HK1075271B - Fiber-reactive azo dyes, preparation thereof and use thereof - Google Patents

Description

Fiber-reactive azo dyes, their preparation and their use

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

Fibre-reactive azo dye mixtures and their use for dyeing hydroxyl-and/or carboxamido-containing materials to yellowish to reddish brown are known, for example, from the documents JP 8060017, WO00/06652 and DE 19600765 a 1. However, they have certain application drawbacks such as, for example, the colour yield is excessively dependent on changing the dyeing parameters in the dyeing process or an insufficient or uneven dye accumulation on the cotton (good dye accumulation results from the ability of the dye to provide proportionally stronger dyeing when dyed in higher concentrations in the dyebath). The consequence of these drawbacks is the poor reproducibility of the dyeings obtainable, which ultimately impairs the economics of the dyeing operations. Thus, there is still a need for new reactive dyes with improved properties such as high substantivity and good washout properties of the unfixed portion. They will furthermore additionally provide good colour yields and have high reactivity, and they will in particular provide dyeings having high degrees of fastness.

Accordingly, the present invention provides dyes having these high properties. The novel dye mixtures are notable in particular for a high amount of fixation on the fibers and the easy washout properties of the unfixed parts. In addition, the dyes should have good general fastnesses, such as, for example, high light fastness and good wet fastnesses.

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

wherein

D¹And D²Independently represents a group of formula (1):

wherein

R¹And R²Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; and

X¹is hydrogen or formula-SO₂-a group of Z,

wherein

Z is-CH ═ CH₂、-CH₂CH₂Z¹Or a hydroxyl group, or a mixture thereof,

wherein

Z¹Is hydroxy or a base-removable group; or

D¹And D²Independently represents a naphthyl group of the general formula (2):

wherein

R³And R⁴Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; and

X²having X¹One of the meanings of (a); or

D¹And D²Independently represents a group of the general formula (3):

wherein

R⁵And R⁶Independently have R¹And R²One of the meanings of (a);

R⁷is hydrogen, (C)₁-C₄) -alkyl, unsubstituted phenyl or (C)₁-C₄) -alkyl-, (C)₁-C₄) -alkoxy-, sulfo-, halogen-or carboxy-substituted phenyl; and

Z²is a group of the general formula (4) or (5) or (6):

wherein

V is fluorine or chlorine;

U¹、U²independently fluorine, chlorine or hydrogen; and

Q¹、Q²independently chlorine, fluorine, cyanamido, hydroxyl, (C)₁-C₆) Alkoxy, phenoxy, sulfophenoxy, mercapto, (C)₁-C₆) -alkylthio, pyrido, carboxypyrido, carbamoylpyrido, or a group of general formula (7) or (8) below:

wherein

R⁸Is hydrogen or (C)₁-C₆) Alkyl, sulfo- (C)₁-C₆) -alkyl or unsubstituted phenyl or (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, sulfo, halogen, carboxyl, acetamido, ureido-substituted phenyl;

R⁹and R¹⁰Independently have R⁸One or a combination of the meanings of (A) forms the formula- (CH)₂)_jA ring system of (a) wherein j is 4 or 5, or a combination forms- (CH)₂)₂-E-(CH₂)₂A ring system of (a) wherein EIs oxygen, sulfur, sulfo, -NR¹¹Wherein R is¹¹＝(C₁-C₆) -an alkyl group;

w is unsubstituted phenylene or phenylene which is substituted by 1 or 2 substituents, such as (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, carboxy, sulfo, chloro, bromo; or is (C)₁-C₄) Alkylene-arylene or (C)₂-C₆) Alkylene which may be interrupted by oxygen, sulfur, sulfo, amino, carbonyl, carboxamide groups; or is phenylene-CONH-phenylene which is unsubstituted or substituted by (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, amido, ureido or halogen substitution; or naphthylene, which is unsubstituted or substituted by one or two sulfo groups; and

z is as defined above; or

D¹And D²Independently a group of formula (9):

wherein

R¹²Is hydrogen, (C)₁-C₄) -alkyl, aryl or substituted aryl;

R¹³and R¹⁴Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; and

a is a phenylene group of the general formula (10),

wherein

R¹⁵And R¹⁶Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; or

A is a naphthylene group of the general formula (11):

wherein R is¹⁷And R¹⁸Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; or

A is a polymethylene group of the general formula (12):

-(CR¹⁹R²⁰)_k- (12)

wherein

k is an integer greater than 1, and

R¹⁹and R²⁰Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, cyano, amido, halogen or aryl; and

X³having X¹One of the meanings of (a); and

R、R^*independently hydrogen, (C)₁-C₄) -alkyl or sulfomethyl; and

m is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, with the proviso that the dyes of the general formula (I) contain at least one fibre-reactive group of the general formulae (4) to (6).

The individual symbols in the above and below formulae may have identical or different meanings under their definitions, irrespective of whether these symbols have identical or different designations.

(C₁-C₄) The alkyl radical R may be linear or branched, and is in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. Methyl and ethyl are preferred. The same logic applies to (C)₁-C₄) -alkoxy groups.

Aryl R is in particular phenyl. Substituted aryl radicals R⁸To R¹⁰Or R¹²In particular by one, two or three independently selected from (C)₁-C₄) Alkyl radicals, (C)₁-C₄) Phenyl substituted by alkoxy, hydroxy, sulfo, carboxy, amido and halogen radicals.

Halogen R is in particular fluorine, chlorine or bromine, preferably fluorine and chlorine.

Z is eliminable by alkali in the beta-position of the ethyl group of Z¹Including, for example, halogen atoms such as chlorine and bromine; ester groups of organic carboxylic and sulfonic acids such as alkanoyloxy groups of 2 to 5 carbon atoms, particularly acetoxy, benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxy and p-tolylsulfonyloxy, such as alkyl carboxylic acids, substituted or unsubstituted benzoic acids and substituted or unsubstituted benzenesulfonic acids; also included are ester groups of inorganic acids such as phosphoric acid, sulfuric acid, and thiosulfuric acid (phosphato, sulfato, and thiosulfato groups); analogous dialkylamino radicals having in each case an alkyl radical having up to 4 carbon atoms, such as dimethylamino and diethylamino.

Z is preferably vinyl or β -chloroethyl, particularly preferably β -sulfatoethyl.

The radicals "sulfo", "carboxyl", "thiosulfato", "phosphato" and "phosphato" include not only their acid forms but also their salt forms. Thus, sulfo is of the formula-SO₃The radical corresponding to M, the thiosulfato radical being of the formula-S-SO₃M is a group corresponding to the formula-COOM, carboxyl is a group corresponding to the formula-COOM, and phosphate is a group corresponding to the formula-OPO₃M₂A uniform radical, and sulfate radicalThe radical of the formula-OSO₃M is identical to the radicals, in each case M is as defined above.

The dyes of the formula (I) may have different fibre-reactive groups-SO within the meaning of Z₂And Z. More specifically, the fiber-reactive group-SO₂Z may be vinylsulfonyl on the one hand and-CH on the other hand₂CH₂Z¹The radical, preferably β -sulfatoethylsulfonyl. If the dyes of the formulae (I) to (I11) contain vinylsulfonyl groups in some cases, the proportion of each dye having vinylsulfonyl groups is up to about 30 mol%, based on the amount of the respective total dye.

The base M is in particular lithium, sodium or potassium. M is preferably hydrogen or sodium.

R¹And R²Preferably hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, sulfo or carboxyl, more preferably hydrogen, methyl, methoxy or sulfo.

R³To R⁶And R¹²To R²⁰Preferably hydrogen, R³To R⁶、R¹⁷And R¹⁸Also preferred is a sulfo group.

R⁷To R¹⁰Preferably hydrogen or methyl, R⁷And R⁸Preferably phenyl, and R⁹And R¹⁰Preferably 2-sulfoethyl, 2-, 3-or 4-sulfophenyl or R⁹And R¹⁰Combined to form the formula- (CH)₂)₂-O-(CH₂)₂-a ring system of (a).

Group D of the general formulae (1) and (2)¹And D²Examples of (B) are 2- (. beta. -sulfatoethylsulfonyl) phenyl, 3- (. beta. -sulfatoethylsulfonyl) phenyl, 4- (. beta. -sulfatoethylsulfonyl) phenyl, 2-carboxy-5- (. beta. -sulfatoethylsulfonyl) phenyl, 2-chloro-4- (. beta. -sulfatoethylsulfonyl) phenyl, 2-chloro-5- (. beta. -sulfatoethylsulfonyl) phenyl, 2-bromo-4- (. beta. -sulfatoethylsulfonyl) -phenyl, 2-sulfo-4- (. beta. -sulfatoethylsulfonyl) phenylPhenylsulfonyl) phenyl, 2-sulfo-5- (. beta. -sulfatoethylsulfonyl) phenyl, 2-methoxy-5- (. beta. -sulfatoethylsulfonyl) phenyl, 2-ethoxy-5- (. beta.0-sulfatoethylsulfonyl) phenyl, 2, 5-dimethoxy-4- (. beta.1-sulfatoethylsulfonyl) phenyl, 2-methoxy-5-methyl-4- (. beta.2-sulfatoethylsulfonyl) phenyl, 2-methyl-4- (. beta.3-sulfatoethylsulfonyl) phenyl, 2-or 3-or 4- (. beta.4-thiosulfatoethylsulfonyl) phenyl, 2-methoxy-5- (. beta.5-thiosulfatoethylsulfonyl) phenyl, 2-sulfo-4- (. beta.6-phosphatoethylsulfonyl) phenyl, 2-or 3-or 4-vinylsulfonylphenyl, 2-sulfo-4-vinylsulfonylphenyl, 2-chloro-4- (. beta.7-chloroethylsulfonyl) phenyl, 2-chloro-5- (. beta.8-chloroethylsulfonyl) phenyl, 3-or 4- (. beta.9-acetoxyethylsulfonyl) phenyl, 6-or 8- (. beta. -sulfatoethylsulfonyl) naphthalen-2-yl, 6- (. beta.0-sulfatoethylsulfonyl) -1-sulfonaphthalen-2-yl and 8- (. beta. -sulfatoethylsulfonyl) -6-sulfo-naphthalen-2-yl, preference is given to 3- (. beta. -sulfatoethylsulfonyl) phenyl, 4- (. beta. -sulfatoethylsulfonyl) phenyl, 2-sulfo-4- (. beta. -sulfatoethylsulfonyl) phenyl, 2-methoxy-5- (. beta. -sulfatoethylsulfonyl) phenyl, 2, 5-dimethoxy-4- (. beta. -sulfatoethylsulfonyl) phenyl, 2-methoxy-5-methyl-4- (. beta. -sulfatoethylsulfonyl) phenyl, and 3-or 4-vinylsulfonylphenyl, or D¹And D²A group corresponding to the general formula (3) or (9) wherein R⁵To R⁷And R¹²To R¹⁴Have the preferred meanings mentioned above.

When D is present¹And D²In the case of the group of the formula (2), the bond to the diazo group is preferably located at the beta-position of the naphthalene nucleus.

When A is phenylene and X³is-SO₂Z is, SO₂The Z group is preferably located in the meta or para position relative to the nitrogen atom. In the radical of the formula (9), the carboxamide group is preferably located para or meta to the diazo group. When A is naphthylene, the bond to the diazo group is preferably located at the beta-position of the naphthalene nucleus.

Examples of substituents A are in particular 1, 2-phenylene, 1, 3-phenylene, 1, 4-phenylene, 2-chloro-1, 5-phenylene, 2-bromo-1, 4-phenylene, 2-sulfo-1, 5-phenylene, 2-methoxy-1, 5-phenylene, 2-ethoxy-1, 5-phenylene, 2, 5-dimethoxy-1, 4-phenylene, 2-methoxy-5-methyl-1, 4-phenylene, 2, 6-naphthylene, 2, 8-naphthylene, 1-sulfo-2, 6-naphthylene, 6-sulfo-2, 8-naphthylene or 1, 2-ethylene and 1, 3-propylene.

A is particularly preferably 1, 3-phenylene, 1, 4-phenylene, 2-sulfo-1, 4-phenylene, 2-methoxy-1, 5-phenylene, 2, 5-dimethoxy-1, 4-phenylene, 2-methoxy-5-methyl-1, 4-phenylene or 1, 2-ethylene and 1, 3-propylene, and in the case of the two last-mentioned alkylene groups the radical R1 is preferably phenyl or 2-sulfophenyl.

k is preferably 2 or 3.

W is preferably 1, 3-phenylene, 1, 4-phenylene, 2-sulfo-1, 4-phenylene, 2-methoxy-1, 5-phenylene, 2, 5-dimethoxy-1, 4-phenylene, 2-methoxy-5-methyl-1, 4-phenylene, 1, 2-ethylene or 1, 3-propylene.

Group Q in the general formula (5)¹And Q²Examples of (A) are independently fluorine, chlorine, hydroxyl, methoxy, ethoxy, phenoxy, 3-sulfophenoxy, 4-sulfophenoxy, methylthio, cyanamido, amino, methylamino, ethylamino, morpholino, piperidino, phenylamino, methylphenylamino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 2, 4-disulfo-phenylamino, 2, 5-disulfo-phenylamino, 2-sulfoethylamino, N-methyl-2-sulfoethylamino, pyrido, 3-carboxypyrido, 4-carboxypyrido, 3-carbamoylpyrido, 4-carbamoylpyrido, 2- (2-sulfatoethylsulfonyl) phenylamino, 3- (2-sulfatoethylsulfonyl) phenylamino, 4- (2-sulfatoethylsulfonyl) phenylamino, N-ethyl-3- (2-sulfatoethylsulfonyl) phenylamino, N-ethyl-4- (2-sulfatoethylsulfonyl) phenylamino, 2-carboxy-5- (2-thio)Acidoethylsulfonyl) phenylamino, 2-chloro-4- (2-sulfatoethylsulfonyl) phenylamino, 2-chloro-5- (2-sulfatoethylsulfonyl) phenylamino, 2-bromo-4- (2-sulfatoethylsulfonyl) phenylamino, 2-sulfo-5- (2-sulfatoethylsulfonyl) phenylamino, 2-methoxy-5- (2-sulfatoethylsulfonyl) phenylamino, 2, 5-dimethoxy-4- (2-sulfatoethylsulfonyl) phenylamino, 2-methoxy-5-methyl-4- (2-sulfatoethylsulfonyl) phenylamino, 2-methyl-4- (2-sulfatoethylsulfonyl) phenylamino, 2- (vinylsulfonyl) phenylamino, 3- (vinylsulfonyl) phenylamino, 4- (vinylsulfonyl) phenylamino, N-ethyl-3- (vinylsulfonyl) phenylamino, N-ethyl-4- (vinylsulfonyl) phenylamino, 6- (2-sulfatoethylsulfonyl) naphthalen-2-ylamino, 8- (2-sulfatoethylsulfonyl) -6-sulfonaphthalen-2-ylamino, 3- (2- (2-sulfatoethylsulfonyl) ethylcarbamoyl) phenylamino, 4- (2- (2-sulfatoethylsulfonyl) -ethylcarbamoyl) -phenylamino, 3- (2- (vinylsulfonyl) -ethylcarbamoyl) -phenylamino, 4- (2- (vinylsulfonyl) ethylcarbamoyl) phenylamino, 4- (N-methyl-2- (2-sulfatoethylsulfonyl) ethylcarbamoyl) phenylamino, 4- (N-phenyl-2- (2-sulfatoethylsulfonyl) ethylcarbamoyl) phenylamino, 4- (3- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 4- (4- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 3- (3- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 3- (4- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 3- (2-sulfatoethylsulfonyl) propylamino, N-methyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino, N-phenyl-N- (3- (2-sulfatoethylsulfonyl) propyl) amino.

Preferably, the group Q in the formula (5)¹And Q²Independently is fluorine, chlorine, cyanamide, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, N-methylThe group-2-sulfoethylamino, 3-carboxypyrido, 4-carboxypyrido, 3-carbamoylpyrido, 4-carbamoylpyrido, 3- (2-sulfatoethylsulfonyl) phenylamino, 4- (2-sulfatoethylsulfonyl) phenylamino, 3- (vinylsulfonyl) phenylamino, 4- (3- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 4- (4- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 3- (3- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 3- (4- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 3- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, N-methyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino, N-phenyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino.

More preferably, the group Q in the formula (5)¹And Q²Independently fluorine, chlorine, cyanamide, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 3- (2-sulfatoethylsulfonyl) phenylamino, 4- (2-sulfatoethylsulfonyl) phenylamino, 3- (vinylsulfonyl) phenylamino, 4- (vinylsulfonyl) phenylamino, N-methyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino, N-phenyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino.

Group Z²Examples of (a) 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, or a compound having Q as defined above¹And Q²Examples of (3) are a group of the general formula (5) or a 2, 3-dichloroquinoxaline-6-carbonyl group.

Preferably, Z²Is 2, 4-difluoropyrimidin-6-yl, 4, 6-difluoropyrimidin-2-yl, 5-chloro-2, 4-difluoropyrimidin-6-yl, 5-chloro-4, 6-difluoropyrimidin-2-yl or has Q as described above¹And Q²Examples of (3) are a group of the general formula (5).

More preferably, Z²Is 2, 4-difluoropyrimidin-6-yl, 5-chloro-2, 4-difluoropyrimidin-6-yl, or has Q as described above¹And Q²A group of the general formula (5) of a particularly preferred example of (3).

Preferred dyes conform to the general formula (Ia):

in the general formula (Ia), D¹、D²M and R have the abovementioned meanings.

Optionally, the dye mixtures according to the invention may also comprise one or more monoazo dyes of the general formula (13), (14) or (15) in an amount of up to 10% by weight, preferably up to 5% by weight:

wherein D¹、D²、R、R^*And M has the above-mentioned meaning. More preferably, R^*Is hydrogen.

The dye mixtures according to the invention can be present in the formulations in solid or liquid (dissolved) form. In solid form, they contain, according to the requirements of some extent, electrolyte salts which are customarily used in water-soluble dyes, in particular fibre-reactive dyes, such as sodium chloride, potassium chloride and sodium sulfate; and may additionally contain auxiliaries commonly used in industrial dyes, such as buffer substances capable of adjusting the pH of an aqueous solution to 3 to 7, such as sodium acetate, sodium citrate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate and disodium hydrogen phosphate; dye auxiliary agent, dust-proof agent and a small amount of drier; when they are present in the form of liquid, aqueous solutions (comprising thickeners conventionally used in printing pastes), they may also comprise substances which ensure a long life of these formulations, such as mildewcides.

When present in solid form, the dye mixtures of the invention are generally powders or granules which comprise electrolyte salts, which are generally referred to hereinafter as a formulation with or without at least one of the abovementioned auxiliaries. In this formulation, the dye mixture is present in an amount of 20 to 90% by weight, based on the formulation in which it is contained. The total amount of buffer substances present is generally up to 5% by weight, based on the formulation.

When the dye mixtures according to the invention are present in the form of aqueous solutions, the total dye content of these aqueous solutions is up to about 50% by weight, for example from 5 to 50% by weight, the electrolyte salt content of these aqueous solutions preferably being less than 10% by weight, based on the aqueous solution; the aqueous solutions (liquid preparations) may contain the abovementioned buffer substances in general up to 5% by weight and preferably up to 2% by weight.

The dyes of the general formulae (13), (14) and (15) are in some cases formed during the synthesis of the dyes of the general formula (I).

The dyes of the invention can be prepared, for example, by diazotizing one equivalent of an amine of the formula (16) in a conventional manner in a first stage and reacting the resulting diazo compound with one equivalent of an aqueous solution or suspension of a coupling component of the formula (17) in an acid medium to form a monoazo dye of the formula (13),

D¹-NH₂ (16)

wherein D is¹The definition of (A) is the same as that of (B),

r, R therein^*And each of M is as defined above,

and subsequently in a second stage, diazotizing one equivalent of an amine of the formula (18) in the customary manner and coupling the diazo compound obtained with the monoazo dye of the formula (13) obtained in the first stage to form the disazo dye of the formula (I),

D²-NH₂(18) wherein，D¹The definition of (A) is as above.

When the radical D of the formula (I)¹And D²Having the same meaning, they can be prepared by reacting, in a conventional manner, two equivalents of an amine of the formula (16) in which D is¹As defined above) and reacted with one equivalent of a coupling component of the general formula (17) in an acidic medium to form a monoazo dye of the general formula (13), followed by a second coupling by increasing the pH to form a disazo dye of the general formula (I), wherein D¹And D²Have the same meaning.

The isolation of the dyes of the invention can be carried out in a conventional manner, for example by salting out using sodium chloride or potassium chloride or by spray drying or evaporation.

Similarly, the synthetically obtained dye solution of the general formula (I) can be used directly as a liquid preparation for dyeing after suitable addition of buffer substances and after suitable concentration.

Dye mixtures which contain vinylsulfonyl as active group in addition to β -chloroethylsulfonyl or β -thiosulfatoethylsulfonyl or β -sulfatoethylsulfonyl can be synthesized not only starting from appropriately substituted vinylsulfonylanilines or naphthylamines but also by reacting dye mixtures in which Z is β -chloroethyl, β -thiosulfatoethyl or β -sulfatoethyl with the desired moiety of a base and converting the β -substituted ethylsulfonyl into vinylsulfonyl. This transformation is carried out in a manner well known to the person skilled in the art.

The invention also provides an aqueous liquid preparation which contains 5 to 90 wt% of the above reactive dye.

The dyes of the general formula (I) according to the invention have useful application properties. They can be used for dyeing and printing hydroxyl-and/or carboxamido-containing materials, for example in the form of sheet-like structures such as paper and leather, or in the form of films such as films composed of polyamide, or in bulk such as polyamide and polyurethane, but are used in particular for dyeing and printing these materials in the form of fibers. Similarly, the synthetically obtained dye solution of the general formula (I) can be used directly as a liquid preparation for dyeing after suitable addition of buffer substances and after suitable concentration or dilution.

The present invention therefore also provides the use of the dyes of the general formula (I) according to the invention for dyeing or printing these materials or processes 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 fibre materials or regenerated products thereof and polyvinyl alcohol. The cellulose fiber material is preferably cotton, and other plant fibers such as flax, hemp, jute and ramie fibers are also selected; regenerated cellulose fibers are, for example, short and long viscose, and chemically modified cellulose fibers, such as aminated cellulose fibers or those described in WO 96/37641 and WO 96/37642 and in EP 0538785 and EP 0692559.

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 dye mixtures according to the invention can be applied and fixed to the materials, in particular the fibre materials, by the application techniques known for water-soluble dyes, in particular fibre-reactive dyes. For example, the dye mixtures of the present invention produce dyeings on fibers with excellent dye yields by the exhaust process using a variety of acid binding agents and optionally neutral salts such as sodium chloride or sodium sulfate at large and small bath ratios such as liquor to fabric ratios of 5: 1 to 100: 1, preferably 6: 1 to 30: 1. Preferably at 45 to 105 c, optionally at superatmospheric pressure up to 130 c, but preferably in an aqueous bath at 30 to 95 c, in particular at 45 to 65 c, in the presence or absence of customary dyeing auxiliaries. One possible method in this context is to introduce the material into a warm bath and gradually heat the warm bath to the desired dyeing temperature and complete the dyeing process at this temperature. Neutral salts to promote exhaustion of the dye may be added to the dye bath as required after the actual dyeing temperature is reached.

The pad dyeing process likewise provides excellent dye yields and excellent dye build-up on cellulosic fibers, which can be fixed in a conventional manner in batches by room temperature or at elevated temperatures, e.g. at temperatures up to about 60 ℃, in a continuous manner, e.g. by pad-dry-pad steaming process, steaming or dry heat treatment.

Similarly, conventional printing processes for cellulose fibers produce 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, such as by printing with neutral or weakly acidic printing dyes, followed by fixing by overbiadding the printed material through a hot alkaline bath containing an electrolyte or with a padding liquor containing a basic electrolyte and then over-padding the package of material over-padded with alkali or by steaming or subsequent dry heat treatment of the over-padded material with alkali. Changes in the fixing conditions have only a minor effect on the printing result.

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

Acid-binding agents for fixing the dyes of the general formula (I) according to the invention to cellulose fibres are, for example, water-soluble basic salts of alkali metals and alkaline earth metals of inorganic or organic acids, or compounds which release alkali on heating, and also alkali metal silicates. 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, sodium phosphate or water glass or mixtures thereof, for example mixtures of aqueous sodium hydroxide solution and water glass.

The dyes of the general formula (I) according to the invention have outstanding tinctorial strength when applied to cellulosic fibre materials by dyeing or printing in the absence or in very small amounts of alkali or alkaline earth metal compounds. For example, a light shade requires no electrolyte salt, a medium shade requires at most 5g/L of electrolyte salt, and a dark shade requires at most 10g/L of electrolyte salt.

According to the invention, light shades mean the use of 2% by weight of dye, based on the substrate to be dyed, medium shades mean the use of 2 to 4% by weight of dye, based on the substrate to be dyed, and dark shades mean the use of 4 to 10% by weight of dye, based on the substrate to be dyed.

Dyeings and prints obtained using the dyes of the general formula (I) according to the invention can have bright shades; more particularly, the dyeings and prints on cellulosic fibre materials have good light fastness and particularly good wet fastnesses, such as fastness to washing, grinding, water, sea water, cross-dyeing and acidic and alkaline perspiration, and also fastness to pleating, hot pressing and rubbing. In addition, the cellulosic dyeings obtained after conventional post-treatment with rinsing to remove the unfixed dye moieties exhibit excellent wet fastness, particularly because the unfixed dye moieties are easy to wash off due to their good solubility in cold water.

In addition, the dyes of the general formula (I) according to the invention can also be used for the fibre-reactive dyeing of wool. In addition, wool which has been subjected to both non-felting finishing and low-felting finishing (see, for example, H.Path, Lehrbuchker texthemie, Springer Vertag, third edition (1972), page 295-299, especially by Hercosett processes (298); 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. In order to obtain dyes with acceptable levelling properties, it is advisable to add conventional levelling agents, such as levelling agents based on the reaction products of cyanuric chloride with tripling molar amounts of aminobenzenesulfonic acid and/or aminonaphthalenesulfonic acid, or based on the reaction products of, for example, octadecylamine with ethylene oxide. For example, the dyes of the general formula (I) according to the invention are preferably subjected to an initial exhaustion of the dyebath which is acid with a pH value of about 3.5 to 5.5 and then becomes neutral as the dyeing time approaches the end pH value and optionally is weakly basic with a pH value of at most 8.5, with complete reactive bonding between the dyes of the dye mixtures according to the invention and the fibers, in particular for deep-dyeing. At the same time, the dye moiety that is not actively bound is removed.

The process described herein is also applicable to the formation of dyeings on fibrous materials composed of other natural polyamides or synthetic polyamides and polyurethanes. Generally, the material to be dyed is introduced into a dye bath at a temperature of about 40 ℃ with stirring for a certain time, and the dye bath is then 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 the boiling point or at a temperature of up to 106 ℃ in a sealed dyeing apparatus. Since the dyes of the general formula (I) according to the invention are excellent in water solubility, they can also be advantageously used in conventional continuous dyeing processes. The dye mixtures according to the invention have a high tinctorial strength.

The dyes of the general formula (I) according to the invention can dye the abovementioned materials, preferably fiber materials, to yellowish to reddish-brown shades having good fastness properties.

The examples which follow serve to illustrate the invention. Parts and percentages are by weight unless otherwise indicated. Parts by weight versus parts by volume refer to kilograms versus liters. The compounds described in the examples with the formula are all shown in the form of the free acids, since they are usually prepared and isolated as salts, preferably as sodium or potassium salts, and used for dyeing in the form of salts. The starting compounds described in the examples below can be used in the synthesis in the form of the free acids or likewise in the form of their salts, preferably in the form of alkali metal salts, such as sodium or potassium salts. The maximum absorption of UV/Vis in the report is determined with water as solvent.

Example 1

a) 302 parts of a product obtained by condensing 134 parts of 2, 4, 6-trifluoropyrimidine with 188 parts of 2, 4-diaminobenzenesulfonic acid are suspended in 2500 parts of ice water and 350 parts of 30% hydrochloric acid, and diazotized at 5 ℃ by dropwise addition of 175 parts of a 40% sodium nitrite solution. After removing excess nitrite with sulfamic acid, 333 parts of 4-hydroxy-7- (sulfomethylamino) naphthalene-2-sulfonic acid prepared by reacting 239 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid with 147 parts of formaldehyde sodium bisulfite in an aqueous medium at pH5.5-6 and 40-50 ℃ are added and a coupling reaction is carried out at 5-10 ℃ and pH below 1.5 to form a red-orange monoazo dye of formula (13-1).

b) In a second separate vessel 281 parts of 4- (. beta. -sulfatoethylsulfonyl) aniline are suspended in 700 parts of ice-water and 180 parts of 30% hydrochloric acid and diazotized by dropwise addition of 174 parts of 40% sodium nitrite solution. Subsequently, excess nitrite is removed with sulfamic acid solution and the resulting diazotised suspension is pumped after the first coupling stage into the solution of the monoazo dye (13-1) of a) while adjusting and maintaining the pH at 5-6 with sodium carbonate below 25 ℃.

The slightly yellowish red disazo dye formed after the end of the second coupling reaction is isolated by spray drying or evaporation under reduced pressure and by salting out with sodium chloride or potassium chloride.

Alternatively, the resulting dye solution may be buffered at pH5.5-6 by the addition of phosphate buffer and further adjusted by dilution or concentration to give a liquid formulation of defined strength.

The dyes according to the invention obtained dye cotton to a yellowish red colour with good general fastness.

Example 2

a) 361 parts of 2-amino-5- (. beta. -sulfatoethylsulfonyl) benzenesulfonic acid are suspended in 1500 parts of ice water and 300 parts of concentrated sulfuric acid and diazotized at 10 ℃ by dropwise addition of 175 parts of a 40% sodium nitrite solution. After removing excess nitrite with sulfamic acid, 239 parts of an aqueous solution of 7-amino-4-hydroxynaphthalene-2-sulfonic acid (pH6.5-7) were added and a coupling reaction was carried out at a pH below 1.3 and at 5-10 ℃ to form a red monoazo dye of formula (13-2).

b) In a second, separate reaction vessel, the product obtained by condensing 134 parts of 2, 4, 6-trifluoropyrimidine with 180 parts of 2, 4-diaminobenzenesulphonic acid is suspended in 3000 parts of ice water and mixed with 174 parts of 40% sodium nitrite solution. This mixture was added dropwise to a vessel initially containing 1000 parts ice and 330 parts 30% hydrochloric acid, followed by stirring the contents at 10 ℃ until diazotization was complete. Excess nitrite is subsequently removed with sulfamic acid solution and the resulting diazotised suspension is pumped after the first coupling stage into the solution of the monoazo dye (13-2) of a) while adjusting and maintaining the pH at 5-6 with sodium carbonate below 15 ℃.

The yellowish red disazo dye (I-2) formed after the end of the second coupling reaction can suitably be isolated by evaporation under reduced pressure after removal of the reaction solution. The dyes obtained by the present invention dye cotton to a yellowish red colour with good general fastness.

Example 3

336.5 parts of a product obtained by condensation of 168.5 parts of 5-chloro-2, 4, 6-trifluoropyrimidine with 188 parts of 2, 4-diaminobenzenesulphonic acid are diazotized in a manner analogous to example 1a) or 2b), admixed, after removal of excess nitrite with sulfamic acid, with 166.5 parts of 4-hydroxy-7- (sulphomethylamino) naphthalene-2-sulphonic acid (prepared by reacting 119.5 parts of 7-amino-4-hydroxynaphthalene-2-sulphonic acid with 74 parts of formaldehyde sodium bisulphite in aqueous medium at pH5.5-6 and 40-50 ℃) and coupled in a first reaction stage at 5-10 ℃ and pH below 1.5 to form a red-orange monoazo dye of the general formula (13-3).

After the end of the first coupling to form the monoazo dye (13-3), the pH was adjusted to 5-6 with sodium carbonate at 25 ℃ and this value was maintained with sodium carbonate until the end of the second coupling reaction. The resulting yellowish red disazo dye of the formula (I-3) can be isolated by evaporation under reduced pressure.

The dyes obtained by the present invention dye cotton to a yellowish red colour with good general fastness.

Examples 4 to 70

The examples of the following tables further describe the dyes of the general formula (Iaa) according to the invention. The dyes provide a yellowish to brownish red colour with good general fastness on cotton, for example by the dyeing process usually used for reactive dyes.

Dyes of example 1 or 2

Examples 71 to 82

The examples of the following tables further describe the dyes of the general formula (Iab) according to the invention. The dyes provide a yellowish to brownish red colour with good general fastness on cotton by, for example, the dyeing processes usually used for reactive dyes.

Dye of example 3

Application example 1

2 parts of the dye obtained in examples 1 to 3 and 50 parts of sodium chloride are dissolved in 999 parts of water, 5 parts of sodium carbonate, 0.7 part of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent are added. To this dye bath was added 100g of cotton fabric. The temperature of the dye bath is first held at 25 ℃ for 10 minutes and then raised to the final temperature (40-80 ℃) within 30 minutes and held at this level for an additional 60-90 minutes. The dyed material was then rinsed initially with tap water for 2 minutes and then with deionized water for 5 minutes. The dyeing material was neutralized at 40 ℃ for 10 minutes in 1000 parts of an aqueous solution containing 1 part of 50% acetic acid. This was followed by rinsing with deionized water at 70 c, then soaping with detergent at the boil for 15 minutes, rinsing again and drying. Strong reddish yellow to reddish brown with excellent fastness properties are obtained.

Application example 2

2 parts of the dye obtained in example 3, 43, 44, 47, 48 or 68 are dissolved in 999 parts of water, 5 parts of sodium carbonate, 0.7 part of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent are added. To this dye bath was added 100g of cotton fabric. The rest of the process was as described in application example 1. Strong reddish yellow to reddish brown with excellent fastness properties are obtained.

Application example 3

4 parts of the dye obtained in example 3, 43, 44, 47, 48 or 68 and 5 parts of sodium chloride are dissolved in 999 parts of water, and 7 parts of sodium carbonate, 0.7 part of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent are added. To this dye bath was added 100g of cotton fabric. The rest of the process was as described in application example 1. Strong reddish yellow to reddish brown with excellent fastness properties are obtained.

Application example 4

8 parts of the dye obtained in example 3, 43, 44, 47, 48 or 68 and 10 parts of sodium chloride are dissolved in 999 parts of water, and 10 parts of sodium carbonate, 1.3 parts of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent are added. To this dye bath was added 100g of cotton fabric. The rest of the process was as described in application example 1. Strong reddish yellow to reddish brown with excellent fastness properties are obtained.

Claims (9)

1. Reactive dyes of the general formula (I):

wherein

D¹And D²Independently represents a group of formula (1):

wherein

R¹And R²Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; and

X¹is hydrogen or formula-SO₂-a group of Z,

wherein

Z is-CH ═ CH₂、-CH₂CH₂Z¹Or a hydroxyl group, or a mixture thereof,

wherein

Z¹Is hydroxy or a base-removable group; or

D¹And D²Independently represents a naphthyl group of the general formula (2):

wherein

R³And R⁴Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; and

X²having X¹One of the meanings of (a); or

D¹And D²Independently represents a group of the general formula (3):

wherein

R⁵And R⁶Independently have R¹And R²One of the meanings of (a);

R⁷is hydrogen, (C)₁-C₄) -alkyl, unsubstituted phenyl or (C)₁-C₄) -alkyl-, (C)₁-C₄) -alkoxy-, sulfo-, halogen-or carboxy-substituted phenyl; and

Z²is a group of the general formula (4) or (5) or (6):

wherein

V is fluorine or chlorine;

U¹、U²independently fluorine, chlorine or hydrogen; and

Q¹、Q²independently chlorine, fluorine, cyanamido, hydroxyl, (C)₁-C₆) Alkoxy, phenoxy, sulfophenoxy, mercapto, (C)₁-C₆) -alkylmercapto, pyrido, carboxypyrido, carbamoylpyrido, or a group of general formula (7) or (8):

wherein

R⁸Is hydrogen or (C)₁-C₆) Alkyl, sulfo- (C)₁-C₆) -alkyl or unsubstituted phenyl or (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, sulfo, halogen, carboxyl, acetamido, ureido-substituted phenyl;

R⁹and R¹⁰Independently have R⁸One or a combination of the meanings of (A) forms the formula- (CH)₂)_j-wherein j is 4 or 5; or in combination form- (CH)₂)₂-E-(CH₂)₂A ring system of (a) wherein E is oxygen, sulfur, sulfo or-NR¹¹Wherein R is¹¹＝(C₁-C₆) -an alkyl group;

w is unsubstituted phenylene or phenylene substituted with 1 or 2 substituents selected from (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, carboxyl, sulfo, chlorine and bromine; or is (C)₁-C₄) Alkylene-arylene or (C)₂-C₆) Alkylene which may be interrupted by oxygen, sulfur, sulfo, amino, carbonyl, carboxamide groups; or is phenylene-CONH-phenylene which is unsubstituted or substituted by (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, amido, ureido or halogen substitution; or naphthylene, which is unsubstituted or substituted by one or two sulfo groups; and

z is as defined above; or

D¹And D²Independently a group of formula (9):

wherein

R¹²Is hydrogen, (C)₁-C₄) -alkyl, aryl or substituted aryl;

R¹³and R¹⁴Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; and

a is a phenylene group of the general formula (10),

wherein

R¹⁵And R¹⁶Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; or

A is a naphthylene group of the general formula (11):

wherein R is¹⁷And R¹⁸Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; or

A is a polymethylene group of the general formula (12):

-(CR¹⁹R²⁰)_k- (12)

wherein

k is an integer greater than 1, and

R¹⁹and R²⁰Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, cyano, amido, halogen or aryl; and

X³having X¹One of the meanings of (a); and

R、R^*independently hydrogen, (C)₁-C₄) -alkyl or sulfomethyl; and

m is hydrogen, an alkali metal or one equivalent of an alkaline earth metal, with the proviso that the dye of the formula (I) comprises at least one fibre-reactive heterocyclic radical of the formula (4) or (6).

2. Reactive dyes according to claim 1, characterized in that the substituents are

R¹And R²Is hydrogen, methyl, methoxy or sulfo,

R³to R⁶Is a hydrogen or a sulfo group,

R⁷and R⁸Is hydrogen, methyl or phenyl, or a salt thereof,

R⁹and R¹⁰Is hydrogen, methyl, 2-sulfoethyl, 2-, 3-or 4-sulfophenyl, or R⁹And R¹⁰Combined to form a combined formula- (CH)₂)₂-O-(CH₂)₂-a ring system of (a),

R¹²to R¹⁶And R¹⁹To R²⁰Is hydrogen, and

R¹⁷to R¹⁸Is hydrogen or sulfo.

3. A reactive dye according to claim 1 or 2, wherein the substituent R is hydrogen or sulphomethyl, and R^*Is hydrogen.

4. Reactive dyes according to claim 1 or 2, characterized in that Z is vinyl, β -chloroethyl or β -sulfatoethyl.

5. RightsReactive dyes according to claim 1 or 2, characterized in that Q in the formula (5)¹And Q²Independently fluorine, chlorine, cyanamide, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 3- (2-sulfatoethylsulfonyl) phenylamino, 4- (2-sulfatoethylsulfonyl) phenylamino, 3- (vinylsulfonyl) phenylamino, 4- (vinylsulfonyl) phenylamino, N-methyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino or N-phenyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino.

6. A process for the preparation of a reactive dye of general formula (I) according to claim 1, which comprises:

in the first stage, one equivalent of an amine of the formula (16) is diazotized in a conventional manner,

D¹-NH₂ (16)

wherein D is¹Is as defined in claim 1, wherein,

the resulting diazo compound is reacted with one equivalent of an aqueous solution or suspension of a coupling component of the general formula (17),

r, R therein^*And M is each as defined in claim 1,

to form a monoazo dye of the general formula (13),

and subsequently, in a second stage, diazotizing one equivalent of an amine of the formula (18) in a conventional manner,

D²-NH₂ (18)

wherein D is²Is as defined in claim 1, wherein,

the resulting diazo compound is coupled with the monoazo dye of the general formula (13) obtained in the first stage to form the disazo dye of the general formula (I).

7. A process for the preparation of reactive dyes of the general formula (I) as claimed in claim 1, wherein the radical D of the general formula (I)¹And D²Having the same meaning, the method comprises:

two equivalents of the amine of the formula (16) are diazotized in the first stage in a conventional manner,

D¹-NH₂ (16)

wherein D is¹Is as defined in claim 1, wherein,

and reacted with one equivalent of a coupling component of the formula (17),

r, R therein^*And M is each as defined in claim 1,

to form a monoazo dye of the general formula (13),

followed by a second coupling to form the disazo dye of the general formula (I) in which D¹And D²Have the same meaning.

8. An aqueous liquid preparation comprising 5 to 90% by weight of a reactive dye according to any one of claims 1 to 5.

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