DE2050921A1 - Process for fixing dyes on textile fibers - Google Patents

Description

TELEGRAMS: KARPATENT NUSSBAUMSTRa'sSE 10

October 16, 1970 ¥. 40 140/70 - Eo / H

Martin Marietta Corporation New York, NY (V.St.A.)

Process for fixing dyes on textile fibers

The method according to the invention for fixing dyes on natural or regenerated cellulose textile fibers comprises the step of contacting an alkaline or neutral aqueous oxidizing solution containing water and Ua ₅ Fe (GIi) ₆ , K ₃ Fe (CN) ₆ , K ₂ NaZ ^- Fe ( CN) ₆ / or (NH ₄ J ₅ Fe (CN) ₆ contains, with these fibers that carry thereon at least one dye in reduced form, this dye from the group of (1) dyes which in their reduced form have at least one have bound mercaptide group per molecule of the dye, and (2) dyes which in their reduced form have at least one bound mercapto group per molecule of the dye is selected.

The invention relates to a method for fixing dyes on natural or regenerated cellulose textile fibers.

The textile fibers can be in any desired form, for example knitted or woven cloth, yarn, warp wrap, non-woven fabrics or raw materials.

Illustrative and non-limiting examples of dyes which are fixed by the process according to the invention can be given below. In reduced

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These dyes have at least one bound mercaptide or bound mercapto group per molecule of the dye. Examples are:

(a) Sulfur dyes including sulfurized ones Indophenol dyes, pre-reduced liquid sulfur dyes and thiosulfuric acid derivatives of sulfur dyes;

(b) Azo dyes with a disulfide group in the molecule or with at least one bound thiosulfate group or one attached -SCN group per molecule of the dye;

(c) Phthalocyanine or metal phthalocyanine dyes having one disulfide group in the molecule or at least one bound thiosulfate or bound -SCH group per molecule of the dye;

(d) Perylene dyes with at least one attached -SCN group per molecule of the dye and

(e) Anthraquinone dyes with at least thinner bound Mercapto or mercaptide group per molecule of the dye in the reduced form.

Those of the dyes listed above which are in their oxidized form will of course be in their reduced form on the fiber at the time of initial contact with the oxidizing solution when carrying out the present process .

If desired, the fibers can also with a mixture of the above dyes, for example one Mixture of a sulfur dye and an azo dye with a bound thio3ulfate group.

The method according to the invention is explained in detail below.

The present process can be used for dyeing or printing textile fibers. The dyes

1 U 9 8 1 9/2 0 5 0

can be applied to the fibers in any desired manner, for example by jigger dyeing, padding, skid dyeing, pressure rollers or packaging machines are applied. The dye can be used on the fibers both in reduced form as well as in oxidized form; in the latter case the dye will be in its mercapto or mercaptide form transferred before contacting with the oxidizing solution. Of course, dyes can be bound with Thiosulfate or attached -SCN groups into the mercapto form be converted by hydrolysis under acidic or alkaline conditions as well as by reduction.

If desired, the fibers can optionally during For a certain period of time they can be munched, steamed or dried to prevent the dye from penetrating into the skin To lighten fibers or to assist in the reduction of the oxidized dye.

The fibers with the dye thereon in the reduced form are then nit the oxidizing solution contacted to fix the dye, for example by immersing the fibers in the oxidation solution.

The neutral or alkaline aqueous oxidation solution contains water and Ha ₃ Fe (CN) ₆ , K ₅ Fe (CN) ₆ , K ₂ Na / Pe (CN) g7 or (NHi) ^ Fe (CiOg. For economic reasons, Na ₅ Fe (CN) ₆ , K ₅ Fe (CU) ₆ or K ₂ NaFe (ClO ₆ preferred. The oxidation solution can also contain a simple electrolyte such as NaCl, Na ₂ SO. Or MgSO ₄ ; the electrolyte increases the rate of oxidation (fixing reaction) and also inhibits the bleeding of dyes that tend to bleed into the oxidizing solution. If desired, the oxidizing solution can also contain a nonionic or anionic surface-active agent, for example a

1 η μ η 1 π /? η 5 0

medium included. If desired, the oxidation solution can also contain about 1% sodium salt of ethylenediaminetetraacetic acid for chelating with free iron (III) and iron (II) ions, which are foreign to the system were added, for example from impure treatment water.

The amount of the above ferricyanide used in the aqueous oxidation solution depends mainly on the amount of the dye used. Sufficient ferricyanide is used to oxidize the amount of leukoform of the dye on the fibers and no detrimental results occur when using as much ferricyanide as it dissolves in the water. For most purposes, a neutral or alkaline aqueous oxidation solution containing a wt .- ^ Na ₅ Fe (CN) ₆ , K ₅ Fe (CN) ₆ , K ₂ Na ^ Fe (CN) ₆ / or (NH ^) ₃ Fe (CN) ₆ contains, suitable and inexpensive, and neutral or alkaline aqueous oxidation solutions which, based on weight, contain 0.2 to 10 % Na ₅ Fe (CN) ₆ , K ₅ Fe (CN) ₆ , K ₂ Na / Fe (CN) ₆ / or (NH ^) ₅ Fe (CN) ₆ and 0 to 30 # NaCl were found to be beneficial in the present process. Small amounts of Na ₂ CO ₅ can be added to the oxidation solution to keep it neutral or alkaline.

The oxidizer may be about 1 (up to 200 ⁰ F 35) are up to 95 ⁰ C, when contacted with the fibers having thereon the reduced dye. (Leuco form) in contact and preferably has a temperature between room temperature to about 70 ⁰ C au3 reasons of economy. At room temperature, even in the absence of an electrolyte, the oxidation reaction proceeds rapidly and is practically over when the dye and the oxidation solution have been in contact for about 30 to 45 seconds,

which is very favorable for the continuous high-speed dyeing of sulfur dyes in the padding-steam range. By an electrolyte in the oxidizer solution, for example, 3 wt -.% NaCl, the rate of oxidation reaction is accelerated considerably.

After the dye has been fixed, the fibers can be washed and dried in the usual way.

The dyeings and prints have excellent wash fastness and a surprising softness of the handle, as they are obtained according to the invention.

According to the above method, natural and regenerated cellulose textile fibers can be dyed and incorporated into In some cases, polyacrylic and polyamide textile fibers can also be dyed, whatever the specially chosen one Dye is dependent. Mixtures of natural or regenerated cellulose textile fibers with polyacrylic, polyamide or synthetic linear polyester textile fibers can be used in the process, being in this Case the natural or regenerated cellulose is colored, while polyacrylic and polyamide fibers by some Dyes are colored and not by others and the polyester remains practically unaffected by the process. Furthermore, paper textiles which are derived from natural cellulose can also be used according to the present invention Procedure to be colored.

The method of the invention has a number of advantages over previous methods, of which some are given below.

The method according to the invention is particularly advantageous for the application of sulfur dyes to textiles. In technical practice, either hydrogen peroxide or sodium dichromate is used in a mixture with acetic acid

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- D -

(called chromium and acid) commonly used to oxidize sulfur dyes on textiles. These Both known methods have certain disadvantages which are overcome by the present invention.

Using numerous sulfur dyes results in chromium and acid on cotton or regenerated textile fibers a coloration with a rough handle. This will cause excessive wear and tear of needles and fiber breakage during of sewing and knitting and the use of glidants or lubricants during yarn and knitting Raw material dyeing becomes necessary to soften the rough yarn. According to the present process with sulfur dyes dyed cotton and regenerated cellulosic textile fibers are surprisingly soft Handle, which avoids the need to use lubricants or lubricants.

Cotton and cotton dyed with sulfur dyes regenerated Celluloae textile fibers, in which chromium and acid were used as oxidizing agents, are not Easily wettable again, which means that wetting agents can be used in all subsequent wet finishing operations becomes necessary, while the pasers dyed by the method according to the invention are light again in the subsequent wet finishing operations are wettable and no wetting agents have to be used.

After the sulfur dye has been oxidized on cotton or regenerated cellulose yarn, it is difficult to washing to remove the remaining chromium and acid, and it is common practice to keep the yarn at boiling point to soap during this wash. When the invention Procedure is a soapy at the boiling point and an excessive one

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Washing after oxidation is not necessary as the residues obtained during oxidation are water-soluble salts are, for example ferrocyanides. By avoiding of soapy at the boiling point, one cause of the yarn weight loss during dyeing is avoided and reduces treatment costs.

The acid caused in the process with chromium and acid an unfavorable release of B ^ S during the Oxidation level and the remaining acid accelerate the tendency of the cotton to age, while with the No acid needs to be used in the oxidation stage according to the invention, since it is below neutral or alkaline Conditions is executed.

The waste liquid (effluent) that occurs during oxidation the dyes with chromium and acid are created, causing problems in terms of water pollution, since bichromate is known to be toxic, and the authorities responsible for water pollution are starting to call for changes in the previous practice of discharging these effluents in certain areas. The drain in the present process causes fewer water pollution problems than the effluent in the Chromium and acid oxidation, since ferricyanide and ferrocyanide ions are stable, do not release HCN under the usual conditions and are therefore not to be regarded as toxic refer to Kirk-Othner, Encyclopedia of Chemical Technology, Vol. 4, p. 724 (1954). Furthermore, the process can easily be removed from internal procedures precipitated with alum in settling tanks for effluent removal, while chromium and acid are cumbersome are to be precipitated. Furthermore, the used oxidation bath can be recovered according to the invention, such as is given below.

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Hydrogen peroxide has the following three main disadvantages as an oxidizing agent for sulfur dyes when used with cotton and regenerated cellulosic textile fibers. The washing fastness of this dyeing is considerably lower than when chromium and acid are used as oxidizing agents is used, and not all sulfur dyes can, disadvantageously especially those Sulfur dyes produced by the sulfurization of 4-hydroxydiphenylamine were not completely oxidized to stable tints with hydrogen peroxide and the Concentration of the peroxide in the oxidation bath is both critical for the fastness properties of the obtained Coloring and laborious to regulate, so that a frequent determination of the peroxide concentration either by time-consuming Titrations or by using expensive devices to determine the optical density and thus the hydrogen peroxide concentration are necessary in the ultraviolet region of the spectrum. In surprising contrast, the present Method (a) dyeing from sulfur dyes with better wash fastness than in the case of application of chromium and acid as oxidizing agents and with remarkably better wash fastness than in the case of application obtained from peroxide as an oxidizing agent, (b) there is a fixation of all sulfur dyes, even those that by sulfurization of 4-hydroxydiphenylamine and (c) a simple and visual control of the ferricyanide concentration in the oxidation bath possible because aqueous ferricyanide ions are deep lemon yellow in solution, this color decreasing when the oxidizing power is exhausted and they are reduced to colorless ferrocyanide ions.

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The used oxidation bath in the present one Process can, if desired, be recovered, regenerated and be used again. Incfem consumed Bath, the ferricyanide ions are reduced to ferrocyanide ions and by chemical measures, for example Chlorine gas or sodium hypochlorite, or electrolytic measures, for example electrodes, can use the ferrocyanide ions back to the ferricyanide ions and the oxidizing agent regenerated in this way be led back to the system. Of course, this can be recovery, oxidation of the ferrocyanide and recycling be synchronized so that an efficient continuous process is obtained.

The following examples serve to illustrate embodiments of the invention. The references in the Examples based on the C.I. designations and numbers of the Sulfur dyes refer to Color Index, 2nd Edition, Amendment 1963, The Society of Dyers and Colourists, Yorkshire, England.

All parts and percentages are by weight unless otherwise specified.

example 1

In Baumwollshirting woven weighing from about 110 g / 0.83 m was bolster a reduced dye solution of 66 ⁰ C of about 570 g (20 oz) of a $ 20 ~ aqueous dye CI Leuco Sulfur Elack 1, CI no. 53185 per 3.78 1 of water was applied, whereupon the cloth was squeezed so that a 60 $ moisture absorption, based on the weight of the cloth, was obtained. The cloth was ^{steamed at 110 0} C for 1 minute, through four wash boxes that contained water and with squeeze

19/2060

rollers were equipped, out, then in an oxidation solution of room temperature of 1 56% aqueous Na, Pe (CN) g immersed for 30 seconds, by three Wash boxes that contained warm water and were equipped with squeeze rollers, guided and well rinsed and dried. A black coloration with excellent softness to the touch, excellent rewettability and excellent fastness to washing was obtained.

Example 2

A Gaston Countjr yarn dyeing machine was loaded with cotton yarn. The yarn was boiled in a conventional manner with 1 io acetic acid and 2 fo sulphonate as a wetting agent for 30 minutes at 93 ⁰ C, drained da3 bath and feeding the engine with 1% NatriurasuIfid again; the machine then ran for 10 minutes at 49 ⁰ C, whereupon the machine and the above solution 15 $> an aqueous solution with 200 g / l of the dye CI Leuco Sulfur Yellow 4, CI no. 53160, were added in 4 portions during 20 minutes at 71 ⁰ C. Without clogging of the Badüberlaufes was set up using water of 32 ⁰ C by circulation through the yarn package in the outside-inside direction washed until the upper reaches was clear. The pumping direction was then reversed and the inside-outside washing continued until the overflow was clear. The fume cupboard was then closed and a circuit wash was carried out at 49 ^° C. for 10 minutes. The bath was dropped, the machine again filled with water at 49 ⁰ C, to which .5 fo K, Fe (CN) - were added, followed by 10 minutes run at 49 ⁰ C. The bath was then drained, the yarn washed with water and

1 098 1 9/2050

the water drained and the machine again filled with water of 82 ⁰ C, to which 0.5% tetrasodium pyrophosphate and 1 were added ia synthetic detergent, followed by 10 minutes run at 82 ⁰ C. The bath was drained and the yarn was rinsed with water until it was clear. All percentages given in this example are based on the weight of the cotton fiber to be dyed. The solution to fiber ratio was 10: 1 by weight. All of the chemicals listed above were added to the water to form aqueous solutions prior to addition to the machine. The concentration of K ₅ Fe (CN) ₆ was 0.5 $ in the aqueous solution of the above fixing bath.

A yellow yarn with excellent washfastness and soft hand was obtained.

Example 3

This example was carried out as in Example 1, except that 110 g of the 20% strength aqueous dye CI Leuco Sulfur Yellow 2, CI no. 53120 ^ e 3.7 8 1 of water is used as the dye and a 0.2 # aqueous solution of (NH _/ ,), Fe (CN) g is used as the oxidation solution. A yellow dyeing with excellent wash fastness, improved luminosity compared to fixation with chromium and acid and a soft handle was obtained.

Example 4

A dye base made from 170 g of the 20 # aqueous dye CI Leuco Sulfur Black 1, CI No. 53185 was padded onto a cotton cloth, and the cloth was dried with an aqueous solution of 1 # K ₂ IIaZFe (CN) ₆ / and 15 # NaCl at 35 ^° C

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padded, held for 45 seconds, washed and dried. A charcoal gray color with excellent "Fastness to washing, wettability and softness of the hand were obtained.

Example 5

This example was carried out as in Example 1, but about 680 g of a 20% aqueous dye C.I. Leuco Sulfur Blue 7, C.I. No. 534440 each 3.7 l of water as a dye used and the amount of Na, Fe (CN), - increased to $ 10. A blue dyeing with excellent wash fastness, wettability and a soft hand was obtained, the one had improved luminosity compared to fixation with chromium and acid.

Example 6

On a viscose rayon cloth a dye composition which g to 3.78 1 of water an amount of about 565 was a 20 $ aqueous dye CI at 49 ⁰ C. Solubilized Sulfur Yellow 2, CI.-No. 53121, which was pre-reduced with sodium sulfide, contained, padded; the cloth was squeezed to a pickup of 60 fo, dried, mixed with 1% aqueous K -igera ₅ Fe (CN) padded at 93 ⁰ C _6, steamed for 1 minute at 110 ⁰ C, washed and dried. A yellow coloration with excellent wash fastness, wettability and softness of the handle was obtained.

Example 7

A reduced dye mass was padded on a viscose rayon cloth at 49 ⁰ C, which consists of about 680 g of the dye CI. Solubilized Sulfur Black 1, CI. No. 53186

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and 141 g of sodium sulfide 3.78 1 of water had been produced depending on which squeezed the cloth to a wet pick-up of 60 $> for 1 minute at 104 ⁰ C in air-free steam steamed, rinsed with water at room temperature, 45 seconds in a 1 $ -ige aqueous solution of KgNa / FeCCN), - / was immersed at room temperature, washed and dried. A black dyeing of excellent wash fastness, wettability and softness of the handle was obtained.

Example 8

On a cotton cloth, a reduced dye composition was padded at 38 ⁰ C, the g from about 56 sodium sulfide as reducing agent and 11Og of a dye formed by coupling a molar proportion of tetrazotized 4,4'-Diaminodiphenyldisulfid and two molecular proportions of 1-phenyl-3 -methyl-5-pyrazolone had been obtained, each 3.78 liters of water had been produced, whereupon the cloth was squeezed to a 60% moisture absorption, dried, and immersed in an aqueous oxidation solution of 30% NaCl and 2 io (ΝΗ. ) ₃ Ι'β (ΟΝ) _{6 was} immersed at 60 ⁰ C (ratio liquid: good 30: 1), washed and dried. A bright yellow coloration with excellent wash fastness, wettability and softness of the handle was obtained.

Example 9

A reduced dye mass was applied to a cotton cloth at 60 T padded out, which consists of 56 g of sodium sulfide and 85 g of a dye obtained by coupling a molecular proportion of tetrazotized 4,4'-diaminodiphenyl disulfide and two molar proportions of 1 (4-chlorophenyl) -3-

1 fl q H 1 q / 9 Π S 0

methyl-5-pyrazolone had been obtained, each 3.78 l of water had been prepared, whereupon the cloth was squeezed off to a wet pick-up of 60 $, dried, in an aqueous oxidation solution of 30 # NaCl and 2 % Ha ₅ Fe (CN) ₆ immersed in room temperature, washed and dried. A bright yellow color with excellent stability was obtained.

Example 10

On a cotton cloth was padded on a reduced dye composition at 60 ⁰ C, consisting of 56 g of sodium sulfide and 85 g of a dye, .the by coupling a molar proportion of tetrazotized 4,4'-diamino-2,2 ^l -dichlordiphenyldisulfid and two molar proportions of of 5'-chloro-3-hydroxy-2 ', 4'-dimethoxy-2-naphthanilide, 3.78 liters of water each had been prepared, whereupon the cloth was squeezed off to a wet pick-up of 60 #, dried, with a aqueous oxidation solution of 20 I> NaCl and 5 # K, Fe (CN) g padded from room temperature, passed through air for 15 seconds, washed and dried. A red dyeing with excellent wash fastness and a soft hand was obtained.

Example 11

On a cotton cloth, a reduced dye composition was measured at 38 ⁰ C au.fgeklotzt consisting of 56 g of sodium sulfide and 110 g of a dye by coupling a molecular proportion of tetrazotized ^{4,4'-dimethoxy-l-3,3} Diaicino diphenyl disulfide and two molecular fractions of 1-phenyl-3-methyl-5-pyrazolone had been obtained, each 3.78 water had been produced, whereupon the cloth was ^{squeezed off to a wet absorption of 60 u} /> , dried, at room temperature

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temperature was padded with an aqueous oxidation solution of 25 % NaCl and 10% K ₂ Na / Fe (CN) g /, passed through air for 30 seconds, washed and dried. A bright orange coloration of excellent washfastness and softness of the handle was obtained.

Example 12

On a cotton cloth, a reduced dye composition was padded at 49 ⁰ C, consisting of 56 g of sodium sulfide and 85 g of a dye by coupling equimolar amounts of diazotized S-4-Aminophenylthioschwefelsäure and 1-phenyl-3-methyl-5-pyrazolone obtained was, depending 3j78 1 water was prepared, after which the cloth to a wet pick-up of 60 io squeezed in a dampening roller for 30 Minutengebatscht, in an aqueous oxidizer solution of 20 $> NaCl, 1 fo (NHY) ₅ Fe (CN) ₆ and 0.1 $ Na ₃ CO ₅ immersed at room temperature (ratio liquid: good 5: 1)> washed and dried. A bright yellow coloration with good wash fastness and excellent softness of the handle was obtained.

Example 13

4.25 g of the dye

OH

(~ \ - H = HC = C I CH, -C = N

Cl °

were reduced at 60 ⁰ C with 190 g of thiourea and 85 g per maoh 3.7 1 water. The reduced dye composition v / urde on a cotton cloth at 71 ^{1 is} T- padded, whereupon squeezed off the cloth on a NaSaufnahme of 60 fs, dried at 110 ^c C for 1 minute in an air-free steam steamed for 45 seconds in an aqueous oxidizer solution from 5 £ NaCl and 1 fo Na-Fe (CNV was immersed at room temperature, washed and dried. A bright yellow dye with good wash fastness and excellent softness of the handle was obtained.

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Example 14

A printing paste consisting of $ 5 by weight was applied to cotton cloth

OH NaS-

5- <VJT = N-C = C ^ / \

C = N '\ /

CH

10 $ urea, 2.5 $ thiourea, 16 $ etherified Locust bean gum, 1 $ emulsifier, 40 $ of the petroleum solvent Varsol and 25.5 $ water, whereupon the cloth was dried for 45 seconds in an oxidizing solution of 10 g of K ₅ Pe ( CN) ₆ and 200 g NaCl per liter of water were immersed at room temperature, squeezed off, rinsed with water, soaped, rinsed with water and dried. A yellow print with excellent washfastness and softness of the hand was obtained.

Example 15

142 g of a dye which had been obtained by coupling equimolar proportions of diazotized S-4-aminophenylthiosulfuric acid and 1-phenyl-3-methyl-5-pyrazolone was reduced with 110 g of sodium sulfide each 3.7 1 V / water. The reduced dye was padded onto a cotton cloth at 66 ⁰ C, steamed and then the cloth for 1 minute at 110 ⁰ C, for 30 seconds auo in an aqueous oxidizer solution 15 $ NaCl and 2 $ KpNa ^ e (CN) ₆ / immersed from room temperature ,

1 q /

washed and dried. A yellow coloration with excellent washfastness and a soft hand was found obtain.

Example 16

142 g of a dye obtained by coupling a molecular proportion of diazotized sodium 8-4-aminophenylthiosulfate and a molecular proportion of 8-amino-2-naphthol and coupling a molar proportion of the product obtained with a molecular proportion of diazotized S. -4-aminophenyl thiosulphate had been prepared, was reduced with 110 g of aqueous sodium sulphide per 3.78 l of water. A cotton cloth was padded with the resulting reduced dye ^{mass at 32 0} G, whereupon the cloth was squeezed to absorb moisture, dried, padded at room temperature with an aqueous oxidation solution of 20% NaCl and 1 $ (NH ₄ UFe (CN) ₆ , through air was passed for 20 seconds, washed and dried, and a black dyeing excellent in fastness to washing and softness of the hand was obtained.

Examples 17-23

In the examples listed in the table below, the colorations were obtained by reducing the dye given in the second column with 4% aqueous sodium sulfide, padding on a dye mass of 110 g of the reduced dye (calculated as the dyestuff) per 3.78 l of water at 49 °? on cotton cloth, squeezing off to a moisture regain of 60 $, based on fabric weight, drying, attenuation at 110 ⁰ C for 60 seconds, immersion for 45 seconds in

; · Γι w rt

an aqueous solution of 20 $ NaGl and 256 des in the Third column indicated perricyanide produced at room temperature, washing and drying. The received Dyeings showed the color indicated in the fourth column and had excellent softness Handle and very good wash fastness.

inQ «IQ

Tabel

Example dye ferricyanide color

No.

17 'NCS- (-VN = NC C-CH, Na, Fe (CN) <; yellow

HO-C ₁

- * ι

^ f 18 Product of the implementation of equimolar K, Fe (CN) ₆ turquoise _ *

^ j amounts of 30 ^

σ · ». ι

^ΡΟΧ ^ 30

Ύ ° 3 ^ 0.5

and 4,4 -'-diamino-2 ₁ 2 ^l -dimethyldiphenyl disulfide, in which Pc denotes
Means phthalocyanine residue.

19 As in example 18, but be (NH.), Fe (CN) ₆ turquoise

Pc interprets the copper phthalo- 4 5 ο ^ ₀

cyanine residue °

CD CO K)

Table (continued)

ro ο err O

Example no.

20th

21st

22nd

23

dye

Ferricyanide

Product of the condensation of 1 mole of copper phthalocyanine trisulfonyl chloride and 3 moles of sodium S-4-aminophenylthio sulfate

Product of the reaction of 1 mol of diazotized copper tetra (4) aminophthalocyanine and 4 moles of sodium thiocyanate

As in Example 21, but the phthalocyanine was metal-free Na ₃ Fe (CN) ₆

K ₃ Fe (CN) ₆
K ₂ NaFe (CN) ₆

colour

turquoise

green

green

Red

SCN

Example 24

On cotton cloth was at 49 ⁰ C in a concentration of 110 g per 3.7 1 of water (calculated as dye solid), the conversion of 2 molecular proportions of 1,4-diaminoanthraquinone and 1 molecular portion of cyanuric chloride, conversion of 1 molecular portion of the Product and 1 molecular portion of aniline, conversion of a molecular portion of the product and 2 molecular portions of cyanuric chloride, conversion of 1 molecular portion of the product and 3 molecular portions of thiourea formed dye after hydrolysis with water to free mercapto form. The cloth was squeezed to a wet pick-up of 60 $, dried, padded at room temperature with an aqueous solution of 5 $ K ₂ NaFe (CN) ₆ and 20 $ NaCl, steamed for 30 seconds at 110 ⁰ C, washed and dried. A violet dyeing of good fastness was obtained.

Example 25

565 g of the 20% aqueous dye C.I. Leuco Sulfur Yellow 4, C.I. No. 53160 and 56 g

SOo-NH- / V-

r> SO ₂ -NH- ^ ν- sii / _{2 f 3}

CuPc '"^'

wherein CuPc represents the copper phthalocyanine, depending 3.78 1 v / ater was padded on the cotton cloth at 49 ⁰ C. The cloth was squeezed to a wet pick-up of 60 $, steamed for 1 minute at 110 ⁰ C, 30 seconds

an aqueous oxidation solution of 2 $ Na, Fe (CN) g, 20 $ NaCl and 1 $ of the sodium salt of ethylenediaminetetraacetic acid immersed from room temperature, washed and dried. A green dye with excellent wash fastness and Hand softness was maintained.

Example 26

The reduction of 110 g of the dye CI. Sulphir Red 10 (CI No. 53228) with sodium sulfide produced dye, which was diluted to 3 »78 1 with water, was ^{padded at 71 0} C on a woven cotton shirt fabric with a weight of about 110 g / 0.83 m, whereupon the cloth to a wet pick-up of 60 $, based on fabric weight, squeezed, for 1 minute steamed at 110 "C, by four wash boxes which contained water, and were equipped with pinch rolls, out during 30 seconds in an aqueous oxidizer solution of 66 ⁰ C from 1 $ K, Fe (CN) g and 10 $ NaCl was immersed, rinsed with warm water and dried. A Bordeaux dyeing with good wet fastness and excellent softness of the handle was obtained.

Example 27

670 g.einer 7 $ aqueous solution of the reduced sulfurized Indophenolfarbstoffes according to Example 10 of U.S. Patent No. 2,657,112 (7 # calculated as Farbstoffeststoff) per 3.78 1 v / ater were at 49 ⁰ C on a cotton linen weighing 110 g / 0.83 m padded on. The cloth was added to a wet pick-up of 66 $, based on fabric weight, squeezed out, dried at 54 ⁰ C with a

Solution of 85 g of NaOH and 85 g of sodium hydrosulfite padded 3.78 1 of water each, ^{steamed for 1 minute at 104 0} C in air-free steam, passed through four block boxes containing cold water to the laundry, for 45 seconds in 1, 2 ^ iges aqueous KpNa / Fe (CN) ? / Immersed at room temperature, washed and dried. A blue dyeing with excellent wash fastness and softness of the hand was obtained.

In the above examples, the wet pick-up in% by weight is based on the weight of the textile fibers.

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Claims (4)

Claims Process for fixing dyes on natural or regenerated cellulose textile fibers, characterized in that an alkaline or neutral aqueous oxidizing solution containing water and Na ₃ Fe (CN) ₆ , K ₃ Fe (CN) ₆ , K ₂ Na / Fe (CN ) g7 or (NH ^) ₃ Fe (CN) _{6 is} brought into contact with natural or regenerated cellulose textile fibers which carry at least one dye in reduced form, the dye consisting of (1) dyes in their reduced form at least have one bound mercaptide group per molecule of the dye, and / or (2) dyes which in their reduced form have at least one bound mercapto group per molecule of the dye. 2. The method according to claim 1, characterized in that the aqueous oxidizing solution 0.2 to 105S Na ₅ Fe (CN) ₆ , K ₃ Fe (CN) ₆ , K ₂ Na ^ Fe (CN) ₆ / or (NH ^) ₃ Fe (CN) ₆ and 0 to 3054 NaCl. 3. The method according to claim 1 or 2, characterized in that the temperature of the oxidizing solution is 1 to 95 ^C C (35-200 ⁰ F). 4. The method according to claim 1 to 3, characterized in that that the dye in the reduced form consists of a sulfur dye. 109819/2050