DE1815133A1 - Process for the production of water-soluble, fiber-affine sulfur dyes - Google Patents

Description

CASSELLA FARBWERKE MAINKUR Ref. 2855

SHARED COMPANY

FRANKFURT (MAIN) -FECHENHEIm 6 Frankfurt (Main) -Fechenheim,

December 16, 1968

Dr.Rdm / mi

Process for the production of water-soluble , ■ fiber-affine sulfur dyes

The water-insoluble sulfur dyes are in practice dissolved with alkaline sulfur, in particular sodium sulfur, applied from the dye liquors thus obtained in the form of their leuco compounds to cellulose-containing textiles and the insoluble sulfur dyes by a subsequent Oxidation process fixed on the fiber.

The water-soluble ones are stained in an analogous manner Thiosulfuric acids of the sulfur dyes. Also here are Alkaline sulfur required to remove the thiosulfuric acid residues split off with the formation of the fiber-affine leuco compounds and thus enable the dyes to be absorbed onto the fiber.

In the case of the dyeing processes mentioned, it is necessary that larger ones fall Amounts of wastewater with a high concentration of sulfur, which are difficult to render harmless. One has therefore been around since endeavored for a long time to develop processes that allow it «, Fix sulfur dye © on cellulose-containing tissues without adding reducing agents,

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In the German patent specification 1 004 586, for example, a method is described by which fixation can also be achieved thereby can that cotton and regenerated cellulose with "the solutions of the water-soluble thiosulfur! acid derivatives of sulfur dyes, that do not contain reducing agents, blocks and then the block Material heated to an elevated temperature. However, this method is related to the fixation of the dyes and the fastness properties the dyeings obtained therewith the aforementioned dyeing process carried out with the addition of alkaline sulfur inferior.

From the Swiss patent specification 423.711 is still a Process known by which the textiles are padded with dye liquors which, in addition to the water-soluble Thiosehwefalsäuren Sulphurous substances or their salts hi ™ or polyfunctional Suhiätansim, which are stable reaction products with the sulfur dyes supply, as well as optionally acidic oclsr alkaline Contain catalysts, the so treated TaxtilJan if necessary after drying a damp or tronksnan heat treatment subordinated and taxed in the usual way.

One disadvantage, however, is that the thioic acidic acids the sulfur dyes with reducing agents!: rsiar application none Have an affinity for cellulose fibers and therefore not dyed by the exhaust process who can da η ',

BATH ORIGINAL

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It has now been found that water-soluble, fiber-affine, reducing agent-free colorable sulfur dyes are obtained if water-insoluble sulfur dyes, their reduction products or thiosulfuric acid derivatives in the neutral to weakly acidic pH range, preferably in the presence of catalysts, with optionally substituted alkylene imines, especially ethylene imine, are reacted . ^l

In addition to ethyleneimine, e.g. 1,2-propyleneimine, N-acetylethyleneimine, ß-ethyleneiminopropionamide, N-methylethyleneimine, 2,2-dimethylethyleneimine, 2,3-Dimethyläthylenimin, ß-Äthyleniminopropionsäuremethylester and 2-ethylethyleneimine.

Catalysts favoring the reaction are e.g. ethylene chloride and epichlorohydrin.

The reaction with the alkylenimines takes place in an aqueous medium or in an organic solvent that can be diluted with water, where the starting dyes are either in suspension or can be dissolved or partially dissolved, at temperatures from about 40-120 ° C.

If one assumes water-insoluble sulfur dyes, then after the reaction has ended, i.e. when a sample of the reaction product is completely in the - if necessary weakly acidified Water, put :, any still available, unreacted

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Alkyleneimine can be polymerized by adding a catalyst, such as, for example, ethylene chloride or epichloxhydrin, and introducing CO ₂ or SO ₂ .

The reaction of the dyes in the reduced form or as thiosulfuric acid derivatives with alkyleneimines is only triggered after a neutral or weakly acidic pH range has been set, for example by introducing CO ₂ or SO ₂ into the reaction mixture? it then runs exothermically, with some of the alkylenimine probably reacting at the same time with polymerization.

The sulfur dyes produced by the process according to the invention fall than pastes that are easily soluble in, possibly slightly acidified, or more or less viscous pastes at. They have an affinity for cellulose fibers and can therefore be used for dyeing cellulose-containing fibers without the addition of reducing agents Textiles are used after the exhaust process. Further they can be padded onto cellulose materials, for example, with the fixing of the Dyes can be brought about by a dry or moist heat treatment.

In this way one obtains in a simple manner, with the elimination of sulfur-containing ones Sewage ,. strong colors ,. which are distinguished by good fastness properties, in particular very good wet fastness properties.

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Example 1 ;

a) 100 g of Hydrosollxchtgelb G (Color Ind. Solubilized Sulfur Yellow 5; thiosulfuric acid from Immediallichtgelb GWL, the constitution of which is described in Coll. Czech. Chem. Comm. 21_ (1962) 1533-48) were suspended in 80 ml of water. 48 ml of ethyleneimine were then added dropwise at room temperature with stirring and the reaction vessel was placed in a heating bath at 80 ° C. As soon as the temperature of the reaction mixture had risen to 55 ° C., 0.7 ml of epichlorohydrin were added and a weak stream of CO _{2 was initiated.} The temperature then rose by itself to 99 ° C. within 15 minutes. The C0 _? Feed was now interrupted and the reaction mixture was stirred at 100 ° C. for a further hour. After cooling, a brown, viscous dye paste which is readily soluble in water was obtained.

b) 1 g of this dye paste is dissolved in about 50 ml of water at 50-60 ° C. and made up to 200 ml with cold water. The dye liquor prepared in this way is adjusted to pH 7 with acetic acid. One goes at 25-30 ° C with 10 g of cotton hank and handled. The liquor ratio is 1:20. The temperature of the dyebath is then increased to 90-95 ° C in about 30 minutes and the dyeing is carried out at this temperature for one hour while temporarily handling the cotton hank until the dye is absorbed. The colored strand is then thoroughly rinsed and dried. A strong yellow dyeing with good wet fastness properties is obtained.

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By adding 3 g / l urea to the dye liquor, the dye can be extracted even better.

Example 2 :

100 g of Hydroso11ichtgeIb G (see Example la) were made into a _{paste with 40 ml of H 0} O and then 60 ml of ethyleneimine were added. After the addition of 0.3 ml of ethylene chloride, CO ₂ was passed into the reaction mixture at 40.degree. An exothermic reaction took place, the temperature rising to 106 ° C. in the course of 18 minutes. The _{CO 2} supply was then switched off and the mixture was stirred at a bath temperature of 100 ° C. for a further 4 hours.

The resulting viscous, brown dye paste is easily soluble in water. It behaves similarly in terms of coloring like that obtained in Example 1.

Example 3 ;

100 g of hydroscopic gel G (see example la) were suspended _{in 80 ml of H 3 O.} After adding 48 ml of ethyleneimine and 0.2 ml of 10N HCl, the reaction mixture was slowly heated to 90.degree. A viscous, brown product was obtained in the course of 2 hours without an exothermic reaction occurring.

Instead of 0.2 ml of 1On HCl, it was possible to achieve the same degree of success use: .

0.1 ml diethyl sulfate

0.1 ml of ion sulfuric acid.

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In, all cases, water-soluble, viscous products were obtained, those on cellulosic material without the addition of reducing agents yellow dyeings with good fastness properties provided,

Example 4:

100 g of hydrosol light gel G (see example la) were suspended in 80 ml of H_0. After adding 48 ml of ethyleneimine, the reaction mixture was heated to 80 ° C. and SO gas was passed in at this temperature. The temperature of the reaction mixture rose to 103 ° C. in the course of 12 minutes. After the S0 ₂ feed had been switched off, the mixture was stirred at a bath temperature of 100 ° C. for a further 1 hour.

The reaction product, a brown, viscous paste, is readily soluble in water; in terms of color it behaves similarly to the after products described in the previous examples.

Example 5;

20 g.Immediallichtgelb GWL (Color Ind. Sulfur Yellow 5? Sulfur dye, the constitution of which is described in Coll. Czech. Chem. Comm. 27 , (1962) 1533-48) were suspended _{in 60 ml of H 2 O.} After adding 24 ml of ethyleneimine, the mixture was refluxed for 6 hours. The reaction mixture was then cooled to 40 ° C. and a further 15 ml of ethyleneimine were added. _{Subsequently, SO 2} was passed into the reaction mixture, the temperature rising to 94 ° C. in the course of 14 minutes. After the

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ι ·

The exothermic reaction, the _{supply of SO 2 was} switched off and the mixture was stirred at a bath temperature of 100 ° C. for a further 1 hour.

A brown, viscous mass which _{dissolves well in H 2} O was obtained.

Example 6:

100 g of Hydrosollxchtgelb G (see Example 1a) were dissolved in 80 ml of H “0 suspended. After adding 48 ml of ethyleneimine and 0.1 ml of epichlorohydrin, SO «was introduced at room temperature. the The temperature of the reaction mixture rose to 102 ° C. in the course of 10 minutes. After the exothermic reaction has subsided the S0 ~ supply was interrupted and the mixture was stirred at a bath temperature of 100 ° C. for a further 4 hours.

The reaction product, a brown, viscous paste, is good soluble in HpO.

Example 7 ;

A mixture of 10 g of Immediallichtgelb GWL (see Example 5) and 50 ml of ethyleneimine was refluxed for 3 hours. Of the after distilling off the unreacted ethyleneimine (38 ml) The remaining brown residue dissolves in water acidified with acetic acid to give a clear solution.

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50 g of medial light yellow GWL (see Example 5) were _{suspended in 100 ml of H 2} O and, with the addition of 17 g of Na ₃ S (60% flakes), boiled until the dye had dissolved. The solution was cooled to 50 ° C., then 50 ml of ethyleneimine and 0.1 ml of epichlorohydrin were added and a C0 _o stream was passed through the reaction mixture. The temperature rose to 100 ° C. over the course of 10 minutes. After the exothermic reaction had subsided, stirring was continued at a bath temperature of 120 ° C. for 1 hour.

The product thus obtained, a brown, viscous mass, is in Clearly soluble in dilute acetic acid.

Example 9; .

50 g Iinmediallichtgelb GWL (s. Example 5) were suspended in 75 ml H ₀ O. _{17 g of Na 3} S (60% flakes) were introduced into the aqueous suspension and refluxed until the dye had dissolved. After cooling to 50 ° C., 50 ml of 1,2-propyleneimine and 0.1 ml of epichlorohydrin were then added and CO _{2 was passed} into the reaction mixture. The temperature rose to 91 ° C. in the course of 10 minutes. After the exothermic reaction had subsided, the mixture was stirred at a bath temperature of 120 ° C. for a further 1 hour. The resulting product is a slightly viscous, brown mass that dissolves to give a clear solution in water that has been slightly acidified with acetic acid.

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In an analogous manner, the implementation according to the invention could with

N-acetyl-ethyleneimine,

ß-ethyleneiminopropionamide,

N-methylethyleneimine,

2,2-dimethylethyleneimine,

2,3-dimethylethyleneimine,

ß-Ethyleniminopropionic acid methyl ester and

2-ethylethyleneimine

be performed.

Example 10 ;

50 g of Immediallichtgelb GWL (see Example 5) were suspended in 75 ml of HO. After 17 g of Na2S (60%, flakes) had been introduced, the mixture was refluxed until the dye had dissolved. After cooling to 50 ° C., 35 g of ß-ethyleniminopropionamide, 10 ml of ethyleneimine and 0.1 ml of epichlorohydrin were added. _{CO 2 was} then passed in, the temperature of the reaction mixture rising to 84 ° C. in the course of 16 minutes. After the exothermic reaction had subsided, stirring was continued at a bath temperature of 120 ° C. for 1 hour.

The reaction product is a viscous, brown mass, which is clearly soluble in dilute acetic acid.

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The implementation could with a similar result with a mixture of

- 20 ml of ethylene imine and

30 ml of propyleneimine are carried out.

Example 11 :

a) 100 g of a green sulfur dye, prepared according to of US Pat. No. 2,395,117, Example 1, were disclosed in 1150 ml of water suspended. After adding 70 g of Na “S (60%, flakes) was refluxed for so long until a deep green solution was formed. After cooling to 60 ° C., 125 ml of ethyleneimine and 10 ml of epichlorohydrin were added admitted. C0_ was then passed into the reaction mixture, the temperature being increased over the course of 40 minutes rose to 84 C. After the exothermic reaction has subsided the viscous mass was stirred at a bath temperature of 110 ° C. for a further 30 minutes.

The product produced in this way is a viscous, deep green mass which dissolves clearly in dilute acetic acid.

b) A cotton cross rinse is dyed on the dyeing machine with 5 % of the dye thus obtained in liquor 1:10 * For this purpose, the dye is dissolved in 60 ° C hot water and diluted to the liquor ratio 1:10 by adding cold water. This creates a fleet

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temperature of 25-30 C. The dye liquor is now adjusted to pH 7 with acetic acid, 5 g / l urea is added and the process begins to dye changing liquor direction. After about 15 minutes, the dye liquor is heated to 90-95 ° C in 30 minutes and Maintained at this temperature for 1 hour. It is then rinsed with cold water. The dye bath is colorless moved out. A strong green dyeing of excellent levelness and good wet fastness properties is obtained.

c) A Dralon cotton blend fabric 50/50 is dyed in a single bath with 3% of the green dye obtained according to the above example and 3 % Astrazonorange R (Color Index 48040 "Basic orange 27"). The dyes dissolved separately in hot water at about 70-80 ° C. are combined and added to the dyebath previously charged with 5 g / l urea and adjusted to pH 6 with acetic acid. The dyeing starts at 30.degree. C., the temperature is increased to 105.degree. C. in the course of 1/2 hour and dyeing is carried out at this temperature for 1 hour. After slowly cooling down to 50 ° C., it is rinsed thoroughly. The colored material is then soaped at 80-90 ° C and finished after rinsing again. A bicolor dyeing with good fastness properties is obtained.

Example 12 ;

a) 50 g of Immediallichtbraun GGL (Color Index 5332 7) were suspended in 100 ml of water. After adding 50 g of Na ₃ S (60%, flakes), the mixture was heated under reflux until a brown solution had formed. The reaction mixture

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was then cooled to 60 ° C. and 1OO ml of ethyleneimine and 1.0 ml of epxchlorohydrin were added. Then CO _{2 was} introduced. A strongly exothermic reaction set in immediately. The reaction was controlled by cooling so that it proceeded under gentle reflux. The temperature of the reaction mixture rose to 102 ° C. in the course of 50 minutes. After the exothermic reaction had subsided, the mixture was stirred at a bath temperature of 120 ° C. for a further 2 hours. The product thus obtained, a brown, viscous mass, is clearly soluble in water.

b) 60 g of the dye thus obtained are dissolved in 300 ml of distilled water and made up to 1 liter with cold water. The result is a liquor of 20-25 ° C. which is adjusted to pH 5 with acetic acid. A cotton fabric is impregnated with this liquor on the padder and the fabric is squeezed in such a way that it retains 75% of its weight in dye liquor. The impregnated fabric is dried, then heated to 200 ° C. for 1 minute. A brown-dyed cotton fabric with very good wet fastness properties is obtained.

You can add the above-described padding liquor from 25-30 ° C at pH 5 to pH 7 10-20 g / l urea, whereby the Fixation of the dye is improved somewhat.

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Ref. 2855

The following sulfur dyes were converted according to the method given in Example 12.

example
No. Sulfur dye Color.Ind. H ₂ O
ml Ethylene
imin ml Na ₂ S g
6o% Epichlor
hydrin
ml 13th Immedialindon RR
50 g 53440 120 50 30th 0.2 14th ImmediaIrοt-
brown 3B 50 g 53720 100 50 30th 0.2 15th ImmediaIgeIb-
brown G 50 g 53055 100 50 - 20th 0.2 16 Immedial Orange
brown RR 50 g 53015 100 50 30th 0.2 17th ImmediaIgeIb-
olive 5G 50 g 53065 100 50 20th 0.2 18th Immedial light
katechu 4RL 50 g 53320 250 50 25th 0.2 19th Indocarbon CL
conc, - 50 g 53290 100 60 25th 0.1 20th Immedial new
blue FBL 50 g 53470 100 50 25th 0.2 21 Immedialdirekt-
blue RL 50 g 53235 150 65 30th 0.2 22nd Hydron blue G
50 g 53640 100 100 35 0.3 23 Immedia1 black
brown AN 50 g 53000 100 50 25th 0.2 24 Immedialcarbon CBO
50 g 53185 100 100 30th 0.2

The conversion products are viscous dye pastes, which in Are easily soluble in water or dilute acetic acid and on materials containing cellulose, without the use of reducing agents, Result in dyeings with good fastness properties,

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Example 25:

50 g Immedialcarbon CBO (Color Index 53185) were in 80 ml KLO -suspended and, after adding 100 ml of ethyleneimine, heated under reflux for 3 hours. After cooling to 60 ° C, 0.1 ml Ethylene chloride was added and then C0 "passed into the reaction mixture, the temperature in the course of ' Rose to 85 C for 12 minutes. After the exothermic reaction had subsided, the temperature was continued for 1 hour at a bath temperature of 120.degree touched. The reaction product, a viscous, black paste, is easily soluble in water; she delivers on cellulosic Textiles black dyeings with good wet fastness properties.

Example 26 :

50 g of Immedialcarbon CBQ were suspended in 80 ml of water and heated under reflux for 2 hours after adding 100 ml of ethyleneimine. After cooling to 60 ° C., the reaction mixture was added S0 "initiated, the temperature over the course of 10 minutes rose to 94 C. After the exothermic reaction had subsided, the mixture was stirred at a bath temperature of 120 ° C. for a further hour.

The translation product, a viscous, black paste, is good soluble in water; "it corresponds in its coloring properties the dye obtained according to Example 25.

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Example 27 ;

50 g of Immedialindon RR extra (Color Index 53440) were _{suspended in 80 ml of H 9} O and 48 ml of ethyleneimine were slowly added, an exothermic reaction starting. The feed rate of the ethyleneimine was controlled so that the reaction proceeded under gentle reflux. The temperature rose to 98 ° C. towards the end of the reaction. After the exothermic reaction had subsided, the mixture was stirred for a further hour at a bath temperature of 120 ° C., then cooled to 60 ° C. and, after the addition of 1.0 ml of epichlorohydrin, CO _{2 was passed in for} 15 minutes. The reaction mixture was then reheated for a further 1 hour at a bath temperature of 120.degree.

The reaction product obtained in this way, a viscous, blue paste, dissolved in acidic, aqueous solution of pH = 6.8.

Example 28 ;

50 g of immediate red-brown 3B (color index 53 720) were in 80 ml of H_0 suspended. After adding 48 ml of ethyleneimine, the mixture was refluxed for 3 hours. Then the reaction mixture was on It was cooled to 6.0 ° C., 1.0 ml of epichlorohydrin was added and CO 2 was introduced. The temperature rose to 102 ° C. in the course of 8 minutes. After the exothermic reaction had subsided, was still Stirred at 120 ° C. for 1 hour. The reaction product obtained in this way is a brown, viscous paste which dissolves in water Easily dissolves and red-brown colorations with good fastness properties on cellulose material without the addition of reducing agents supplies.

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Following the procedure described in Example 28, the following sulfur dyes were made water-soluble with ethyleneimine Products implemented.

example
No. Sulfur dye Color ind H ₀ O
ml Ethylene
imin ml Epichlorine
hydrin ml 29 Immedial yellow olive
5G extra 50 g '■ 53065 80 48 1.0 30th Immedial light green
BB conc. 50 g 53571 80 100 1.0 31 Immedial light
katechu 4RL 50 g 53320 80 100 1.0 32 Immedial yellow olive
5G 50 g 53065 80 100 1.0 33 Immedial new blue
FBL 50 g 53470 80 100 1.0 34 Immedial light
brown GGL 50 g 5332 7 80 100 1.0 35 Indocarbon CL
50 g 53290 80 100 1.0 36 Immedialcarboh CBO
50 g 53185 100 48 1.0 37. Immedial Orange
brown RR 50 g 53015 80 100 1.0 38 Immedial Orange
brown RR 50 g 53015 80 48 1.0 39 ImmediaIge Ib-
brown G 50 g 53055 80 48 1.0 40 Hydrosol black BW
100 g 53186 140 10 0.1 41 Hydroso! Black BW
50 g 53186 80 48 1.0

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Example 42 ;

50 g Immedialneublau FBL extra (Color Index 5347O) were suspended _{in 80 ml H 3 O.} 100 ml of ethyleneimine were then added dropwise with cooling so that the temperature of the reaction mixture did not rise above 90.degree. After the exothermic reaction had subsided, stirring was continued for 45 minutes at a bath temperature of 100 ° C. and then unreacted ethyleneimine was distilled off under vacuum. The dye solution obtained in this way can be diluted indefinitely with water.

In an analogous way were

Immediate light brown GGL - Color Index 53327

Indocarbon CL conc. "" 53290

immedialcarbon CBO - "" 53185

Immedialindon RR "" 53440

converted to water-soluble dyes. .. ■ _ ..

Example 43 ;

50 g of Hydronbläu G (Color Index 53640) were suspended in 200 ml of ethanol and, after addition of 75 ml of ethyleneimine, heated under reflux for 3 hours. The cold reaction mixture was filtered off with suction. There remained on the filter 53 g of a finely powdery blue dye which was clearly soluble in acidified water with a pH of <fö.

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The deep blue filtrate was obtained after evaporation in vacuo another 32 g of a blue, viscous paste, which is in water cleared up.

The two reaction products gave on cellulose fibers, without Reducing agent colored, deep blue, real shades.

Example 44 :

50 g of Immedialindon RR extra (Color Index 53440) were suspended in 200 ml of methanol and, after addition of 75 ml of ethyleneimine Heated under reflux for 3 hours. After cooling, the reaction mixture was filtered, 52 g of a black-brown Dye powder could be isolated, which is in acidified Water at pH <6 dissolved with blue color.

By evaporating the filtrate in vacuo, 72 g of a pasty residue were obtained which, in water, turned blue was soluble.

The solid and pasty reaction product yielded cellulose-containing Materials blue dyeings with good fastness properties.

Example 45 ;

20 g of a green sulfur dye, prepared according to US Pat. No. 2,395,117, Example 1, were suspended in 230 ml of dimethylformamide and heated to 80.degree. After adding 14 g of Na ₂ S (6O%, flakes), a deep blue dye solution resulted.

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The temperature was then increased to 90 ° C. and held there for 30 minutes. 0.2 ml of epichlorohydrin and 25 ml of ethyleneimine were added to the solution, which had been cooled to 60.degree. When CO _{2 was} subsequently passed into the reaction mixture, the temperature rose to 80 ° C. in the course of 15 minutes.

After the exothermic reaction had subsided, the mixture was stirred at a bath temperature of 100 ° C. for a further hour. The reaction product, a slightly viscous, green solution could be diluted indefinitely with acidified water with a pH of <6.

On cellulose fibers, dyed without the addition of reducing agents, it gave clear green dyeings with good fastness properties.

The reaction in dimethylformamide / water mixtures led to similar results.

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Claims (3)

- 21 - Ref. 2855 Patent claims \ lj process water, faseraffiner, reducing agents free dyeable for preparing sulfur dyes, characterized in that water-insoluble sulfur dyes, their reduction products or Thioschwefe! acid derivatives in the neutral to weakly acidic pH range, preferably in the presence of catalysts, with optionally substituted alkyleneimines, especially ethyleneimine, implements. 2. Water-soluble, fiber-affine, reducing agent-free dyeable sulfur dyes, prepared by the process of Claim 1. 3. Cellulosic dyed with dyes according to claim 1 or 2 Materials. 009828/1505