EP0242324A1 - Process for dyeing cellulosic fibres without tailing - Google Patents

Abstract

The invention relates to a process for the end-to-end dyeing of cellulosic materials, or blends that contain cellulose, with direct and/or reactive dyes by the pad dyeing process, which comprises using an aqueous liquor that contains at least one water-soluble direct or reactive dye and at least one water-soluble anionic, colorless organic compound having an affinity factor A, at a concentration of 0.2 to 0.3 g/l, for mercerized cotton of 1.1 to 4, said factor A being the quotient of the concentration of the water-soluble, colorless organic compound in a liquor without addition of dye, before impregnation, divided by the concentration of the water-soluble, colorless organic compound in the residual liquor without dye after impregnation. The process of this invention is suitable for dyeing textile cellulosic materials or blends containing cellulose to give end-to-end dyeings of good fastness properties.

Description

The present invention relates to a novel process for dyeing textile cellulosic fibers with direct or reactive dyes according to the padding, padding or pad process by using an aqueous liquor which, in addition to at least one direct or reactive dye, has at least one water-soluble, anionic , fiber-affine, colorless organic compound contains.

The foulard, padding or pad process is a dyeing process known for cellulose fibers, which allows large amounts of wear and tear to be obtained by soaking or impregnating the fiber with the dye solution in a trough with the shortest liquor ratio and usually only passing through the pad once with a short dyeing time to dye textile fiber materials and then fix them.

A known disadvantage of this procedure is the end inequality of the dyed fiber materials (lots) that can be observed in many cases.

Tailing / reversed tailing is the difference in strength and nuance between the beginning and the end of a game. When only one dye is used, the end unevenness is noticeable in differences in strength, whereas shifts in the shade can often occur with combination dyeings.

Tailing is a weakening of the color strength between the beginning and end of the batch, which is due to a decrease in the dye concentration in the trough. This dye depletion of the liquor is caused by the dye being drawn up during the padding process. Differences in strength and shade based on tailing occur particularly with dyes with medium to high substantivity, and very particularly often when coloring light shades.

Reversed tailing is an increase in color strength between the beginning and end of the batch, which is due to the increase in the dye concentration in the trough. This dye accumulation in the padding liquor is caused by a preferred water adsorption in the padding process. Differences in strength and shade based on reversed tailing occur with dyes of low substantivity, especially when coloring dark shades.

The present invention relates to a novel process for dyeing cellulose fibers at the same end, preferably in light shades.

The on the basis of the studies on the end inequality [Joumal of the Society of Dyers and Colourists, 71 (1955), pages 13 to 20; or SVF (Swiss Association of Dyeing Experts) - Fachorgan 16 (1961), pages 341 to 3511 measures taken to improve this disadvantageous effect, e.g. Shortening the dipping time, specific dye selection and the dye concentration of the padding liquor, which is continuously adapted to suit the affinity of the dye on the respective fiber or the dyeing process, have not been successful in practice. For heavy, tightly packed or insufficiently hydrophilic and slowly swelling goods, too short a diving time has a negative effect; the use of fewer, selected dyes means fewer options for setting shades and limited use of such dyes to only light or only dark shades; and the varied dye concentration in the make-up liquor is often too complicated for practice, e.g. due to lack of reproducibility.

There has long been a need to improve the end unevenness of a lot.

Surprisingly, a new process has now been found which does not have the disadvantages mentioned and which allows textile cellulose fibers with direct and / or reactive dyes to be dyed in a simple manner, in particular in light shades, using the padding, padding or pad process .

The present invention thus relates to a process for dyeing cellulose fibers or cellulose-containing mixed fibers with direct and / or reactive dyes using the padding process, which is characterized in that an aqueous liquor is used which contains at least one water-soluble direct or reactive dye and at least one Water-soluble anionic, fiber-affine, colorless organic compound with an affinity factor A at a concentration of 0.2-0.3 g / l on mercerized cotton from 1.1 to 4, the factor A being the quotient of the concentration of the water-soluble, fiber-affine, colorless organic compound in a dye-free liquor before being impregnated to the concentration of the water-soluble, fiber-affine, colorless organic compound in the dye-free liquor squeezed.

In the process according to the invention, compounds are termed colorless if their absorption maximum lies outside the visible spectral range or their absorption is very low in the visible range.

The water-soluble, fiber-affine, colorless organic compound used in the process according to the invention is a compound with "dye character", i.e. the behavior of this compound under dyeing conditions corresponds to the behavior of a substantive dye, i.e. the compound has a certain substantivity for cellulose.

The fiber-affine, colorless organic compounds advantageously contain 1 to 6, preferably 1 to 4 acidic water-solubilizing groups, which are in particular carboxyl groups or especially sulfonic acid groups. Preferably contain the water-soluble, fiber-affine, colorless organic Compounds no further ionic groups and no halogen-containing heterocycles of aromatic character, such as halotriazines.

Surprisingly, the process according to the invention is suitable for all pure cellulose fibers, e.g. mercerized or leached or bleached cotton or cellulose, as well as for cellulose-containing mixed fibers, e.g. Polyester / cellulose blended fabrics, equally applicable, without being limited to certain direct or reactive dyes or certain fiber-reactive groups of the reactive dyes; It is also surprising that regardless of the concentration of the dyes, regardless of the electrolyte content or alkali, regardless of conventional dyeing aids (wetting agents) and regardless of the dipping time and the trough content, identical dyeings are obtained.

The direct dyes which can be used in the process according to the invention are the customary direct dyes, for example the "Direct Dyes" mentioned in Color Index, 3rd edition (1971) Volume 2 on pages 2005 to 2478.

Reactive dyes are understood to be the usual dyes that form a chemical bond with the cellulose, e.g. the "Reactive Dyes" listed in Color Index, Volume 3 (3rd edition, 1971) on pages 3391 to 3560 and in Volume 6 (revised 3rd edition, 1975) on Pages 6268 to 6345.

In particular, direct or reactive dyes with an affinity factor B for mercerized cotton at a concentration of 0.1 gram per liter of at least 1.1 are used in the process according to the invention, the affinity factor B being the quotient of the concentration of the dye in the original liquor without addition the water-soluble, fiber-affine, colorless organic compound to the concentration of the dye in the squeezed liquor.

If dye mixtures are used in the process according to the invention, e.g. Mixtures of different reactive dyes or different direct dyes or mixtures of different direct and reactive dyes, at least one of the dyes used should have an affinity factor B of at least 1.1.

The determination of the affinity factor A for the water-soluble, fiber-affine, colorless organic compound or the determination of the affinity factor B for the direct or reactive dyes is carried out by measuring the concentration of the original liquor and the squeezed liquor by forming the ratio of the measured concentrations, ie

The concentration of the original liquor corresponds to the amounts of dye or colorless organic compound used. The concentration in the squeezed or original liquor is measured by methods known per se, such as spectrophotometric e.g. at the absorption maximum or by chromatographic means (e.g. HPLC).

Mercerized cotton is used both for the determination of the affinity factor A from 1.1 to 4 and for the determination of the affinity factor B of at least 1.1, the concentration of water-soluble, fiber-affine, colorless organic compound being 0.2 to 0.3 g / I and 0.1 g / I of direct or reactive dye in the original liquor.

To determine the affinity factor A or B, the water-soluble, fiber-affine, colorless organic compound alone or the direct or reactive dye alone is used.

When determining the affinity factors A and B one proceeds in such a way that the mercerized cotton [140 g / m ² , thread count / cm ² : warp / weft 25/22, yarn number: Tex warp / weft 30/30] 25 ° C and 60% relative humidity is conditioned to constant weight, the fabric is impregnated with a liquid absorption of approx. 200 percent by weight at room temperature with the original liquor containing a salt, in particular Na ₂ S0 _4, for example 10 g / l Na ₂ S0 ₄ is squeezed to 70% weight gain after a diving time of approx. 2-4 seconds (including air passage) and the concentration of the squeezed liquor of dye or colorless compound is determined.

The amount of dyes in the process according to the invention generally depends on the desired color strength, with end unevenness especially in the case of light shades, i.e. at a concentration of 0.05 g / l or less to about 20 g / l.

• a) eine wässrige Flotte verwendet, worin die Konzentration an Direkt- oder Reaktivfarbstoff zusammen mit der wasserlöslichen faseraffinen, farblosen organischen Verbindung maximal 20 g/l, insbesondere maximal 10 g/I und vorzugsweise 3 g/I bis 8 g/I ist.
• b) eine wässrige Flotte verwendet, worin die Konzentration an Direkt- oder Reaktivfarbstoff insgesamt geringer als 5 g/l, insbesondere geringer als 3 g/1 ist.
• c) eine wasserlösliche anionische, faseraffine, farblose organische Verbindung mit einem Affinitätsfaktor A von 1,15 bis 2,5 vorzugsweise 1,2 bis 1,6 gemäss den oben angegebenen Testbedingungen verwendet.

Preferred embodiments of the method according to the invention are characterized in that

• a) an aqueous liquor is used, in which the concentration of direct or reactive dye together with the water-soluble fiber-affine, colorless organic compound is a maximum of 20 g / l, in particular a maximum of 10 g / l and preferably 3 g / l to 8 g / l.
• b) an aqueous liquor is used in which the total concentration of direct or reactive dye is less than 5 g / l, in particular less than 3 g / 1.
• c) a water-soluble anionic, fiber-affine, colorless organic compound with an affinity factor A of 1.15 to 2.5, preferably 1.2 to 1.6 according to the test conditions specified above.

A particularly preferred embodiment of the process according to the invention is characterized in that a mixture of (1) at least one direct or reactive dye or at least one direct and at least one reactive dye and (2) at least one water-soluble anionic, fiber-affine, colorless organic compound is used, so that the dye affinity factor (B) in the mixture is 0.9 to 1.15, in particular 0.95 to 1.1.

The designation g / I means grams per liter.

The amount of water-soluble, fiber-affine, colorless organic compound in the process according to the invention depends in particular on the amount of dye used and the factor B, a minimum amount of 0.5 g / l having proven to be advantageous.

• (a) den Azinverbindungen der Formel
  
  worin
  • Q =CH-Rx oder besonders =N-
  • R_x Wasserstoff, Halogen, Cyan, C₁-C₄-Alkyl oder C₁-C₄-Alkyt-sulfonyl,
  • V und W, unabhängig voneinander, je R₂-X₂-, R₃-X₃-, Hydroxy, C₁-C₄-Alkoxy oder eine unsubstituierte oder durch einen C₁-C₄-Alkylrest mono- oder disubstituierte Aminogruppe, wobei der Alkylrest unsubstituiert oder durch Hydroxy, Cyano, Sulfo (-SO₃H) oder Sulfato (-OSO₃H) substituiert ist,
  • Ri, R₂ und Rs, unabhängig voneinander, je einen aromatischen oder heteroaromatischen Rest,
  • X₁, X₂ und Xs, unabhängig voneinander, je
    
    oder
    -NH-CO-Phen-NH-,
  • R₄ Wasserstoff, C₁-C₄-Alkyl oder Phenyl,
  • Phen eine unsubstituierte oder substituierte Phenylengruppe,
  • Z eine saure, wasserlöslichmachende Gruppe und
  • m 1 bis 6 bedeuten, oder
• (b) den Verbindunaen der Formel
  
  worin R₁, R₂, Z und m die angegebene Bedeutung haben,
  A die direkte Bindung, -CO-, -CONH- oder
  
  bedeutet und die Ringe a und β unsubstituiert oder substituiert sind, oder
• (c) den Verbindungen der Formel
  
  worin
  • Rs und Rs, unabhängig voneinander, je -NH₂, -NH-CO-R₇. -N0₂ oder
    
  • R₇ C₁-C₈-Alkyl, wie z.B. Methyl, Ethyl, oder Aryl, wie z.B. Phenyl bedeuten und
  • V, W, Z und m die oben angegebene Bedeutung haben, oder
• (d) den Verbindungen der Formel
  
  worin
  • R₈ Wasserstoff oder Rs-CO- und
  • R₉ einen aliphatischen, aromatischen oder heterocyclischen Rest,
  • insbesondere C₁-C₄-Alkyl oder Phenyl bedeuten,
  • die Ringe a und β unsubstituiert oder substituiert sind und
  • Z und m die oben angegebene Bedeutung haben.

Preferred colorless compounds which can be used according to the invention correspond

• (a) the azine compounds of the formula
  
  wherein
  • Q = CH-Rx or especially = N-
  • R _{x is} hydrogen, halogen, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkyl sulfonyl,
  • V and W, independently of one another, each R ₂ -X ₂ -, R ₃ -X ₃ -, hydroxy, C ₁ -C ₄ alkoxy or an unsubstituted or mono- or disubstituted amino group or substituted by a C ₁ -C ₄ alkyl radical, wherein the alkyl radical is unsubstituted or substituted by hydroxy, cyano, sulfo (-SO ₃ H) or sulfato (-OSO ₃ H),
  • Ri, R ₂ and Rs, independently of one another, each have an aromatic or heteroaromatic radical,
  • X ₁ , X ₂ and Xs, independently of one another, each
    
    or
    -NH-CO-Phen-NH-,
  • R _{4 is} hydrogen, C ₁ -C ₄ alkyl or phenyl,
  • Phen is an unsubstituted or substituted phenylene group,
  • Z is an acidic, water solubilizing group and
  • m is 1 to 6, or
• (b) the compounds of the formula
  
  wherein R ₁ , R ₂ , Z and m have the meaning given,
  A the direct bond, -CO-, -CONH- or
  
  means and the rings a and β are unsubstituted or substituted, or
• (c) the compounds of the formula
  
  wherein
  • Rs and Rs, independently of one another, each have -NH ₂ , -NH-CO-R ₇ . -N0 ₂ or
    
  • R _{7 is} C ₁ -C ₈ alkyl, such as methyl, ethyl, or aryl, such as phenyl and
  • V, W, Z and m have the meaning given above, or
• (d) the compounds of the formula
  
  wherein
  • R _{8 is} hydrogen or Rs-CO- and
  • R _{9 is} an aliphatic, aromatic or heterocyclic radical,
  • are in particular C ₁ -C ₄ alkyl or phenyl,
  • the rings a and β are unsubstituted or substituted and
  • Z and m have the meaning given above.

C ₁ -C ₄ alkyl means alkyl radicals or alkyl constituents which contain 1 to 4 carbon atoms and can be straight-chain or branched. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. Butyl, isobutyl and tert. Butyl.

Halogen means for example fluorine, bromine or preferably chlorine.

Acyl is especially formyl, C 1 -C ₄ -alkylcarbonyl, such as acetyl or propionyl, or benzoyl.

Suitable water-solubilizing group Z are, in particular, carboxyl groups or especially sulfonic acid groups. A compound can contain both only carboxy groups or only sulfo groups as well as both carboxy and sulfo groups.

m is preferably 1 to 4. Compounds of the formulas (1) to (3) preferably contain 2 to 4 acidic water-solubilizing groups Z, while the other compounds of the formula (4) contain in particular 1 or 2 water-solubilizing groups Z.

The phen group and the rings a and β are hydroxy, cyano, nitro, halogen, such as fluorine, chlorine or bromine, C 1 -C ₄ -alkyl, such as, for example, methyl, ethyl, propyl, isopropyl or butyl, trifluoromethyl, C _i - C ₄ alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, C ₂ -Cs alkoxycarbonyl, amino, mono- or di-Ci-C ₄ -alkylamino, phenylamino, carbamoyl, sulfamoyl, ureido, Ci-C7- Acylamino, such as acetylamino, propionylamino or benzoylamino, Ci-C ₄ alkylsulfonyl, such as methylsulfonyl, sulfomethyl or sulfatoethyl contain.

In the compounds of formula (1), V is preferably R ₂ -X ₂ - and W is especially R ₃ -X ₃ -. Compounds of the formula (1) in which X _i , X ₂ and X _{3 are} -NH- or V and W, independently of one another, are preferably -OH or -NH ₂ are particularly preferred. Compounds of the formula (1) in which R 1, R ₂ and R _{3 represent} an aryl radical, such as, for example, a naphthyl or especially a phenyl radical, are very particularly preferred.

Furthermore, compounds of the formula (3) in which Rs and R ₆ each represent a triazinylamino radical of the formula (3a) are of great interest.

worin R_x die angegebene Bedeutung hat,

• V' und W', unabhängig voneinander, je Hydroxy, C_i-C₄-Alkoxy, oder eine unsubstituierte oder durch einen Ci-C₄-Alkylrest mono- oder disubstituierte Aminogruppe, wobei der Alkylrest unsubstituiert oder durch Hydroxy, Cyano, Sulfo oder Sulfato substituiert ist und V' auch den Rest R₂-X₂-,
• Ri, R₂ und R₃, unabhängig voneinander, je einen aromatischen oder hereroaromatischen Rest darstellen, wie z.B. den Phenyl-, Biphenylyl-, Naphthyl-, Stilbenyl- oder Chinolinylrest bedeuten, wobei Ri, R₂ und Rs ausser Z beliebige weitere nicht-ionogene Substituenten enthalten können, wie z.B. Alkylgruppen mit 1 bis 4 Kohlenstoffatomen, wie z.B. Methyl, Aethyl, Propyl, Isopropyl oder Butyl, Alkoxygruppen mit 1 bis 4 Kohlenstoffatomen, wie Methoxy, Aethoxy, Propoxy, Isopropoxy oder Butoxy, Acylaminogruppen mit 1 bis 7 Kohlenstoffatomen, wie z.B. Acetylamino, Propionylamino oder Benzoylamino, Amino, Mono- oder Dialkylamino mit 1 bis 4 Kohlenstoffatomen im Alkylrest, Phenylamino, Alkoxycarbonyl mit 1 bis 4 Kohlenstoffatomen im Alkoxyrest, Nitro, Cyano, Trifluormethyl, Halogen, wie z.B. Fluor, Chlor oder Brom, Sulfamoyl, Carbamoyl, Ureido, Hydroxy, C₁-C₄-Alkylsulfonyl, wie z.B. Methylsulfonyl, oder Sulfomethyl (HO₃S-CH₂-),
• X₁, X₂ und X₃, unabhängig voneinander, je -O-, -S-, -N(R₄)- oder
  
  sind, wobei R₄ Wasserstoff, Ci-₄-Alkyl oder Phenyl ist und die Benzringe a und β durch einen oder mehrere der für R₁ angegebenen nicht-ionogenen Substituenten substituiert sein können, Z eine wasserlöslichmachende Gruppe, wie z.B. die Carboxyl- oder vorzugsweise Sulfonsäuregruppe ist und m = 2, 3, 4, 5 oder 6, vorzugsweise 2 bis 4 ist.

From the large number of possible water-soluble, fiber-affine, colorless organic compounds, for example, compound types of the following formulas come into consideration:

where R _{x has} the meaning given,

• V 'and W' each independently represents hydroxy, C _i -C ₄ alkoxy, or an unsubstituted or mono- by a Ci-C ₄ alkyl or disubstituted amino, wherein the alkyl group is unsubstituted or substituted by hydroxyl, cyano, sulfo or Sulfato is substituted and V 'also the radical R ₂ -X ₂ -,
• Ri, R ₂ and R ₃ , independently of one another, each represent an aromatic or hereroaromatic radical, such as, for example, the phenyl, biphenylyl, naphthyl, stilbenyl or quinolinyl radical, where Ri, R ₂ and Rs apart from Z are any other non- may contain ionogenic substituents, such as alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl or butyl, alkoxy groups with 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, acylamino groups with 1 to 7 carbon atoms , such as acetylamino, propionylamino or benzoylamino, amino, mono- or dialkylamino with 1 to 4 carbon atoms in the alkyl radical, phenylamino, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy radical, nitro, cyano, trifluoromethyl, halogen, such as fluorine, chlorine or bromine, Sulfamoyl, carbamoyl, ureido, hydroxy, C ₁ -C ₄ alkylsulfonyl, such as methylsulfonyl, or sulfomethyl (HO ₃ S-CH ₂ -),
• X ₁ , X ₂ and X ₃ , independently of one another, each -O-, -S-, -N (R ₄ ) - or
  
  where R _{4 is} hydrogen, Ci- ₄ alkyl or phenyl and the benz rings a and β can be substituted by one or more of the non-ionic substituents specified for R ₁ , Z is a water-solubilizing group, such as the carboxyl or preferably Is sulfonic acid group and m = 2, 3, 4, 5 or 6, preferably 2 to 4.

In the foreground of interest are triazine compounds of the formula (7) in which X ₁ , X ₂ and X ₃ each have -NH-, R ₁ , R ₂ and Rs, independently of one another, phenyl or naphthyl, Z the sulfonic acid group and m 2 or preferably 3 means.

Particularly interesting compounds correspond to the formulas, for example

The compounds used in the process according to the invention are either in the form of the free acid or preferably as their salts. Examples of suitable salts are the alkali metal, alkaline earth metal or ammonium salts or the salts of an organic amine. Examples include the sodium, potassium or ammonium salts or the salt of triethanolamine.

The water-soluble, fiber-affine, colorless organic compounds used in the process according to the invention are known per se and can be prepared by methods known per se.

A preferred embodiment of the process according to the invention is characterized in that at least one water-soluble reactive dye of the formula
D- (X) q (25),
where D is the rest of an organic dye, for example the monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, nitroaryl, dioxazine, phenazine or stilbene series, X is a fiber-reactive radical of the aliphatic, aromatic or heterocyclic series which is bonded directly or via a bridge member to the radical D and q = 1, 2, 3, 4, 5 or 6 is used.

In the process according to the invention, the reactive dyes of the formula (25) can contain up to six identical or different types of reactive radicals.

Fiber-reactive radicals X are to be understood as those which react with the hydroxyl groups of cellulose, the amino, carboxy, hydroxyl and thiol groups in wool and silk, or with the amino and possibly carboxy groups of synthetic polyamides to form covalent chemical bonds capital.

X is preferably a fiber-reactive radical of the aliphatic, aromatic or heterocyclic series which is bonded to the radical D directly or via a bridge member.

X is preferably directly or via an optionally monoalkylated amino group, such as, for example, -NH-, -N (CH ₃ ) -, -N (C ₂ Hs) - or -N (C ₃ H ₇ ) - or via a bridge member containing an amino group , for example phenylene bound to the radical D.

The fiber-reactive radicals X in formula (25) are, for example the following aliphatic or aromatic radicals into consideration:

Vinylsulfonyl-, β-chloroethylsulfonyl-, β-sulfatoethylsulfonyl-, acetoxy-ethylsulfonyl-, phosphonooxyethylsulfonyl-, β-thiosulfatoethylsulfonyl, N-methyl-N- (ß-sulfatoethylsulfonyl) -amino, acryloyl or trichloro as -CO-CCI = CH ₂ , -CO-CH = CH-CI, -CO-CCI = CHCI, -CO-CCI = CH-CH ₃ ; Mono-, di- or tribromoacryloyl such as -CO-CBr = CH ₂ , -COCBr = CHBr, -CO-CH = CH-Br, -CO-CBr = CH-CH ₃ ; and -CO-CCl = CH-COOH, -CO-CH = CCI-COOH, -CO-CBr = CH-COOH, -CO-CH = CBr-COOH; -CO-CCI = CCI- _COOH , -CO-CBr = CBr-COOH; Precursors of the acryloyl radical and the derivatives of the acryloyl radical such as β-chloro- or β-bromopropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl, 3-chloro-3-phenylsulfonylpropionyl, 2,3-dichloropropionyl, 2,3-dibromopropionyl; as well as 2-fluoro-2-chloro-3,3-difluorocyclobutane-2-carbonyl, 2,2,3,3-tetrafluorocyclobutane-carbonyl-1- or sulfonyl-1-, β- (2,2,3,3- Tetrafluorocyclobutyl-1) -acryloyl, a- or β-alkenyl or arylsulfonyl-acryloyl group such as a- or β-methylsulfonylacryloyl, propiolyl, chloroacetyl, bromoacetyl, 4- (ß-chloroethylsulfonyl) butyril, 4-vinylsulfonyl- butyryl, 5- (β-chloroethylsulfonyl) valeryl, 5-vinylsulfonylvaleryl, 6- (β-chloroethylsulfonyl) caproyl, 6-vinylsulfonylcaproyl; as well as 4-fluoro-3-nitro-benzoyl, 4-fluoro-3-nitrophenylsulfonyl, 4-fluoro-3-methyl-sulfonylbenzoyl, 4-fluoro-3-cyanobenzoyl, 2-fluoro-5-methylsulfonyl-benzoyl.

Furthermore, fiber-reactive radicals X of the heterocyclic series should be mentioned, such as, for example, 2,4-dichlorotriazinyl-6, mono-, di- or trihalopyrimidinyl radicals, such as 2,4-dichloropyrimidinyl-6, 2,4,5-trichloropyrimidinyl-6 -, 2,4-dichloro-5-nitro- or 5-methyl- or -5-carboxymethyl- or -5-carboxy- or -5-cyano- or -5-vinyl- or -5-sulfo- or -5 -mono-, -di or -trichloromethyl- or 5-methylsulfonylpyrimidinyl-6-, 2,5-dichloro-4-methylsulfonyl-pyrimidinyl-6-, 2-fluoro-4-pyrimidinyl-, 2,6-difluoro-4 -pyrimidinyl-, 2,6-difluoro-5-chloro-4-pyrimidinyl-, 2-fluoro-5,6-dichloro-4-pyrimidinyl-, 2,6-difluoro-5-methyl-4-pyrimidinyl-, 2nd , 5-difluoro-6-methyl-4-pyrimidinyl-, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl-, 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl-, 5- Bromine-2-fluoro-4-pyrimidinyl-, 2-fluoro-5-cyan-4-pyrimidinyl-, 2-fluoro-5-methyl-4-pyrimidinyl-, 2,5,6-trifluoro-4-pyrimidinyl-, 5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl-, 2,6-difluoro-5-bromo-4-pyrimidinyl-, 2-fluoro-5-bromo-6-chloro-methyl-4-pyrimidinyl- , 2,6-dif uor-5-chloromethyl-4-pyrimidinyl, 2,6-difluoro-5-nitro-4-pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-6-methyl -4-pyrimidinyl-, 2-fluoro-5-chloro-4-pyrimidinyl-, 2-fluoro-6-chloro-4-pyrimidinyl-, 6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl-, 6 -Trifluoromethyl-2-fluoro-4-pyrimidinyl-, 6-trifluoromethyl-2-fluoro-4-pyrimidinyl-, 2-fluoro-5-nitro-4-pyrimidinyl-, 2-fluoro-5-trifluoromethyl-4-pyrimidinyl- , 2-fluoro-5-phenyl- or 5-methylsulfonyl-4-pyrimidinyl-, 2-fluoro-5-carbonamido-4-pyrimidinyl-, 2-fluoro-5-carbomethoxy-4-pyrimidinyl-, 2-fluoro-5 -bromo-6-trifluoromethyl-4-pyrimidinyl-, 2-fluoro-6-carbonamido-4-pyrimidinyl-, 2-fluoro-6-carbomethoxy-4-pyrimidinyl-, 2-fluoro-6-phenyl-4- pyrimidinyl, 2-fluoro-6-cyano-4-pyrimidinyl, 2,6-difluoro-5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-sulfonamido-4-pyrimidinyl, 2-fluoro-5- chloro-6-carbomethoxy-4-pyrimidinyl-, 2,6-difluoro-5-trifluoromethyl-4-pyrimidinyl; 2,4-bis-methylsulfonyl-pyrimidinyl-4-, 2,5-bis-methyl-sulfonyl-5-chloro-pyrimidinyl-4-, 2-methylsulfonyl-pyrimidinyl-4-, 2-phenylsulfonyl-pyrimidinyl-4-, 2- Methylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-bromo-6-methylpyrimidinyl-4-, 2-methylsulfonyl-5-chloro-6-ethyl-pyrimidinyl-4-, 2-methylsulfonyl -5-chloro-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5 nitro-6-methyl-pyrimidinyl-4-, 2,5,6-tris-methylsulfonylf-pyrimidinyl-4-, 2-methylsulfonyl-5 , 6-dimethyl-pyrimidinyl-4-, 2-ethylsulfonyl-5-chloro-6-methylpyrimidinyl-4-, 2-methylsulfonyl-6-chloropyrimidinyl-4-, 2,6-bis-methylisulfonyl-5-chloro pyrimidinyl-4-, 2-methylfutfonyf-6-carboxypyrimidinyl-4-, 2-methylsulfonyl-5-sutfopyrimidinyl-4-, 2-methylsulfonyl-6-carbomethoxypyrimidinyl-4-, 2-methylsulfonyl-5- carboxypyrimidinyl-4-, 2-methylsulfonyl-5-cyan-6-methoxypyrimidinyl-4-, 2-methylsulfonyl-5-chloropyrimidinyl-4-, 2-sulfoethylsulfonyl-6-methylpyrimidinyl-4-, 2- Methylsulfonyl-5-bromo-pyrimidinyl-4-, 2-phenylsulfonyl-5-chloropy rimidinyl-4-, 2-carboxymethylsulfonyl-5-chloro-6-methyf-pyrimidinyt-4-, 2,4-dichloropyrimidine-6-carbonyl or 6-sulfonyl, 2,4-dichloropyrimidine-5-carbonyl- or 5-sulfonyl , 2-chloro-4-methylpyrimidine-5-carbonyl, 2-methyl-4-chforpyrimidine-5-carbonyl, 2-methylt-hio-4-fluoropyrimidine-5-carbonyl, 6-methyl-2,4-dichloropyrimidine-5 -carbonyl, 2,4,6-trichtoropyrimidine-5-carbonyl, 2,4-dichloropyrimidine-5-sulfonyl, 2,4-dichloro-6-methyl-pyrimidine-5-carbonyl or 5-sulfonyl, 2-methylsulfonyl-6 -chloropyrimidine-4- and 5-carbonyl, 2,6-bis- (methylsulfonyl) -pyrimidine-4- or -5-carbonyl, 2-ethylsulfonyl-6-chloropyrimidine-5-carbonyl, 2,4-bis- (mefhytsutfonyl ) -pyrimidine-5-sulfonyte, 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine-5-sulfonyl- or -5-carbonyl, 2-chloroquinoxaline-3-carbonyl, 2- or 3-monochloroquinoxaline-6-carbonyl , 2- or 3-monochloroquinoxaline-6-sulfonyl, 2,3-dichloroquinoxaline-5- or -6-carbonyl, 2,3-dichloroquinoxaline-5- or -5-sulfonyl, 1,4-dichlorophthalazine-6- sulfonyl- or -6-carbonyl, 2,4-dichlo rchinazoline-7- or -6-sulfonyl- or -carbonyl, 2,4,6-trichloroquinazoline-7- or -8-sulfonyl, 2- or 3- or 4- (4 ', 5'-dichloropyridazone-6 '-yl-1') - phenylsulfonyf- or -carbonyl, β- (4 ', 5'-dichloropyridazinon-6'-yl-1') - propionyt, 3,6-dichloropyridazin-4-carbonyl or 4- sulfonyl, 2-chlorobenzthiazole-5- or 6-carbonyl- or -5- or -6-sulfonyl, 2-arylsulfonyl- or -alkylsulfonylbenzthiazole-5- or -6-carbonyl- or -5- or -6-sulfonyl, such as 2-Methylsulfonyl- or 2-ethylsulfonylbenzthiazole-5- or -6-sulfonyl- or -carbonyl, 2-phenylsulfonyl-benzothiazole-5- or -6-sulfonyl- or -carbonyl and the corresponding 2-sulfonylbenzothiazole containing sulfo groups in the fused benzene ring -5- or -6-carbonyl- or -sulfonyl-derivatives, 2-chlorobenzoxazole-5- or -6-carbonyl-or -sulfonyl, 2-chlorobenzimidazole-5- or -6-carbonyl- or -sulfonyl, 2-chlorine -i-methylbenzimidazot-5- or -6-carbonyl- or -sulfonyl, 2-chloro-4-methylthiazole- (1,3) -5-carbonyl) or -4- or -5-sulfonyl; triazine rings containing ammonium groups, such as 2-trimethylammonium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -amino-triazinyl-6-, 2- (1,1-dimethylhydrazinium) -4-phenylamino- or -4- (o-, m- or p-sulfophenyl) aminotriazinyl-6-, 2- (2-isopropylidene-1,1-dimethyl) hydrazinium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6-, 2-N-aminopyrrolidinium- or 2-N-aminopiperidinium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6- , furthermore 4-phenylamino or 4- (sulfophenylamino) triazinyl-6 radicals which, in the 2-position, the 1,4-bis-aza-bicyclo [2,2,2] octane or the 1, via a nitrogen bond, Contain 2-bis-aza-bicyclo- [0,3,3] octane bound in a quaternary manner, 2-pyridinium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -amino-triazinyl-6 - And corresponding 2-oniumtriazinyt-6 radicals, which are in the 4-position by alkylamino, such as methylamino, ethylamino or β-hydroxyethylamino, or alkoxy, such as methoxy or ethoxy, or aryloxy, such as phenoxy -, or sulfophenoxy Gr groups are substituted.

wobei als Substituenten Q₁ am Triazinring insbesondere zu nennen sind:

• -NH₂, Alkylamino, N,N-Dialkylamino-, Cycloalkylamino-, N,N-Dicycloalkylamino-, Aralkylamino-, Arylaminogruppen, gemischt substituierte Aminogruppen, wie N-Alkyl-N-cyclohexylamino- und N-Alkyl-N-arylaminogruppen, ferner Aminogruppen, die heterocyclische Reste enthalten, welche weitere ankondensierte carbocyclische Ringe aufweisen können, und Aminogruppen, worin das Aminostickstoffatom Glied eines N-heterocyclischen Ringes ist, der gegebenenfalls weitere Heteroatome enthält, sowie Hydrazino und Semicarbazido. Die oben genannten Alkylreste können geradkettig oder verzweigt, niedrigmolekular oder höhermolekular sein, bevorzugt sind Alkylreste mit 1 bis 6 Kohlenstoffatomen; als Cycloalkyl-, Aralkyl- und Arylreste kommen insbesondere Cyclohexyl-, Benzyl-, Phenäthyl-, Phenyl-und Naphthylreste in Frage; heterocyclische Reste sind vor allem Furan-, Thiophen-, Pyrazol-, Pyridin-, Pyrimidin-, Chinolin-, Benzimidazol-, Benzthiazol- und Benzoxazolreste; und als Aminogruppen, worin das Aminostickstoffatom Glied eines N-heterocyclischen Ringes ist, kommen vorzugsweise Reste von sechsgliedrigen N-heterocyclischen Verbindungen in Betracht, die als weitere Heteroatome Stickstoff, Sauerstoff oder Schwefel enthalten können. Die oben genannten Alkyl-, Cycloalkyl-, Aralkyl- und Arylreste, die heterocyclischen Reste sowie die N-heterocyclischen Ringe können weitersubstituiert sein, z.B. durch: Halogen, wie Fluor, Chlor und Brom, Nitro, Cyan, Trifluormethyl, Sulfamoyl, Carbamoyl, C₁-₄-Alkyl, C₁-4-Alkoxy, Acylaminogruppen, wie Acetylamino oder Benzoylamino, Ureido, Hydroxy, Carboxy, Sulfomethyl oder Sulfo. Als Beispiele für derartige Aminogruppen seien genannt: -NH₂, Methylamino, Aethylamino, Propylamino, Isopropylamino, Butylamino, Hexylamino, ß-Methoxyäthylamino, y-Methoxypropylamino, ß-Aethoxyäthylamino, N,N-Dimethylamino, N,N-Diäthylamino, β-Chloräthylamino, β-Cyanäthylamino, y-Cyanpropylamino, β-Carboxyäthylamino, Sulfomethylamino, β-Sulfoäthylamino, β-Hydroxyäthylamino, N,N-Di-ß-hydroxyäthylamino, y-Hydroxypropylamino, Benzylamino, Phenäthylamino, Cyclohexylamino, Phenylamino, Toluidino, Xylidino, Chloranilino, Anisidino, Phenetidino, N-Methyl-N-phenylamino, N-Aethyl-N-phenylamino, N-ß-Hydroxyäthyl-N-phenylamino, 2-, 3- oder 4-Sulfoanilino, 2,5-Disulfoanilino, 4-Sulfomethylanilino, N-Sulfomethylanilino, 2-, 3- oder 4-Carboxy phenylamino, 2-Carboxy-5-sulfophenylamino, 2-Carboxy-4-sulfophenylamino, 4-Sulfonaphthyl-(1)-amino, 3,6-Disulfonaphthyl-(1)-amino, 3,6,8-Trisulfonaphthyl-(1)-amino, 4,6,8-Trisulfonaphthyl-(1)-amino, 1-Sulfonaphthyl-(2)-amino, 1,5-Disulfonaphthyl-(2)-amino, 6-Sulfonaphthyl-(2)-amino, Morpholino, Piperidino, Piperazino, Hydrazino und Semicarbazido.

Particularly interesting fiber-reactive residues are fluorine or chloro-1,3,5-triazine residues of the formula

where the substituents Q ₁ on the triazine ring are in particular:

• -NH ₂ , alkylamino, N, N-dialkylamino, cycloalkylamino, N, N-dicycloalkylamino, aralkylamino, arylamino groups, mixed substituted amino groups, such as N-alkyl-N-cyclohexylamino and N-alkyl-N-arylamino groups, furthermore amino groups which contain heterocyclic radicals which may have further fused-on carbocyclic rings, and amino groups in which the amino nitrogen atom is a member of an N-heterocyclic ring which optionally contains further heteroatoms, and hydrazino and semicarbazido. The abovementioned alkyl radicals can be straight-chain or branched, low molecular weight or higher molecular weight; alkyl radicals having 1 to 6 carbon atoms are preferred; suitable cycloalkyl, aralkyl and aryl radicals are, in particular, cyclohexyl, benzyl, phenethyl, phenyl and naphthyl radicals; heterocyclic radicals are especially furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole and benzoxazole; and as amino groups in which the amino nitrogen atom is a member of an N-heterocyclic ring, preference is given to residues of six-membered N-heterocyclic compounds which may contain nitrogen, oxygen or sulfur as further heteroatoms. The above-mentioned alkyl, cycloalkyl, aralkyl and aryl radicals, the heterocyclic radicals and the N-heterocyclic rings can be further substituted, for example by: halogen, such as fluorine, chlorine and bromine, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C. _1-4 alkyl, C ₁ -4 alkoxy, acylamino groups such as acetylamino or benzoylamino, ureido, hydroxyl, carboxyl, sulfomethyl or sulfo. Examples of such amino groups are: -NH ₂ , methylamino, ethylamino, propylamino, isopropylamino, butylamino, hexylamino, ß-methoxyethylamino, y-methoxypropylamino, ß-ethoxyethylamino, N, N-dimethylamino, N, N- Diethylamino, β-chloroethylamino, β-cyanoethylamino, y-cyanopropylamino, β-carboxyethylamino, sulfomethylamino, β-sulfoethylamino, β-hydroxyethylamino, N, N-di-ß-hydroxyethylamino, y-hydroxypropylamino, benzylamino, phenoethylamino, phenoethylamino Toluidino, xylidino, chloranilino, anisidino, phenetidino, N-methyl-N-phenylamino, N-ethyl-N-phenylamino, N-ß-hydroxyethyl-N-phenylamino, 2-, 3- or 4-sulfoanilino, 2,5- Disulfoanilino, 4-sulfomethylanilino, N-sulfomethylanilino, 2-, 3- or 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino, 4-sulfonaphthyl- (1) -amino, 3.6 -Disulfonaphthyl- (1) -amino, 3,6,8-trisulfonaphthyl- (1) -amino, 4,6,8-trisulfonaphthyl- (1) -amino, 1-sulfonaphthyl- (2) -amino, 1,5 -Disulfonaphthyl- (2) -amino, 6-sulfonaphthyl- (2) -amino, morpholino, piperidino, piperazino, hydrazino and semicarbazido.

verwendet, worin D der Rest eines Monazo-, Disazo-, Metallkomplexazo-, Anthrachinon-, Formazan- oder Dioxazinfarbstoffes, Ka ein Kation und n = 1, 2, 3, 4, 5, oder 6 ist, und X und q die unter Formel (25) angegebenen Bedeutungen haben. Insbesondere ist q = 1 oder 2 und unabhängig davon n = 2, 3 oder 4.Water-soluble reactive dyes of the formula are preferably used in the process according to the invention

used, wherein D is the residue of a monazo, disazo, metal complex azo, anthraquinone, formazan or dioxazine dye, Ka is a cation and n = 1, 2, 3, 4, 5, or 6, and X and q are the under Formula (25) have the meanings given. In particular, q = 1 or 2 and independently of it n = 2, 3 or 4.

The cation Ka in formula (26) means e.g. a hydrogen, sodium, potassium, lithium or ammonium ion or the cation of an organic amine, e.g. of triethanolamine.

Suitable water-soluble reactive dyes of the formula (26) are the dye residues D given under formula (25) which contain one to six, in particular up to two, reactive residues X.

The reactive dyes of the formula (25) or (26) can contain up to six identical or different reactive groups.

The reactive dyes of the formula (25) or (26) preferably contain highly reactive radicals X. These are radicals X which are more reactive than the 2-chloro-1,3,5-triazinyl radicals which are in the 4-position by one of the above mentioned substituents Q _{1 are} substituted. Examples of such highly reactive radicals X are, for example: 2-fluoro-4- (Q ₁ ) -triazinyl-6-, where the substituents given above for Q ₁ are suitable, 2,4-dichlorotriazinyl-6-, 2, 4-dichloropyrimidine-5-carbonyl-, 5-cyano- or 5-methylsulfonyl-2,4-dichloropyrimidinyl-6-, difluorochloropyrimidinyl-, such as 2,4-difluoro-5-chloropyrimidinyl-6-, 2,3-dichloroquinoxaline 6-carbonyl, vinylsulfonyl, β-sulfatoethylsulfonyl, β-chloroethylsulfonyl, β-thiosulfato-ethylsulfonyl, β-acetoxyethylsulfonyl.

bedeutet, worin R Wasserstoff oder Ci-4-Alkyl, wie z.B. Methyl, Aethyl, Propyl, Isopropyl, Butyl, sek.-Butyl, Isobutyl oder tert.-Butyl, und Q₂ eine gegebenenfalls substituierte Aminogruppe ist, einen über einen Phenylendiaminrest gebundenen Difluorchlorpyrimidinylrest oder einen direkt oder über ein aromatisches oder aliphatisches Brückenglied gebundenen Vinylsulfonyl-, β-Sulfatoäthylsulfonyl-, β-Thiosulfatoäthylsulfonyl-, ß-Chloräthylsulfonyl-oder β-Acetoxyäthylsulfonylrest bedeutet.Reactive dyes of the formula (26) in which X is a radical of the formula are particularly preferably used in the process according to the invention

means in which R is hydrogen or Ci-4-alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl or tert-butyl, and Q _{2 is} an optionally substituted amino group, a bonded via a phenylenediamine radical Difluorochloropyrimidinylrest or means a vinylsulfonyl, β-sulfatoethylsulfonyl, β-thiosulfatoethylsulfonyl, β-chloroethylsulfonyl or β-acetoxyethylsulfonyl radical bonded directly or via an aromatic or aliphatic bridge member.

• 1. Monoazoverbindungen der Formel
  
  worin Di einen Rest der Benzol- oder Naphthalinreihe bedeutet, wie z.B. den Phenyl-, Naphthyl-, Stilben-, Diphenyl-, Benzthiazolylphenyl- oder Diphenylaminrest, der durch Sulfogruppen, Halogen, wie z.B. Chlor, Acylaminogruppen, wie z.B. Acetylamino oder Benzoylamino, Aminogruppen, wie z.B. -NH₂ und Methylamino, Alkoxy, wie z.B. Methoxy, Hydroxy oder Carboxy sowie faserreaktive Reste X substituiert sein kann, X vorzugsweise direkt oder über eine Aminogruppe, wie z.B. -NH₂ oder -NHCH₃, an die 5-, 6-, 7- oder 8-Stellung des Naphthalinkerns gebunden ist und X die unter Formel (25) angegebene Bedeutung hat.
• 2. Disazoverbindungen der Formel (28), worin D₁ einen Rest der Azobenzol-, Azonaphthalin- oder Phenylazonaphthalinreihe bedeutet und Di und der Naphthalinkem, wie in Klasse 1 angegeben, substituiert sein können.
• 3. Disazoverbindungen der Formel
  
  worin mindestens ein X vorhanden ist und X die unter Formel (25) angegebene Bedeutung hat und D₂ und D₃, unabhängig voneinander, die für D₁ unter Formel (28) angegebenen Bedeutungen haben.
• 4. Monoazoverbindungen der Formel
  
  worin Di einen unter Formel (28) angegebenen Rest, insbesondere einen Disulfonaphthyl- oder Stilbenrest bedeutet und X die unter Formel (25) angegebene Bedeutung hat und der Benzolkem weitere Substituenten, wie z.B. Halogenatome oder Alkyl-, Alkoxy-, Carbonsäure-, Ureido- oder Acylaminogruppen enthalten kann.
• 5. Mono- oder Disazoverbindungen der Formel
  X-D₄-N=N-K₁ (31),
  worin D₄ einen Rest der Azobenzol-, Azonaphthalin- oder Phenylazonaphthalinreihe oder vorzugsweise einen Rest der Benzol- oder Naphthalinreihe, der durch die für Di unter Formel (28) angegebenen Substituenten substituiert sein kann, bedeutet und K₁ den Rest einer Naphtholsulfonsäure oder den Rest einer Ketomethylenverbindung, wie z.B. ein Acetoacetarylid, insbesondere Acetoacetanilid oder eines 5-Pyrazolons, insbesondere 1-Phenyl-3-methyl-5-pyrazolon, mit der OH-Gruppe in Nachbarstellung zur Azogruppe bedeutet und X direkt oder über eine Aminogruppe, wie z.B. -NH₂, Methylamino oder Benzoylamino an D₄ gebunden ist. Vorzugsweise bedeutet D₄ einen Rest der Benzolreihe, der eine Sulfonsäuregruppe enthält. X hat die unter Formel (25) angegebene Bedeutung.
• 6. Mono- oder Disazoverbindungen der Formel
  D₁-N=N-K₂-X (32),
  worin D₁ einen der für D₁ in den Klassen 1. und 2. oben definierten Reste und K₂ den Rest einer enolisierbaren Ketomethylenverbindung, wie z.B. ein Acetoacetarylid, insbesondere Acetoacetanilid oder ein 5-Pyrazolon, insbesondere 1-Phenyl-3-methyl-5-pyrazolon, mit der OH-Gruppe in Nachbarstellung zur Azogruppe bedeuten und X die in den Klassen 1. bis 5. angegebene Bedeutung hat.
• 7. Metallkomplexverbindungen, wie z.B. Kupfer-, Chrom- oder Kobaltkomplexe, der Farbstoffe der Formeln (28) bis (32), worin D₁ bis D₄, Ki und K₂ die angegebenen Bedeutungen haben und ferner eine metallisierbare Gruppe, wie z.B. eine Hydroxyl-, Methoxy- oder Carbonsäuregruppe, in Nachbarstellung zur Azogruppe enthalten.
• 8. Anthrachinonverbindungen, welche den Rest X an einer Alkylamino-oder Arylaminogruppe, die selbst an die a-Stellung des Anthrachinonkems gebunden ist, enthalten, insbesondere Anthrachinonverbindungen der Formel
  
  worin R₁ Wasserstoff, Alkyl oder Aryl, insbesondere Phenyl, und M ein Brückenglied bedeutet, welches vorwiegend ein zweiwertiger Rest der Benzolreihe ist, wie z.B. ein Phenylen-, Diphenylen-, 4,4'-Stilben-oder Azobenzolrest. Vorzugsweise sollte das Brückenglied M eine Sulfonsäuregruppe für jeden vorliegenden Benzolring enthalten. Der Anthrachinonkem kann zusätzlich eine Sulfonsäuregruppe in der 5-,6-,7- oder 8-Stellung enthalten. Der Rest X ist direkt oder über eine Aminogruppe an M gebunden und hat die unter Formel (25) angegebene Bedeutung.
• 9. Phthalocyaninverbindungen der Formel
  
  worin Pc einen Phthalocyaninkern, vorzugsweise Kupferphthalocyanin, Wi = -OH und/oder -NH₂, M₁ ein Brückenglied, vorzugsweise eine aliphatische, cycloaliphatische oder aromatische Brücke bedeuten, und o und p jedes 1, 2 oder 3 bedeuten und gleich oder verschieden sein können, vorausgesetzt, dass o + p nicht grösser als 4 ist. Vorzugsweise enthalten die Phthalocyaninverbindungen eine wasserlöslichmachende Gruppe, wie z.B. eine Sulfonsäuregruppe, und eine Gruppe -Mi-N(R)-X, worin R Wasserstoff oder Alkyl ist und X die unter Formel (25) angegebene Bedeutung hat.
• 10. Nitrofarbstoffe der Formel
  
  worin D_s ein Naphthalinkern oder Benzolkern, welcher weitersubstituiert sein kann, ist, das Stickstoffatom N in o-Stellung zur Nitrogruppe steht, Zi Wasserstoff oder einen gegebenenfalls substituierten Kohlenwasserstoffrest und T Wasserstoff oder einen an den Stickstoff durch ein Kohlenstoffatom gebundenen organischen Rest bedeutet, und worin T und Zi nicht beide Wasserstoff sind, oder T an Zi, wenn Zi ein Kohlenwasserstoffrest ist, oder an Ds in ortho-Stellung zum Stickstoffatom N, jeweils unter Bildung eines heterocyclischen Ringes gebunden sein kann, und welche wenigstens einen Rest X, insbesondere einen Rest -N(R)-X, worin R Wasserstoff oder Alkyl ist und X die unter Formel (25) angegebene Bedeutung hat enthalten; insbesondere Nitrofarbstoffe der Formel N0₂-V_I-NH-B-N(R)-X (36)
  worin V_i und B monocyclische Arylkerne bedeuten und die Nitrogruppe in Vi in o-Stellung zur -NH Gruppe steht.
• 11. Metallkomplexe von Formazanfarbstoffen der Formel
  
  worin Y ein organischer Rest, eine Nitro- oder Cyanogruppe ist, A und B Reste von Diazokomponenten der Benzol-, Naphthalin- oder heterocyclischen Reihe und Y₁ und Y₂ je einen in o-Stellung zur Azogruppe gebundenen, zur Komplexbildung mit einem Schwermetall befähigten Substituenten bedeuten und X die unter Formel (25) angegebene Bedeutung hat und q = 1 oder 2 ist.
  Der Rest Y ist vor allem ein Rest der Benzolreihe, wie z.B. Phenyl oder Sulfophenyl, oder ein Alkylrest, wie z.B. Methyl, eine niedrigmolekulare Alkanoylgruppe, wie z.B. Acetyl, eine Carbalkoxygruppe mit bis zu 4 Kohlenstoffatomen, eine Benzoylgruppe oder ein heterocyclischer Rest, und A und B sind vorzugsweise mit Sulfo-, Sulfonamido- oder Alkylsulfonylgruppen substituierte Phenylreste. Yi und Y₂ sind vor allem OH- und COOH-Gruppen. Geeignete Schwermetalle sind Kupfer, Chrom, Kobalt und Nickel.
• 12. Dioxazine der Formel
  
  worin Rio Ci-₄-Alkyl, wie z.B. Methyl, oder Halogen wie z.B. Chlor ist und X die unter formel (25) angegebene Bedeutung hat.

The reactive dyes of the formula (25) or (26) are derived in particular from the following dyes:

• 1. Monoazo compounds of the formula
  
  wherein Di is a residue of the benzene or naphthalene series, such as, for example, the phenyl, naphthyl, stilbene, diphenyl, benzthiazolylphenyl or diphenylamine residue, which is replaced by sulfo groups, halogen, such as chlorine, acylamino groups, such as acetylamino or benzoylamino, amino groups , such as -NH ₂ and methylamino, alkoxy, such as methoxy, hydroxy or carboxy, and fiber-reactive radicals X can be substituted, X preferably directly or via an amino group, such as -NH ₂ or -NHCH ₃ , to the 5-, 6th -, 7- or 8-position of the naphthalene nucleus and X has the meaning given under formula (25).
• 2. Disazo compounds of formula (28), wherein D _{1 is} a radical of the azobenzene, azonaphthalene or Phenylazonaphthalene series means and Di and the naphthalene core, as indicated in class 1, can be substituted.
• 3. Disazo compounds of the formula
  
  wherein at least one X is present and X has the meaning given under formula (25) and D ₂ and D ₃ , independently of one another, have the meanings given for D ₁ under formula (28).
• 4. Monoazo compounds of the formula
  
  in which Di is a radical indicated under formula (28), in particular a disulfonaphthyl or stilbene radical and X has the meaning given under formula (25) and the benzene nucleus has further substituents, such as halogen atoms or alkyl, alkoxy, carboxylic acid, ureido, or may contain acylamino groups.
• 5. Mono- or disazo compounds of the formula
  XD ₄ -N = NK ₁ (31),
  wherein D _{4 is} a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series or preferably a radical of the benzene or naphthalene series, which may be substituted by the substituents indicated for Di under formula (28), and K _{1 is} the radical of a naphtholsulfonic acid or the radical a ketomethylene compound, such as, for example, an acetoacetarylide, in particular acetoacetanilide or a 5-pyrazolone, in particular 1-phenyl-3-methyl-5-pyrazolone, with the OH group adjacent to the azo group and X denotes directly or via an amino group, such as, for example, NH ₂ , methylamino or benzoylamino is bound to D ₄ . D ₄ preferably denotes a residue of the benzene series which contains a sulfonic acid group. X has the meaning given under formula (25).
• 6. Mono- or disazo compounds of the formula
  D ₁ -N = NK ₂ -X (32),
  wherein D _{1 is} one of the radicals defined above for D ₁ in classes 1. and 2. and K _{2 is} the radical of an enolizable ketomethylene compound, such as, for example, an acetoacetarylide, in particular acetoacetanilide or a 5-pyrazolone, in particular 1-phenyl-3-methyl 5-pyrazolone, with the OH group adjacent to the azo group and X has the meaning given in classes 1 to 5.
• 7. Metal complex compounds, such as copper, chromium or cobalt complexes, the dyes of the formulas (28) to (32), in which D ₁ to D ₄ , Ki and K _{2 have} the meanings given and also a metallizable group, such as a Hydroxyl, methoxy or carboxylic acid group, adjacent to the azo group.
• 8. Anthraquinone compounds which contain the radical X on an alkylamino or arylamino group which is itself bound to the a position of the anthraquinone nucleus, in particular anthraquinone compounds of the formula
  
  wherein R _{1 is} hydrogen, alkyl or aryl, especially phenyl, and M is a bridge member which is predominantly a divalent radical of the benzene series, such as a phenylene, diphenylene, 4,4'-stilbene or azobenzene radical. Preferably, the bridge member M should contain a sulfonic acid group for each benzene ring present. The anthraquinone nucleus can additionally contain a sulfonic acid group in the 5-, 6-, 7- or 8-position. The radical X is bonded to M directly or via an amino group and has the meaning given under formula (25).
• 9. Phthalocyanine compounds of the formula
  
  wherein Pc is a phthalocyanine nucleus, preferably copper phthalocyanine, Wi = -OH and / or -NH ₂ , M _{1 is} a bridge member, preferably an aliphatic, cycloaliphatic or aromatic bridge, and o and p are each 1, 2 or 3 and are the same or different can, provided that o + p is not greater than 4. The phthalocyanine compounds preferably contain a water-solubilizing group, such as a sulfonic acid group, and a group -Mi-N (R) -X, where R is hydrogen or alkyl and X has the meaning given under formula (25).
• 10. Nitro dyes of the formula
  
  wherein D _{s is} a naphthalene nucleus or benzene nucleus, which may be further substituted, the nitrogen atom N is in the o-position to the nitro group, Zi is hydrogen or an optionally substituted hydrocarbon radical and T is hydrogen or an organic radical bonded to the nitrogen by a carbon atom, and wherein T and Zi are not both hydrogen, or T can be bound to Zi if Zi is a hydrocarbon radical, or to Ds ortho to the nitrogen atom N, in each case to form a heterocyclic ring, and which have at least one radical X, in particular one Radical -N (R) -X, where R is hydrogen or alkyl and X has the meaning given under formula (25); especially nitro dyes of the formula N0 ₂ -V _I -NH-BN (R) -X (36)
  where V _i and B are monocyclic aryl nuclei and the nitro group in Vi is in the o-position to the -NH group.
• 11. Metal complexes of formazan dyes of the formula
  
  wherein Y is an organic radical, a nitro or cyano group, A and B are residues of diazo components of the benzene, naphthalene or heterocyclic series and Y ₁ and Y ₂ each have an o-position to the azo group and are capable of complexing with a heavy metal Mean substituents and X has the meaning given under formula (25) and q = 1 or 2.
  The radical Y is above all a radical of the benzene series, such as phenyl or sulfophenyl, or an alkyl radical, such as methyl, a low molecular weight alkanoyl group such as acetyl, a carbalkoxy group with up to 4 carbon atoms, a benzoyl group or a heterocyclic radical, and A and B are preferably phenyl radicals substituted by sulfo, sulfonamido or alkylsulfonyl groups. Yi and Y ₂ are mainly OH and COOH groups. Suitable heavy metals are copper, chromium, cobalt and nickel.
• 12. Dioxazines of the formula
  
  wherein Rio is Ci- ₄ alkyl, such as methyl, or halogen such as chlorine and X has the meaning given under formula (25).

• a) mindestens 2 oder 3 Reaktivfarbstoffe der Formel (25) verwendet.
• b) zum Trichromiefärben mindestens einen gelb- oder orangefärbenden Reaktivfarbstoff, mindestens einen rotfärbenden Reaktivfarbstoff und mindestens einen blaufärbenden Reaktivfarbstoff verwendet.
• c) reine Cellulosefasern färbt.
• d) Polyester/Cellulose-Mischfasern färbt.
• e) kontinuierlich färbt.
• f) reine Cellulosefasern mit Reaktivfarbstoffen färbt und diese mit Dampf bei einer Temperatur von 100° C bis 150° C während 30 Sekunden bis 12 Minuten fixiert.
• g) die fixierten Färbungen mit heissem und/oder kaltem Wasser gegebenenfalls in Gegenwart eines Waschmittels spült.

Preferred embodiments of the method according to the invention are characterized in that

• a) at least 2 or 3 reactive dyes of the formula (25) are used.
• b) used for trichromatic dyeing at least one yellow or orange-dyeing reactive dye, at least one red-dyeing reactive dye and at least one blue-dyeing reactive dye.
• c) colors pure cellulose fibers.
• d) Polyester / cellulose mixed fibers dye.
• e) colors continuously.
• f) dyes pure cellulose fibers with reactive dyes and fixes them with steam at a temperature of 100 ° C to 150 ° C for 30 seconds to 12 minutes.
• g) the fixed dyeings are rinsed with hot and / or cold water, if appropriate in the presence of a detergent.

The dye liquor can also contain alkaline compounds for fixing the reactive dyes, for example sodium carbonate, sodium bicarbonate, sodium hydroxide, disodium phosphate, trinatri umphosphate, borax, aqueous ammonia or alkali donors, such as sodium trichloroacetate. In particular, a mixture of water glass and a 30% aqueous sodium hydroxide solution has proven itself very well as an alkali. The pH of the dye liquors containing alkali is generally 7.5 to 13.2, preferably 8.5 to 11.5.

The padding liquors are expediently prepared by dissolving the dye and by adding the water-soluble, fiber-affine, colorless organic compound and alkali. Depending on the dye used, the dyeing liquors can contain other conventional additives, e.g. Electrolytes, e.g. Sodium chloride or sodium sulfate as well as urea, glycerin and / or sodium formate. If necessary, thickeners such as e.g. Alginates, starch ether or locust bean gum may be contained therein.

It has proven to be advantageous in many cases to add commercially available alkali-resistant wetting agents, e.g. Sulfonates of polycarboxylic acid esters, e.g. Dihexyl sulfosuccinate or dioctyl sulfosuccinate; Straight chain or branched chain alkylarylsulfonates with at least 6 carbon atoms, e.g. Dodecylbenzenesulfonates or preferably alkylsulfonates whose alkyl chain contains 8 to 20 carbon atoms, e.g. Add dodecyl sulfonates or pentadecyl sulfonates. The sulfonates mentioned as wetting agents are generally present as alkali metal salts, in particular as sodium salts or also as ammonium salts.

The amounts in which the wetting agents are added to the padding liquor are more appropriately between 1 to 10 g, preferably 0.5 to 3 g, per liter of liquor.

The dye fixation on pure cellulose fibers is carried out by customary methods, the fixing time and fixing temperature depending on the fiber material and, in the case of reactive dyes, on the reactivity of the reactive dyes used. Steaming times in saturated steam between 30 seconds and 15 minutes at 100 to 105 ° C are generally sufficient to achieve a uniform and optimal dye fixation. High-temperature steaming or dry heat steaming is used to fix at 105-190 ° C for 20 seconds to 8 minutes. In particular, the reactive dyes are fixed with steam at a temperature of 100 ° C to 150 ° C for 30 seconds to 12 minutes. On mixed fabrics, such as Polyester / cellulose blended fabrics, the dyes containing at least one reactive dye are fixed at 100 to 200 ° C, the fixing time being in particular between 10 seconds and 10 minutes, preferably 150 ° C to 200 ° C. If necessary, the textile material is dried before fixing.

Furthermore, the fixation can also be carried out using the cold dwell process; such as. 6 to 12 hours residence time at room temperature.

After the dyeing process, the dyed cellulose material can be washed out in the usual way to remove unfixed dye. For this purpose, the substrate is treated, for example, at from 40 ° C. to cooking temperature in a solution which contains soap or synthetic detergent. Treatment with a fixative can then be carried out to improve wet fastness.

The dyeings are completed by rinsing in hot and / or cold water and, if appropriate, with subsequent washing in the presence of a commercially available detergent, followed by rinsing in water and drying.

Suitable cellulose fibers are natural fibers, such as mercerized or bleached cotton and linen (bleached), and regenerated fibers, such as viscose, polynosic and copper rayon. Mainly woven or knitted fabrics of these fibers are used.

The following examples serve to illustrate the invention. The parts are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius.

The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimeters. The amounts of dye given relate to commercially available dye.

• 0,62 g/I des orangefärbenden Farbstoffes der Formel
  
• 10 g/l Natriumsulfat, kalziniert,
• 1 g/l eines Netzmittels und
• 7,5 g/1 der Verbindung der Formel
  

Example 1: A bleached cotton cretonne fabric is impregnated with a padding liquor of the following composition on the foulard with a squeezing effect of 70% liquor absorption:

• 0.62 g / l of the orange dye of the formula
  
• 10 g / l sodium sulfate, calcined,
• 1 g / l of a wetting agent and
• 7.5 g / 1 of the compound of the formula
  

The dive time is 2 seconds. The affinity factor B _{1 of} the dye specified above in the padding liquor above is 1.05.

The affinity factor is determined spectrophotometrically (UVICON 810), the concentration of the padding liquor prior to impregnation and the concentration of the squeezed liquor being determined. The spectrophotometric measurement is carried out at the absorption maximum of the dye (λmax = 486 nm).

The affinity factor is defined as:

The affinity factor is a critical variable for the end inequality based on differences in affinity of the dyes. With a value approximating the ideal affinity factor of 1.0 of approx. 0.95 to 1.05, no end inequality is discernible.

The quantity stated for the water-soluble, fiber-affine, colorless organic compound and the numerical values for the affinity factor A relate to commercially available pure substances with an active substance content of at least 70%.

The affinity factor of the compound of formula (201) is determined as follows: A mercerized cotton fabric is impregnated with a liquor containing 10 g / l of Na ₂ SO ₄ and containing 0.3 g / l of the compound of formula (201). The affinity factor is determined spectrophotometrically (UVICON 810), the concentration of the liquor before impregnation and the concentration of the squeezed liquor (squeezing effect = 70% liquor absorption) being determined. The spectrophotometric measurement is carried out at λmax = 352 nm. The affinity factor A ₁ is 1.35.

After padding, the cotton cretonne fabric is dried at 100 ° for one minute, padded with a liquor containing 250 g / l NaCl and 10 ml / l 30% NaOH with a squeezing effect of about 80% and then for one minute fixed in saturated steam at 101 to 103 °.

The cotton cretonne fabric is then rinsed first with cold water and then with hot to boiling water, soaped at the boil with 1 to 2 g / l of a detergent, rinsed again with hot and then with cold water and then dried.

A cotton cretonne fabric dyed in the same orange color with good fastness properties is obtained.

Comparative Example 1: If the procedure described in Example 1 is followed, but a padding liquor is used without the compound of the formula (201), then a cotton cretonne fabric dyed differently in orange color is obtained, the beginning of the lot towards the end of the lot is colored darker because the squeezed liquor is depleted of dye and thus diluted. The affinity factor of the orange-colored dye from Example 1 in the padding liquor without the compound of the formula (201) is 1.23.

• 0,675 g/I des roten Farbstoffes der Formel
  
• 50 g/I Harnstoff,
• 20 g/l Natriumbikarbonat,
• 1 g/l eines Netzmittels und
• 7,2 g/l der Verbindung der Formel
  

Example 2: A bleached, mercerized cotton cretonne fabric is impregnated on the foulard with a squeezing effect of 70% liquor absorption with a padding liquor having the following composition:

• 0.675 g / l of the red dye of the formula
  
• 50 g / l urea,
• 20 g / l sodium bicarbonate,
• 1 g / l of a wetting agent and
• 7.2 g / l of the compound of the formula
  

The dive time is 2 seconds. The affinity factor of the dye given above in the padding liquor above, determined according to the information in Example 1 at λmax = 550 nm, is 1.04.

The affinity factor of the compound of the formula (202) is 1.54 under the standard conditions given in Example 1 at λmax = 328 nm.

The padded fabric is then dried on the hot flue at 100 ° for 1 minute and then heat set on the hot flue at 160 ° for 1 minute.

After rinsing, soaping, rinsing and drying according to the information in Example 1, a cotton cretonne fabric dyed in the same shade of red with good fastness properties is obtained.

Comparative Example 2: If the procedure described in Example 2 is followed, but a padding liquor is used without the compound of the formula (202), a cotton cretonne fabric dyed in different shades of red is obtained, the beginning of the lot compared to the end of the lot is colored much darker. The affinity factor of the red-coloring dye from Example 2 in the padding liquor without the compound of the formula (202) is 1.21; determined according to the information in Example 1.

• 0,5 g/I des gelbfärbenden Farbstoffes der Formel
  
• 0,15 g/l des rotfärbenden Farbstoffes der Formel (102)
• 0,12 g/l des blaufärbenden Farbstoffes der Formel
  
• 10 g/I Natriumsulfat kalziniert,
• 10 g/I Natriumbikarbonat,
• 50 g/I Harnstoff
• 1 g/I Netzmittel und
• 7 g/I der Verbindung der Formel

Example 3: A fabric made from leached cellulose cretonne is impregnated with a liquor of the following composition on the pad with a squeezing effect of 82% liquor absorption:

• 0.5 g / l of the yellowing dye of the formula
  
• 0.15 g / l of the red-coloring dye of the formula (102)
• 0.12 g / l of the blue-coloring dye of the formula
  
• 10 g / l calcined sodium sulfate,
• 10 g / l sodium bicarbonate,
• 50 g / l urea
• 1 g / l wetting agent and
• 7 g / l of the compound of the formula

Die Tauchzeit beträgt 4 Sekunden. Die Affinitätsfaktoren der oben angegebenen Farbstoffe in obiger Klotzflotte sind

• für den gelbfärbenden Farbstoff: 1,02 bei λmax = 425 nm
• für den rotfärbenden Farbstoff: 0,99 bei λmax = 550 nm
• für den blaufärbenden Farbstoff: 1,00 bei λmax = 600 nm
• gemäss den Angaben in Beispiel 1.

The dive time is 4 seconds. The affinity factors of the above dyes in the padding liquor above are

• for the yellowing dye: 1.02 at λmax = 425 nm
• for the red-coloring dye: 0.99 at λmax = 550 nm
• for the blue-coloring dye: 1.00 at λmax = 600 nm
• according to the information in Example 1.

The affinity factor of the compound of formula (203) is 1.49 [λmax = 330nm], determined according to Example 1.

After padding, the cellulose is steamed with saturated steam at 101 to 103 ° for one minute.

It is then rinsed, soaped, rinsed again and dried as indicated in Example 1.

A cellulosic cretonne fabric dyed in beige color with good fastness properties is obtained.

• für den gelbfärben Farbstoff: 1,13 bei λmax = 425 nm
• für den rotfärbenden Farbstoff: 1,11 bei λmax = 550 nm
• für den blaufärbenden Farbstoff: 1,19 bei λmax = 600 nm
• bestimmt gemäss den Angaben in Beispiel 1.

Comparative Example 3: If the procedure is as described in Example 3, but a padding liquor is used without the compound of the formula (203), a cellulosic cretonne fabric dyed in beige color is obtained. The affinity factors of the dyes used in the padding liquor without the compound of formula (203) are

• for the yellow colored dye: 1.13 at λmax = 425 nm
• for the red-coloring dye: 1.11 at λmax = 550 nm
• for the blue-coloring dye: 1.19 at λmax = 600 nm
• determined according to the information in Example 1.

• 0,6 g/I des blaufärbenden Farbstoffes der Formel
  
• 10 g/I Natriumchlorid,
• 1 g/I Netzmittel,
• 2 g/I Reduktionsschutzmittel (Natriumsalz der m-Nitrobenzolsulfonsäure)
• 7,5 g/l der Verbindung der Formel
  

Example 4: A bleached, mercerized cotton fabric is impregnated on the pad with a squeezing effect of 70% liquor absorption with a liquor of the following composition:

• 0.6 g / l of the blue-coloring dye of the formula
  
• 10 g / l sodium chloride,
• 1 g / l wetting agent,
• 2 g / l reducing agent (sodium salt of m-nitrobenzenesulfonic acid)
• 7.5 g / l of the compound of the formula
  

The dive time is 2 seconds. The affinity factor of the dye given above in the above liquor, determined according to the information in Example 1 at λmax = 625 nm, is 1.02.

The affinity factor of the compound of the formula (204) is 1.72 [λmax = 276 nm], measured in accordance with the conditions given in Example 1.

After padding, the cotton fabric is dried on the hot flue for one minute, padded with a liquor containing 250 g / l NaCl and 10 ml / l 30% NaOH with a squeezing effect of about 80% and then with saturated steam at 101 to 103 ° steamed for a minute.

It is then rinsed, soaped, rinsed again and then dried as indicated in Example 1.

A cotton fabric dyed in the same shade of blue with good fastness properties is obtained.

Comparative Example 4/1: If the procedure is as described in Example 4, but a padding liquor is used without the compound of the formula (204), a cotton fabric dyed in a different shade of blue is obtained. The affinity factor of the dye used in the padding liquor without the compound of the formula (204) is 1.40.

verwendet, bei einer Tauchzeit von 4 Sekunden, so ist der Affinitätsfaktor des oben angegebenen Farbstoffes in der obigen Färbeflotte 1,86 [λmax = 625 nm]. Wird eine Klotzflotte ohne die oben angegebene H-Säure verwendet, so erhält man einen Affinitätsfaktor von 1,90 [λmax = 625 nm].Comparative Example 4/2: If the procedure is as described in Example 4, but 0.3 g / l of the dye of the formula (105) and instead of 7.5 g / l of the compound of the formula (204) 3 g / l of the compound of the formula

used, with a dipping time of 4 seconds, the affinity factor of the above-mentioned dye in the above dyebath is 1.86 [λmax = 625 nm]. If a padding liquor without the H-acid specified above is used, an affinity factor of 1.90 [λmax = 625 nm] is obtained.

The affinity factor of H-acid in a block liquor containing 10 g / I Na ₂ S0 ₄ with 0.3 g / I H-acid is: 1.00.

A colorless, water-soluble, organic compound with an affinity factor of 1.0 used in the padding liquor has no influence on the affinity factor of the dye used and thus the end imbalance is not improved.

• 0,75 g/l des blaufärbenden Farbstoffes der Formel
  
• 1 g/l Netzmittel und
• 7 g/l der Verbindung der Formel
  

Example 5: A bleached, mercerized cotton cretonne fabric is continuously impregnated on the pad with a squeezing effect of 70% liquor absorption with a liquor of the following composition:

• 0.75 g / l of the blue-coloring dye of the formula
  
• 1 g / l wetting agent and
• 7 g / l of the compound of the formula
  

The dive time is 2 seconds. The affinity factor of the dye is 1.0 (determined according to Example 1 at λmax = 586 nm). The goods speed is 10 m / minute. The fabric is then fixed in a continuous steamer with saturated steam from 101 ° to 103 ° for 2 minutes. The fabric is then rinsed and dried several times. The affinity factor of the compound of formula (205) is 2.0 [λmax = 370 nm] determined according to Example 1.

A continuously dyed fabric with good fastness properties is obtained.

• 1,25 g/I des gelbfärbenden Farbstoffes der Formel
  
• 20 g/I Natriumkarbonat
• 50 g/I Harnstoff
• 1 g/I Netzmittel
• 7 g/I der Verbindung der Formel
  

Comparative Example 5: If the procedure is as described in Example 5, but a padding liquor is used without the compound of the formula (205), a piece of fabric colored differently blue is obtained. The affinity factor of the dye without the compound of formula (205) in the padding liquor is 1.11. Example 6: A polyester / cotton blend with a polyester content of 67% by weight is impregnated on the pad with a squeezing effect of 47% liquor absorption with a liquor of the following composition:

• 1.25 g / I of the yellowing dye of the formula
  
• 20 g / l sodium carbonate
• 50 g / l urea
• 1 g / l wetting agent
• 7 g / l of the compound of the formula
  

The dive time is 2 seconds. The affinity factor of the dye given above in the padding liquor above is 1.04 (λmax = 420 nm).

The affinity factor of the compound of formula (206) is 1.39 [λmax = 347 nm] determined according to Example 1.

The polyester / cotton blend is then dried at 100 ° for 1 minute and then thermosolated at 210 °.

After the washing, soaping and rinsing and drying given in Example 2, a piece of fabric of the same color, dyed in yellow, is obtained.

Comparative Example 6: If the procedure is as described in Example 6, but a padding liquor is used without the compound of the formula (206), a polyester / cotton blend fabric dyed yellow is obtained. The affinity factor of the dye without the compound of formula (206) in the padding liquor is 1.24.

• 0,425 g/I des gelbfärbenden Farbstoffes der Formel (103)
• 0,35 g/I des blaufärbenden Farbstoffes der Formel (105)
• 50 ml/l 30 %-iges Natronwasserglas
• 2 ml/l 30 %-ige Natronlauge
• 1 g/I Netzmittel
• 7 g/I der Verbindung der Formel
  

Example 7: Bleached, mercerized cotton jersey is impregnated on the foulard with a squeezing effect of 95% liquor absorption with a liquor of the following composition:

• 0.425 g / l of the yellowing dye of the formula (103)
• 0.35 g / l of the blue-coloring dye of the formula (105)
• 50 ml / l 30% sodium water glass
• 2 ml / l 30% sodium hydroxide solution
• 1 g / l wetting agent
• 7 g / l of the compound of the formula
  

• gelber Farbstoff: 1,05 λmax 425 nm
• blauer Farbstoff: 1,07 λmax 625 nm

The dive time is 2 seconds. The affinity factor of the dyes in the padding liquor specified above is:

• yellow dye: 1.05 λmax 425 nm
• blue dye: 1.07 λmax 625 nm

The affinity factor of the compound of the formula (207) is 1.47 [λmax = 275] determined according to Example 1.

The cotton jersey is then left to stand for 6 hours at room temperature with no air.

A piece of fabric dyed green with good fastness properties is obtained.

• gelber Farbstoff: 1,19 λmax 425 nm
• blauer Farbstoff: 1,25 λmax 625 nm

Comparative Example 7: If the procedure is as described in Example 7, but a padding liquor is used without the compound of the formula (207), a jersey piece which is colored differently in the end is obtained. The affinity factor without the compound of formula (207) in the padding liquor is:

• yellow dye: 1.19 λmax 425 nm
• blue dye: 1.25 λmax 625 nm

verwendet, so erhält man ebenfalls endengleiche Ausfärbungen.If the procedure is as described in Examples 1 to 7, but instead of the compounds of the formulas (201) to (207) in equimolar amounts, one of the compounds of the formulas (13), (14), (16), (17) or ( 18) in the form of sodium salt or a melamine compound of the formula

used, you also get the same colorations.

Claims (35)

1. A process for dyeing cellulose fibers or cellulose-containing mixed fibers with direct and / or reactive dyes according to the padding process, characterized in that an aqueous liquor is used which contains at least one direct or reactive dye and at least one water-soluble anionic, fiber-affine, colorless organic compound with an affinity factor A for mercerized cotton at a concentration of 0.2-0.3 grams per liter from 1.1 to 4, where factor A is the quotient of the concentration of the water-soluble, fiber-affine, colorless organic compound in a dye-free liquor before Impregnate to the concentration of the compound in the dye-free squeezed liquor. 2. The method according to claim 1, characterized in that direct or reactive dyes are used which have an affinity factor B for mercerized cotton at a concentration of 0.1 gram per liter of at least 1.1, the factor B being the quotient of the concentration of the dye in the original liquor without adding the colorless organic compound to the concentration of the dye in the squeezed liquor. 3. The method according to claim 1, characterized in that one uses an aqueous liquor, wherein the concentration of the dye together with the water-soluble, fiber-affine, colorless organic compound is a maximum of 20 grams per liter. 4. The method according to claim 3, characterized in that the concentration of the dye and the colorless compound together is a maximum of 10 grams per liter. 5. The method according to claim 4, characterized in that the concentration of the dye and the colorless compound together is 3 to 8 grams per liter. 6. The method according to claim 1, characterized in that the concentration of the dye is less than 5 grams per liter, in particular less than 3 grams per liter. 7. The method according to claim 1, characterized in that one uses a water-soluble anionic, fiber-affine, colorless organic compound with an affinity factor A of 1.15 to 2.5, in particular 1.2 to 1.6. 8. The method according to claim 1, characterized in that one uses a mixture (1) of at least one direct or reactive dye or their mixture together with (2) at least one water-soluble anionic, fiber-affine, colorless organic compound, the affinity factor B for the Dye in the mixture is 0.9 to 1.15, in particular 0.95 to 1.1. 9. The method according to claim 1, characterized in that one as a colorless organic compound (a) a compound of the formula

wherein Q = CH-R _x or = N- Rx is hydrogen, halogen, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkylsulfonyl, V and W, independently of one another, each R ₂ -X ₂ -, R ₃ -X ₃ -, hydroxy, C ₁ -C ₄ alkoxy or an unsubstituted or mono- or disubstituted amino group or substituted by a C ₁ -C ₄ alkyl radical, in which the alkyl radical is unsubstituted or substituted by hydroxy, cyano, sulfo or sulfato, R 1, R ₂ and R ₃ , independently of one another, each an aromatic or heteroaromatic radical, X ₁ , X ₂ and X ₃ , independently of one another, each

or
-NH-CO-Phen-NH- R _{4 is} hydrogen, C ₁ -C ₄ alkyl or phenyl, Phen is an unsubstituted or substituted phenylene group, Z is an acidic, water solubilizing group and m is 1 to 6, or b) a compound of the formula

where Ri, R ₂ , Z and m have the meaning given,
A the direct bond, -CO-, -CONH- or

means and the rings a and β are unsubstituted or substituted, or (c) a compound of the formula

wherein Rs and R ₆ , independently of one another, are each -NH ₂ , -NH-CO-R ₇ , -NO ₂ or

R _{7 is} C ₁ -C ₈ alkyl or aryl and V, W, Z and m have the meaning given above, or (d) a compound of the formula

wherein R _{8 is} hydrogen or R ₉ -CO- and R _{9 is} an aliphatic, aromatic or heterocyclic radical
the rings a and β are unsubstituted or substituted and Z and m have the meaning given above. 10. The method according to claim 9, characterized in that one uses a compound of formula (1) in which Q - N =. 11. The method according to any one of claims 9 and 10, characterized in that one uses a compound of formula (1) in which VR ₂ -X ₂ - and WR ₃ -X ₃ represent. 12. The method according to any one of claims 9 to 11, characterized in that in formula (1) Xi, X ₂ and Xs each mean -NH-. 13. The method according to any one of claims 9 to 12, characterized in that in formula (1) R 1, R ₂ and Rs each represent an aryl radical. 14. The method according to any one of claims 9 to 10, characterized in that V is hydroxyl and WR ₃ -X ₃ in formula (1). 15. The method according to claim 9, characterized in that in formula (3) Rs and R ₆ each the triazinyl radical

mean. 16. The method according to any one of claims 9 to 15, characterized in that m is 1 to 4 in the corresponding formulas. 17. The method according to any one of claims 9 to 16, characterized in that Z is the sulfonic acid group. 18. The method according to claim 9, characterized in that a colorless organic compound is a compound of the formula

used where R _{x is} hydrogen, halogen, cyano, Ci-C4-alkyl or C ₁ -C ₄ alkylsulfonyl R 1, R ₂ and Rs, independently of one another, each have a phenyl, biphenylyl, naphthyl, stilbenyl or quinolinyl residue which is unsubstituted or by C ₁ -C ₄ alkyl, halogen, trifluoromethyl, nitro, cyano, hydroxy, Ci C ₄ -alkoxy, amino, mono-C ₁ -C ₄ -alkylamino, di-C ₁ -C ₄ -alkylamino, phenylamino, C ₁ -C ₇ -acylamino, carbamoyl, ureido, sulfamoyl, C ₂ -Cs-alkoxycarbonyl, ci- C ₄ alkylsulfonyl or sulfomethyl is substituted, Xi, X ₂ and X ₃ , independently of each other, each -O-, -S-, - N -R ₄ or

where R _{4 is} hydrogen, C ₁ -C ₄ alkyl or phenyl and the benz ring a is unsubstituted or substituted by a substituent specified for R ₁ , Z is a carboxyl or sulfonic acid group and m is 2 to 6. 19. The method according to claim 9, characterized in that a colorless organic compound is a compound of the formula

used where R _{x is} hydrogen, halogen, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkylsulfonyl, V 'and W', independently of one another, are each hydroxyl, C ₁ -C ₄ -alkoxy or an unsubstituted or mono- or disubstituted amino group or substituted by a C ₁ -C ₄ -alkyl radical, the alkyl radical being unsubstituted or by hydroxyl, cyano, sulfo or Sulfato is substituted and V 'also the radical R ₂ -X ₂ -, R ₁ and R ₂ independently of one another, each a phenyl, biphenylyl, naphthyl, stilbenyl or quinolinyl radical which is unsubstituted or by C ₁ -C ₄ alkyl, halogen, trifluoromethyl, nitro, cyano, hydroxy, C ₁ -C ₄ -alkoxy, amino, mono-Ci-C ₄ -alkylamino, di-Ci-C ₄ -alkylamino, phenylamino, C ₁ -C ₇ -acylamino, carbamoyl, ureido, sulfamoyl, C ₂ -Cs-alkoxycarbonyl, C ₁ - C ₄ alkylsulfonyl or sulfomethyl is substituted, X ₁ and X ₂ , independently of one another, each -O-, -S-, - NR ₄ or

where R _{4 is} hydrogen, C ₁ -G ₄ alkyl or phenyl and the benz ring a is unsubstituted or substituted by a substituent specified for R ₁ , Z is a carboxyl or sulfonic acid group and m is 2 to 4. 20. The method according to claim 9, characterized in that a colorless organic compound is a compound of the formula

used where R 1, R ₂ and R ₃ , independently of one another, each have a phenyl, biphenylyl, naphthyl, stilbenyl or quinolinyl residue which is unsubstituted or by C 1 -C ₄ -alkyl, halogen, trifluoromethyl, nitro, cyano, hydroxy, Ci- C ₄ alkoxy, amino, mono-C _i -C ₄ alkylamino, di-C ₁ -C ₄ alkylamino, phenylamino, C ₁ -C ₇ acylamino, carbamoyl, ureido, sulfamoyl, C ₂ -C ₅ -AIKoxycarbonyl , C ₁ -C ₄ alkylsulfonyl or sulfomethyl is substituted, Xi, X ₂ and X ₃ , independently of each other, each -O-, -S-, -

-R ₄ or

where R _{4 is} hydrogen, C ₁ -C ₄ alkyl or phenyl and the benz ring a is unsubstituted or substituted by a substituent specified for R ₁ , Z is a carboxyl or sulfonic acid group and m is 2 to 6. 21. The method according to claim 20, characterized in that one uses a triazine compound of formula (7), wherein X ₁ , X ₂ and X ₃ each -NH-, Ri, R ₂ and R ₃ , independently of one another, each phenyl or naphthyl , Z is the sulfonic acid group and m is 2 or 3. 22. The method according to claim 9, characterized in that a colorless organic compound is a compound of the formula

used where V 'and W, independently of one another, are each hydroxyl, C ₁ -C ₄ alkoxy or an unsubstituted or monosubstituted or disubstituted amino group by a C ₁ -C ₄ alkyl radical, the alkyl radical being unsubstituted or by hydroxyl, cyano, sulfo or sulfato is substituted and V` also the radical R ₂ -X ₂ -, R ₁ and R ₂ , independently of one another, each have a phenyl, biphenylyl, naphthyl, stilbenyl or quinolinyl radical which is unsubstituted or by C _i -C ₄ alkyl, halogen, trifluoromethyl, nitro, cyano, hydroxy, C ₁ - C ₄ -affoxy, amino, mono-C ₁ -C ₄ -alkylamino, di-C ₁ -C ₄ -alkylamino, phenylamino, C ₁ -C ₇ -acylamino, carbamoyl, ureido, sulfamoyl, C ₂ -C ₅ -alkoxycarbonyl, C ₁ -C ₄ alkylsulfonyl or sulfomethyl is substituted, Xi and X ₂ , independently of each other, each -O-, -S-, -

-R ₄ or

wherein R _{4 is} hydrogen, C ₁ -C ₄ alkyl or phenyl and the benz ring a is unsubstituted or by one for R _i is substituted, Z is a carboxyl or sulfonic acid group and m is 2 to 4. 23. The method according to claim 9, characterized in that a colorless organic compound is a compound of the formula

used where R ₁ and R ₂ , independently of one another, each have a phenyl, biphenylyl, naphthyl, stilbenyl or quinolinyl radical which is unsubstituted or by C ₁ -C ₄ alkyl, halogen, trifluoromethyl, nitro, cyano, hydroxy, C ₁ - C ₄ alkoxy, amino, mono-C ₁ -C ₄ alkylamino, di-C ₁ -C ₄ alkylamino, phenylamino, C ₁ -C ₇ acylamino, carbamoyl, ureido, sulfamoyl, C ₂ -Cs alkoxycarbonyl, C ₁ -C ₄ alkylsulfonyl or sulfomethyl is substituted, Z is a carboxyl or sulfonic acid group and m is 2 to 4. 24. The method according to claim 9, characterized in that a colorless organic compound is a compound of the formula

used where R ₁ and R ₂ , independently of one another, each have a phenyl, biphenylyl, naphthyl, stilbenyl or quinolinyl radical which is unsubstituted or by C ₁ -C ₄ -alkyl, halogen, trifluoromethyl, nitro, cyano, hydroxy, C ₁ -C _4- alkoxy, amino, mono-Ci-C ₄ -alkylamino, di-Ci-C ₄ -alkylamino, phenylamino, C ₁ -C ₇ -acylamino, carbamoyl, ureido, sulfamoyl, C ₂ -Cs-alkoxycarbonyl, C1-C4 Alkylsulfonyl or sulfomethyl is substituted, Z is a carboxyl or sulfonic acid group and m is 2 to 4. 25. The method according to claim 9, characterized in that a colorless organic compound is a compound of the formula

used where R ₁ and R ₂ , independently of one another, each have a phenyl, biphenylyl, naphthyl, stilbenyl or quinolinyl radical which is unsubstituted or by C ₁ -C ₄ alkyl, halogen, trifluoromethyl, nitro, cyano, hydroxy, C ₁ - C ₄ alkoxy, amino, mono-Ci-C4-alkylamino, di-Ci-C4-alkylamino, phenylamino, C ₁ -C ₇ -acylamino, carbamoyl, ureido, sulfamoyl, C ₂ -C ₅ -alkoxycarbonyl, Ci-C _4- alkylsulfonyl or sulfomethyl is substituted, Z is a carboxyl or sulfonic acid group and m is 2 to 4. 26. The method according to claim 9, characterized in that a colorless organic compound is a compound of the formula

used where R ₁ and R ₂ , independently of one another, each have a phenyl, biphenylyl, naphthyl, stilbenyl or quinolinyl radical which is unsubstituted or by C ₁ -C ₄ alkyl, halogen, trifluoromethyl, nitro, cyano, hydroxy, C ₁ - C ₄ -alkoxy, amino, mono-Ci-C4-alkylamino, di-Ci-C ₄ -alkylamino, phenylamino, C ₁ -C ₇ -acylamino, carbamoyl, ureido, sulfamoyl, C ₂ -Cs-alkoxycarbonyl, C ₁ - C ₄ alkylsulfonyl or sulfomethyl is substituted, Z is a carboxyl or sulfonic acid group and m is 2 to 4 and the benz rings a and β are unsubstituted or substituted by a substituent specified for R ₁ . 27. The method according to claim 1, characterized in that at least one water-soluble reactive dye of the formula
D- (X) q (25),
wherein D is the residue of an organic dye of the monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, nitroaryl, dioxazine, phenazine or stilbene series, X is a fiber-reactive residue of the aliphatic, aromatic or hetero -cyclic series, which is bonded directly or via a bridge member to the radical D and q = 1,2,3,4, or 6, is used. 28. The method according to claim 27, characterized in that at least 2 or 3 reactive dyes of the formula (25) are used. 29. The method according to claim 28, characterized in that at least one yellow or orange-dyeing reactive dye, at least one red-dyeing reactive dye and at least one blue-dyeing reactive dye are used for trichromatic dyeing. 30. The method according to claim 27, characterized in that at least one water-soluble reactive dye of the formula

used, wherein D is the remainder of a monoazo, disazo, metal complex azo, anthraquinone, formazan or dioxazine dye, Ka is a cation and n = 1, 2, 3, 4, 5 or 6, and X and q are the in Claim 27 have meanings given under formula (25). 31. The method according to claim 30, characterized in that at least one water-soluble reactive dye of the formula (26) is used, wherein X is a radical of the formula

means in which R is hydrogen or Ci-4-alkyl, Q _{2 is} an optionally substituted amino group, a difluorochloropyrimidinyl radical bonded via a phenylenediamine radical or a vinylsulfonyl-, β-sulfatoethylsulfonyl-, β-thiosulfatoethylsulfonyl bonded directly or via an aromatic or aliphatic bridge member , β-chloroethylsulfonyl or β-acetoxyethylsulfonyl and Y 'are fluorine or chlorine. 32. The method according to claim 1, characterized in that pure cellulose fibers are dyed. 33. The method according to claim 1, characterized in that dyeing polyester / cellulose mixed fibers. 34. The method according to claim 1, characterized in that dyeing is carried out continuously. 35. The method according to claim 1, characterized in that cellulose fibers are dyed with reactive dyes and these are fixed with steam at a temperature of 100 ° C to 150 ° C for 30 seconds to 12 minutes.