EP0202436A2 - Process for dyeing or printing cellulosic fibres or cellulosic mixed fibres - Google Patents

Abstract

Process for dyeing cellulose fibers or cellulose mixed fibers, characterized in that the fibers mentioned are mixed with water-soluble reactive dyes which contain at least one structural element of the formula <IMAGE> in the dye molecule, in which Y is a hydroxyl, hydroxymethyl, alkoxyC1-C4, aldehyde , Carboxylic acid amide, carboxylic acid monoalkyl C1-C4 amide, carboxylic acid dialkyl C1-C4-amide, carboxylic acid monophenylamide, cyano, carboxylic acid alkyl C1-C4 ester or sulfonic acid group or a halogen atom, in aqueous medium in the pH range 4- 11 colors.

Description

The invention relates to a method for dyeing or printing cellulose fibers or cellulose mixed fibers with water-soluble reactive dyes with a certain structural element. In the case of fiber mixtures, the process according to the invention is particularly suitable for the single-bath dyeing of mixtures of cellulose and polyester fibers with combinations of water-soluble reactive dyes containing a certain structural element and disperse dyes.

DE-OS 1 419 859, DE-PS 1 209 describes the use of dyes which contain a pyridinium residue or a pyridinium residue substituted by a methyl group bonded to the dye residue via the s-triazine ring for dyeing textile materials, in particular cellulose fiber materials 544, GB-PS 946 998, GB-PS 1 005 240 and GB-PS 1 012 625 known. The dyes are applied in conjunction with the use of acid-binding agents, such as sodium carbonate, sodium hydroxide, trisodium phosphate or sodium metasilicate, i.e. in an alkaline medium at temperatures from 0 to 100 ° C.

The dyeing of cellulose fiber materials with reactive dyes which contain a pyridinium radical substituted in the 3-position by a carboxyl group or sodium carboxylate group via the s-triazine ring bonded to the dye radical, in the presence of acid-binding agents such as hydroxides, carbonates or alkali metal phosphates at temperatures from 30 to 90 ° C is worked, is known from DE-OS 1 544 352 and DE-OS 1 544 356.

Compared to the reactive dyes used according to the invention, the dyes used according to the processes cited in the references cited above have clear disadvantages with regard to their lower absorbency in the exhaust dyeing process when dyeing cellulose fiber materials.

The use of reactive dyes, which are in the 3-position by a carboxyl or. Contain alkali metal carboxylate substituted pyridinium residue bound to the dye residue via the s-triazine ring, for dyeing cellulose fibers, or together with disperse dyes for dyeing cellulose mixed fibers, such as cellulose / polyester mixed fibers, by a one-bath process within a pH range of 4-10 at temperatures of 95-150 ° C is described in DE-OS 33 14 663.

Compared to the dyes used by this known method, the fixing optimum of the reactive dyes used according to the invention is not in the alkaline range, but preferably around the neutral range, which makes them more suitable in a mixture with disperse dyes for single-bath dyeing of cellulose / polyester fiber mixtures. This avoids damage to the disperse dyes caused by the alkaline agents normally required in the one-step dyeing process for fixing the reactive dyes, which damage is manifested in color deviations, a reduction in the fastness level and loss of color strength. In addition, the hydrolysis of the reactive dyes used at the same time in the alkaline range, which occurs in the temperature range 110-140.degree. C., which is required for dyeing the polyester fiber portion with disperse dyes, can be prevented, with the result that the dyeing yield is reduced.

enthalten, in welcher Y eine Hydroxyl-, Hydroxymethyl-, AlkoxyC₁-C₄, Aldehyd-, Carbonsäureamid-, Carbonsäuremonoalkyl_c,-_C, amid-, Carbonsäure-dialkyl _c,-_C. amid-, Carbonsäuremonophenylamid-, Cyano-, Carbonsäure-alkyl-_c,-_C, ester-oder Sulfonsäuregruppe oder ein Halogenatom, beispielsweise ein Chlor-oder Bromatom, bedeutet, in wäßrigem Medium im pH-Bereich 4-11 färbt.It has been found that cellulose fibers or cellulose mixed fibers can be dyed very advantageously by treating the fibers mentioned with water-soluble reactive dyes which contain the structural element of the formula (1) at least once in the dye molecule.

contain in which Y is a hydroxyl, hydroxymethyl, alkoxyC ₁ -C ₄ , aldehyde, carboxamide, carboxylic acid monoalkyl _c , - _C , amide, carboxylic acid dialkyl _c , - _C. amide, carboxylic acid monophenylamide, cyano, Carboxylic acid alkyl _c , - _C , ester or sulfonic acid group or a halogena tom, for example a chlorine or bromine atom, means dyeing in an aqueous medium in the pH range 4-11.

The mixture with the cellulose fibers can contain both synthetic fibers, such as, for example, polyester, polyamide, acid-modified polyacrylonitrile fibers or cellulose triacetate fibers, and native fibers, such as, for example, silk or wool, the fiber materials in any shape, for example as fibers, filaments, Strands or fabrics can be present.

When dyeing mixed fibers which, in addition to the cellulose fiber, contain native fibers, such as silk or wool, or the synthetic polyamide fiber, both the cellulose fiber portion and the portion of native fiber or synthetic polyamide fiber are dyed by the (acidic) reactive dyes used according to the invention alone.

For dyeing cellulose fibers from, for example, regenerated cellulose, linen or in particular cotton, or cellulose fibers in a mixture with silk or wool, the reactive dyes with the structural element of the formula (1) mentioned, both after the exhaust process at temperatures of about 30-90 ° C., are preferred about 40-80 ° C, and also suitable for the padding process at temperatures of about 20-50 ° C, the optimum dyeing temperature to be used in each case depending on the cellulose fiber or cellulose mixed fiber to be dyed. When dyeing according to the padding process, the fiber material is impregnated with aqueous, optionally salt-containing dye solutions and the dyes are then optionally fixed under the action of heat.

When dyeing mixed fibers which, in addition to the cellulose fiber, contain synthetic fibers, such as polyester or acid-modified polyacrylonitrile fibers, or cellulose triacetate fibers, the reactive dyes mentioned are used together with the dyes suitable for the synthetic fibers, for example disperse dyes in the presence of mixed fibers made of cellulose and polyester or cellulose triacetate fibers in the temperature range from about 95 ° C. to about 150 ° C. at pH values between about 4 and 8, the addition of alkaline agents being generally unnecessary. It is advisable to add a suitable buffer system to maintain a precisely defined pH value. Since dyes are fixed with the structural element of formula (1) even without alkaline agents, cellulose-polyester or. Color cellulose-cellulose triacetate mixed fibers evenly from a bath without causing damage to the disperse dyes used at the same time.

When dyeing mixed fibers made from cellulose fibers and acid-modified polyacrylonitrile fibers, the reactive dyes mentioned are used together with cationic dyes.

When carrying out the process according to the invention for dyeing fiber mixtures of cellulose fibers and polyester or cellulose triacetate fibers, the two categories of dyes (reactive and disperse dyes) are dissolved or predispersed in a conventional manner and added to the aqueous dye liquor with the amount of electrolyte customary for exhaust processes. The pH of the dye liquor is adjusted to a pH between 4 and 8.

Then the dye liquor containing the material to be dyed is heated and dyed at 95 ° C. to 150 _° C., preferably 110 ° C. and 135 ° C., for 30 to 90 minutes, or dyeing is carried out beforehand with a dye liquor containing a disperse dye and - for example, pre-stained for 20 minutes Completion of the dyeing process, the solution of the reactive dye in the high-temperature dyeing process in progress.

The dyeings obtained by the process according to the invention are subjected to thorough rinsing with cold and hot water, if appropriate with the addition of an agent which has a dispersing action and promotes the diffusion of the unfixed portions.

As already explained, reactive dyes which contain the structural element of the formula (1) one or more times are suitable for dyeing cellulose fibers or the cellulose fiber fraction and, if appropriate, the other, non-synthetic fiber fraction of fiber mixtures by the process according to the invention, such dyes being used one or more times are preferred, which are characterized by a high affinity for cellulose fiber.

worin D, D' und D" Reste eines organischen Farbstoffs der Mono-oder Polyazo-, Metallkomplexazo-, Formazan-, Anthrachinon-, Phthalocyanin-, Dioxazin-, Phenazin-, Azomethin-, Xanthen-, Pyrenchinon-oder Perylentetracarbonsäureimid-Reihe, R ein Wasserstoffatom oder eine gegebenenfalls substituierte Alkyl_c,-C_. gruppe, X einen aliphatischen, araliphatischen oder aromatischen Diaminrest, Y eine Hydroxyl-, Cyano-, Hydroxymethyl-, AlkoxyC₁-C₄, Aldehyd-, Carbonsäureamid-, Carbonsäure-monalkylC₁-C₄ amid-, Carbonsäure-dialylC₁-C₄ amid-, Carbonsäure-Reactive dyes suitable for the process according to the invention are, for example, those of the following formulas:

wherein D, D 'and D "are residues of an organic dye of the mono- or polyazo, metal complex azo, formazane, anthraquinone, phthalocyanine, dioxazine, phenazine, azomethine, xanthene, pyrenequinone or perylene tetracarboximide series, R is a hydrogen atom or an optionally substituted alkyl _c , -C _. Group, X is an aliphatic, araliphatic or aromatic diamine residue, Y is a hydroxyl, cyano, hydroxymethyl, alkoxyC ₁ -C ₄ , aldehyde, carboxamide, carboxylic acid monalkylC ₁ -C ₄ amide, carboxylic acid dialylC ₁ -C ₄ amide, carboxylic acid

monophenylamide or carboxylic acid alkyl _c , -C ₄ ester group, for example the carboxylic acid methyl, carboxylic acid ethyl, carboxylic acid or i-propyl ester group, furthermore a sulfonic acid group or a halogen atom, for example a chlorine or bromine atom, and Z is an unsubstituted, mono- or -disubstituted amino group, an alkoxy _c , - _C , or phenoxy group.

The dye residues D and D 'of the general formulas (3) and (5) can be the same (D = D') or different from one another (D ‡ D ').

The dye residues D, D 'and D "of the general formulas (2) to (7) can be substituted in the customary manner, in particular by one or more sulfonic acid groups. Examples of further substituents are alkyl groups with 1 to 4 carbon atoms, such as in particular Methyl, ethyl, n- or i-propyl; alkoxy groups with 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy and butoxy; acylamino groups with 1 to 4 carbon atoms, such as in particular acetylamino and propionylamino; the amino group, alkylamino groups with 1 up to 4 carbon atoms, phenylamine and alkoxycarbonyl groups with 1 to 4 carbon atoms in the alkoxy radical; furthermore hydroxyl, carboxy, sulfonic acid, nitro, cyano, carbamoyl, sulfamoyl and ureido groups and halogen atoms, such as chlorine or bromine atoms.

A straight-chain or branched alkylC ₁ -C ₄ radical, which can be substituted by, for example, hydroxyl, sulfonic acid, sulfato or cyano groups, is suitable for R in formulas (2) to (7). Examples of R are methyl, ethyl, sulfomethyl, β-hydroxyethyl, β-hydroxypropyl, β-sulfoethyl, β-sulfatoethyl and β-cyanoethyl.

mit n = 2 bis 6, wobei die Kohlenwasserstoffkette auch durch Heteroatome wie 0, S und N unterbrochen sein kann,

und

wobei R₂ -S0₃H, -Cl, -Br oder -OAlkyl mit 1 bis 4 C-Atomen, und X₁ eine direkte Bindung oder die Gruppen -CH₂-; -CH₂ ^CH ₂-; -NH-; -CONH-; -CO-; -0-; -S-; -SO₂-; -NHCONH-; -NHCSNH- und -CH=CH- bedeuten.Intermediates X in general formulas (4) and (5) are residues of a diamine, for example the following:

with n = 2 to 6, where the hydrocarbon chain can also be interrupted by heteroatoms such as 0, S and N,

and

where R ₂ -S0 ₃ H, -Cl, -Br or -Oalkyl with 1 to 4 carbon atoms, and X ₁ a direct bond or the groups -CH ₂ -; -CH ₂ ^CH ₂ -; -NH-; -CONH-; -CO-; -0-; -S-; -SO ₂ -; -NHCONH-; -NHCSNH- and -CH = CH- mean.

Suitable substituents Z in the general formulas (2), (4), (6) and (7) are the amino group and alkylC ₁ -C ₄ amino groups, it being possible for the alkyl groups to be substituted, for example, by hydroxy, methoxy, carboxy, sulfato , Sulfo, cyano, alkylC ₁ -C ₄ amino or di (alkyl) C ₁ -C ₃ amino, where the alkyl radicals can in turn be substituted, for example by hydroxy, methoxy and sulfato, and an alkyl radical in Oi (alkylc, -C ₃ ) -amino can be substituted by hydroxy, methoxy, sulfo, sulfato, carboxy and halogen, such as chlorine and bromine, further residues of cyclic amines such as piperidino, morpholino and piperazino, anilino, the latter optionally substituted by alkylC ₁ -C ₄ alkoxy C ₁ - C ₄ , chlorine, carboxy, sulfo and nitro; furthermore come as substituents Z alkoxyC ₁ -C ₄ groups that can be substituted by alkoxyC ₁ -C ₄ , such as methoxy, ethoxy or propoxy, and also the phenoxy groups, which can be substituted, for example, by methyl, chlorine, sulfo, carboxy or nitro.

The following groups are examples of individual examples of the substituent Z:

Amino, methyl, ethyl, n- and i-propyl and n- and i-butylamino, β-hydroxyethyl, β-methoxyethyl, β-carboxyethyl, β-sulfatoethyl, β-sulfoethyl, β-cyanoethyl -, Carboxymethyl-, ß-Dimehylaminoethyl-, y-Dimethylaminopropyl-, ß-Hydroxypropyl- and β-Sulfatopropylamino-, Dimethyl-, Diethyl-, Diethanol-, Methyl-ßhydroxyethylamino-, Methyl-β-methoxyethylamino-, Methyl-ß- sulfoethylamino-, methyl-ßsulfatoethylamino-, methyl-ß-carboxyethylamino-, methyl-carboxymethylamino- and methyl-β-chloroethylamino-, anilino, o-, m- or p-toluidino-, o-, m- or p-methoxyanlino- , o-, m- or p-chloroanilino-, o-, m- or p-carboxyanilino-, 2,4- and 2,5-dicarboxyanilino-, o-, m- or p-sulfoanilino-, 2,4- and 2,5-disulfoanilino, m-nitroanilino, 2-methyl and 2-methoxy-4-sulfoanilino, 4-chloro and 4-methyl-2-sulfoanilino, N-methylanilino, N-methyl m-toluidino, N-methyl-p-sulfoanilino, N-ethylanilino, N-ß-hydroxyethylanilino and N-ß-hydroxyethylm-toluidino, furthermore methoxy, ethoxy, propoxy, butoxy, methoxy thoxy-, methoxypropoxy-, ethoxyethoxy- and propoxy-, ethoxy-, phenoxy-, o-, m- and p-chlorophenoxy-, o-, m- and p-sulfophenoxy-, o-, m- and p-carboxyphenoxy- or p-nitrophenoxy-.

The dyes of the aforementioned general formulas (2) to (7) can be prepared, for example, by reacting the corresponding halotriazine dyes, where halogen is fluorine, chlorine or bromine, with pyridine derivatives in aqueous solution in the temperature range from about 40 ° C. to 120 ° C. in weakly acidic to alkaline pH range (pH approx. 5 to 9).

• Pyridin-3-carbonamid, Pyridin-4-carbonamid, Pyridin-3-carbonsäuremethylester, Pyridin-3-car- bonsäureethylester, Pyridin-4-carbonsäuremethyl-und -4-carbonsäureethylester, Pyridin-3-carbonitril, Pyridin-4-carbonitril, 3-und 4-Chlor-pyridin, 3-und 4-Brom-pyridin, 3-und 4-Methoxy-pyridin, Pyridin-3-sulfonsäure, Pyridin-3-und 4-aldehyd, Nicotinsäure-dimethyl-und -diethylamind, Isonicotinsäure-dimethyl-und -diethylamind, 3-und 4-Hydroxypyridin und 3-und 4-(Hydroxymethyl)-pyridin.

The following are suitable as pyridine derivatives, for example:

• Pyridine-3-carbonamide, pyridine-4-carbonamide, pyridine-3-carboxylic acid methyl ester, pyridine-3-carboxylic acid ethyl ester, pyridine-4-carboxylic acid methyl and -4-carboxylic acid ethyl ester, pyridine-3-carbonitrile, pyridine-4-carbonitrile, 3-and 4-chloro-pyridine, 3-and 4-bromo-pyridine, 3-and 4-methoxypyridine, pyridine-3-sulfonic acid, pyridine-3-and 4-aldehyde, nicotinic acid dimethyl and diethylamine, Isonicotinic acid dimethyl and diethylamine, 3 and 4-hydroxypyridine and 3 and 4- (hydroxymethyl) pyridine.

In the case of dye structures of the general formulas (2), (3), (4), (5) and (7), in which D and D 'are the residues of monoazo, polyazo or metal complexazo dyes, the reactive residue of the general Formula (1) may be bound either to the rest of the diazo component or to the rest of the coupling component.

In the case of D "of the general formulas (6) and (7), the reactive radicals of the general formula (1) are connected both to the rest of the diazo component and to the rest of the coupling component.

worin R' = H oder CH₃, und Acyl beispielsweise Acetyl oder gegebenenfalls substituiertes Benzoyl bedeuten.Preferred dye structures of DN (R) -, D'-N (R) - and - (R) ND "-N (R) - of the general formulas - (2) to (7) are, for example, the following, where n, and n _{2 can be} zero or 1 and for D and D 'either n or n _{2 is} zero and for D "n and n ₂ each represent 1:

wherein R '= H or CH ₃ , and acyl, for example acetyl or optionally substituted benzoyl.

Metal complexes of dyes of the following structures:

1: 1 Cu complexes or 1: 2 Cr and 1: 2 Co complexes are preferred.

The ring systems marked by dashed lines are to alternatively symbolize possible naphthalene rings.

where MePc means the Cu or Ni phthalocyanine residue and the number of substituents on the metal phthalocyanine residue is on average 3 to 4.

wobei R" einen aliphatischen oder cycloaliphatischen Rest bedeutet,

Dioxazine dye residues of the following structures:

where R "is an aliphatic or cycloaliphatic radical,

The dye residues of all the structures mentioned can be further substituted in the alkyl or aryl residues, in particular by the substituents mentioned in the characterization of D, D 'and D ".

In a special variant, the dyeing process according to the invention can also be carried out in such a way that in the dye bath the dyes of the general formulas (2) to (7) from the corresponding halotriazine-containing dyes and the pyridine derivatives mentioned in the pH range from 5 to 8 immediately before or during the Dyeing process can be produced. Halogen triazine-containing dyes are understood to mean those which contain a fluorine, chlorine or bromine atom on the s-triazinyl ring.

The dye liquors can contain the generally customary additives, such as, for example, inorganic salts, such as alkali metal chlorides or alkali metal sulfates, or urea, and also dispersants and leveling aids.

The dyeings produced with the dyes used according to the invention are distinguished by clear shades and by a high dye-fiber binding stability, by good to very good light fastness and very good wet fastness properties, such as fastness to washing, water, over-dyeing and perspiration, and through good pleating fastness, ironing fastness and rubbing fastness.

The following examples are intended to illustrate the invention without restricting it to the content of the examples.

The parts given are parts by weight, the temperature data relate to degrees Celsius.

example 1

sowie 50 Teilen Na₂SO. und 1 Teil m-nitrobenzolsulfonsaurem Natrium in 900 Teilen Wasser.A dyebath is prepared by dissolving 2 parts of the dye of the formula

and 50 parts of Na ₂ SO. and 1 part sodium m-nitrobenzenesulfonic acid in 900 parts water.

The dyebath is mixed with 50 parts of a cotton fabric at 40 ° C. and, after 45 minutes, 100 parts of a solution containing 2 parts of calcined soda are added. The temperature of the dyebath is kept at 60 ° C. for a further 45 minutes. The dyed cotton fabric is then rinsed, soaped at the boil with a nonionic detergent for about 10 minutes, rinsed again and finally dried. An intensely golden yellow color with very good fastness properties is obtained. '

Example 2

werden in 200 Teilen Wasser gelöst. Zu der Lösung gibt man 800 Teile einer wäßrigen Lösung, die 50 Teile Na₂S0₄ enthält, und stellt mit 2 Teilen Phosphatpuffer (aus NaH₂PO₄ und Na₂HPO₄.12H₂O) einen pH-Wert von 6,5 ein. In dieses Färbebad bringt man 100 Teile eines Baumwollgewebes ein. Dann wird unter statischem Druck die Temperatur innerhalb von ca. 20 Minuten auf 125°C gesteigert und das Färben 1 Stunde lang bei dieser Temperatur fortgesetzt. Danach läßt man das Färbebad abkühlen.2 parts of the reactive dye of the formula

are dissolved in 200 parts of water. 800 parts of an aqueous solution containing 50 parts of Na ₂ SO ₄ are added to the solution, and a pH of 6.5 is set with 2 parts of phosphate buffer (from NaH ₂ PO ₄ and Na ₂ HPO ₄ .12H ₂ O) a. 100 parts of a cotton fabric are placed in this dye bath. The temperature is then raised to 125 ° C. in about 20 minutes under static pressure and dyeing is continued at this temperature for 1 hour. Then the dye bath is allowed to cool.

The dyed goods are then rinsed with water, soaped at the boil with a nonionic detergent for about 15 minutes, rinsed again with water and dried. A deep bluish red color is obtained which has very good fastness properties.

Example 3

2 Teilen C.I. Disperse Orange 25,11 227, 20 Teilen Na₂S0., 1 Teil Natrium-m-nitrobenzolsulfonat und 2 Teilen eines bei Dispersionsfarbstoffen gebräuchlichen Dispersionsmittels, wie Ligninsulfonsäure.A dyebath is prepared from 800 parts of water, 1 part of a reactive dye of the following formula

2 parts CI Disperse Orange 25.11 227, 20 parts Na ₂ S0., 1 part sodium m-nitrobenzenesulfonate and 2 parts of a dispersing agent customary in disperse dyes, such as lignosulfonic acid.

At 40 ° C., 100 parts of cotton / polyester blend (50:50) are added to the dyebath, which is adjusted to pH 6.5, and the liquor is quickly heated to the dyeing temperature of 130 ° C. under static pressure and dyed at this temperature for 1 hour. The dyeing thus produced is further processed by rinsing and soapy in the usual way.

The result is a lively orange color on both fiber parts, which has good fastness properties.

• 15,7 Teile des Chlortriazinfarbstoffs der Formel
  
  werden in 350 Teilen Wasser verrührt und mit einer alkalisch gestellten Lösung von 2,1 Teilen Pyridin-3-sulfonsäure in 20 Teilen Wasser versetzt. Man erhitzt bei dem pH-Wert 6,5 auf 80°C und rührt bei dieser Temperatur 12 bis 16 Stunden lang, wobei der Fortgang der Reaktion durch Dünnschichtchromatogramm verfolgt wird.

The reactive dye of the above structure used for coloring the cotton portion was prepared as follows:

• 15.7 parts of the chlorotriazine dye of the formula
  
  are stirred in 350 parts of water and mixed with an alkaline solution of 2.1 parts of pyridine-3-sulfonic acid in 20 parts of water. The mixture is heated to 80 ° C. at pH 6.5 and stirred at this temperature for 12 to 16 hours, the progress of the reaction being monitored by thin layer chromatogram.

After completion of the reaction, the resulting dye is salted out with sodium chloride at room temperature, suction filtered, washed with a 5% sodium chloride solution and dried.

The reactive dyes used according to Examples 1 and 2 were prepared quite analogously by reacting the corresponding monochlorotriazine dyes with nicotinamide or 3-chloropyridine.

Example 4

1,5 % des Reaktivfarbstoffs der Formel

und 60 g/l Natriumchlorid enthält. Der pH-Wert der Färbeflotte wird auf 6,0 eingestellt.In a HT dyeing machine at a liquor ratio of 1:20, a blend of 67% polyester fibers and 33% cotton is dyed with an aqueous liquor which - based on the weight of the dry goods - 1.5% of the disperse dye (in commercial form and Texture) of the formula

1.5% of the reactive dye of the formula

and contains 60 g / l sodium chloride. The pH of the dye liquor is adjusted to 6.0.

The textile material is dyed with this dyebath at 130 ° C. for 1 hour. After the usual rinsing and soaping process, a lively turquoise blue color is obtained on both fiber portions, which has very good fastness properties.

To produce the reactive dye, the monochlorotriazine dye is reacted with iso-nicotinamide within 16 hours at 80 ° C.

Example 5

und 50 g/l Natriumchlorid enthält. Der pH-Wert wird auf 6,2 eingestellt. Man geht mit dem Färbegut bei Raumtemperatur in das Färbebad ein, heizt die Flotte auf die Färbetemperatur von 120°C und färbt die Ware ca. 1 Stunde lang bei dieser Temperatur. Dann läßt man abkühlen, spült die erhaltene Färbung heiß und kalt mit Wasser und trocknet schließlich das gefärbte Baumwollgam. Man erhält eine intensive marineblaue Färbung, die gute Echtheiten zeigt.In a HT dyeing machine at a liquor ratio of 1:20, cross-wound bobbins made of mercerized cotton yarn are dyed with a liquor which contains an aqueous solution of 1% (by weight of the dry yarn) of the reactive dye of the formula

and contains 50 g / l sodium chloride. The pH is adjusted to 6.2. The material to be dyed is passed into the dyebath at room temperature, the liquor is heated to the dying temperature of 120 ° C. and the goods are dyed at this temperature for about 1 hour. The mixture is then left to cool, the dyeing obtained is rinsed hot and cold with water and the dyed cotton yarn is finally dried. An intense navy blue coloration is obtained which shows good fastness properties.

Example 6

A dyebath is prepared from 1100 parts of water, 1 part of the reactive dye described in Example 5, 3 parts of CI Disperse Blue 79 (in commercial form), 50 parts of Na ₂ SO ₄ . and 1 part of the sodium salt of m-nitrobenzenesulfonic acid and adjust the pH to 6. A cotton / polyester blend (50:50) is added and the liquor is heated to the dyeing temperature of 130 ° C. After dyeing for 50 minutes, the mixture is allowed to cool and an intensive marine blue dyeing is obtained on both parts of the fiber by customary post-cleaning.

Example 7

deren Ausgangs-pH-Wert 7,5 beträgt, ein und färbt das Textilgut weitere 45 Minuten unter diesen Bedingungen. Die Weiterbehandlung der so erzeugten Färbung erfolgt in üblicher Weise. Man erhält auf beiden Faseranteilen eine tiefe Blaufärbung.In a HT dyeing machine at a liquor ratio of 1:20, a mixed fabric of polyester fibers and cotton (60:40) is treated with an aqueous liquor which, based on the weight of the dry goods, -1.5% of the disperse dye Cl Disperse Blue 333 ( in commercial form and quality) and 40 g / I sodium chloride. The fiber mixture in this liquor is first dyed at 130 ° C. for 45 minutes and then an aqueous solution is passed in, based on the weight of the dry goods, 1.5% of the reactive dye of the formula

whose initial pH is 7.5, and dyes the fabric for another 45 minutes under these conditions. The dyeing thus produced is further processed in the usual way. A deep blue color is obtained on both fiber parts.

Example 8

2 Teilen C.I. Disperse Red 358 (in handelsüblicher Form) und 50 Teilen Na₂SO₄ bereitet und auf pH 7,2 eingestellt wurde, färbt man ein Polyester/Baumwolle-Mischgewebe (50 : 50) 45 Minuten bei 135°C. Nach üblicher Nachbehandlung erhält man auf beiden Faseranteilen eine intensive klare Rotfärbung.In a dye bath consisting of 900 parts of water, 1 part of the reactive dye of the formula

2 parts of CI Disperse Red 358 (in commercial form) and 50 parts of Na ₂ SO ₄ and adjusted to pH 7.2, a polyester / cotton blend (50:50) is dyed at 135 ° C. for 45 minutes. After the usual aftertreatment, an intense clear red color is obtained on both fiber parts.

Example 9

A navy blue dyeing, as obtained according to Example 6, can also be produced on a polyester / cotton blended fabric by carrying out the dyeing process according to the instructions there and using an aqueous liquor which, based on the weight of the dry goods,

sowie 60 Teile Na₂SO₄ enthält.1.8% of the dye CI Disperse Blue 56, 63 285, 0.5% of the dye CI Disperse Brown 1, 11 152, 0.5% of the dye CI Disperse Violet 48 - (each in the customary form and nature) and 0, 9% of the reactive dye mentioned in Example 5, 0.2% of the reactive dye of the formula

and contains 60 parts of Na ₂ SO ₄ .

Equally good dyeings with comparable fastness properties are also obtained with dyes which can be prepared analogously to Example 3 by reacting the halotriazine dyes listed in the following table with the pyridine derivatives mentioned on page 6.

Example 41

A blend of 67 parts of polyester fibers and 33 parts of cotton is printed with a printing paste that contains 1 kg

30 g of the Disperse Red dye from C.I. 60 756.

(die Farbstoffe in handelsüblicher Form und Beschaffenheit),30 g of the reactive dye of the formula

(the dyes in a commercial form and texture),

600 g alginate thickening (4%) and

340 g water

1000 g printing paste.

The fabric is steamed for 5 minutes at 130 ° C after printing to fix the dye. The pressure obtained is then rinsed hot with water, soaped hot and neutral for 5 minutes with an aqueous bath with the addition of 0.5 g / l of a nonionic detergent, rinsed again with water and dried.

The result is brilliant and level red prints with a change effect on both fiber parts.

Example 42

A mixed fabric of polyester fibers / cotton (67/33) with 70% liquor absorption (by weight of the dry goods) is padded with an aqueous padding liquor

18 g / l of Disperse Blue 56 dye from C.I. 63 285.

5 g / l of Disperse Brown 1 dye from C.I. 11 152.

20 g/I des Reaktivfarbstoffes der Formel

(die Farbstoffe in handelsüblicher Form und Beschaffenheit) und 10 g/I eines Hilfsmittels auf Basis eines Gemisches von Alkyl-und Aryloxyäthylaten.5 g / l of the disperse dye of the formula

20 g / I of the reactive dye of the formula

(the dyes in commercial form and quality) and 10 g / l of an auxiliary based on a mixture of alkyl and aryloxyethylates.

The fabric is then steamed for 10 minutes at 125 ° C to fix the dyes. The dyeing is then boiled for 10 minutes with an aqueous bath with the addition of 0.5 g / l of the reaction product of 1 mol of nonylphenol with 8 mol of ethylene oxide.

A deep blue dyeing of the fabric with good tone-on-tone coverage of both fiber components is obtained.

Example 43

A dye bath consisting of 250 parts of water, 20 parts of sodium sulfate and 0.5 part of the dye of the formula is prepared

The pH is adjusted to 6.5 by adding sodium phosphate. This dye bath is entered at 40 ° C. with 12 parts of a mercerized cotton fabric, the temperature is raised to 95-100 ° C. within 10 minutes and dyeing is carried out at this temperature for 45 minutes. The fabric is then rinsed cold and hot with water and soaped at the boil for 10 minutes with a nonionic detergent. A strong, brilliant red color is obtained which is very resistant to washing treatments and exposure to light.

Example 44 (Comparative example) _'

A dye bath consisting of 250 parts of water, 20 parts of sodium sulfate and 0.5 part of the dye of the formula is prepared

The pH is adjusted to 6.5 by adding sodium phosphate. This dye bath is entered at 40 ° C. with 12 parts of a mercerized cotton fabric, the temperature is raised to 95-100 ° C. within 10 minutes and dyeing is carried out at this temperature for 45 minutes. The fabric is then rinsed cold and hot with water and soaped at the boil for 10 minutes with a nonionic detergent. The cotton fabric thus obtained is dyed pale pink.

The example shows that the dye containing the chlorotriazinyl group is practically not fixed in the absence of an acid-binding agent on the fiber material.

Example 45

Die Flotte wird unter lebhafter Zirkulation auf 110°C gebracht und 1 Stunde bei dieser Temperatur belassen. Anschließend wird die Restflotte abgelassen, gespült und 10 Minuten kochend geseift.100 parts of a mixed fabric of 50 parts of cellulose and 50 parts of polyamide fibers are mixed on a HT reel runner with a 70 ° C warm liquor consisting of 2000 parts of water, 6 parts of sodium m-nitrobenzenesulfonate, 50 parts of sodium sulfate and 3 parts of the dye of formula

The liquor is brought to 110 ° C. with vigorous circulation and left at this temperature for 1 hour. The remaining liquor is then drained off, rinsed and soaped at the boil for 10 minutes.

A uniform blue color is obtained on both fiber components.

Claims (10)

1. A process for dyeing cellulose fibers or cellulose mixed fibers, characterized in that said fibers with water-soluble reactive dyes, which in the dye molecule at least once the structural element of the formula

contain in which Y is a hydroxyl, hydroxymethyl, alkoxyC ₁ -C ₄ , aldehyde, carboxamide, carboxylic acid monoalkyl _c , - _C. amide, carboxylic acid dialkyl C ₁ -C ₄ amide, carboxylic acid monophenylamide, Cyano-, Carbonsäurealkyl _c , - _Cc ester or sulfonic acid group or a halogen atom, colors in an aqueous medium in the pH range 4-11. 2. The method according to claim 1, characterized in that the cellulose fibers alone or in a mixture with synthetic polyamide fibers, silk or wool after the exhaust process at temperatures of about 30-90 ° C or after the padding process at temperatures of about 20-50 ° C. with subsequent fixation of the reactive dyes, possibly under the influence of heat. 3. The method according to claim 1, characterized in that after cellulose fibers in a mixture with polyester fibers or cellulose triacetate fibers. a one-bath process in the pH range 5-8 and at a temperature of 95-150 ° C with the addition of disperse dyes. 4. The method according to claim 1, characterized in that cellulose fibers in admixture with acid-modified polyacrylonitrile fibers under Zu set of cationic dyes colors. 5. Process according to claims 1 -4, characterized in that water-soluble reactive dyes from the series of monoazo, polyazo, metal complex, formazan, anthraquinone, phthalocyanine, dioxazine, phenazine, azomethine or xanthene dyes used. 6. Process according to claims 1-4, characterized in that water-soluble reactive dyes of the general formula

used, in which D, D 'represent residues of a dye of the monoazo, polyazo, metal complex azo, formazane, anthraquinone or dioxazine series, where D and D' can be the same or different, R is a hydrogen atom or an Al- kylC ₁ -C ₄ group, X the rest of a diamine of the formula

or

means, and Y has the meanings mentioned in claim 1. 7. Process according to Claims 1 -4, characterized in that water-soluble reactive dyes of the general formula

used, in which D "represents the remainder of a dye of the disazo, polyazo, metal complex azo, formazan, metal phthalocyanine or dioxazine series, Z denotes an unsubstituted or substituted amino, alkoxy or phenoxy group, and Y claims 1, and R have the meanings mentioned in claim 6. 8. The method according to claims 1-7, characterized in that water-soluble reactive dyes are used in which Y in the formulas of claims 1, 6 and 7, the carboxamide, carboxylic acid monoalkyl _c , - _C , amide, carboxylic acid dialkyl _c , - _{C4 means} amide or carboxylic acid monophenylamide group in the 3 or 4 position. 9. The method according to claims 1-7, characterized in that water-soluble reactive dyes are used, in which Y in the formulas of claims 1, 6 and 7 means the carboxylic acid methyl ester or carboxylic acid ethyl ester group in the 3 or 4 position. 10. The method according to claims 1-7, characterized in that water-soluble reactive dyes are used in which Y in the formulas of claims 1, 6 and 7 means the sulfonic acid group in the 3-position.