DE1287556B - Process for dyeing or printing nitrogen-containing fibers - Google Patents

Description

Can work near the miscibility gap. The io acid group or not in the complex formation The pH value of the preparations is contained in the carboxylic acid group involved in wool not particularly beneficial alkaline range. · Which 2 dye molecules complex on 1 atom Aids suitable for coacervation are bound in chromium or cobalt, complexes the German patent specification 605 973 described. Chromium or cobalt compounds in the complex Die 15 molecules more than one water-solubilizing group suitable as leveling and dispersing agent Compounds are, however, in such concen- trations (sulfonic acid and / or carboxylic acid groups) ent- " Trations used, which do not hold the coacervate formation and in which 2 dye molecules complex sufficient. Therefore there is no indication that 1 atom of chromium or cobalt is bound, on the fact that when dyeing or printing particularly sulfonic acid group-containing copper phthalocyanines, good results can be achieved when two-phase reactive dyes, for example those with mono-area is being worked on. or dichlorotriazine residues, di- or trichloropyrimi-

The present process relates to the dyeing of residues or HO3S - O - CH ₂ - CH ₂ groups, or printing of nitrogen-containing fibers with acrylamide or «-haloacrylamide groups or aqueous preparations which, in addition to a water-soluble wool dye, which can be converted into such groups, contain a coacervate-forming Auxiliary acid esters of leuco vat dyes. contain agents, the preparations in continuous For dyeing mixtures of wool with

Natural working method applied to the fibers other fibers are in addition to the water-soluble and the proportions between water and wool dyes are the same as for other fibers which optionally contains further additives, and the dyes used, for acetate silk and poly auxiliaries is chosen so that coacervation ester fibers z. B. disperse dyes, for cell access and the fiber material, after impregnation, contains loose-fiber substantive dyes or for poly without Intermediate drying of a moist heat acrylonitrile fibers or disperse dyes subject to treatment, characterized in that basic dyes.

the preparations are acidic to neutral and contain the invention as addition to the dye

Auxiliaries 0.4 to 10%, based on the total preparation used, an 'auxiliary for the dyeing niche Preparation, a compound of the formula (1).

mel These tools are obtained when the above

mentioned alcohols, acids oder.Alkylphenole with 1 to 5 moles of ethylene oxide, preferably 1 to 3 moles where Ri is an aliphatic, cycloaliphatic ₄ o ethylene oxide, reacted and then with a halogen or aliphatic-aromatic hydrocarbon radical or oxycarboxylic acid, such as. B. chloroacetic acid, with 10 to 22 carbon atoms, X for an acidic or etherified with the help of an organic dicar water-solubilizing atom group and η for acid, such as maleic acid, malonic acid or amber an integer not greater than 5, contain. stinic acid, but preferably with an inorganic such radicals are derived from alcohols, such as 45 niche polybasic acid, such as orthophosphorus lauryl, tridecyl, oleyl, octadecyl or hydro- acid or, in particular, sulfuric acid, in an abietyl alcohol, from carboxylic acids how to convert lauric acid esters. or coconut fatty acid, but especially of alkyl- Particularly suitable for the present process

phenols such as octyl or nonyl phenol. are thus compounds of the formula

The nitrogen-containing fibers in the 50

lying procedure z. B. polyamide fibers, namely _-0 p

those made from F-caprolactam as well as those made from hexa- ^L »i ^H 2mTi / υ-th H ₂ methylenediamine and adipic acid, or 1,12-amfnoundecanoic acid, fibers made from regenerated protein, where m stands for an integer in the value of min- Silk, but especially wool, are at least 7, η for an integer ranging from 1 to, if necessary, in a mixture with other fibers, such as 5, preferably 1 to 3, and X for an acidic water-solubilizing atomic grouping, preferably the remainder a polybasic inorganic acid. It is also possible to use mixtures of auxiliaries 60 of the formulas (1) to (3), in particular those whose

-fCH ₂ - CH ₂ - Ofe- "residues

are not uniform, so the average value

Chromating dyes, complex chromium compounds 65 von / 1 no longer represents an integer, i.e. with sulfonic acid group-containing dyes, which can be, for example, about 1.5. With advantage 1 atom of copper or preferably chromium complex is not, however, the acidic ethers and esters contain bound to 1 dye molecule, granular for the production of the aqueous preparations

Ri - O - (CH ₂ - CHa - O) _e - X (D.

Acetate silk, polyester, polyacrylonitrile or cellulose fibers (Half wool). Furthermore, non-textile nitrogenous materials with a fibrous structure are also like leather and furs, to mention.

Water-soluble wool dyes are used as dyes for dyeing wool by the exhaust dyeing process useful dyes are used.

Examples are: acidic wool dyes,

applies, but their alkali, ammonium or amine salts.

The auxiliaries to be used according to the invention form, if appropriate, further additives in water contains, a two-phase system. The aids to be used for the present procedure;, nittel are hydrophilic, colloidal solutions-forming, surface-active impacts that enable coacervation are.

The colloidal chemical term coacervation means the separation of a colloidal solution of a hydrophilic colloid into two liquid phases, with the phase richer in body as coacervate and the lower body phase can be referred to as equilibrium fluid. The coacervate is through excellent that little colloid contains a relatively large amount of dissolved water. A coacervated System is a modified two-phase system according to the definition given above.

Without disturbing these two-phase systems, the preparations can also contain additives of acids and salts, which can be used when dyeing textiles, of hydrotropic substances etc. included. Additions of antifoams, such as higher branched alcohols, e.g. B. 2-ethylhexanol or 3,5,5-trimethylhexanol and Silicone oils, or additives that accelerate the dissolution of the coacervate-forming compound, such as z. B. lower alcohols do not adversely affect the formation of the two-phase system. Such additives can also be contained in a suitable dye preparation and do not have to be the first aqueous preparation can be added.

The amounts in which the compounds to be used according to the invention are used, can fluctuate within fairly wide limits. They are mainly dependent on the one you want Depth of color of the material to be dyed and are 0.4 to 10%, based on the entire preparation, preferably but 0.5 to 7 ° / o.

If the dye is "incorporated" into such a two-phase system, it usually becomes when stirred for the most part to practically completely absorbed by the phase with more resources and at least partially dissolved, as it has a significantly higher absorption capacity than water alone, while the phase with fewer auxiliaries usually contains less dye. This two-phase system, which consists essentially of water, the auxiliary and the dye, can in general be homogenized by stirring without the addition of emulsifiers in such a way that one for the Duration of use sufficiently stable, statistically uniform preparation is obtained, which is now in matching Way must be applied to the fiber material. By adding a thickener such as B. British rubber, the resistance of the preparations in terms of homogeneous Mixing can be increased.

The preparations to be used according to the invention are continuous in a manner known per se applied to the fiber material, e.g. B. in print or particularly advantageous on the padder, very little time is needed. For example, it is sufficient to use dry wool (sliver or piece) from above between two horizontally adjacent padding rollers, the padding solution only in the small one above the line of contact between the two rollers There is a gap (this method of operation is here as "padding in the gusset of a two-roll pad" designated).

However, immersion and subsequent suction or centrifugation of the excess impregnating liquid can also come into consideration.
Usually the dry goods are brought to the

to lard fleet received. In special cases, e.g. B. if loose wool immediately after the last tub of the Washing leviathans can also be impregnated with meshed and heavily squeezed goods To be received.

The temperature of the liquor in the padder can vary within wide limits, for example from room temperature to 80 C, but preferably the impregnation is carried out at room temperature performed. The more auxiliary phase, which contains the dye, is not immediately attached to the fiber fixed, but initially only adheres mechanically and can be removed by washing with cold water completely removed from the surface of the wool fiber.

Instead of applying the impregnating liquid to the fiber material in the padder, you can do this also lead over felt-covered transfer rollers, which rotate in the liquid. The liquid is absorbed by the felt and wiped off onto the fiber material in an easy-to-dose amount.

Furthermore, the fiber material can also be fine by one produced from the impregnation liquid Direct spray or mist and thereby load it with the required amount of dye preparation. All methods known in the textile industry for conditioning or moistening can be used for this purpose and devices are applied.

After impregnating the fiber with the two-phase system the fixation follows in moist heat.

As a rule, the wet goods are taken to the steam room or the fixing room. Under Sattdainpf Furthermore, a direct overheating or direct overheating or the supply of hot air is only so easy Superheated steam to understand that the impregnated material to be dyed without significant condensation on the one hand and without drying on the other hand is brought to the desired steaming temperature and then lingers in a saturated steam atmosphere. The following apply to the moist heat treatment Treatment conditions under consideration:

a) Saturated steam at atmospheric pressure, either for 2 to 60 minutes, e.g. B. in Mather-Platt, other continuous dampers, in a J-box or on the pad roll machine or during a longer period of time in the boiler damper.

b) saturated steam at a higher temperature, e.g. B. for 3 minutes at 120 C in a pressure damper.

c) Moist heat below 100 ⁰ C, z. B. 60 C by approximately airtightly on Foulard impregnated and rolled-up piece goods with a rubber blanket umrollt and closes and ^allowed to rest for 12 hours in a room of 80 · C

This is followed by the removal of excess dye, thickeners and the rest Aids, cleaning is essential. This cleaning

Treatment is usually done through a warm treatment in a bath that has a surface active agent Detergents and / or alkalis can be added. When dyeing wool tops For example, these wet treatments can advantageously be carried out on the Lisseuse.

If chromating dyes are used, they are without the addition of a chromium-releasing agent obtained dyeings to obtain the dye complex then in a known manner in .to treat a hot acid bath with bichromate. But if you want to create the Chromium complexes on the fiber also work continuously, so it is necessary to pre-colored Goods in a continuous manner, expediently again on the padder, with a solution of Treating chromate, steaming it again, washing it out thoroughly and acidifying it if necessary. Dyeings with sulfuric acid esters of leuco vat dyes are, as usual, an oxidation treatment to subjugate.

But the present process can not only be used for re-chrome plating, but also when single-bath metallization is carried out. The impregnation liquor must be used a suitable metal donor, e.g. B. chromium or cobalt releasing agents are added, whereupon the material to be dyed is treated in the manner indicated.

As chromium and cobalt releasing agents come z. B. salts of these metals into consideration. Among the chromium-releasing agents, alkali and ammonium dichromates (Na ₂ Cr ₂ Or, K ₂ Cr ₂ O ?, [NHj] ₂ CrOO ₇ ), chromium fluoride (CrF ₃ ) and chromium acetate should be mentioned. Complex compounds of chromium and cobalt with oxycarboxylic acids, such as tartaric acid, lactic acid, salicylic acid or salicylic acid sulfonic acid, are also suitable.

The oxalato or rhodanato complex salts of chromium can also be used. For the production of cobalt dye complexes, cobalt ammine complexes do a good job. One such cobalt-releasing agent is obtained when cobalt (H) acetate is mixed with aqueous ammonia Added in excess, a complex cobalt (III) compound being formed. Also the complex cobalt (III) compounds of the formulas

ter wool are produced. A printing ink is used whose composition is as above corresponds to padding liquors described, with an addition of urea and / or glycerine required is and possibly the consistency of the printing ink due to higher amounts of thickeners can be regulated to the desired extent. The further course of treatment of the prints corresponds the dyeing process.

ίο When using the aids mentioned, it is possible to lower the pH of the dye preparations as desired down to about 1, which for some Applications can be beneficial. The pH value shifts into the acidic range preferably with acetic acid, occasionally with formic acid or sulfuric acid. Acid preparations require acid-resistant thickeners, such as etherified carubic acids made from locust bean gum. The process is also very suitable for leather, fur and skins. In particular, allow the invention Applicable auxiliaries a dyeing at pH values, which largely protect the Guarantee wool.

Finally, the present method also proves to be advantageous for cleaning and simultaneous cleaning Dyeing of wool containing fatty substances, for example sweat wool. This wool, which z. B. Contains natural wool fat, spinning oils or spinning melts, according to the present process treated and after steaming, instead of in a normal rinsing bath, in a bath, which contains ammonia or sodium carbonate and possibly also a detergent, getting cleaned. If the staining was carried out without the addition of acid, this is also unnecessary Addition of ammonia or sodium carbonate.

In the examples below, the parts mean, unless otherwise noted, parts by weight, and the percentages are percentages by weight.

example 1

Combed wool passes through a horizontal two-roll foulard and is in the gusset of the foulard impregnated with a liquor at room temperature and the following composition:

[Co (NH ₃ ) H] Cl ₃ [Co (NH ₃ ) SCl] Cl ₂
[Co (NH ₃ ) ₅ H ₂ O] Cl ₃

[Co (NH ₃ ), • CO ₃ ] NO ₃ • 1/2 H ₂ O

50 parts of dye of the formula
OH

OH

HO ₃ S

can be used to advantage.

The application of the method according to the invention in Vigoureux printing on top draw results higher yield of the dyes and generally allows a shortening of the steaming time. With With the help of the Vigoureux printing machine, tops can also be drawn in color evenly if the relief rollers are replaced by solid rollers.

For direct printing on pieces of wool, it was previously essential to chlorinate the wool, since otherwise you will only get completely unsatisfactory print results. By using the invention Process', especially with reactive dyes, very beautiful prints can also be produced on non-chlorinated

N = N

NO,

60 parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol.
200 parts of a 5% aqueous thickener of

derived carubic acids,
630 parts of water,
40 parts of chromium fluoride,
20 parts of 85% formic acid.

The impregnated, squeezed off, wet sliver then passes into a steam bath with saturated steam

of 102 ⁰ C filled space and is steamed in this way for one hour. This will be washed in a rinsing bath of 40 ⁰ C. The top is dyed washfast black.

The 44% strength solution of the auxiliary is prepared as follows: 308 parts of the adduct of 1 mole of p-nonylphenol and 2 moles of ethylene oxide are mixed with 105 parts of urea in 15 minutes and then with 105 parts of sulfamic acid in 30 minutes ^{at 60 ° C.} offset. This mixture is boiled for 6 hours

A. 20 parts of dye of the formula

left the water bath. The mixture is then allowed to cool to 60 ^° C. and 410 parts of water are added. A viscous mass is obtained which contains about 44% ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol.

Instead of the above liquor , other dyeing preparations can also be used with otherwise the same procedure. Similar results are achieved with the following fleets :

OH

H, C

SO ₂ -O - <^ ^> - N =

40 parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide with 1 mole of p-nonylphenol, 200 parts of a 5% aqueous thickener of etherified carubic acids, 720 parts of water,

20 parts of 40% acetic acid.

Steaming time: 20 minutes. The ridge is colored washfast red. B. 35 parts of dye of the formula

O NH ₂ H ₂ N

40 parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide with 1 mole of p-nonylphenol, 200 parts of a 5% aqueous thickener of etherified carubic acids, 705 parts of water,

20 parts of 40% acetic acid.

Steaming time: 20 minutes. The top is colored washfast blue.

C. 30 parts of the chromium complex, which is based on 1 atom of chromium 1 molecule of the dye formula

OH HO SO ₃ H

N = N-

HO ₁ S

contains,

50 parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol,

200 parts of a 5% aqueous thickener of etherified carubic acids,

695 parts of water,
25 parts of 85% formic acid.

55

6o steaming time: 40 minutes. The top is colored washfast blue.

D. 20 parts of dye of the formula

OH

HO ₃ S - <^ p> - N = N - |

OH

<C-N

C = N
CH ₃

909504/1835

OH

HO ₃ S

30th

15 parts * of the dye of the formula

HO ₃ S HO NH

■ = N · HO ₃ S

10 parts of the dye of the formula

SO ₃ HH ₃ C-CO-NH-

ίο

50 parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide with 1 mole of p-nonyl-. phenol,

300 parts of a 5% aqueous thickener

of etherified carubic acids, 627 parts of water,
3 parts of chloro-pentammine cobalt dichloride

[Co (NH ₃ ) SCl] Cl ₂ . ίο

As described in Example 1, woolen sliver is impregnated on a two-roll foulard. the However, the fleet has the following composition:

Example 2

Steaming time: 40 minutes. A very true, red-brown coloration of the cobalt complex is obtained above dye.

20 parts of the chromium complex, which is based on 1 atom of chromium per 1 molecule of the dyes Formulas

contains,

90 parts of a 45% solution of the ammonium salt of the acid sulfuric acid ester of Adduct of 1 mole of ethylene oxide with 1 mole of p-nonylphenol, 200 parts of a 5% aqueous thickening of

etherified carubic acids, 660 parts water,
30 parts of 40% acetic acid.

The steaming and rinsing are carried out as in Example 1, but a steaming time of 20 minutes is sufficient. The ridge is colored washfast red.

The preparation of the 45% solution of the aid takes place analogously to Example 1 with the difference that 264 parts of the adduct of 1 mol p-Nonylphenol esterified with 1 mol of ethylene oxide and diluted with 320 parts of water.

Example 3

Combed wool is impregnated according to Example 1 on a two-roll foulard. The fleet continues but are composed as follows:

C-NH ₂

SO ₃ H

OH

HO ₃ S

Cl

N N

NH-C

C-NH

SO, H

90 parts of a 45% solution of a mixture of the ammonium salts of the acid sulfuric acid esters the adducts, which contain an average of 1.5 moles of ethylene oxide per mole of p-tert-octylphenol,

200 parts of a 5% aqueous thickener of etherified carubic acids, 655 parts of water,.
30 parts of 40% acetic acid.

The steaming and rinsing are carried out as in Example 1 , but the steaming time is 30 minutes. The ridge is colored washfast red.

The 45% solution of the auxiliary is prepared analogously to Example 1 with the difference that 272 parts of a mixture of the adduct of 1 mole of p-tert-octylphenol and an average of 1.5 moles of ethylene oxide are esterified and dissolved in 330 parts of water will.

Instead of the above liquor, other color preparations can also be used with otherwise the same procedure. Similar results are achieved with the following fleets:

11

A. 20 parts of dye of the formula

O NH ₂

SO ₃ H

SO ₂ CH ₂ CH ₂ • O • SO ₂ OH

o NH - <^ - y

B. 20 parts of the dye of the formula

Parts of a 44% solution of the ammonium salt the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide with 1 mole of p-nonylphenol, Parts of a 5% aqueous thickening

of etherified carubic acids,
Parts of water,
Parts 40% acetic acid.

Steaming time: 30 minutes. The top is colored washfast blue.

HO ₁ S

40 parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol, 200 parts of a 5% aqueous thickener of etherified carubic acids, 730 parts of water,

10 parts of 40% acetic acid.
Steaming time: 30 minutes. The top is dyed washfast blue-red.

C. 10 parts of dye of formula

SO ₁ H

HO NH - CO - CH, - CH ₇ Cl

SO ₃ H

40 parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol, 200 parts of a 5% aqueous thickener of etherified carubic acids, 740 parts of water,

10 parts of 40% acetic acid.

Steaming time: 20 minutes. The ridge is colored washfast red.

Similar results are achieved with the analogous dyes, but which have a CH> = CH - CO group instead of the chloropropionyl group.

D. 10 parts of dye of the formula O NH,

SO ₃ H

OHN- / Y)

Br Br HN-CO-CH-CH ₂ parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide with 1 mole of p-nonylphenol, parts of a 5% aqueous thickening

of etherified carubic acids,
Parts of water,
Parts 40 "/ o acetic acid.

Steaming time: 30 minutes. The top is colored washfast blue.

Similar results are achieved with analogous dyes, but instead of the dibromopropionyl group one

CH »= C - CO group
Br

exhibit.

Example 4

Combed wool is impregnated according to Example 1 on a two-roll foulard. The composition the fleet, however, is as follows:

10 parts of the cobalt complex, which is based on 1 atom of cobalt per 1 molecule of the dyes Formulas

OH

OH

OH

OC - 0 - CH ₃
OH

N = N-C

SO ₂ CH ₃

I ^CH3

contains,

30 parts of a 50% solution of the ammonium salt of the acidic phosphoric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol,
200 parts of a 5% aqueous thickener of

etherified carubic acids,
730 parts of water,
30 parts of 40% acetic acid.

The steaming and rinsing are carried out as in Example 1, but the steaming time is 20 minutes. Of the The top is dyed brown, which is washable.

The 50% strength solution of the auxiliary is prepared as follows: 27.6 parts of urea phosphate are melted together with 31.2 parts of urea at 70 to 80 ° C., heated to 155 ° C. in one hour and held at 150 to 160 ° C. for 30 minutes. Then allowed to cool to 110 to 120C, the molten product added with 46.5 parts of the adduct of 2 moles of ethylene oxide and 1 mole of nonylphenol and holding for 1 hour at 145 to 150 ⁰ C. then allowed to cool to 110 ⁰ C, solves the Reaction product in 30 parts of water and then further diluted with water to 131 parts.

80 parts of a 50% solution of the sodium salt of the acidic maleic acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of nonylphenol,
200 parts of a 5% aqueous thickener of

etherified carubic acids, 680 parts water,
20 parts of 40% acetic acid.

The steaming and rinsing are carried out as in Example 1, but the steaming time is 20 minutes. Of the The top is dyed gray.

The 50% strength solution of the auxiliary is prepared as follows: 62 parts of the adduct of 2 moles of ethylene oxide with 1 mole of nonylphenol are ^{heated to 70 to 75 °} C. and 21.6 parts of maleic anhydride are added at this temperature in the course of 30 minutes. It is 30 minutes at 100 ⁰ C and 30 minutes at 120 ⁰ C.gehalten. It is then cooled to 6O ⁰ C., neutralized with 3O ° / cent sodium hydroxide solution and diluted with water to 172 parts.

Example 6

Combed wool is impregnated according to Example 1 on a two-roll foulard. The composition the fleet is as follows:

20 parts of the cobalt complex, which is based on 1 atom of cobalt 2 molecules of the dye formula

OH

HO Cl

N = N

SO ₇ NH,

Cl

Example 5

Combed wool is impregnated according to Example 1 on a two-roll foulard. The composition the fleet, however, is as follows:

20 parts of the chromium complex, which is based on 1 atom of chromium 2 molecules of the dye formula

OH

OH

N = N

SO ₂

CH ₃
contains.

contains,

80 parts of a 50% solution of the ammonium salt of the acid sulfuric acid ester of Adduct of 5 moles of ethylene oxide with 1 mole of p-nonylphenol, 200 parts of a 5% aqueous thickening

of etherified carubic acids, 680 parts of water,
20 parts of 85% formic acid.

The steaming and rinsing are carried out as in Example 1, but the steaming time is 20 minutes. Of the The top is dyed in a colorfast bordo red.

The 50% strength solution of the auxiliary is prepared analogously to Example 1 with the.

The difference is that 440 parts of the adduct of 5 moles of ethylene oxide and 1 mole of nonylphenol are esterified and be dissolved in 420 parts of water.

Example 7

Instead of the auxiliaries used in Examples 1 to 6, the following can be used with equal success Preparations can be used:

a) 95 parts of a 42% solution of the ammonium salt of the acid sulfuric acid ester of the lauryl sorbitan ester. The production takes place in the same way the information in Example 1 with the difference that 360 parts of a commercially available lauryl

Sorbitan ester are used in place of the ethylene oxide addition product and that Reaction product is dissolved in 510 parts of water.

b) 160 parts of a 25% strength solution of the Na salt of the acid sulfuric acid ester of the adduct of 1 mol of ethylene oxide and 1 mol of tridecyl alcohol. ^{It is prepared as follows: 122 parts of chlorosulfonic acid at 5 to 10 3} C are added dropwise to 244 parts of the adduct of 1 mole of ethylene oxide and 1 mole of tridecyl alcohol in a stirred vessel. Stirring is then continued for 1 hour at the same temperature. The hydrogen chloride formed is driven off by passing in nitrogen. The viscous sulfonation product is slowly added, with stirring, to 180 parts of 30% strength sodium hydroxide solution which still contains 210 parts of ice. Finally, it is diluted to 1,380 parts with water.

c) 80 parts of a 50% solution of the ammonium salt of the acid sulfuric acid ester of coconut fatty acid diethylene glycol ester. Production: 220 parts of coconut fatty acid, 110 parts of diethylene-25 glycol and 1.1 parts of p-toluenesulfonic acid 6 hours at 110 to 115C under a pressure of 50 to 100 mm Hg in a stirred vessel kept with descending condenser, with water being distilled off. 312 parts of this esterification pro-30 ducts are esterified according to the information in Example 1 with sulfamic acid and then in 300 parts of water dissolved.

d) 40 parts of the sodium salt of glycolic acid ether of the adduct of 4 moles of ethylene oxide with 1 mole of p-tert-octylphenol. Preparation: 382 parts of the adduct of 4 moles of ethylene oxide and 1 mol of p-tert-octylphenol are mixed for about 4 hours at 4O ⁰ C with 50 parts of powdered sodium hydroxide. After this time, the sodium hydroxide has largely dissolved, and 130 parts of sodium chloroacetate are introduced in portions at 40 to 50 ° C. over the course of 2 hours. The mixture is kept at 50 to 55 ° C. for 4 hours, benzene is then added, undissolved residue is filtered off with suction and finally the benzene is distilled off in vacuo.

e) 40 parts of the sodium salt of the acid sulfuric acid ester of the adduct of 4 moles of ethylene oxide with 1 mole of hydroabietyl alcohol. Preparation: In a stirred vessel, 103 parts of chlorosulfonic acid are added dropwise to 745 parts of anhydrous pyridine at about 5 ° C. For this purpose, 373 parts of the adduct of 4 moles of ethylene oxide and 1 mole of hydroabietyl alcohol are slowly added at 40 ⁰ C. It is kept at 40 to 45 ^° C. for 2 to 3 hours, cooled to 20 to 30 ° C. and neutralized with 30% strength sodium hydroxide solution. After standing for 12 hours, the solid residues are filtered off and the pyridine and water are removed in vacuo.

Example 8

Combed wool is impregnated according to Example 1 in a two-roll foulard. The composition the fleet, however, is as follows:

Parts of the cobalt complex that is based on 1 atom of cobalt 2 molecules of the dye formula

OH

NH - CH (CH ₃ ) ₂

contains,

Parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of nonylphenol,
Parts of water,

Parts 40% acetic acid.

The steaming and rinsing are carried out as in Example 1, but the steaming time is 20 minutes. Of the The top is colored washfast red.

Example 9

Combed sliver is impregnated according to Example 1 in a two-roll foulard. The composition the fleet, however, is as follows:

Parts of the cobalt complex, which is based on 1 atom of cobalt per 1 molecule of the dyes Formulas

OH

OH

OC - OCH ₃

and

OH

N = N-C

OH

C-N

^S C = N
CH ₃

contains,

Parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of nonylphenol,
Parts of a 5% aqueous thickening of etherified carubic acids,
Parts of water,
Parts 40% acetic acid.

Steaming and rinsing are carried out as in the example !, but the steaming time is 10 minutes. Man takes on a light brown color.

Example 10

Piece goods are evenly impregnated with the following liquor on a foulard:

909 504/1835

17 18

20 parts of the chromium complex, which is based on 1 atom of chromium per 1 molecule of the dyes of the formulas

OH

OH

OH

OH

= N

and

NO ₂

contains,

Parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide with 15 1 mole of nonylphenol,
Parts of a 5% aqueous thickening of etherified carubic acids, parts of water,
Parts 40% acetic acid. 20th

= N-C

CH ₃

Then is steamed in a continuous wide steamer at about 103 ⁰ C, and then rinsed in water at 40 ⁰ C. The piece of wool is dyed brown in a washable color.

Similar results are obtained with the following dyes, which have 2 molecules of the dyes per atom of the following formulas:

dye N S
i ^C1 I.
CH ₃ <
HO ₃ S- / N ^ Ν / \ C = N Cl metal colour Oh?
COOH I ) \
I y C - y N -ζ SO ₃ H <
DH
NN = NC Cl CH ₃ 1 / V. _{N == N} _ _C
\ / \
C =]
I. 3H
: -1 the same Cr yellow <- <Z> ^ci OH OH
II 2 Y \ C = N Ho ₃ S - <^ y ~ N = N - <^ y Cr orange NO ₂ CH ₃ O O OH
OH I s ν
X / ^c - ⁿ - <> OH
Γ Η _Ογ ^ HO ₃ S - / VN = NC 3 Cr Red 4th Co Yellow-brown 5 Cr Navy blue 6th Cr Gray

Continuation.

Metal dye

colour

OH

HO ₃ S

Co

Red-brown

Co

green

NO ₂

Example 11

SO ₃ H

Loose wool is dipped into the liquor described below and then squeezed off.

Parts of the chromium complex, which is based on 1 atom of chromium, 2 molecules of the dye Formula -, o

CH ₃

HO ₃ S

35

NO ₂

contains,

Parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of Adduct of 2 moles of ethylene oxide with 1 mole of nonylphenol,

Parts of water,

Parts 40% acetic acid.

contains,

40 parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of nonylphenol,
200 parts of a 50% aqueous thickener of

British rubber,
720 parts of water,
20 parts of 40% acetic acid.

The steaming and rinsing are carried out according to the information in Example 1, with the steaming duration but is 20 minutes. The top is printed in a washable brown color.

Example 13

The steaming and rinsing are carried out as in Example 1, the wool top is, as described in Example 1,

however, the steaming time is 30 minutes. The impregnated on a two-roll foulard. The liquor wool is dyed black, which is washable. _{However, 50} has the following composition:

Example 12

Woolen tops are printed on a Vigoureux printing machine with the following printing paste:

Parts of the chromium complex, which is based on 1 atom of chromium per 1 molecule of the dyes Formulas

30 parts of dye of the formula
OH

HO ₃ S

60

HO ₃ S

OH

CH,

60 parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol,
200 parts of a 5% aqueous thickener of

etherified carubic acids,
690 parts of water,
10 parts of potassium chromate,
10 parts of 40% acetic acid.

IO

■ Steaming and rinsing are carried out as described in example 1. The top is washable dyed red.

Instead of 10 parts of potassium chromate and 40% acetic acid and 690 parts of water 10 parts of potassium dichromate, 3 parts of 40% acetic acid and 697 parts of water can also be used will.

Example 14

Raw, fatty sheep wool, so-called sweat wool, is sprayed with a dye preparation and squeezed on a two-roll foulard. The composition of the fleet is as follows:

10 parts of the cobalt complex, which is based on 1 atom of cobalt per 1 molecule of the dyes Formulas

OH

OH

SO ₂ CH ₃

and

OH

OC - O - CH,

OH

, C-N

N = N-C

C = N
CH ₃ course washed and at the same time dyed brown.

The 50% strength solution of the auxiliary is prepared as described in Example 4.

Example 15

A pure wool worsted molton that has not been washed after weaving is made on a Impregnated two-roll foulard. The composition of the fleet is as follows:

20 parts of the chromium complex, which is based on 1 atom of chromium 2 molecules of the dye formula

OH

20th

OC - O - CH,

contains,

80 parts of a 50% solution of the sodium salt of the acidic maleic acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol,
200 parts of a 5% aqueous thickener of etherified carubic acids, 700 parts of water.

Steam on a continuous piece steamer (Mather-Platt system) for 15 minutes and washes at 50 C. It is then rinsed clean in water. A gray-colored piece of goods is obtained, which was freed from the spinning melt and colored in one and the same operation.

The 50% strength solution of the auxiliary is prepared as described in Example 5.

40 Example 16

contains,

50 parts of a 50% solution of the ammonium salt of the acidic phosphoric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol,
200 parts of a 5% aqueous thickening of

etherified carubic acids,

710 parts of water, 30 parts of 40% acetic acid.

The impregnated, squeezed, wet greasy wool then left enters a boiler damper and is there for 40 minutes at 102 ⁰ C in a steam atmosphere. The steamed wool is then rinsed out in a bath at 50 "C, which contains 2 parts of sodium carbonate per 1000 parts of water. In this bath, the loose wool loses most of its fat and other impurities. In two to four further baths, that contain water at 50 "C is washed clean. The loose wool was in the same work-Unwashed, loose wool (sweat wool) is impregnated with a dye liquor and squeezed off. The dye liquor has the following composition:

30 parts of the chromium complex, which is based on 1 atom of chromium 2 molecules of the dye formula

OH

SO ₂
CH,

N = N
HN

OC - O - CH,

contains,

80 parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of Addition product of 2 moles of ethylene oxide with 1 mole of p-nonylphenol,

200 parts of a 5% aqueous thickener of etherified carubic acids,

690 parts of water.

The impregnated goods are then steamed in a steam kettle for 30 minutes

23 24

102 C treated. This is repeated several times with example! 7

hot water on a Leviathan, for example

washed. A gray-colored and clean wool muslin made from non-chlorinated wool is obtained

washed, from adhering natural fat of a Vigoureux printing machine in 50 "/ niger coverage

freed wool. 5 printed with the following printing paste:

! 5 parts of dye of the formula HO, S

CH _2x χ _ / CH ₂ QH \ H ₅ C ₂ ⁷

H ₅ C ₂ -N-C ₂ H ₅

40 parts of a 44% strength solution of the ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol.
200 parts of a 5 ° / _o aqueous solution of the etherified Carubinsäuren,

20 parts of 40% acetic acid, 725 parts of water.

The goods printed in this way are finished according to the information given in Example 1 for tops. Man receives a real violet print.

Example 18

Half-wool pieces, consisting of 50 parts of wool and 50 parts of viscose wool, are impregnated on a padder and squeezed. The padding liquor has the following composition:

30 parts of dye of the formula

HO ₁ SO Cu OO Cu O

'X X

[■ 'Y Vn = N

Ο - ι
V- -Cu Y

-OCH ₃

8 parts dye of the mold!

D N)

O NH ₂

Br

Ii T

O NH-ί / -CH ₃

SO ₃ H

40 parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the addition

products of 2 moles of ethylene oxide to 1 mole of p-nonylphenol.
200 parts of a 5% aqueous thickening of etherified carubic acids.

10 parts of reaction products of naphthalenesulfonic acids with formaldehyde,
692 parts of water,

20 parts of 40% acetic acid.

Then it is steamed in a continuously working wide steamer at about 102 C and then in washed in a rinsing bath at 40 C. The piece of semi-wool is colored blue tone-on-tone.

Example !')

Elastic ski curtain made of pohamid crimped yarn in the warp and wool in the weft Impregnated and squeezed off on a pad roll machine foulard. The padding liquor has the following composition:

909 504 Ί 835

30 parts of dye of the formula

O NH ₂

SO ₃ H

H ₂ N 0

O NH

4 parts of dye of the formula
HO O NH -CH ₃

H ₂ N

50 parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol, 250 parts of a 5% aqueous thickener of etherified carubic acids, 646 parts of water,

20 parts of 40% acetic acid.

Immediately afterwards, the impregnated goods pass a short infrared heat zone, are then rolled up in a steam room with a wet bulb thermometer of around 95 C and remain there for an hour. After storage, it is washed thoroughly in a washing machine with warm water and dried on the stenter. The fabric is colored washable blue. Parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the addition product of 2 moles of ethylene oxide and 1 mole of p-nonylphenol,
Parts of a 5% thickening of etherified carubic acids,
Parts of water,
Parts 85 "per cent formic acid.

Example 20

Piece goods, which consists of 50 parts of wool and 50 parts of polyacrylonitrile, are placed on a padder impregnated and squeezed. The foulard fiotte has the following composition:

10 parts of dye of the formula

(CH ₃ J ₂ N

(CH ₃ J ₂ N

5 parts of dye of the formula
Cl

CH - OH

Then it is steamed in a continuously operating wide steamer at about 102 C and then rinsed in water at 40 C. The wool is bluish red. the polyacrylonitrile fiber is colored blue.

Example 21

Carpet with a base made of jute, but the pile made of polyamide crimped yarn, is sold on Impregnated and squeezed foulard of a pad roll machine The foulard fillet has the following composition:

Parts of the chromium complex, which is based on 1 atom of chromium 1 molecule of the dye formula

HOjS OH

JL

NN
HO _Ä S

HO NH - SO,

J, λ '

- SO ₁ H

55

fio N --- N

Cl

OH

C N

-C

SO ₃ H

CH, contains,

cn,

H, C SO., H

O NH

-CH,

H ₃ C

H ₃ C

O NH

-CH,

H ₃ C SO ₃ H

40 parts of a 44% solution of the ammonium salt ties acidic sulfuric acid ester of the adduct of 2 moles of ethylene oxide with 1 mole of p-nonylphenol,
KK) parts of a 5% aqueous thickening of

etherified carubic acids.
820 parts of water,
10 parts of 80'Y-: iige acetic acid.

The goods treated in this way are squeezed off to 100% liquid absorption, wrapped in a plastic film and stored in a heating cabinet at 60 ° C. for 4 to 10 hours. The unfixed dye component is then washed out in a neutral to alkaline bath. If desired, the goods treated in this way can be rinsed off in an antic or acetic acid bath. A blue coloration which is fast to rubbing is obtained.

Similar results can be obtained with other leathers obtained by a conventional chrome tanning process. z. B. I country shoe. Clothing ^ - or split leather, achieved will.

Example 23

Hin wool sheepskin is dyed with a dye by means of fin brushes; the weight gain is thereby 200%. The color liquor has the following composition:

40 parts of a 44% solution of the ammonium salt of the acid sulfuric acid ester of the general storage product of 2 moles of ethylene oxide and 1 mole of p-nonylphenol.
200 parts of a 5% aqueous thickener of

etherified carubic acids,
690 parts of water,
30 parts of 85% formic acid.

Immediately afterwards, the impregnated goods pass through a short infrared heat zone and then become rolled up in a steam room, which has about 92 C Naßkugelthermomeier, and remains there for 90 minutes. After storage, washing is carried out in a rinsing bath at 40.degree. The polyamide fiber is colorfast red.

Example 22

Suede leather produced using a conventional chrome tanning process is completely Dyeing immersed in a dye bath that has the following composition:

30 parts of dye of the form!

40 parts of dye of the formula

HO ₃ S HO NH

HO ₃ S

_l

SO, H

CC - NH ₁

Il!

N N

Cl

40 parts

a 44% solution of the ammonium salt of the acid sulfuric acid ester of the addition product of 2 moles of ethylene oxide an I mole of p-nonylphenol, "

100 parts of a 5% aqueous thickener of etherified carubic acids.

810 parts of water.
10 parts of 80% acetic acid.

The fur treated in this way is wrapped in a plastic film for 6 to 10 hours at 60 C in one Heated cabinet stored. Then the unfixed dye portion is neutral to alkaline Washed out bath. If desired, the goods treated in this way can be placed in an antic or acetic acid bath be acidified. A rubbing red color is obtained.

Claims (3)

Patent claims: 1. A process for dyeing or printing made of nitrogen-containing fibers or those containing material with aqueous preparations, in addition to a water-soluble Wool dye contain a coacervate-forming auxiliary, the preparations in continuous Working method to be applied to the fibers and the quantitative ratio between Water, which optionally contains further additives, and the auxiliary is chosen so that .daß Coacervation occurs and the fiber material after impregnation without intermediate drying a is subjected to moist heat treatment, characterized in that the acidic to neutral preparations as auxiliaries 0.4 to 10%, based on the total dyeing Preparation, a compound of the formula R ₁ O f CH, CH ₂ OY _n X contain, where Ri stands for an aliphatic, cycloaliphatic or aliphatic-aromatic hydrocarbon radical with 10 to 22 carbon atoms, X for an acidic water-solubilizing atom group or its alkali, ammo i'5 nium and amine salts and /; for an integer is not greater than 5. 2. The method according to claim 1, characterized in that for dyeing mixed genes made of wool and polyamide or cellulose fibers in addition to the water-soluble wool dyes uses the dyes customary for the other fibers. 3. The method according to any one of claims 1 and 2, characterized in that the steaming takes place in continuous operation.