EP1516019A1

EP1516019A1 - Water-soluble fibre-reactive disazo dyes, method for producing the same and the use thereof

Info

Publication number: EP1516019A1
Application number: EP03735585A
Authority: EP
Inventors: Günther SCHWAIGER; Werner Russ; Stefan Meier
Original assignee: Dystar Textilfarben GmbH and Co Deutschland KG
Current assignee: Dystar Textilfarben GmbH and Co Deutschland KG
Priority date: 2002-06-11
Filing date: 2003-06-10
Publication date: 2005-03-23
Also published as: ZA200409480B; CN1659240A; BR0311754A; TW200401809A; TWI273122B; US7132517B2; CA2489248A1; US20050241079A1; AU2003236722A1; MA27253A1; MXPA04012314A; WO2003104335A1; DE10225859A1

Abstract

The invention relates to dyes of general formula (1), in which R1<1>, R<2>, M, Z, v and x are defined as cited in claim 1, to the production of the same and to the use of said dyes for colouring or printing material containing hydroxy and/or carbonamide groups, preferably fibrous material.

Description

Water-soluble fiber-reactive disazo dyes, processes for their preparation and their use

DESCRIPTION

The invention is in the technical field of fiber-reactive copper complex

Disazo dyes.

Copper complexes of fiber-reactive disazo compounds containing one or more

4 fiber-reactive groups are, for example, from DAS 1 544 541, DAS 1 644 * 155,

EP 668 328, DE 32 02 120, EP 085 378, EP 040 806, EP 085 378, EP 203 505, DE

3941620, DE 4039866, EP 281898, EP 395951 known. However, these have certain application-related deficiencies, such as an excessive dependence of the color yield on changing dye parameters in the dyeing process, or an inadequate or irregular color build-up on cotton, whereby a good color build-up results from the ability of a dye when using increased dye concentrations in the dye bath to deliver the correspondingly stronger coloring. Furthermore, these dyes only show unsatisfactory fixation yields d. H. the proportion of dye which is permanently fixed on the goods to be dyed is too low, especially at low temperatures, and unsatisfactory fastness to washing and light.

However, for ecological and economic reasons it is important to provide dyes which have particularly high fixation yields in order to keep the proportion of unfixed dye in the dyeing waste water as low as possible. Dyes should also be as independent of changing coloring parameters as possible, e.g. Dyeing temperature in the dyeing process, always deliver uniformly strong dyeings. Furthermore, greater demands are placed on wash fastness these days.

With the present invention it has now been found that dyes of the general formula (1) surprisingly provide significantly better wash fastness and light fastness with very good build-up. Have these dyes in addition, higher fixation yields and a significantly lower parameter dependency during dyeing. They can therefore also be better combined with other dyes that fix at significantly lower temperatures.

The invention thus relates to dyes of the general formula (1):

(1) where

M represents hydrogen, alkali, ammonium or the equivalent of an alkaline earth

Ions, v is 0 or 1 and Z is -CH = CH _2l -CH ₂ CH ₂ Z ¹ , in which

Z ^{1 is} hydroxy or an alkali-releasable group and R ^{1 is} hydrogen or C 1 -C 4 -alkyl; R ^{2 represents} a grouping of the general formulas (2), (3), (4), or (5).

(2) (3) (4) (5)

wherein

T ^{1 is} hydrogen, methyl, fluorine or chlorine,

T ^{2 is} hydrogen, fluorine or chlorine, but not simultaneously for T ² and T ¹

Is hydrogen; T ^{3 is} hydrogen, fluorine or chlorine; AC ₁ to C ₄ -alkyl, which can be substituted with up to two substituents from the series chloro, bromo, hydroxy or carboxy, C ₂ to C ₄ alkenyl which can be substituted with up to two substituents from the series chloro, bromo, hydroxy, may be substituted or is phenyl,

L is phenylene or naphthylene, which can be substituted with up to two substituents from the series chloro, bromo, hydroxy, Ci to C alkyl, in particular methyl, ethyl, sulfo, cyano, or is a C ₂ to CΘ alkylene;

Z represents -CH = CH ₂ , -CH ₂ CH ₂ Z ¹ , in which Z ^{1 is} hydroxy or a group which can be split off under the action of alkali.

(CC ₄ ) -alkyl groups representing substituents A and R ¹ can be straight-chain or branched and are in particular methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl , Methyl and ethyl are preferred. Substituted C 1 to C ₄ alkyl groups which stand for substituents A are in particular carboxyethyl, carboxypropyl, 1, 2-dibromoethyl or chloromethyl. Substituted alkenyl radicals representing substituents A are preferably 2-bromoethenyl or 2-chloroethenyl.

R ² radicals of the general formula (2) are preferred, for example: 2,4-difluoropyrimidin-6-yl, 4,6-difluoropyrimidin-2-yl, 5-chloro-2,4-difluoropyrimidine -6-yl, 5-chloro-4,6-difluoropyrimidin-2-yl, 4,5-difluoropyrimidin-6-yl, 5-chloro-4-fluoropyrimidin-6-yl, 2,4 , 5-trichloropyrimidin-6-yl, 4,5-dichloropyrimidin-6-yl, 2,4-dichloropyrimidin-6-yl, 4-fluoropyrimidin-6-yl, 4-chloropyrimidine -6-yl. R ² particularly preferably represents 2,4-difluoropyrimidin-6-yl, 5-chloro-2,4-difluoropyrimidin-6-yl.

A radical of the general formula (3) which stands for R ² is, for example, preferably 2,3-dichloroquinoxaline-6-carbonyl. R ² radicals of the general formula (4) are, for example, preferably acetyl-, n-propionyl-, n-butyryl; R ² particularly preferably denotes acetyl.

R ² radicals of the general formula (5) are, for example, preferably 3-chloroethylsulfonylbenzoyl or 2-chloroethylsulfonylpropionyl.

Both in the above general formulas and in the general formulas given below, the individual formula elements, both of different and of the same name within a general formula, can have the same or different meanings from one another within the meaning of their meaning.

The dyes of the general formula (1) can have different fiber-reactive groups -S0 ₂ Z within the meaning of Z. Alkaline eliminable substituents Z \ which are in the β-position of the ethyl group of Z are, for example, halogen atoms, such as chlorine and bromine, ester groups of organic carboxylic and sulfonic acids, such as alkyl carboxylic acids, optionally substituted benzene carboxylic acids and optionally substituted benzenesulfonic acids, such as the groups alkanoyloxy of 2 to 5 carbon atoms, of which in particular acetyloxy,

Benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxy and toluylsulfonyloxy, furthermore acidic ester groups of inorganic acids, such as phosphoric acid, sulfuric acid and thiosulfuric acid (phosphato, sulfato and thiosulfato groups), as well as dialkylamino groups with alkyl groups of 1 to 4 dimethylamino and diethylamino, such as 1-dimethylamino, and the like.

In particular, the fiber-reactive groups -SO ₂ Z on the one hand vinylsulfonyl groups and on the other groups -CH ₂ CH ₂ Z \ preferably ß-thiosulfatoethyl and in particular ß-sulfato-ethylsulfonyl groups.

The groups "sulfo", "carboxy" include both their acid form and their salt form. Accordingly, sulfo groups mean groups corresponding to the general formula -SO ₃ M, carboxy groups corresponding to the general formula -COOM, in which M has the meaning given above.

Of the disazo compounds of the general formula (1), those are preferred which correspond to the general formula (1 a).

where M, R ¹ and R ^{2 have} the meaning given above.

The dyes of the general formula (1) according to the invention can be prepared, for example, by diazotizing a substituted aromatic amine of the general formula (6)

(6)

and coupling to a substituted amino naphthol of the general formula (7)

(7) followed by diazotization of the resulting amino monoazo dye of the general formula (8)

(8) and coupling at a pH of 6 to 9, optionally in the presence of a dispersing agent, to the terminal coupling component of the general

Formula (9)

followed by a subsequent coppering reaction with copper sulfate pentahydrate.

Diazotizable amines with complexing radicals of the general formula (6) are, for example, 3-amino-4-hydroxy-5-sulfophenyl-β-sulfatoethylsulfone, or 3-amino-4-hydroxy-5-sulfophenyI-vinylsulfone.

Compounds of the general formula (7) are, for example, 2-amino-5-hydroxy-naphthalene-7-sulfonic acid, 2-amino-8-hydroxy-naphthalene-6-sulfonic acid, 2-amino-5-hydroxy-naphthalene-1, 7 -disulfonic acid and 2-amino-8-hydroxy-naphthalene-3,6-disulfonic acid.

Compounds of the general formulas (8) and (9) are known, for example, from EP 0 085 378, EP 0 084 849 and can be prepared by customary processes.

The compounds of general formula (1) according to the invention can be separated and isolated from the aqueous synthesis solutions by generally known methods for water-soluble compounds, for example by precipitation from the reaction medium by means of an electrolyte, such as sodium chloride or potassium chloride, or by evaporation of the reaction solution itself, for example by spray drying. If the latter type of insulation is chosen, it is often advisable to remove any amounts of sulfate present in the solutions by evaporation as calcium sulfate and separation by filtration before evaporation.

The dyes according to the invention can be present as a preparation in solid or in liquid (dissolved) form. In solid form, they generally contain those customary for water-soluble and in particular fiber-reactive dyes

Electrolyte salts, such as sodium chloride, potassium chloride and sodium sulfate, and can additionally contain the auxiliaries customary in commercial dyes, such as buffer substances which are able to adjust a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium hydrogen carbonate, sodium dihydrogen phosphate, sodium tricitrate and disodium hydrogen phosphate, small amounts of siccatives or, if they are in liquid, aqueous solution (including the content of thickening agents, as are common for printing pastes), substances that ensure the durability of these preparations, such as mold-preventing agents.

In general, the dyes according to the invention are present as dye powder with a content of 10 to 80% by weight, based on the dye powder or the preparation, of an electrolyte salt, which is also referred to as an adjusting agent. These dye powders can also contain the abovementioned buffer substances in a total amount of up to 10% by weight, based on the dye powder. If the dyes according to the invention are in aqueous solution, the total dye content in these aqueous solutions is up to about 50% by weight, for example between 5 and 50% by weight, the electrolyte salt content in these aqueous solutions preferably being below 10% by weight. %, based on the aqueous solution, is; the aqueous solutions (liquid preparations) can generally contain the abovementioned buffer substances in an amount of up to 10% by weight, preferably up to 2% by weight. The dyes according to the invention have valuable performance properties. They are used for dyeing or printing materials containing hydroxyl and / or carbonamide groups, for example in the form of sheets, such as paper and leather or of films, for example made of polyamide, or in bulk, for example of polyamide and polyurethane, but especially of these Materials used in fiber form. The solutions of the dyestuffs according to the invention obtained in the synthesis of the azo compounds can also be used directly as a liquid preparation for dyeing, if appropriate after adding a buffer substance, if appropriate also after concentrating or diluting.

The present invention thus also relates to the use of the dyes according to the invention for dyeing or printing these materials or to processes for dyeing or printing such materials in procedures which are conventional per se and in which dyes according to the invention are used as

Colorant is used. The materials are preferably used in the form of fiber materials, in particular in the form of textile fibers, such as fabrics or yarns, such as in the form of strands or packages.

Materials containing hydroxyl groups are of natural or synthetic origin, such as cellulose fiber materials or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton, but also other vegetable fibers, such as linen, hemp, jute and ramie fibers; Regenerated cellulose fibers are, for example, cellulose and viscose rayon.

Materials containing carbonamide groups are, for example, synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hair, silk, leather, polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4.

The dyes according to the invention can be prepared on the substrates mentioned, in particular on the fiber materials mentioned, according to those for water-soluble, Apply and fix in particular using the application techniques known for fiber-reactive dyes.

They are used to obtain dyeings with very good fastness to washing on cellulose fibers using the exhaust process from a long liquor using a wide variety of acid-binding agents and, if appropriate, neutral salts, such as sodium chloride or sodium sulfate. Dyeing is preferably carried out in an aqueous bath at temperatures between 40 and 105 ° C., if appropriate at a temperature up to 130 ° C. under pressure, and if appropriate in the presence of customary dyeing auxiliaries. The procedure can be such that the material is introduced into the warm bath and this is gradually heated to the desired dyeing temperature and the dyeing process is completed at this temperature. The neutral salts which accelerate the removal of the dyes can, if appropriate, also be added to the bath only after the actual dyeing temperature has been reached.

After the padding process, excellent color yields and a very good color build-up are also obtained on cellulose fibers, which can be fixed in the usual way by staying at room temperature or elevated temperature, for example up to about 60 ° C., by steaming or with dry heat.

Also according to the usual printing processes for cellulose fibers, which are single-phase - for example, by printing with a printing paste containing sodium bicarbonate or another acid-binding agent and then steamed at 100 to 103 ° C, - or two-phase - for example, by printing with neutral or weakly acidic printing ink and then fixing either by passing through a hot electrolyte-containing alkaline bath or by padding with an alkaline electrolyte-containing pad liquor and then lingering or steaming or treatment with dry heat of the alkaline-padded material, - you get strong-colored prints with a good shape of the contours and a clear white background. The failure of the prints is only slightly dependent on changing fixing conditions. Hot air from 120 to 200 ° C is used for fixing with dry heat using the usual heat-setting processes. In addition to the usual steam from 101 to 103 ° C, superheated steam and pressure steam at temperatures up to 160 ° C can also be used.

The acid-binding agents and the fixation of the dyes according to the invention on the cellulose fibers are, for example, water-soluble basic salts of the alkali metals and also alkaline earth metals of inorganic or organic acids or compounds which release alkali in the heat. In particular, the alkali metal hydroxides and alkali metal salts of weak to moderately strong inorganic or organic acids are to be mentioned, the alkali compounds preferably referring to the sodium and potassium compounds. Such acid-binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium trichloroacetate, water glass or trisodium phosphate.

After the usual aftertreatment by rinsing to remove unfixed dye components, the cellulose dyeings show very good dye properties and, according to the application and fixing methods customary in the art, for fiber-reactive dyes on the materials mentioned in the description, such as cellulose fiber materials, in particular cotton and viscose, have strong colors dark blue dyeings and prints with very good fastness properties, from which the very good fastness to washing, light, alkali, acid, water, sea water, sweat and rubbing can be emphasized. The dyeings are further characterized by their high degree of fixation and good structure on the cellulose materials. The good washfastness of the dyeings, the high fixation value and the low temperature dependence compared to the prior art are particularly advantageous.

Furthermore, the dyes according to the invention can also be used for fiber-reactive dyeing of wool. You can also use felt-free or low-finished wool (see, for example, H. Rath, Textbook of Textile Chemistry, Springer-Verlag, 3rd edition (1972), pp. 295-299, especially the equipment according to the so-called Hercosett method (p. 298); J. Soc. Dyers and Coloirists 1972, 93-99, and 1975, 33-44) with very good fastness properties.

The process of dyeing on wool is carried out in a customary and known way of dyeing from an acidic environment. So you can, for example, the dye bath

Add acetic acid and / or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate to get the desired pH. In order to achieve a useful levelness of the coloring, it is advisable to add conventional leveling aids, such as, for example, based on a reaction product of cyanuric chloride with 3 times the molar amount of an aminobenzenesulfonic acid and / or an aminonaphthalenesulfonic acid or on the basis of a reaction product of, for example, stearylamine with ethylene oxide. For example, the dyes according to the invention are preferably first subjected to the exhaust process from an acidic dye bath with a pH of about 3.5 to 5.5 while checking the pH, and then, towards the end of the dyeing time, the pH is neutral and optionally weak alkaline range raised to a pH of 8.5, in order to bring about the full reactive bond between the dyes according to the invention and the fiber, in particular to achieve high color depths. At the same time, the non-reactive dye component is removed.

The procedure described here also applies to the production of dyeings on fiber materials from other natural polyamides or from synthetic polyamides and polyurethanes. As a rule, the material to be dyed is introduced into the bath at a temperature of approx. 40 ° C, agitated there for some time, the dyebath is then adjusted to the desired weakly acidic, preferably weakly acetic acid, pH value and the actual dyeing at one Temperature between 60 and 98 ° C carried out. The dyeings can also be carried out at boiling temperature or in closed dyeing machines at temperatures up to 106 ° C. Since the water solubility of the invention

Dyes is very good, they can also be used with advantage in conventional continuous dyeing processes. The dyes according to the invention provide deep blue colorations on the materials mentioned. The following examples serve to illustrate the invention. The parts are parts by weight, the percentages represent percentages by weight, unless stated otherwise. The compounds described by formula in the examples are given in part in the form of the free acids; in general, they are prepared and isolated in the form of their salts, preferably sodium or potassium salts, and used in the form of their salts for dyeing. Likewise, the starting compounds mentioned in the following examples, in particular table examples, in the form of the free acid as such or in the form of their salts, preferably alkali metal salts, such as sodium or potassium salts, can be used in the synthesis.

example 1

377 parts of 4-β-sulfatoethylsulfonyI-2-amino-phenoI-6-sulfonic acid are diazotized with sodium nitrite and coupled at pH 6-7 to 239 parts of 2-amino-5-hydroxy-naphthalene-7-sulfonic acid. This monoazo compound

is diazotized and to 361 parts of N-acetamino-3,6-disulfo-8-hydroxy-naphthalene

coupled. The bisazo dye obtained

is then metallized with 245 parts of copper sulfate pentahydrate. The blue dye obtained, which has the formula A

(λ max. = 587 nm)

corresponds, is salted out with sodium chloride, filtered off and dried in vacuo at 50 ° C. It gives dark blue dyeings and prints of strong color on cotton, with very good fastness properties, of which in particular the fastness to light, washing, water and sweat as well as the fastness to chlorine bath water, solvents, rubbing and ironing can be emphasized.

The following table examples describe further dyes of the general formula (IA) according to the invention. According to the dyeing methods customary for reactive dyes, for example on cotton, the dyes provide deep blue dyeings with good general fastness properties.

Compounds of the general formula (IB) mentioned below can also be obtained by the process described in Example 1. According to the dyeing methods customary for reactive dyes, for example on cotton, they deliver scarlet to brown-red dyeings with good general fastness properties.

Compounds of the general formula (IC) mentioned below can also be obtained according to the process described in Example 1. You deliver later the dyeing methods customary for reactive dyes, for example on cotton, scarlet to brown-red dyeings with good general fastness properties

Claims

claims:

1. Dyes of the general formula (1):

(1) where

M represents hydrogen, alkali, ammonium or the equivalent of an alkaline earth ion, v represents 0 or 1 and

Z represents -CH = CH ₂ , -CH ₂ CH ₂ Z ¹ , wherein

Z ^{1 is} hydroxy or an alkali-releasable group and R ^{1 is} hydrogen or CC ₄ alkyl; R ^{2 represents} a grouping of the general formulas (2), (3), (4), or (5).

(2) (3) (4) (5)

wherein

T ^{1 is} hydrogen, methyl, fluorine or chlorine,

T ^{2 is} hydrogen, fluorine or chlorine, where T ² and T ^{1 are} not simultaneously hydrogen;

T ^{3 is} hydrogen, fluorine or chlorine; A Cι to C ₄ alkyl, which can be substituted with up to two substituents from the series chloro, bromo, hydroxy, or carboxy, C ₂ to C ₄ alkenyl which with up to two substituents from the series chloro, bromo, hydroxy, may be substituted or is phenyl,

L is phenylene or naphthylene, which can be substituted with up to two substituents from the series chloro, bromo, hydroxy, C 1 to C ₄ alkyl, in particular methyl, ethyl, sulfo, cyano, or a C ₂ to C ₆ alkylene;

Z represents -CH = CH _2l -CH ₂ CH ₂ Z ¹ , in which Z ^{1 is} hydroxy or a group which can be split off under the action of alkali.

2. Dyes according to claim 1 wherein R ² corresponds to a grouping of the general formula (4).

3. Dyes according to claim 1 or 2 wherein v is 0.

4. Dyes according to at least one of claims 1 to 3 wherein the SO ₂ Z group is in the meta position to the azo group.

5. Dyes according to at least one of claims 1 to 4, wherein R ^{2 is} a CH ₃ CO radical.

6. A process for the preparation of compounds according to claim 1

Diazotization of a substituted aromatic amine of the general formula (6)

(6) and coupling to a substituted amino naphthol of the general formula

(7)

(8) and coupling at a pH of 6 to 9, on the terminal coupling component of the general formula (9)

followed by a subsequent coppering reaction with copper sulfate pentahydrate.

7. Use of the dyes according to at least one of claims 1 to 6 for dyeing or printing material containing hydroxyl and / or carbonamide groups, preferably fiber material.

8. Process for dyeing or printing material containing hydroxyl and / or carbonamide groups, preferably fibrous material, in which one or more dyes are applied to the material in dissolved form and fixes the dye or dyes on the material by means of heat or with the aid of an alkaline agent or by means of both measures, characterized in that at least one of claims 1 to 5 is used as the dye.

9. dyeing preparation containing a dye according to at least one of claims 1 to 6.