HK1075671B - Water-soluble fiber-reactive dyes, preparation thereof and use thereof - Google Patents

Description

Water-soluble fiber reactive dye, preparation method and application thereof

The present invention relates to the field of fiber-reactive azo dyes.

Copper complexes of fibre-reactive monoazo compounds containing one or more fibre-reactive groups are known from, for example, EP-A-526792, DE-A-4332255, DE-A-2049664, EP0040806, EP-A-069376, DE-A-3941620, DE-A-4039866, EP-A-281898, EP-A-0345577, EP-A-395951 or EP 497174. However, they have certain application drawbacks, for example, the colour yield is excessively dependent on the variation of parameters in the dyeing process, or the dye accumulation on cotton is insufficient or uneven, good dye accumulation resulting from the ability of the dye to provide a stronger dyeing when dyed in a higher concentration dye bath. Furthermore, these dyeings exhibit unsatisfactory degrees of fixation, i.e. the fraction of the dye permanently fixed to the material being dyed is too low, in particular at low temperatures, and unsatisfactory wash and light fastnesses.

However, for ecological and economic reasons it is important to provide dyes with particularly high fixation yields in order to minimize the unfixed dye fraction in the dye house waste water. Furthermore, the dyes should always provide a uniform strong dyeing, theoretically independently of changes in the dyeing parameters, such as the dyeing temperature in the dyeing process. In addition, there is a more urgent need for wash fastness and light fastness.

The present invention now provides dyes of the general formula (1) which surprisingly provide distinctly excellent wash and light fastness with good dye build-up. In addition, these dyes have a higher degree of fixation and a significantly lower dyeing parameter dependence. Thus, they are more compatible with other dyes that fix at lower temperatures.

Accordingly, the present invention provides a dye of formula (1):

wherein

M is hydrogen, alkali metal, ammonium or equivalent alkaline earth metal ions,

x is 0 or 1, and X is a hydrogen atom,

y is-CH ═ CH₂or-CH₂CH₂Z¹，

Wherein

Z¹Is a hydroxyl group or a base-removable group, and

R¹is hydrogen or C₁-C₄-an alkyl group;

R²is a group of the following general formula (2), (3) or (4):

wherein

Y' is-CH ═ CH₂or-CH₂CH₂Z¹，

Wherein

Z¹Is a hydroxyl group or a base-removable group, and

T¹is hydrogen, methyl, fluorine, chlorine or bromine,

T²is hydrogen, fluorine, chlorine or bromine, with the proviso that T²And T¹Not hydrogen at the same time;

T³is hydrogen, methyl, fluorine, chlorine or bromine,

l is phenylene or naphthylene: which may be substituted by up to two groups selected from chlorine, bromine, hydroxy, C₁-C₄-alkyl, in particular methyl, ethyl, sulfo, cyano; or is C₂-C₆Alkylene which may be interrupted by 1 to 2 hetero radicals such as oxo, thio, amino, C₁-C₄-an alkylamino interruption.

L is preferably phenylene, ethylene, propylene or 3-oxopentylene.

(C₁-C₄) -alkyl radical R¹Can be linear or branched, and is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. Methyl and ethyl are preferred.

Preferred R of the formula (2)²Examples of radicals are: 2, 4-difluoropyrimidin-6-yl, 4, 6-difluoropyrimidin-2-yl, 5-chloro-2, 4-difluoropyrimidin-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-chloropyrimidin-6-yl, 2-fluoro-4-methylpyrimidin-6-yl.

Particularly preferred R²Is 2, 4-difluoropyrimidin-6-yl or 5-chloro-2, 4-difluoropyrimidin-6-yl.

In the above and subsequent formulae, the individual symbols, whether having the same or different nomenclature in any one of the formulae, may have the same or different meanings from one another under their definitions.

The dyes of the general formula (1) may have different fibre-reactive groups-SO within the meaning of Y and Y', respectively₂Y and-SO₂Y' is provided. The base-eliminable substituent Z1 in the β -position of the ethyl groups of Y and Y' is a halogen atom, such as chlorine and bromine; ester groups of organic carboxylic and sulfonic acids, such as alkyl carboxylic acids, optionally substituted benzoic acids and optionally substituted benzenesulfonic acids, such as alkanoyloxy groups of 2 to 5 carbon atoms, particularly acetoxy, benzoyloxy, sulfobenzoyloxy, benzenesulfonyloxy, and p-toluenesulfonyloxy; and acid ester groups of inorganic acids, such as acid ester groups of phosphoric acid, sulfuric acid, thiosulfuric acid (phosphato, sulfato, and thiosulfato); analogously to dialkylamino having in each case alkyl radicals of 1 to 4 carbon atoms, such as dimethylamino and diethylamino.

More specifically, the fiber-reactive group-SO₂Y and-SO₂Y' may be firstly vinylsulfonyl and secondly the group-CH₂CH₂Z¹Beta-chloroethyl and especially beta-sulfatoethylsulfonyl are preferred.

The radicals sulfo, carboxyl, phosphato and sulfato include not only their acid forms but also their salt forms. Thus, sulfo is a radical of the formula-SO₃M, carboxyl is a radical of formula-COOM and phosphate is a radical of formula-OPO₃M₂With sulfate radical to form a radical of the formula-OSO₃The radical of M, M in each of which is as defined above.

The dyes of the general formula (1) according to the invention can be prepared, for example, by customary diazotization of aromatic amines of the general formula (8) and coupling with coupling components of the general formula (9) and subsequent complexation with copper, preferably copper sulfate pentahydrate, in a manner known to those skilled in the art,

wherein M, Y and x are each as defined above

Wherein T is¹、T²、T³And M are each as defined above.

Diazotized amines having a complexing group of the formula (8) are, for example, 3-amino-4-hydroxyphenyl β -hydroxyethylsulfone, 3-amino-4-hydroxyphenyl β -sulfatoethylsulfone, 3-amino-4-hydroxyphenyl vinylsulfone, 4-amino-5-hydroxyphenyl β -hydroxyethylsulfone, 4-amino-5-hydroxyphenyl β -sulfatoethylsulfone, 4-amino-5-hydroxyphenyl vinylsulfone, 3-amino-4-hydroxy-5-sulfophenyl β -sulfatoethylsulfone, 3-amino-4-hydroxy-5-sulfophenyl vinylsulfone.

The coupling component of the formula (9) can be obtained, for example, by conventional condensation of a compound of the formula (10) with a compound of the formula (11), (12) or (13),

wherein R is¹And M are each as defined above,

wherein T is¹、T²、T³L and Y' are each as defined above. When R is²In the case of the group of the formula (2), the dye may contain two isomers depending on the meaning of the substituent.

The compounds of the general formula (10) are, for example, 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-N-methylamino-5-hydroxynaphthalene-7-sulfonic acid.

The compounds of the general formula (11) are, for example, 2, 4, 6-trifluoropyrimidine, 4, 5, 6-trifluoropyrimidine, 2, 4, 5, 6-tetrafluoropyrimidine, 4, 6-difluoropyrimidine, 2, 4, 5, 6-tetrachloropyrimidine, 2, 4, 6-trichloropyrimidine, 2, 4, 6-tribromopyrimidine, 2, 4, 6-trifluoro-5-chloropyrimidine, 5-methyl-2, 4, 6-trichloropyrimidine, 4, 6-difluoro-5-chloropyrimidine.

Compounds of the general formula (12) are, for example, 3-chloroethylsulfonylbenzoyl chloride, 2-chloroethylsulfonylpropionyl chloride.

The compounds of the general formula (13) are 2, 3-dichloroquinoxaline-5-carbonyl chloride, and 2, 3-dichloroquinoxaline-6-carbonyl chloride.

Alternatively, the diazotization and coupling of the compound of formula (8) onto the compound of formula (10) may be carried out first, followed by copper complexation, preferably copper complexation with copper sulfate pentahydrate, which is then condensed with a compound of formula (11), (12) or (13); or first diazotisation and coupling of the aromatic amine of the formula (8) onto a coupling component of the formula (10) and then condensation with a compound of the formula (11), (12) or (13), which is then complexed with copper sulfate pentahydrate in a manner known to the person skilled in the art,

wherein M, Y and x are each as defined above.

The isolation of the compounds of the general formula (1) according to the invention from the aqueous synthesis solution can be effected according to generally known methods for water-soluble compounds, for example by precipitation from the reaction medium by means of electrolytes, such as sodium chloride or potassium chloride, or by evaporation of the reaction solution itself, for example by spray drying. In the latter case, it is often desirable to first precipitate any sulfate in solution as calcium sulfate and filter off.

The dyes of the present invention may be present as solid or liquid (dissolved) form preparations. In solid form, they usually comprise electrolyte salts commonly used in water-soluble, in particular fibre-reactive dyes, such as sodium chloride, potassium chloride and sodium sulphate, and may additionally comprise auxiliaries commonly used in industrial dyes, such as buffer substances capable of adjusting the pH of the aqueous solution to 3 to 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate and disodium hydrogen phosphate, or small amounts of siccatives; when they are present in the form of liquid aqueous solutions (including thickeners of the type commonly used in printing pastes), they may also contain substances which ensure a long shelf life of these formulations, such as fungicides.

In general, the dyes according to the invention are also present as dye powders which comprise from 10 to 80% by weight, based on the dye powder or formulation, of electrolyte salts, also referred to as standardizing agents. These dye powders may additionally comprise the abovementioned buffer substances in a total amount of up to 10% by weight, based on the dye powder. If the dyes of the present invention are present in aqueous solutions, the total dye content of these aqueous solutions will be up to about 50% by weight, for example from 5 to 50% by weight, and the electrolyte salt content of these aqueous solutions will preferably be less than 10% by weight, based on the aqueous solution; the aqueous solutions (liquid preparations) may contain the above-mentioned buffer substances in general in an amount of up to 10% by weight and preferably up to 2% by weight.

The dyes of the present invention have useful application properties. They are used for dyeing and printing hydroxyl-and/or carboxamido-containing materials, for example sheet-like structures such as paper and leather, or film-like structures such as films composed of polyamide, or in bulk form such as polyamide and polyurethane, but are used in particular for dyeing and printing these materials in fibrous form. Similarly, the dyes of the invention obtained synthetically can be used directly as liquid preparations for dyeing after suitable addition of buffer substances and after suitable concentration or dilution.

The present invention therefore also relates to the use of the dyes according to the invention for dyeing or printing these materials and to a process for dyeing or printing these materials in a conventional manner using the dyes according to the invention as colorants. The material is preferably in the form of a fibrous material, particularly preferably in the form of a fabric, such as a woven fabric or yarn in a bundled or wound form.

Hydroxyl-containing materials are those from natural or synthetic sources, such as cellulosic fiber materials or their remnants and polyvinyl alcohol. The cellulosic fibrous material is preferably cotton, but also other plant fibers, such as flax, hemp, jute and ramie fibers; regenerated cellulose fibers are, for example, short viscose and long viscose.

Carboxamido-containing materials are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hair, silk, leather, nylon-6, nylon-6, nylon 11 and nylon-4.

The dyes according to the invention can be applied and fixed to the abovementioned substrates, in particular the mentioned fibre materials, by the application techniques known for water-soluble dyes, in particular fibre-reactive dyes.

For example, by the dip dyeing process with a large bath ratio, using a variety of acid-binding agents and optionally neutral salts such as sodium chloride or sodium sulfate, they produce dyeings on the fibers having very good wash fastnesses. Preferably in an aqueous dyebath at 45 to 105 c, optionally at superatmospheric pressure at temperatures of up to 130 c, and preferably in the presence of customary dyeing auxiliaries. One possible process is to add the material to a warm dye bath and gradually heat the dye bath to the desired dyeing temperature and complete the dyeing process at that temperature. Neutral salts to facilitate dye exhaust may be added to the dye bath only after the actual dyeing temperature is reached, as desired.

The pad dyeing process likewise provides excellent colour yield and good dye build-up on cellulose fibres, the dyes being fixed in a conventional manner on the material batchwise by steaming or using dry heat at room temperature and at elevated temperature, for example at temperatures of up to 60 ℃.

Similarly, conventional printing processes for cellulose fibers produce strong prints with well-defined contours and a clear white undertone, which can be carried out in one stage, such as by printing with a printing paste containing sodium bicarbonate or some other acid binding agent, and subsequently steaming at a temperature of 100 to 103 ℃; or in two stages, for example by printing with neutral or weakly acidic printing materials, then fixing the printed material by overdyeing through a hot alkaline bath containing electrolyte or and with a padding liquor containing alkaline electrolyte, and subsequently calendering or subsequently steaming or subsequently dry-heat treating the material overdyeed with alkali. Changing the fixation conditions has little effect on the printing result.

When fixing by dry heat according to the conventional hot fixing method, hot air of 120 to 200 ℃ is used. In addition to conventional 101 to 103 ℃ steam, superheated steam and high-pressure steam up to 160 ℃ may also be used.

The acid-binding agents which fix the dyes of the invention to the cellulose fibres are, for example, water-soluble basic salts of alkali metals and alkaline earth metals of inorganic or organic acids, or compounds which liberate alkali on heating. Particularly suitable are alkali metal hydroxides and alkali metal salts of weak to moderately acidic inorganic or organic acids, the preferred alkali metal compounds being sodium and potassium compounds. These acid-binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogen phosphate and disodium hydrogen phosphate, sodium trichloroacetate, water glass or sodium phosphate.

The cellulosic dyeings obtained after the customary aftertreatment by rinsing to remove the unfixed dye fraction exhibit very good dyeing properties and provide on said materials, such as cellulosic fibre materials, in particular cotton and viscose, by the application and fixing methods customary in the art for fibre-reactive dyes, dyeings and prints having very good fastness properties, in particular having very good fastness properties to washing, to light, to alkali, to acid, to water, to sea water, to perspiration and to rubbing. In addition, such dyeings are distinguished by their high degree of fastness and good dye build-up on the cellulosic material. The dyeings have the particular advantages over the prior art of good fastness to washing, high fastness values and low temperature dependence.

In addition, the dye of the invention can also be used for fiber reactive dyeing of wool. Furthermore, wool which has been subjected to a non-felting or low-felting finish (see, for example, H.Path, Lehrbuch der Texturechemie, Springer Vertag, third edition (1972), pages 295-299, especially by Hercosett processes (298) pages; J.Soc.dyers and Colourists, 1972, 93-99 and 1975, 33-44) can be dyed to very good fastness properties.

The process for dyeing wool herein is carried out in a conventional manner in an acidic medium. For example, acetic acid and/or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate may be added to the dye bath to obtain the desired pH. To obtain dyeings of acceptable levelness, it is advantageous to add conventional levelling agents, for example levelling agents based on the reaction product of cyanuric chloride with three molar times the amount of aminobenzenesulfonic acid and/or aminonaphthalenesulfonic acid, or on the reaction product of, for example, octadecylamine with ethylene oxide. For example, the dyes of the invention are subjected to an exhaust process initially in an acid dyebath at a pH of about 3.5 to 5.5 under pH-controlled conditions, and then, with the end of the dyeing time, the pH becomes neutral and optionally weakly basic with a pH of up to 8.5, resulting in a complete reactive bond between the dyes of the invention and the fibers, in particular for deep dyeing. At the same time, the dye moiety that is not reactively bound is removed.

The process described herein is also useful for dyeing on fiber materials composed of other natural or synthetic polyamides and polyurethanes. Generally, the material to be dyed is introduced into a dye bath at a temperature of about 40 ℃ and stirred therein for a certain time, after which the dye bath is adjusted to the desired weakly acidic pH, preferably with weak acetic acid, and the actual dyeing is carried out at a temperature of 60 to 98 ℃, however, the dyeing can also be carried out at boiling or in a sealed dyeing apparatus at temperatures of up to 106 ℃. The dyes of the invention can also be advantageously used in conventional continuous dyeing processes, since their water solubility is very good. The dye of the present invention dyes the material to a ruby red color.

The examples which follow serve to illustrate the invention. Parts and percentages are by weight unless otherwise indicated. The compounds described in the formulae of the examples are represented in the form of the free acids, they are usually prepared and isolated in the form of salts, preferably sodium or potassium salts, and used for dyeing in the form of salts. The starting compounds described in the examples below, in particular in the examples in the tables, can be used in the synthesis in the form of the free acids or likewise in the form of their salts, preferably alkali metal salts, such as sodium or potassium salts.

Example 1

377 parts of 2-amino-4-sulfatoethylsulfonyl-6-phenolsulfonic acid are diazotized with sodium nitrite and coupled at pH 6-7 to 353 parts of a condensation product of 2-amino-5-hydroxynaphthalene-7-sulfonic acid and 2, 4, 6-trifluoropyrimidine and subsequently reacted with 245 parts of copper sulfate pentahydrate. The resulting red dye of formula a was salted out with sodium chloride, filtered and dried at 50 ℃ under reduced pressure. The dyes give ruby-red dyeings and prints on cotton which have very good fastnesses, in particular very good lightfastnesses,

example 2

377 parts of 2-amino-4-sulfatoethylsulfonyl-6-phenolsulfonic acid are diazotized with sodium nitrite and coupled onto 239 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid and subsequently reacted with 250 parts of copper sulfate pentahydrate. Optionally salting out the dye of formula B obtained in the form of sodium chloride, filtering and drying at 50 ℃ under reduced pressure. The dyes give ruby-red dyeings and prints on cotton which have very good fastnesses, in particular very good lightfastnesses,

the dye B is reacted with 2, 4, 6-trifluoropyrimidine to give the dye of the formula (A).

Example 3

Dye C, which has excellent fastness, was obtained using the procedure described in example 1 or 2, using 2-N-methylamino-5-hydroxynaphthalene-7-sulfonic acid as coupling component.

The following table further describes the dyes of the present invention, which can be prepared by way of the above examples, X being fluorine, chlorine or bromine.

Dyeing examples

4 parts of the dye of example 2 are dissolved in 200 parts of water. 20 parts of sodium chloride, 5 parts of aqueous sodium hydroxide solution and 20 parts of cotton fabric are added in a dyeing apparatus before heating to 60 ℃ within 20 minutes. The staining was carried out at 60 ℃ for 45 minutes. The cotton fabric is then rinsed with water and dilute acetic acid and dried. Which gives a ruby red dyeing with very good fastness properties.

Claims (11)

1. A dye of the following general formula (1):

wherein

M is hydrogen, alkali metal, ammonium or equivalent alkaline earth metal ions,

x is 0 or 1, and X is a hydrogen atom,

y is-CH ═ CH₂or-CH₂CH₂Z¹，

Wherein

Z¹Is a hydroxyl group or a base-removable group, and

R¹is hydrogen or C₁-C₄-an alkyl group;

R²is a group of the following general formula (2), (3) or (4):

wherein

T¹Is hydrogen, methyl, fluorine, chlorine or bromine,

T²is hydrogen, fluorine or chlorine, provided that T²And T¹Not hydrogen at the same time;

T³is hydrogen, methyl, fluorine, chlorine or bromine,

y' is-CH ═ CH₂or-CH₂CH₂Z¹，

Wherein

Z¹Is a hydroxyl group or a base-removable group, and

l is phenylene or naphthylene, unsubstituted or substituted by up to two groups selected from chlorine, bromine, hydroxy, C₁-C₄-alkyl, sulfo, cyano; or is C₂-C₆Alkylene which is uninterrupted or selected from oxo, thio, amino, C₁-C₄1 to 2 groups of the alkylamino group are interrupted.

2. The dye of claim 1, wherein R²Is a group of the following general formula (2),

wherein T is¹、T²And T³The definitions of each are as defined in claim 1.

3. A dye according to claim 1 or 2, wherein x is 1, and SO₂The Y group is positioned meta to the azo group.

4. The dye of claim 1 or 2, wherein R²Is difluoropyrimidyl.

5. The dye of claim 3, wherein R²Is difluoropyrimidyl.

6. In claim 1, R²A process for the preparation of compounds which are radicals of the general formula (2) which comprises the customary diazotization of aromatic amines of the general formula (8) and coupling with coupling components of the general formula (9), followed by copper complexation with copper sulfate pentahydrate,

wherein M, Z, Y and x are each as defined in claim 1,

wherein T is¹、T²、T³And M are each as defined in claim 1.

7. A process for the preparation of the compounds of claim 1, which comprises the customary diazotization of aromatic amines of the formula (8) and coupling with coupling components of the formula (10), followed by copper complexation with copper sulfate pentahydrate and condensation with fibre-reactive groups of the formula (11), (12) or (13),

wherein M, Z, Y and x are each as defined in claim 1,

wherein R is¹And M are each as defined in claim 1,

wherein T is¹、T²、T³L and Y' are each as defined in claim 1, and X is fluorine, chlorine or bromine.

8. A process for the preparation of the compounds of claim 1, which comprises the customary diazotization of aromatic amines of the formula (8) and subsequent coupling with coupling components of the formula (10), and condensation with fibre-reactive radicals of the formula (11), (12) or (13) and subsequent copper complexation with copper sulfate pentahydrate,

wherein M, Z, Y and x are each as defined in claim 1,

wherein R is¹And M are each as defined in claim 1,

wherein T is¹、T²、T³L and Y' are each as defined in claim 1, and X is fluorine, chlorine or bromine.

9. Use of a dye according to any one of claims 1 to 5 for dyeing or printing hydroxyl-and/or carboxamido-containing material.

10. A process for dyeing or printing a material containing hydroxyl groups and/or containing carboxamide groups, which process comprises applying one or more dyes in dissolved form to the material and fixing the dye(s) on the material by heating or with the aid of alkaline agents or both, which process uses a dye as claimed in any of claims 1 to 5.

11. A dye formulation comprising a dye according to any one of claims 1 to 5.