 metal complex dyes of the following metals and dye components; 142244 31

Metal_Fapvestofkonrpleks_____Nuance

Co OH

y \ _N = * N-C-C-CHX yellow 1 in I II 5 V hoof SO2 1 NHCH-,

V

CH-, 3

Cr OH HO

tc-N-X V

Λ-Ι = Ι-cT I

Y v

Cl

OH HgN

Co ^ / Y V

OpN-I 1 / S == ~ \ blue

^ Λ_A OH

S02NHCH2CH-CH5 Π

OH HO H0 I

I 0H I. . J

00 A_M_, Κ 1. / -? - 0

\ = / y- / + / vv-N = N-C I

HN-ZY V = / Nj = li so i vy i i

“= OCOCH, SO-H-C

0H% 3 I 2 5 5 4h,

Claims (3)

142244 Metal _ Dye Complex Nuance VH H2? oh ^ green Co i / "CH3 OH ΟρΗ-Γ JJ \ = / + A-w-c / 3 2 X / / Λ P I u0HHCHoCH V | Y 2 CH ^ MISO ^ SO2HHCH (CH3) 20 OH HO HO OH A_h = h_ i V I -. Cr | V = y + HH ^ -fX-M-y / X V ioO fy so CHJKSO „} CH, I '-1 3. ch3 3 hh2 p. OH, O PAIEITEET Method of dyeing nitrogen-containing textile fibers 5 with wool dyes in the presence of (a) quaternary ammonium compounds of polyalkylene glycol compounds and Cb) acidic esters of polyalkylene glycol compounds derived from polybasic ammonium compounds, as characterized by esters in the molecule contain a nitrogen-bonded aliphatic hydrocarbon group of 12-t I 24 C atoms and nitrogen-bonded - (- CH-GH-O - ^ - groups, where k is a completely positive number, with in the molecule there are in »15. all at least 4 -CH-CH-O groups, of which a substantial part or all has the formula -CH 2 -CH 2 -O-, while the other optionals have the formula ZZ in -CH