HK1091853A

HK1091853A - Water-soluble fiber-reactive dyes, their preparation and their use

Info

Publication number: HK1091853A
Application number: HK06112218.5A
Authority: HK
Inventors: 甘特．格利茨; 沃纳．鲁斯
Original assignee: 德意志戴斯达纺织品及染料两合公司
Priority date: 2005-03-26
Filing date: 2006-11-07
Publication date: 2007-01-26

Description

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

Technical Field

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

Background

The OPI document DE-a 3516667 proposes green to olive-colored metal complex dyes as reactive dyes for cotton, wool or nylon. These dyes have certain performance disadvantages, such as an excessive dependence of the color yield (color yield) on the variable parameters of the dyeing operation, or an insufficient or uneven accumulation of the dye on the cotton (color build dup). Good dye accumulation refers to the ability of the dye to produce more intense stains when used at high concentrations in the dye bath. Furthermore, the fastness to washing, the amount of fixation (fixation) of these dyes are unsatisfactory; that is, the fraction of dye permanently fixed to the material to be dyed is too small, especially at low temperatures.

However, for ecological and economic reasons, it is important to minimize the fraction of unfixed dye contained in the dyehouse effluent by providing dyes with exceptionally high fixation levels. In addition, it is desirable that the dye always produce a uniform intense stain regardless of changes in dyeing parameters (e.g., dyeing temperature during the dyeing operation). Furthermore, the requirements for fastness to washing are becoming more stringent at present.

WO 02/08342a1 proposes dyes which largely solve the above-mentioned problems, but these dyes do not cover the desired color space (color space). The coverage of the color space is usually achieved by using dye mixtures, which however often have a significant parameter dependence during dyeing compared to monomolecular chromophores. The advantage of monomolecular chromophores is that the same coloured molecules always migrate to the fibre even if the dye parameters change, whereas when mixtures of dyes are used, the various dyes may migrate to the fibre at different rates under different dyeing conditions, and thus in each case may give rise to different hues (hue) on the substrate.

Disclosure of Invention

The present invention provides dyes of the formula (1) defined below which are surprisingly able to provide wash fastnesses which are distinctly better than those of the dyes described in DE-A3516667. In addition, these dyes have a high amount of fixation and a significantly lower parameter dependence during dyeing, and therefore are also more compatible with other dyes that fix at significantly lower temperatures. In particular, however, the dyes of the formula (1) are able to cover a larger color space than the dyes described in DE-A10035805. The present invention accordingly provides dyes of the formula (1),

wherein

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

x is halogen (e.g. fluorine or chlorine), C₁-C₄Alkoxy (e.g. methoxy or ethoxy), amino, C₁-C₄Alkylamino radical、N，N-(C₁-C₄) A dialkylamino group (e.g. N, N-dimethylamino or N, N-diethylamino), an anilino group, or an anilino group mono-or di-substituted with a sulfonic acid group or a hydroxyl group, or a group of formula (a), (b), (c), or (d)

Wherein A is^-Is fluoride, chloride, or equivalent sulfate ion, and n is 1 or 2;

R¹and R²Independently is C₁-C₆Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, or hexyl), C₁-C₆Alkoxy (e.g. methoxy, ethoxy, propoxy, or butoxy), chloro, C₁-C₄Alkylcarbonylamino (e.g., methylcarbonylamino, ethylcarbonylamino, propylcarbonylamino, or butylcarbonylamino), arylcarbonylamino (e.g., phenylcarbonylamino), or R¹And R²Combine to form a group of formula (f) or (g)

R³Is hydrogen or C₁-C₆Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, or hexyl);

q is a group of the formula (e)

Wherein

R⁴Having R³One of the definitions, or phenyl substituted by chlorine or sulfonic acid groups;

w is C₂-C₆Alkylene which may be interrupted by 1 or 2 oxygen atoms or by-NR⁵Interruption of wherein R⁵Having R³Is defined as one of the above or phenyl, and

y is vinyl or formula CH₂CH₂Z, wherein Z is a base-removable group, e.g. chloro, -OSO₃M、-S₂O₃M、OPO₃M₂、(C₂-C₅) Alkanoyloxy (e.g. acetoxy), sulfobenzoyloxy, or quaternary nitrogen,

or Q is a group of formula (a), (b), (c), or (d) when X is fluorine or chlorine.

Q is particularly preferably a radical of the formula (e), although Q is also preferably a radical of the formulae (a) and (b) when X is fluorine or chlorine.

In the radical of formula (e), R⁴Particularly preferably hydrogen or methyl, W particularly preferably ethylene, propylene or 3-oxopentyl, and Y particularly preferably vinyl or-CH₂CH₂OSO₃And M. Preferred compounds of formula (1) also include those having the following definitions:

m is hydrogen, lithium, sodium, or potassium;

x is fluorine or chlorine;

R¹is methoxy;

R²is methoxy, and/or

R³Is hydrogen or methyl.

Particularly preferred compounds of formula (1) are those wherein M, X, R¹To R³And Q each have the above-mentioned preferred and particularly preferred definitions.

Thus, particularly preferred examples of compounds of formula (1) are represented by formula (1 a):

wherein

M' is hydrogen, sodium, or potassium;

x' is fluorine or chlorine; and is

R^3’And R^4’Independently hydrogen or methyl; and is

W' is ethylene, propylene, or 3-oxopentyl.

The dyes of the formula (1) according to the invention contain-SO₂Dyes of the Z group in relation to fibre-reactive radicals-SO₂The structure in Z can be different and have the same structure in other respects. More specifically, -SO₂Z not only can be-SO₂CH＝CH₂May also be-SO₂CH₂CH₂Z, preferably is β -sulfatoethylsulfonyl, and is otherwise structurally the same. The portion of the dye in the form of the vinylsulfonyl group can be up to 95 mole percent, based on the individual dye chromophore. The molar ratio of vinylsulfonyl dye to β -ethyl-substituted dye is preferably from 5: 95 to 95: 5.

The dyes of formula (1) according to the invention can be formulated in solid or liquid (dissolved) form. In solid form, it generally comprises the electrolyte salts customary in water-soluble dyes, in particular fiber-reactive dyes, such as sodium chloride, potassium chloride, and sodium sulfate; they may also comprise auxiliaries customary in commercially available dyes, for example buffer substances capable of setting the pH of the aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate, sodium citrate, and disodium hydrogen phosphate, or small amounts of desiccants (siccatves). If they are liquid, aqueous solutions (including thickeners of the type customary in printing pastes), they may also contain substances which ensure a longer life of these formulations, for example fungicides.

In general, the dyes of formula (1) according to the invention are in the form of dye powders, containing from 10 to 80% by weight, based on the dye powder or formulation, of electrolyte salts, also known as standardizing agents (standard differentiating agents). These dye powders may also comprise 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 the form of aqueous solutions, the total dye content of these aqueous solutions is up to about 50% by weight (for example between 5 and 50% by weight), and the electrolyte salt content of these aqueous solutions, based on the aqueous solution, is preferably less than 10% by weight; the aforementioned buffer substances can be included in aqueous solutions (liquid preparations) in amounts of generally up to 10% by weight, preferably up to 2% by weight.

The dyes of the formula (1) according to the invention can be prepared from suitable precursors by means of reactions customary in dye chemistry, such as diazotisation, coupling, and metallation, and also by reaction between trihalotriazine compounds and suitably substituted amines. Such methods are well known to those skilled in the art and have been described in great detail in the pertinent literature.

For example, the compound of formula (2) may be diazotized,

wherein R is⁶Is halogen [ e.g. chlorine ] or C₁-C₄Alkoxy [ e.g. methoxy ], with a compound of formula (3)

Coupling the resulting compound of formula (4)

Diazotised with a compound of formula (5)

Coupling, and then reacting the resulting compound of formula (6)

With a suitable nickel compound to form a chromophore of formula (7)

This chromophore of the formula (7) is then reacted with a trihalotriazine compound of the formula (8)

Wherein X¹Is a halogen, and the halogen is a halogen,

to form a compound of formula (9)

And then reacted with a compound of formula H-Q to form a dye of formula (1), although when X is not halogen, the resulting compound must then be reacted with a H-X compound (wherein X is not halogen).

In addition to the above-described method, metallization can additionally be carried out in the following manner. The compound of formula (4) is diazotized and then added to the appropriate nickel compound, and the coupling reaction with the compound of formula (5) is carried out in the presence of ammonia, so that the compound of formula (7) is obtained directly, preferably by subsequent heating.

The diazotisation reaction is advantageously carried out with sodium nitrite in aqueous hydrochloric acid.

Examples of suitable nickel compounds are nickel salts, such as nickel chloride, nickel sulfate, and nickel sulfate hexahydrate. The reaction with the aforementioned nickel salt is preferably carried out in the presence of ammonia at a temperature of from 80 to 100 ℃.

The reaction between the compound of formula (7) and the halotriazine compound of formula (8) is preferably carried out in a neutral or weakly acidic medium at a temperature of about 0 ℃.

The isolation of the compounds of formula (1) according to the invention from the aqueous solution after synthesis can be carried out by generally known methods for water-soluble compounds, for example by precipitation from the reaction medium using electrolytes, such as sodium chloride or potassium chloride, or by evaporation, for example by spray drying, of the reaction solution itself. When the last separation mode mentioned above is used, it is advisable to remove any sulphate present in the solution by precipitation as calcium sulphate and filtration before evaporation.

The dyes of formula (1) according to the invention have useful performance properties. These dyes are used for dyeing or printing hydroxyl-and/or carboxamido-containing materials, for example in sheet-like form (e.g. paper and leather) or in film form, for example composed of polyamide, or in block form, for example polyamide and polyurethane; especially for dyeing or printing the aforementioned materials in fiber form. Likewise, the solutions obtained for the dyes according to the invention during the synthesis of the azo compounds can be used directly as dyeing liquid preparations (where appropriate with the addition of buffer substances before use, where appropriate concentrated or diluted before use).

The use of the dyes according to the invention for dyeing or printing these materials is therefore also provided in the present invention; or, in particular, methods for dyeing or printing these materials in a customary manner using the dyes according to the invention as colorants. These materials are preferably used in the form of fibrous materials, especially textile fibers, such as fabrics or yarns, for example in the form of hanks or wondpackages.

The hydroxyl-containing material may be of natural or synthetic origin, such as cellulosic fibrous material or its remnants and polyvinyl alcohol. The cellulosic fibrous material is preferably cotton, and other vegetable fibers such as flax, hemp, jute, ramie; examples of regenerated cellulose fibers are viscose staple (staple) and viscose filament (filament).

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

The dyes of formula (1) according to the invention can be applied to, fixed on, the aforementioned substrates, in particular the aforementioned fibre materials, using the known application techniques for water-soluble dyes, in particular fibre-reactive dyes. For example, these dyes can produce dyeings on cellulose fibres with excellent wash fastness by the exhaust method (exhaust method) from a large bath ratio (long liquor) using various acid-binding agents and optionally neutral salts such as sodium chloride or sodium sulphate. The application is preferably carried out from a water bath at a temperature of from 40 to 105 ℃, optionally at a temperature of up to 130 ℃ and at superatmospheric pressure (superatmospheric pressure), and optionally in the presence of customary dyeing auxiliaries. One possible step is to feed the material into a warm bath, gradually heating the bath to the desired dyeing temperature, and completing the dyeing process at that temperature. Neutral salts which accelerate the dye exhaustion can also be used if desired, and are added to the bath only after the actual dyeing temperature has been reached.

The padding process also produces excellent color yield and excellent dye accumulation on cellulosic fibers. The dye is fixed to the material by rolling (batching) in a customary manner at room temperature or at elevated temperature (for example up to 60 ℃ C.) by means of steam treatment or by means of dry heat.

Likewise, conventional printing processes of cellulose fibers can also produce strong prints with a well-defined and clear white background. The appearance of the print is not greatly affected by variations in the fixing treatment conditions. The conventional printing process can be carried out in a single stage, for example printing with a printing paste containing sodium bicarbonate or other acid-binding agents, followed by steam treatment at from 100 to 103 ℃; it is also possible to fix the colour in two stages, for example after printing with neutral or weakly acidic printing colorants, by passing the printed material through a hot alkaline bath containing an electrolyte or after over-pressing (over-pressing) with an alkaline pressing liquid (pressing liquid) containing an electrolyte, and then by rolling the material which has been over-pressed with alkali, or by steam treatment or by dry-heat treatment.

In the case of fixing in a dry-heat manner according to the customary thermal fixing method, hot air at 120 to 200 ℃ is used. In addition to the customary 101 ℃ and 103 ℃ steam, superheated steam and high-pressure steam at a temperature of up to 160 ℃ can also be used.

The acid-binding agent for fixing the dye of the present invention on the cellulose fiber includes, for example, water-soluble basic salts of alkali metals of inorganic acids or organic acids, water-soluble basic salts of inorganic acids or organic acids and alkaline earth metals, or compounds which liberate bases when heated. Particularly suitable are alkali metal hydroxides and alkali metal salts of weak to moderate inorganic or organic acids. Preferred alkali metal compounds are sodium compounds and potassium compounds. Such acid-binding agents include, 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 customary aftertreatment by washing to remove the unfixed dye fraction, the cellulosic dyeings obtained exhibit excellent dye properties and, by means of the application, fixing methods customary in the field of fibre-reactive dyes, are capable of providing strong olive dyeings and prints on the aforementioned materials, such as cellulosic fibre materials, especially cotton and viscose, which have excellent fastness properties, especially with respect to washing, light, alkali, acid, water, sea water, perspiration and rubbing. The dye fixing degree of the dyes on the cellulose material is high, and the dye accumulation is good; these dyeings are particularly advantageous in that they have good wash fastness, high fixing values and low temperature dependence compared with the prior art.

In addition, the dye can also be used for fiber reactive dyeing of wool; furthermore, the wool can be dyed with excellent fastness properties by a non-felting or low-felting treatment (cf., for example, H.Rath, Lehrbuch der textile, third edition (1972), p. 295-299, published by Springer-Verlag, in particular by the Hercosett method (p. 298); J.Soc.Dyers and Colourists 1972, 93-99 and 1975, 33-34).

The dyeing of the wool is carried out in the customary 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 achieve the desired pH. In order to obtain stains with an acceptable level of leveling (levelness), it is advisable to add customary leveling agents, for example based on the reaction products of cyanuric chloride with threefold molar amounts of aminobenzenesulfonic acid and/or aminonaphthalenesulfonic acid, or on the reaction products of, for example, stearylamine with ethylene oxide. For example, it is preferred that the dyes of the present invention are first exhaust from an acid bath having a pH of between about 3.5 and 5.5 under pH control, and then the pH is shifted towards the end of the dyeing time to a neutral, optionally weakly basic range of pH up to 8.5 to produce a complete reactive bond between the dyes of the present invention and the fiber for deep dyeing. At the same time, the unreacted bound dye is partially removed.

The steps described herein can also be applied to the production of dyeings on fibrous materials composed of other natural or synthetic polyamides and polyurethanes. Generally, the material to be dyed is fed into a dye bath at about 40 ℃ and after a period of agitation, the dye bath is adjusted to the desired weakly acidic pH (preferably weak acetic acid) and the actual dyeing is carried out at a temperature between 60 and 98 ℃. However, the dyeing can also be carried out in a cooker (boil) or in a closed dyeing apparatus at temperatures of up to 106 ℃. Owing to the excellent water solubility of the dyes according to the invention, these dyes can also be used advantageously in customary continuous dyeing processes. The dyes of the present invention will dye the aforementioned materials to shades of green to olive (shades).

The following examples are intended to illustrate the invention. Wherein parts and percentages are by weight unless otherwise indicated. The compounds represented by the structural formulae in the examples, some of which are shown in the form of the free acids; in general, these compounds are prepared and isolated in their salt form (preferably sodium or potassium salts) and used for dyeing in their salt form. The starting compounds mentioned in the examples below can be used analogously for the synthesis in the form of the free acids or in the form of their salts, preferably alkali metal salts, such as sodium or potassium salts.

Detailed Description

Example 1

a) After 20.3 parts of 3-amino-4-methoxybenzenesulfonic acid was dissolved in 100 parts of water under neutral conditions, it was mixed with 30 parts of concentrated hydrochloric acid and 30 parts of ice. 6.9 parts of sodium nitrite in 100 parts of water are added with stirring and stirring is continued for 60 minutes. Excess nitrite is destroyed by sulfamic acid. 15.3 parts of 3, 4-dimethoxyaniline are added and the pH is adjusted to 4.0 with 10% sodium carbonate solution, this adjustment being completed in the course of 2 hours. The precipitated dye is filtered off with suction.

b) The dye obtained in a) is dissolved under neutral conditions, mixed with 6.9 parts of sodium nitrite and added dropwise with thorough stirring to a mixture comprising 180 parts of ice-water and 30 parts of concentrated hydrochloric acid. The mixture was stirred for a further 60 minutes, while excess nitrite was destroyed with sulfamic acid. To the resultant reaction mixture was added 27 parts of nickel sulfate hexahydrate, and the resultant reaction mixture was added to a solution of 31 parts of 5-hydroxy-1, 7-disulfonyl-2-naphthylamine and 65 parts of 25% ammonia solution in 500 parts of ice-water.

c) Heating the reaction solution obtained in b) to 80-100 ℃ for 1-3 hours, followed by isolating the dye at room temperature by adding a salt to obtain the chromophore of formula (7a)

The compounds of formula (7a) can also be prepared in a similar manner using 3-amino-4-chlorobenzenesulfonic acid. The compound of formula (7a) is dissolved under neutral conditions and desalted by pressure permeation.

d) After the compound of the formula (7a) prepared in c) has been dissolved under neutral conditions, it is mixed at 0 ℃ with 34.4 parts of trifluorotriazine by thorough stirring, while maintaining the pH at 5 with 20% aqueous sodium hydroxide solution. The compound obtained in this way has the formula (9a)

The compound of formula (9a) is mixed with a solution of 15 parts of N-methyl-N- (2-. beta. -sulfatoethylsulfonate) ethylamine for 10 minutes while maintaining the pH at 6 with 20% sodium hydroxide solution. The reaction mixture was then allowed to return to room temperature. Adding a salt to isolate the dye of formula (1b) according to the invention.

Example 2

The compound of formula (7a) prepared according to example 1 is dissolved in 100 parts of water under neutral conditions and reacted with 18.5g of trichlorotriazine at 20-40 ℃ to form the compound of formula (9 b).

The pH of the reaction mixture was maintained by the addition of 10% sodium carbonate solution followed by the addition of 18 parts of an amine compound of the formula

The dye solution is concentrated by a thin film desalting method and then spray dried to obtain the dye of the formula (1c) of the invention.

Example 3

The dye of formula (1c) of example 2 is dissolved in water, the pH is adjusted to 11 with 20% aqueous sodium hydroxide solution at 0 ℃ and then to 7 with 31% hydrochloric acid to give the dye of formula (1d) according to the invention.

Example 4

The dye of formula (1b) of example 1 is dissolved in water under neutral conditions, the pH is adjusted to 11 with 20% aqueous sodium hydroxide solution at 0 ℃ and stirred for 30 minutes, and then the pH is adjusted to 7 with 31% hydrochloric acid to give the dye of formula (1e) according to the invention.

Example 5

The dyes of the formula (1f) according to the invention

Can be prepared in a similar manner following the procedures described in examples 1 to 4.

Example 6

The dyes of the formula (1g) according to the invention

Example 7

2 parts of the dye of the formula (1e) from example 4 are dissolved in 400 parts of water, 20 parts of sodium chloride, 8 parts of sodium carbonate and 20 parts of cotton are added and heated to 60 ℃ in a dyeing machine over a period of 25 minutes. Dyeing is carried out at 60 ℃ for 60 minutes, and the cotton is subsequently washed with water and dilute acetic acid and dried to give a green stain having good light fastness.

Claims

1. A dye represented by the following formula (1)

Wherein

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

x is halogen, C₁-C₄Alkoxy, amino, C₁-C₄Alkylamino, N- (C)₁-C₄) Dialkylamino, anilino, or mono-substituted with sulfonic or hydroxy groupsA substituted or disubstituted anilino group, or a group of formula (a), (b), (c), or (d)

R¹and R²Independently is C₁-C₆Alkyl radical, C₁-C₆Alkoxy, chlorine, C₁-C₄Alkylcarbonylamino, or arylcarbonylamino, or R¹And R²Combine to form a group of formula (f) or (g)

R³Is hydrogen or C₁-C₆An alkyl group;

q is a group of the formula (e)

Wherein

y is vinyl or formula CH₂CH₂A group of Z, wherein Z is a base removable group;

2. The dye according to claim 1, wherein

M is hydrogen, lithium, sodium, or potassium;

x is fluorine or chlorine;

R¹is methoxy:

R²is methoxy; or

R³Is hydrogen or methyl.

3. The dye according to claim 1, wherein

M is hydrogen, lithium, sodium, or potassium;

x is fluorine or chlorine;

R¹is methoxy:

R²is methoxy; and is

R³Is hydrogen or methyl.

4. A dye according to any one of claims 1 to 3, wherein Q is a group of formula (e).

5. A dye according to claim 4, wherein in the group of formula (e), R⁴Is hydrogen or methyl, W is ethylene, propylene, or 3-oxopentyl, and Y is vinyl or CH₂CH₂OSO₃M。

6. A dye according to any one of claims 1 to 3, wherein Q is a group of formula (a) or (b).

7. The dye of claim 1, which is of formula (1a)

Wherein

M' is hydrogen, sodium, or potassium;

x' is fluorine or chlorine; and is

R^3’And R^4’Independently hydrogen or methyl; and is

W' is ethylene, propylene, or 3-oxopentyl.

8. Process for the preparation of a dye of formula (1) as claimed in one or more of claims 1 to 7, comprising diazotisation of a compound of formula (2)

Wherein R is⁶Is halogen or C₁-C₄An alkoxy group,

and with a compound of formula (3)

Coupling the resulting compound of formula (4)

Diazotised with a compound of formula (5)

Coupling, and then reacting the resulting compound of formula (6)

With a suitable nickel compound to form a chromophore of formula (7)

This chromophore of the formula (7) is then reacted with a trihalotriazine of the formula (8)

Wherein X¹Is a halogen, and the halogen is a halogen,

to form a compound of formula (9)

Then reacting with a compound of formula H-Q to form a dye of formula (1); although when X is not a halogen, the resulting compound is then reacted with a H-X compound (wherein X is not a halogen).

9. Use of a dye as claimed in one or more of claims 1 to 7 for dyeing or printing materials containing hydroxyl and/or carboxamide groups.

10. Material containing hydroxyl and/or carboxamide groups which has been dyed or printed by a dye as claimed in one or more of claims 1 to 7.