EP0470932A1 - Process for dyeing cellulose containing fibrous materials with vatdyes - Google Patents

Abstract

A process is described for dyeing cellulose-containing fiber materials with vat dyes, which is characterized in that all or part of the auxiliary chemicals required for the dyeing process are placed in the dyebath and the fiber material is dyed after a lead time by metering the vat dyes or their leuco compounds into the dyebath and then continue the dyeing process, if necessary at elevated temperature. With the new process, level dyeings are obtained, the cellulose material showing a calm appearance and good light and wet fastness properties.

Description

The present invention relates to a method for dyeing textile cellulose materials with vat dyes by means of a metering device and to the cellulose material dyed by means of this method.

• 1. Vorlage von Färbereihilfsprodukten, Farbstoff, Soda und Hydrosulfit bei 20°C. Anschliessend progressives Zudosieren von Natronlauge während 20 Minuten.
• 2. Vorlage von Farbstoff bei 40°C, anschliessend Zugabe der gesamten Menge an Natronlauge während der Aufheizphase, anschliessend lineares Dosieren von Hydrosulfit während 15 Minuten bei 80°C. Bei sogenannten Warmfärbern kann zusätzlich noch eine Salzlösung linear über 15 Minuten vor und während der Abkühlphase zwischen 80 und 60°C zudosiert werden.

It is known that in vat dyeing, metering in of the usual chemicals such as sodium hydroxide solution, hydrosulfite and optionally glacial or common salt compared to the usual processes such as hot pigmentation or leuco processes improves the colorings' level of uniformity. There are basically two ways of dosing technology:

• 1. Submission of dyeing auxiliary products, dye, soda and hydrosulfite at 20 ° C. Then progressive dosing of sodium hydroxide solution over 20 minutes.
• 2. Submission of dye at 40 ° C, then adding the entire amount of sodium hydroxide solution during the heating phase, then linear dosing of hydrosulfite for 15 minutes at 80 ° C. In so-called warm dyes, a salt solution can additionally be metered in linearly over 15 minutes before and during the cooling phase between 80 and 60 ° C.

However, especially in the winding body dyeing industry, the hoped-for advantages with regard to the improvement of fiber levelness did not materialize in full.

Surprisingly, it has now been found that the fiber levelness, in particular the outside / inside levelness of bobbins, is significantly increased using a process in which the chemicals required for the dyeing process are introduced and then the dye or the stock is added to the dye bath.

The present invention therefore relates to a process for dyeing cellulosic fiber materials, characterized in that the for Completely or partially submits the auxiliary chemicals required in the dyeing process to the dye bath, then metered the vat dyes or their leuco compounds with the aid of a metering device over a period of time to the dye bath at temperatures of 20 to 100 ° C and then dyed the fiber material at the same or elevated temperature.

The dye or the leuco compound is expediently metered in continuously over a certain time interval until a sufficient amount of dye has been added for the respective dyeing process. The metering can be linear, on the one hand, i.e. that the same amount of dye is always added in the dosing phase in every time interval. Another possibility is the degressive dosing of the dye, i.e. the amount added per unit of time is very large at the beginning of the dosing phase, but then decreases more and more as the dosing time progresses. If necessary, the dosage can also be progressive, i.e. the amount added per unit of time is very small at the start of the dosing phase, but then increases as the dosing time progresses.

The dye or the leuco compound is advantageously metered directly into the liquor circuit, preferably with automatically controlled devices. For liquid dosing, e.g. pneumatic or electrically driven piston diaphragm pumps. These pumps are equipped with a microprocessor control unit with which the control parameters necessary for the respective dyeing process, such as the amount of dye to be metered, the metering time, the "degressivity" or the "progressivity" can be set. The control units can also be equipped with fixed dosing programs.

For liquid dosing of the vat dyes added to the dyebath, these are expediently used as finely divided dispersions which are obtained by grinding in the presence of customary dispersants.

Preferably, however, it is also possible to use dye dispersions in which the raw dye is only coarsely ground for homogenization, small amounts of nonionic and / or anionic dispersants being used as grinding aids (dye in coarsely dispersed form).

To stabilize these dispersions, the viscosity is adjusted using commercially available thickeners, preferably based on polymeric acrylic acid, set to values between 1x10³ - 2x10⁴ mPas.

Anionic or nonionic surfactants can be used as dispersants, which can be present alone or as mixtures with one another or consisting of an anionic and a nonionic surfactant.

• sulfatierte aliphatische Alkohole, mit 8 bis 18 Kohlenstoffatomen, z.B. sulfatierter Laurylalkohol;
• sulfatierte ungesättigte Fettsäuren oder Fettsäure-C₁-C₅-Alkylester, die im Fettrest 8 bis 20 Kohlenstoffatome aufweisen, z.B. Rizinolsäure und solche Fettsäuren enthaltende Öle, z.B. Rizinusöl;
• Alkylsulfonate, deren Alkylkette 8 bis 20 Kohlenstoffatome enthält, z.B. Dodecylsulfonat;
• Alkylarylsulfonate mit geradkettiger oder verzweigter Alkylkette mit mindestens 4 Kohlenstoffatomen, z.B. Dodecylbenzolsulfonate oder 3,7-Diisobutyl-naphthalinsulfonate;
• Sulfonate von Polycarbonsäureestern, z.B. Dioctylsulfosuccinate;
• die als Seifen bezeichneten Alkalimetall-, Ammonium- oder Aminsalze von Fettsäuren mit 10 bis 20 Kohlenstoffatomen, z.B. Kolophoniumsalze;
• Ester von Polyalkoholen, insbesondere Mono- oder Diglyceride von Fettsäuren mit 12 bis 18 Kohlenstoffatomen, z.B. Monoglyceride der Laurin-, Stearin -oder Ölsäure; und
• die mit einer organischen Dicarbonsäure, wie z.B. Maleinsäure, Malonsäure oder Sulfobernsteinsäure, vorzugsweise jedoch mt einer anorganischen mehrbasischen Säure wie o-Phosphorsäure oder insbesondere Schwefelsäure in einen sauren Ester übergeführten Anlagerungsprodukte von 1 bis 60 Mol Ethylenoxid und/oder Propylenoxid an Fettamine, Fettsäuren oder Fettalkohole mit je 8 bis 22 Kohlenstoffatomen, an Alkylphenole mit 4 bis 16 Kohlenstoffatomen in der Alkylkette oder an drei- bis sechswertige Alkanole mit 3 bis 6 Kohlenstoffatomen.

Examples of suitable anionic surfactants are:

• sulfated aliphatic alcohols with 8 to 18 carbon atoms, for example sulfated lauryl alcohol;
• sulfated unsaturated fatty acids or fatty acid C₁-C₅ alkyl esters which have 8 to 20 carbon atoms in the fat residue, for example ricinoleic acid and oils containing such fatty acids, for example castor oil;
• Alkyl sulfonates whose alkyl chain contains 8 to 20 carbon atoms, for example dodecyl sulfonate;
• Alkylarylsulfonates with a straight-chain or branched alkyl chain with at least 4 carbon atoms, for example dodecylbenzenesulfonates or 3,7-diisobutyl-naphthalenesulfonates;
• Sulfonates of polycarboxylic acid esters, for example dioctyl sulfosuccinates;
• the so-called alkali metal, ammonium or amine salts of fatty acids with 10 to 20 carbon atoms, for example rosin salts;
• Esters of polyalcohols, in particular mono- or diglycerides of fatty acids with 12 to 18 carbon atoms, for example monoglycerides of lauric, stearic or oleic acid; and
• those with an organic dicarboxylic acid, such as maleic acid, malonic acid or sulfosuccinic acid, but preferably with an inorganic polybasic acid such as o-phosphoric acid or, in particular, sulfuric acid, adducts of 1 to 60 mol of ethylene oxide and / or propylene oxide with fatty amines, fatty acids or fatty alcohols converted into an acidic ester each with 8 to 22 carbon atoms, on alkylphenols with 4 to 16 carbon atoms in the alkyl chain or on tri- to hexavalent alkanols with 3 to 6 carbon atoms.

The anionic surfactants are normally in the form of their alkali metal salts, ammonium salts or amine salts.

• Anlagerungsprodukte von vorzugsweise 5 bis 80 Mol Alkylenoxiden, insbesondere Ethylenoxid, wobei einzelne Ethylenoxideinheiten durch substituierte Epoxide, wie Styroloxid und/oder Propylenoxid ersetzt sein können, an höhere ungesättigte oder gesättigte Fettalkohole, Fettsäuren, Fettamine oder Fettamide mit 8 bis 22 Kohlenstoffatomen oder an Phenyl- oder Alkylphenole, deren Alkylreste mindestens 4 Kohlenstoffatome aufweisen;
• Alkylenoxid,- insbesondere Ethylenoxid und/oder Propylenoxid-Kondensationsprodukte; und
• Umsetzungsprodukte aus einer 8 bis 22 Kohlenstoffatome aufweisenden Fettsäure und
  einem primären oder sekundären, mindestens eine Hydroxyniederalkyl- oder Niederalkoxyniederalkylgruppe aufweisenden Amin oder Alkylenoxid-Anlagerungsprodukte der hydroxyalkylgruppenhaltigen Umsetzungsprodukte, wobei die Umsetzung so erfolgt, dass das molekulare Mengenverhältnis zwischen dem hydroxylgruppenhaltigen Amin und Fettsäure 1:1 und grösser als 1, z.B. 1,1:1 bis 2:1 sein kann.

Examples of nonionic surfactants are:

• Addition products of preferably 5 to 80 mol of alkylene oxides, in particular ethylene oxide, where individual ethylene oxide units can be replaced by substituted epoxides, such as styrene oxide and / or propylene oxide, with higher unsaturated or saturated fatty alcohols, fatty acids, fatty amines or fatty amides with 8 to 22 carbon atoms or with phenyl or alkylphenols whose alkyl radicals have at least 4 carbon atoms;
• Alkylene oxide, in particular ethylene oxide and / or propylene oxide condensation products; and
• Reaction products from a fatty acid having 8 to 22 carbon atoms and
  a primary or secondary amine or alkylene oxide adducts of the reaction products containing hydroxyalkyl groups, having at least one hydroxy-lower alkyl or lower alkoxy-lower alkyl group, the reaction being carried out in such a way that the molecular ratio between the hydroxyl group-containing amine and fatty acid is 1: 1 and greater than 1, for example 1.1: Can be 1 to 2: 1.

Aromatic sulfonic acids, such as e.g. Oxiligninsulfonic acid or formaldehyde condensation products from aromatic sulfonic acids, formaldehyde and optionally mono- or bifunctional phenols such as. B. from cresol, β-naphtholsulfonic acid and formaldehyde, from benzenesulfonic acid, formaldehyde and naphthalenesulfonic acid or from naphthalenesulfonic acid, dihydroxydiphenyl sulfone and formaldehyde.

Untreated cellulose is particularly suitable as cellulose material, e.g. Hemp, linen, jute, native cotton, as well as fiber blends e.g. those made of polyacrylonitrile / cotton or polyester / cotton, and fiber materials based on regenerated cellulose (viscose) are also suitable. The cellulose material can be in a wide variety of processing forms, e.g. as loose material, yarn, woven or knitted fabric. Cotton which is processed as yarn is preferably suitable for the process according to the invention.

Depending on the technical requirements, the dyeing of the cotton is dyed in the form of the skein, the pressed or non-pressed cheese or the warp beam.

In principle, all dyeing methods can be used in which dyeing is carried out with a moving liquor and standing fiber material. In the method according to the invention, the dyeing of the fiber material is preferably carried out in the form of the cheese. The spools for the dyeing process are placed on perforated metal spindles or triangular spindles into which the liquors are pressed. Further details on the dyeing of yarn and the apparatuses required for this can be found in H. Rath, "Textbook of Textile Chemistry", 3rd edition, p. 642 ff (1972).

The vat dyes are higher fused and heterocyclic benzoquinones or naphthoquinones and in particular anthraquinone or indigoid dyes. Examples of vat dyes used according to the invention are listed in the Color Index 3rd Edition (1971) Vol. 3 on pages 3649 to 3837 under the name "Vat Dyes".

The amount of dyes added to the dye liquor depends on the desired color strength. In general, amounts of 0.01 to 10, preferably 0.05 to 3 percent by weight, based on the cellulose material used, have proven successful.

In addition to the dye, the dyeing liquors contain the auxiliary chemicals common for vat dyeing. Here, e.g. Alkali such as sodium carbonate, potassium hydroxide, sodium hydroxide or alkali dispenser such as e.g. Sodium chloroacetate into consideration. Sodium hydroxide is preferably used. The reducing agents should also be mentioned, preferably using hydrosulfite.

In addition, the dyeing liquor can also contain other customary dyeing auxiliary products, such as Electrolytes such as sodium chloride or sodium sulfate or commercially available wetting, leveling and dispersing agents. These auxiliary chemicals are added to the dye bath completely or only partially before the actual dyeing process; if the addition is only partial, the rest is added with the dye or the leuco compound.

The dyeings are advantageously carried out from an aqueous liquor using the exhaust process. The liquor ratio depends on the equipment, the substrate and the form of presentation. However, it can be chosen within a wide range, e.g. 1: 4 to 1: 100, but is usually between 1: 6 to 1:15.

The dyeing process according to the invention can be carried out at temperatures from 20 to 110 ° C. will. The temperature is preferably between 30 and 100 ° C or 30 and 80 ° C.

The dyeing process is expediently carried out in such a way that all chemicals are placed in the dyeing liquor and the fiber material is pretreated at a temperature of 20 to 100 ° C., preferably 20 to 80 ° C. The lead time is 5 to 20, preferably 5 to 15 or 5 to 10 minutes. The total amount of dye is then metered in linearly, degressively or, if appropriate, progressively at the same and constant temperature over a period of 15 to 40, preferably 20 to 40 minutes. The temperature of the dyebath is then increased to 60 to 110 ° C. in the course of 15 to 25 minutes, with a corresponding constant heating rate, and dyeing is carried out for 30 to 60 minutes at the final temperature reached. The coloring can also be isothermal, i.e. be carried out at constant temperature. After staining, cool to 50 to 70 ° C. The dyed fiber material is rinsed and oxidized as usual, with hydrogen peroxide usually being used for the oxidation.

After dyeing, the dyed cellulose material is soaped in the usual way. To do this, the substrate is treated at cooking temperature in a solution which contains soap or synthetic detergent and optionally sodium carbonate.

The process according to the invention gives uniform and vivid colorations which are distinguished by good dye yields. In particular, level dyeings are achieved, the cellulose material showing a calm appearance and having good light and wet fastness properties.

In the following examples, the percentages always relate to the weight, unless stated otherwise. The amounts of the dyes relate to commercial, i.e. coupé goods and with the aids on pure substance.

Production of dye dispersions Example 1:

1,6 Teilen

Ethylenoxid/Propylenoxid-Blockpolymer mit einem Molgewicht von ca. 16 000

64,6 Teilen

Wasser

werden in einer Mikrosolmühle mit 4,5 mm Glaskugeln ca. 45 Minuten vermahlen und die jetzt homogene Mischung mit

5,4 Teilen

0,1 n H₂SO₄

auf den pH-Wert 4 eingestellt und mit 1 Teil Polyacrylsäure mit einem Molgewicht von ca. 3x10⁶ in einem Rührkessel mit einem Propellerrührer homogen vermischt. Die Polyacrylsäure wird als 3% ige wässrige Lösung zugesetzt. Anschliessend wird der pH-Wert der Anrührung mit Triethanolamin auf 7,0 eingestellt. Dadurch erhält die Mischung eine puddingartige Konsistenz, wodurch die Sedimentation der groben Farbstoffpartikel verhindert wird.100 parts of the dye preparation consisting of
29.4 parts of the dye of the formula (101)

1.6 parts

Ethylene oxide / propylene oxide block polymer with a molecular weight of approximately 16,000

64.6 parts

water

are ground in a microsol mill with 4.5 mm glass balls for approx. 45 minutes and the now homogeneous mixture with

5.4 parts

0.1 n H₂SO₄

adjusted to pH 4 and homogeneously mixed with 1 part polyacrylic acid with a molecular weight of approx. 3x10⁶ in a stirred tank with a propeller stirrer. The polyacrylic acid is added as a 3% aqueous solution. The pH of the mixture with triethanolamine is then adjusted to 7.0. This gives the mixture a pudding-like consistency, which prevents sedimentation of the coarse dye particles.

Example 2:

0,6 Teilen

Ethylenoxid/Propylenoxid-Blockpolymer mit einem Molekulargewicht von ca. 16000 und

64,6 Teilen

Wasser

werden in einer Mikrosolmühle mit 4,5 mm Glaskugeln ca. 45 Minuten vermahlen und die jetzt homogene Mischung mit

16 Teilen

0,1 n H₂SO₄

auf den pH-Wert 4 eingestellt und mit

1,1 Teilen

Polyacrylsäure mit einem Molekulargewicht von 3x10⁶

in einem Rührkessel mit einem Propellerrührer homogen vermischt. Die Polyacrylsäure wird als 3%ige wässrige Lösung zugestzt. Anschliessend wird der pH-Wert der Anrührung mit Triethanolamin auf 7,0 eingestellt.100 parts of the dye preparation consisting of
18.0 parts of the dye of the formula

0.6 parts

Ethylene oxide / propylene oxide block polymer with a molecular weight of approximately 16000 and

64.6 parts

water

are ground in a microsol mill with 4.5 mm glass balls for approx. 45 minutes and the now homogeneous mixture with

16 parts

0.1 n H₂SO₄

adjusted to pH 4 and with

1.1 parts

Polyacrylic acid with a molecular weight of 3x10⁶

homogeneously mixed in a stirred tank with a propeller stirrer. The polyacrylic acid is added as a 3% aqueous solution. The pH of the mixture with triethanolamine is then adjusted to 7.0.

Example 3:

2,8 Teilen

Ethylenoxid/Propylenoxid-Blockpolymer mit einem Molgewicht von ca. 16 000 und

82,1 Teilen

Wasser

werden in einer Mikrosolmühle mit 4,5 mm Glaskugeln ca. 45 Minuten vermahlen und die jetzt homogene Mischung mit

0,01 Teilen

0,1 n H₂SO₄

auf den pH-Wert 4 eingestellt und mit

1,1 Teilen

Polyacrylsäure mit einem Molekulargewicht von 3x10⁶

in einem Rührkessel mit einem Propellerrührer homogen vermischt. Die Polyacrylsäure wird als 3%ige wässrige Lösung zugestzt. Anschliessend wird der pH-Wert der Anrührung mit Triethanolamin auf 7,0 eingestellt.100 parts of the dye preparation consisting of
15.1 parts of the dye of the formula

2.8 parts

Ethylene oxide / propylene oxide block polymer with a molecular weight of approximately 16,000 and

82.1 parts

water

are ground in a microsol mill with 4.5 mm glass balls for approx. 45 minutes and the now homogeneous mixture with

0.01 parts

0.1 n H₂SO₄

adjusted to pH 4 and with

1.1 parts

Polyacrylic acid with a molecular weight of 3x10⁶

homogeneously mixed in a stirred tank with a propeller stirrer. The polyacrylic acid is added as a 3% aqueous solution. The pH of the mixture with triethanolamine is then adjusted to 7.0.

Application examples Example 4:

0,5 g/l

eines Antischaummittels auf Basis von 2-Ethylhexanol und Silikonöl

0,5 g/l

eines Dispergiermittels auf Basis von Oxi-Ligninsulfonat

1,0 g/l

eines Komplexiermittels

1,0 g/l

eines Egalisiermittels auf Polyamidbasis

26 ml/l

wässrige Natriumhydroxidlösung (30 %) und

60 g

Hydrosulfit.

3 alkaline pretreated cotton press spools of 900 g each, which are 15% pressed, are treated with a liquor (liquor ratio 1: 12.5) in a circulation dyeing machine, e.g. a THIES Ecomat Series II, Type 260/3 KD contains the following additions:

0.5 g / l

an anti-foaming agent based on 2-ethylhexanol and silicone oil

0.5 g / l

a dispersant based on oxi-lignin sulfonate

1.0 g / l

a complexing agent

1.0 g / l

a leveling agent based on polyamide

26 ml / l

aqueous sodium hydroxide solution (30%) and

60 g

Hydrosulfite.

The pretreatment time (lead time) is 10 minutes at 40 ° C. It is driven with one-sided inside / outside circulation. The flow rate is approx. 7 l / kg / min.

und 5,40 g des Farbstoffes der Formel

The dyeing is then carried out in the same bath. Here too, the process is one-sided inside / outside circulation. The following dye mixture is used:
3.25 g of the dye of the formula (102)
4.05 g of the dye of the formula

and 5.40 g of the dye of the formula

This dye mixture is dispersed with 11 g of oxilignin sulfonate in 2 liters of water.

Analogously, one of the dye dispersions of Examples 1 to 3 can also be used.

The liquor is heated to 40 ° C. The dispersed dye mixture is metered in linearly at a temperature of about 60 ml / min within 30 minutes. The mixture is then heated to 80 ° C at a heating rate of 1.5 ° C / minute. The dyeing is continued for 45 minutes at this temperature and then allowed to cool to 60 ° C. at a cooling rate of 2 ° C./minute. The dyed fiber material is then removed from the dyeing machine and oxidized with hydrogen peroxide. The coloring is then completed in the usual way.

Example 5:

The procedure is as described in Example 4, with the difference that in the liquor is replaced by 200 ml of sodium hydroxide solution and 40 g of hydrosulfite instead of 300 ml of sodium hydroxide solution and 60 g of hydrosulfite, and an additional 100 ml of sodium hydroxide solution and 20 g of hydrosulfite are added to the dye mixture, and the resulting leuco form is metered in.

Example 6:

10 ml/l

H₂O₂ 35%

6 ml/l

NaOH 36 Bé

1 ml/l

eines Bleichstabilisators

0,5 g/l

eines silikonfreien Penetrationsbeschleunigers

2 cotton press bobbins of 1050 g each, which are 15% pressed, are pretreated in a circulation dyeing machine, e.g. a THIES Ecomat Series II Type 260/3 KD, with a combined peroxide bleaching liquor (liquor ratio 1: 12.5), the following additives contains:

10 ml / l

H₂O₂ 35%

6 ml / l

NaOH 36 Bé

1 ml / l

a bleach stabilizer

0.5 g / l

a silicone-free penetration accelerator

The mixture is taken in at 40 ° C. and the liquor is heated to 110 ° C. within 30 minutes. At this temperature, treatment is continued for a further 30 minutes and the temperature is then reduced to 85 ° C. within 15 minutes. The goods are then rinsed in the usual way.

0,3 g/l

eines silikonfreien Penetrationsbeschleunigers

3,0 g/l

Oxiligninsulfonat (30%ig)

14 ml/l

wässrige Natriumhydroxidlösung (30 %)

0,5 g/l

eines Eglisiermittels auf Basis einer Benzotriazolverbindung

4,0 g/l

Hydrosulfit

The pre-bleached packages are pretreated for dyeing in the same apparatus with a liquor (liquor ratio 1:12) which contains the following additives:

0.3 g / l

a silicone-free penetration accelerator

3.0 g / l

Oxilignin sulfonate (30%)

14 ml / l

aqueous sodium hydroxide solution (30%)

0.5 g / l

a leveling agent based on a benzotriazole compound

4.0 g / l

Hydrosulfite

The pretreatment time is 15 minutes at a temperature of 80 ° C. It is driven with one-sided inside / outside circulation.

0.040 % des Farbstoffes der Formel

The dyeing is then carried out in the same bath. Here too, the process is one-sided inside / outside circulation. The following dye mixture is used:
0.052% of the dye of the formula (104),
0.048% of the dye of the formula (105)
0.276% of the dye of the formula

0.040% of the dye of the formula

This dye mixture is coarsely dispersed with 11 g of oxilignin sulfonate in 2 liters of water.

The dispersed dye mixture is metered in linearly at a metering rate of approximately 120 ml / min within 15 minutes. The dyeing is isothermal for a further 30 minutes and then allowed to cool to 60 ° C. at a cooling rate of 1.5 ° / minute. The dyed fiber material is then removed from the dyeing machine and oxidized with hydrogen peroxide. The coloring is then finished as usual.

Example 7:

0,5 g/l

eines silikonfreien Penetrationsbeschleunigers

3,0 g/l

Oxiligninsulfonat (30 %)

14 ml/l

wässrige Natriumhydroxidlösung (30 %)

0,2 g/l

eines Egalisiermittels auf Basis einer Benztriazolverbindung

3,5 g/l

Hydrosulfit.

The procedure is as in Example 6, but cross-wound bobbins with viscose yarn (Nm 131/2) of 830 g each and a pretreatment liquor of the following composition are used:

0.5 g / l

a silicone-free penetration accelerator

3.0 g / l

Oxilignin sulfonate (30%)

14 ml / l

aqueous sodium hydroxide solution (30%)

0.2 g / l

a leveling agent based on a benzotriazole compound

3.5 g / l

Hydrosulfite.

The pretreatment time is 15 minutes at 90 ° C.

0,07 %

des Farbstoffs der Formel (104)

0,05 %

des Farbstoffs Vat Red 10 (C.I. Nr. 67000)

0,004 %

des Farbstoffs der Formel

The following dye mixture is added for the coloring (dispersed with 10 g oxilignin sulfonate in 21 water):

0.07%

of the dye of the formula (104)

0.05%

of the Vat Red 10 dye (CI No. 67000)

0.004%

of the dye of the formula

A level coloring of the cross-wound bobbins is obtained.

Claims (10)

Process for dyeing cellulosic fiber materials, characterized in that all or part of the auxiliary chemicals required for the dyeing process are placed in the dye bath, then the vat dyes or their leuco compounds are metered into the dye bath at temperatures of 20 to 100 ° C. over a period of time and then dyes the fiber material at the same or elevated temperature. A method according to claim 1, characterized in that the fiber material is dyed at temperatures from 2o to 110 ° C, the dye bath optionally being heated after the vat dyes or their leuco compounds have been metered in. A method according to claim 1, characterized in that the addition of the dye or the leuco compound takes place continuously over a certain time interval until a sufficient amount of dye has been added for the respective dyeing process. Method according to one of claims 1 to 3, characterized in that the metering takes place in a linear manner. Method according to one of claims 1 to 4, characterized in that the metering takes place degressively. Method according to one of claims 1 to 5, characterized in that the dye is added in a coarsely dispersed form. Method according to one of claims 1 to 6, characterized in that cotton yarn or yarn made from regenerated cellulose is used as the cellulosic fiber material. Method according to one of claims 1 to 7, characterized in that the dyeing is carried out on pressed or non-pressed cheese. Method according to one of claims 1 to 8, characterized in that the dyeing is carried out after a lead time of 5 to 20 minutes. The fiber material dyed according to one of claims 1 to 9.