DE4340160A1 - Water-soluble, metal-free phthalocyanine dyes, processes for their preparation and their use - Google Patents

Description

The invention is in the technical field of fiber-reactive dyes.

The practice of dyeing with fiber-reactive dyes is increasingly increasing Requirements for the quality of the dyeings and the ecological compatibility of dyes and the dyeing process. As a result, it persists especially with regard to the ecological safety of the use the dyes the need for new, especially heavy metal free fiber-reactive dyes, which also have good dyeing qualities and Possess authenticity properties. For example, in U.S. patents No. 4,237,050, 4,350,632 and 4,745,187 fiber reactive Heavy metal complex phthalocyanine dyes, such as in particular copper and Nickel phthalocyanine dyes, with good coloring properties described, the, via an N-arylsulfonamide or N-alkylsulfonamide radical bound, have a fiber-reactive group of the vinyl sulfone series. When decaying this heavy metal complex phthalocyanine dyes, for example Disposal of dyeing waste water and used textiles, will be their Heavy metals released into the environment, so that the heavy metals in the Sewage and sewage sludge get. For the limitation of the burden of Waste water and sewage sludge from heavy metal ions already exist extensive legal regulations, so that a way had to be found the previously known heavy metal phthalocyanine dyes by others without To replace heavy metal ions.

With the present invention, new, water-soluble and heavy metal free phthalocyanine dyes of the following  general formula (1) found with which high quality dyeings in brilliant shades of green with good fastness properties can be obtained.

In this formula:
H₂Pc is the rest of the phthalocyanine of formula (A)

M is hydrogen or an alkali metal such as sodium, potassium or lithium, or another salt-forming metal;
R1 is hydrogen, alkyl of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms, such as methyl and ethyl, or is alkyl of 2 to 6 carbon atoms, preferably of 2 to 4 carbon atoms, such as ethyl and n-Propyl by alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, cyano, alkanoylamino of 2 to 5 carbon atoms, such as acetylamino and propionylamino, carboxy, sulfo, phosphato, sulfato, hydroxy or dialkylamino, each with one Alkyl of 1 to 4 carbon atoms, such as dimethylamino and diethylamino, is substituted,
R² is hydrogen, alkyl of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms, such as methyl and ethyl, or is alkyl of 2 to 6 carbon atoms, preferably of 2 to 4 carbon atoms, such as ethyl and n-propyl, which is substituted by alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, cyano, alkanoylamino of 2 to 5 carbon atoms, such as acetylamino and propionylamino, carboxy, sulfo, phosphato, sulfato, hydroxy, phenyl, sulfophenyl, Carboxyphenyl or dialkylamino, each having an alkyl of 1 to 4 carbon atoms, such as dimethylamino and diethylamino, is substituted, or is phenyl, which may be substituted by sulfo, or
R¹ and R² form together with the nitrogen atom and an alkylene of 3 to 8 C atoms, preferably from 4 to 6 C atoms, or with a further hetero group, such as a nitrogen atom or oxygen atom or a group -NH-, and two alkylenes of 1 to 5 carbon atoms the residue of a 4- to 8-membered heterocyclic ring, such as the N-piperidino, N-piperazino or N-morpholino residue;
B is a radical of the general formula (2a) or (2b)

in which
R³ is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, or alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy,
R⁴ is hydrogen, halogen, such as bromine and chlorine, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, or alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy,
M has the meaning given above,
m stands for number zero or 1 (where if m is zero this group stands for hydrogen), preferably zero,
n is the number zero, 1 or 2, preferably 1 or 2, and in formula (2a) the group -SO₂-Y is preferably bonded in the meta or para position to the sulfonylamino group and in formula (2b) the bond from the naphthalene radical to the sulfonylamino group is preferably in the β-position of the naphthalene radical;
Y is vinyl or is ethyl which contains a substituent in the β-position which can be eliminated by alkali to form the vinyl group, or is β-sulfoethyl or β-hydroxyethyl;
a is a number from zero to 3,
b is a number from zero to 2 and
c is a number from 1 to 4,
where the sum of (a + b + c) is 1 to 4.

The individual formula elements can be related to each other within the meaning have the same or different meanings.

The phthalocyanine dyes according to the invention are generally in the form obtained from mixtures of the individual compounds of the general formula (1), these individual compounds differ from one another by the degree of substitution distinguish the sulfo and sulfonamide groups on the phthalocyanine residue. The Formulas of the phthalocyanine dyes according to the invention therefore have indices which are usually fractional numbers.

Alkaline eliminable substituents which are in the β-position of the ethyl group of Y are, for example halogen atoms such as bromine and chlorine, ester groups organic carboxylic and sulfonic acids, such as alkyl carboxylic acids,  optionally substituted benzene carboxylic acids and optionally substituted benzenesulfonic acids, such as the alkanoyloxy groups from 2 to 5 Carbon atoms, of which in particular acetyloxy, benzoyloxy, sulfobenzoyloxy, Phenylsulfonyloxy and Toluylsulfonyloxy, further acidic ester groups inorganic acids such as phosphoric acid, sulfuric acid and Thiosulfuric acid (phosphato, sulfato and thiosulfato groups) as well Dialkylamino groups with alkyl groups of 1 to 4 carbon atoms each, such as Dimethylamino and diethylamino. Y is preferably β-sulfatoethyl or vinyl and particularly preferably β-sulfatoethyl.

The groups "Sulfo", "Carboxy", "Thiosulfato", "Phosphato" and "sulfato" include both their acid form and their salt form. Accordingly mean sulfo groups according to the general formula -SO₃M Carboxy groups according to the general formula -COOM, Thiosulfato groups according to the general formula -S-SO₃M Phosphato groups according to the general formula -OPO₃M₂ and sulfato groups according to the general formula -OSO₃M, in which M has the meaning given above.

Formula residues of the general formula -B-SO₂-Y are for example: 2- (β-sulfatoethylsulfonyI) phenyl, 3- (β-sulfatoethylsulfonyl) phenyl, 4- (β-sulfatoethylsulfonyl) phenyl, 2-carboxy-S- (β-sulfatoethylsulfonyl) phenyl, 2-chloro-3- (β-sulfatoethylsulfonyl) phenyl, 2-chloro-4- (β-sulfatoethylsulfonyl) - phenyl, 2-bromo-4- (β-sulfatoethylsulfonyl) phenyl, 4-methoxy-3- (β- sulfatoethylsulfonyl) phenyl, 4-chloro-3- (β-sulfatoethylsulfonyl) phenyl, 2-ethoxy- 4- or -5- (β-sulfatoethylsulfonyl) phenyl, 2-methyl-4- (β-sulfatoethylsulfonyl) - phenyl, 2-methoxy-5- or -4- (β-sulfatoethylsulfonyl) phenyl, 2,4-diethoxy-5- (β- sulfatoethylsulfonyl) phenyl, 2,4-dimethoxy-5- (β-sulfatoethylsulfonyl) phenyl, 2,5-dimethoxy-4- (β.sulfatoethylsulfonyl) phenyl, 2-methoxy-5-methyl-4- (β- sulfatoethylsulfonyl) phenyl, 2- or 3- or 4- (β-thiosulfatoethylsulfonyl) - phenyl, 2-methoxy-5- (β-thiosulfatoethylsulfonyl) phenyl, 2-sulfo-4- (β- phosphatoethylsulfonyl) phenyl, 2-sulfo-4-vinylsulfonylphenyl, 2-chloro-4-  or -5- (β-chloroethylsulfonyl) phenyl, 3- or 4- (β-acetoxyethylsulfonyl) phenyl, 5- (β-5-sulfatoethyl-sulfonyl) -naphth-2-yl, 6- or 7- or 8- (β-sulfatoethyl-sulfonyl) - naphth-2-yl, 6- (β-sulfatoethylsulfonyl) -1-sulfo-naphth-2-yl, 5- (β-sulfatoethylsulfonyl) -1-sulfonaphth-2-yl and 8- (β-sulfatoethylsulfonyl) -6- sulfo-naphth-2-yl.

R³ is preferred in the phthalocyanine dyes of the general formula (1) is hydrogen, methyl or methoxy, and preferably R⁴ is the same Hydrogen or methoxy. Compounds of are also preferred general formula (1) in which R¹ and R² are each independently Is hydrogen, methyl or ethyl, where b is 1 to 2, furthermore those in which the index b is zero. Are also preferred Phthalocyanine dyes of the general formula (1), in which a is a number of Is zero to 3, preferably from 1 to 2.5, b is zero to 2, preferably zero and c is a number from 1 to 4, preferably from 1 to 2.

Residues of the general formula -NR¹R² are, for example, amino, methylamino, Ethylamino, butylamino, benzylamino, β-hydroxyethylamino, dimethylamino, Diethylamino, di (isopropyl) amino, N-methylbenzylamino, N-piperidino, N-morpholino, di- (β-hydroxyethyl) amino, β-sulfo-ethylamino, β-carboxy- ethylamino, β- (4-carboxyphenyl) ethylamino, phenylamino, N-methyl phenylamino, 3-sulfophenylamino and 4-sulfophenylamino.

The present invention further relates to a method for producing the Phthalocyanine compounds of the general formula (1), thereby is characterized in that a phthalocyanine sulfonyl chloride general formula (3)

in which H₂Pc and M have the meanings given above, p is a number is from zero to 3 and q is a number from 1 to 4, the sum of (p + q) is 1 to 4, or a mixture thereof in aqueous or not aqueous medium with an amine of the general formula (4)

H₂N-B-SO₂-Y (4)

in which B and Y have the meanings given above and Y here also the May have meaning of β-hydroxyethyl, and optionally with a further amine of the general formula H-NR¹R² with R¹ and R² the above meaning simultaneously or in any order and under simultaneous or subsequent partial hydrolysis of the sulfochloride groups Implemented sulfo groups. If necessary, at the end of the condensation reactions existing sulfochloride groups are hydrolyzed to sulfo groups. At the implementation of the invention is usually a partial hydrolysis of Sulfonic acid chloride groups to sulfo groups inevitable. In case of Use of an amine of the general formula (4) where Y is the same β-Hydroxyethyl can in the phthalocyanine compound obtained β-Hydroxyethylsulfonyl group analogous to generally known procedures in a group of the formula -SO₂-Y with Y equal to one in the β-position by one Ester group substituted ethyl group can be transferred, such as in the β-sulfatoethylsulfonyl group using sulfuric acid or sulfur trioxide containing sulfuric acid or chlorosulfonic acid.

The condensation reactions between the compounds according to the invention of the general formula (3) and the amines of the general formulas (4) and H-NR¹R² are preferred at pH between 3.5 and 8.5 between 4 and 8, in particular between 5.5 and 6.5, and at one Temperature between 0 ° C and 100 ° C, preferably between 20 and 60 ° C, in particular between 45 and 55 ° C. They usually take place in Presence of a catalyst, such as pyridine, a pyridinesulfonic acid, Pyridinecarboxylic acid, pyridine sulfonamide or pyridinecarbonamide compound, such as  preferably of nicotinic acid amide, analogous to those mentioned in the beginning U.S. Patents or U.S. Patent 4,745,187 known procedures.

The starting phthalocyanine sulfonic acid chloride compounds of the general Formula (3) are prepared analogously to known procedures as they are for example from information in the aforementioned U.S. patents and can be seen from German Patent No. 891 121. For example a compound of general formula (3) is prepared in such a way that one enters phthalocyanine of formula (A) in chlorosulfonic acid and the approach at a temperature between 80 and 120 ° C, preferably between 90 and 100 ° C, stirred for several hours, then a chlorinating agent, preferably Thionyl chloride, adds and the approach several hours at 80 to 90 ° C. keeps stirring. The mixture is then stirred into crushed ice and that aspirated precipitated phthalocyanine sulfochloride.

Another way of making a general connection Formula (3) is the reaction of the phthalocyanine of formula (A) with Sulfuric acid / sulfur trioxide in sulfuric acid containing sulfur trioxide (Oleum) with a sulfur trioxide content of about 50 to 65 wt .-% at about 80 ° C. After this implementation, the approach is stirred into an ice-cooled one aqueous solution of sodium chloride and transferred the obtained Phthalocyanine sulfonic acid by conventional procedures, for example by means of thionyl chloride in dimethylformamide, in the Phthalocyanine sulfonic acid chloride.

The deposition of the phthalocyanine dyes produced according to the invention general formula (1), hereinafter referred to as "dyes (1)", from the Synthesis approaches are carried out either according to generally known methods Precipitation from the reaction medium using electrolytes, such as Sodium chloride or potassium chloride, or by evaporating the reaction solution, for example by spray drying, this reaction solution Buffer substance can be added. The dyes (1) have fiber-reactive Properties and have very good dye properties. You can  therefore for dyeing and printing hydroxy and / or material containing carbonamide groups, in particular fiber material, and also of Leather. Likewise, those in the synthesis of the Solutions according to the invention, if appropriate after Add a buffer substance, if necessary after concentration, directly as Liquid preparation can be used for staining.

The present invention therefore also relates to the use of Dyes (1) for dyeing (including printing) of hydroxy and Materials containing carbonamide groups and processes for their use on these substrates. The materials preferably come in the form of Fiber materials for use, especially in the form of textile fibers, such as Yarns, packages and fabrics.

Materials containing hydroxyl groups are natural or synthetic materials containing hydroxyl groups, such as cellulose fiber materials, also in the form of paper, or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton, but also others Vegetable fibers; like linen, hemp, jute and ramie fibers; regenerated Cellulose fibers are, for example, cellulose and viscose rayon.

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

The dyes (1) can, in particular, on the substrates mentioned the fiber materials mentioned, according to those for water-soluble dyes, especially for fiber-reactive dyes, known application techniques apply and fix. So you get with them on cellulose fibers after Extraction process from a long fleet using a wide variety acid-binding agents and optionally neutral salts, such as sodium chloride  or sodium sulfate, dyeings in very good color yields and with excellent color structure. You dye at temperatures between 40 and 105 ° C, if appropriate at temperatures up to 130 ° C under pressure, optionally in the presence of customary dyeing auxiliaries, in aqueous Bath. You can do this by putting the material in the warm bath introduces and gradually warmed to the desired dyeing temperature and complete the dyeing process at this temperature. The undressing of the dye accelerating neutral salts can bath if desired, only after reaching the actual dyeing temperature be added.

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

You can also get the usual printing process for cellulose fibers can be carried out either in one phase, for example by Print with a sodium bicarbonate or other acid binding agent and printing paste containing the colorant and then steaming at 100 to 103 ° C, or which can be carried out in two phases, for example by printing with neutral or slightly acidic, the Printing paste containing colorant and subsequent fixing either by Passing the printed goods through a hot electrolyte alkaline bath or by padding with an alkaline electrolyte Block liquor with subsequent lingering of this treated material or subsequent steaming or subsequent treatment with dry heat, strong-colored prints with good contours and a clear white background. The failure of the prints is little of changing fixing conditions dependent. Both in the dyeing and in the printing works are the ones with the The degrees of fixation obtained according to the invention are very high.  

When fixing with dry heat according to the usual heat setting processes hot air from 120 to 200 ° C is used. In addition to the usual water vapor from 101 to 103 ° C can also superheated steam and pressure steam from Temperatures up to 160 ° C can be used.

The acid-binding and the fixation of the dyes on the cellulose fibers effecting agents are, for example, water-soluble basic salts of Alkali metals and the alkaline earth metals of inorganic or organic Acids, as well as compounds that release alkali in the heat. In particular, the alkali metal hydroxides and alkali metal salts of to name weak to moderate inorganic or organic acids, of the alkali compounds preferably the sodium and Potassium compounds are meant. Such 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.

By treating the dyes (1) with the acid-binding agents, optionally under the action of heat, the dyes are chemically attached to the Cellulose fiber bound; especially the cellulose stains show after the usual post-treatment by rinsing to remove unfixed Dye proportions have excellent wet fastness properties, especially since they did not fix Wash out dye parts easily because of their good cold water solubility to let.

The dyeings on polyurethane and polyamide fibers are usually made from acidic environment. For example, the dyebath can be acetic acid and / or ammonium sulfate and / or acetic acid and ammonium acetate or Add sodium acetate to get the desired pH. For An addition is recommended to achieve a useful levelness of coloration usual leveling aids, such as based on a Reaction product of cyanuric chloride with three times the molar amount of one  Aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or based on a Reaction product of, for example, stearylamine with ethylene oxide. In the Usually the material to be colored is at a temperature of around 40 ° C Bath introduced, moved there for some time, then the dye bath on the desired weakly acidic, preferably weakly acetic acid pH adjusted and the actual coloring at a temperature between 60 and 98 ° C carried out. The dyeings can also at boiling temperature or at temperatures up to 120 ° C (under pressure).

The dyeings and prints produced with the dyes (1) Cellulose fiber materials have a high color strength and also good ones Light fastness and good wet fastness, such as washing, walking, water, Seawater, dyeing and sweat fastness, good as well Fastness to pleating, fastness to ironing and fastness to rubbing.

The following examples serve to illustrate the invention. The Compounds described by formula are in the form of the free acid specified; generally they are made in the form of their alkali metal salts and isolated and used in the form of their salts for coloring. Likewise, the in the following examples, especially table examples, in the form of Starting compounds called free acid as such or in the form of their Salts, preferably alkali metal salts, such as lithium, sodium or potassium salts, be used in the synthesis.

The parts mentioned in the examples are parts by weight; the percentages represent percentages by weight, unless stated otherwise. Parts by weight are related to parts by volume in the ratio of kilograms to liters.

The absorption maxima (λ _max ) in the visible range specified for the compounds according to the invention were determined on the basis of their alkali metal salts in aqueous solution. In the table examples, the λ _max values are given in brackets when specifying the color; the wavelength specification refers to nm.

Example A

20 parts of phthalocyanine are introduced into 120 parts of chlorosulfonic acid, where the temperature of the batch rises to 60 to 70 ° C. You stir six more Hours at 100 ° C, then cools the batch to 80 to 90 ° C and gives slowly add 34 parts by volume of thionyl chloride with thorough stirring. You still stir four hours at 90 ° C, the mixture is then stirred on ice, the precipitated sucks Phthalocyanine sulfochloride with an average degree of substitution of 2.5 and wash it off with ice water.

Example B

20 parts of phthalocyanine are converted into 300 parts of a mixture 150 parts of sulfuric acid monohydrate and 150 parts of 65% oleum registered. The mixture is stirred for a further four hours at 80 ° C. and cooled then decrease to 20 ° C and add it to a mixture of 10,000 parts of ice and 3000 parts of sodium chloride. The precipitation will filtered off, dissolved in about 3000 parts of water and filtered. The filtrate becomes by adding sodium chloride, the phthalocyanine tetrasulfonic acid obtained salted out, filtered off and washed with aqueous ethanol solution. The phthalocyanine tetrasulfonic acid obtained is divided into 200 parts Dimethylformamide stirred in, and there are 200 parts by volume of thionyl chloride added slowly with good stirring. The approach is stirred for about six more Hours at 50 to 55 ° C and isolated the phthalocyanine tetrasulfochloride either by removing the dimethylformamide by distillation and excess thionyl chloride or by stirring the mixture in ice under subsequent filtration.

example 1

A solution with a pH of 6.5 of 46 parts of 4- (β-sulfatoethylsulfonyl) aniline in 120 parts of water are mixed with stirring
added to the moist filter residue from Example A and 4 parts of nicotinamide. The mixture is stirred for a further two hours at 50.degree. C. and then at about 20.degree. C. while maintaining the pH of 6.5. After the condensation reaction has ended, the mixture is filtered and the phthalocyanine dye according to the invention is isolated by salting out using sodium chloride or by evaporating the reaction solution under reduced pressure.

The phthalocyanine dye according to the invention has, in the form of the free acid written the formula

in which H₂Pc represents the rest of the phthalocyanine of formula (A). He shows very good fiber-reactive dye properties, is very easily soluble in water and delivers according to the usual in the art for fiber-reactive dyes Application and fixing methods on those mentioned in the description Materials, such as in particular cellulose fiber materials, such as cotton, brilliant, green colors and prints with good fastness properties.

Example 2

The procedure for the preparation of a phthalocyanine dye according to the invention according to the information in Example 1, but instead of Phthalocyanine sulfochloride from Example A made the phthalocyanine tetrasulfochloride Example B and instead of 4- (β-sulfatoethylsulfonyl) aniline the same amount an 3- (β-sulfatoethylsulfonyl) aniline in the reaction mixture. The resulting phthalocyanine dye of the formula (in the form of free acid)  

in which H₂Pc represents the rest of the phthalocyanine of formula (A) good fiber-reactive, application properties and colors for example cellulose fiber materials, such as cotton, according to the in the Technology for fiber-reactive dyes usual dyeing and printing processes in strong, brilliant, somewhat bluish green tones with good Authenticity properties.

Example 3

To produce a phthalocyanine dye according to the invention, 55 parts of 2,5-dimethoxy-4- (β- sulfatoethylsulfonyl) aniline in 100 parts of water at a pH of 6.5 with the moist filter residue of the phthalocyanine sulfochloride from Example A in Presence of 6 parts of nicotinamide and isolate the dye that Formula (written in the form of free acid)

in which H₂Pc represents the rest of the phthalocyanine of formula (A) in which specified way. It shows very good fiber-reactive dye properties and delivers brilliant green dyeings and prints on cotton, for example good fastness properties.

Example 4

The procedure for producing a phthalocyanine dye according to the invention is followed according to the procedure of Example 3, but goes from 52 parts 2-methoxy-S-methyl-4- (β-sulfatoethylsulfonyl) aniline. You get that Phthalocyanine dye of the formula (in the form of the free acid written)

in which H₂Pc means the rest of the phthalocyanine of the formula (A) with which according to the dyeing and printing processes customary in the art, for example Cotton strong, brilliant green dyeings and prints with good Authenticity properties.

Claims (8)

1. Phthalocyanine dye of the general formula (1) in which mean:
H₂Pc is the rest of the phthalocyanine;
M is hydrogen or an alkali metal or other salt-forming metal;
R¹ is hydrogen, alkyl of 1 to 6 carbon atoms or alkyl of 2 to 6 carbon atoms, which is replaced by alkoxy of 1 to 4 carbon atoms, cyano, alkanoylamino of 2 to 5 carbon atoms, carboxy, sulfo, phosphato, Sulfato, hydroxy or dialkylamino is substituted with in each case an alkyl of 1 to 4 carbon atoms,
R² is hydrogen, alkyl of 1 to 6 carbon atoms or alkyl of 2 to 6 carbon atoms, which is formed by alkoxy of 1 to 4 carbon atoms, cyano, alkanoylamino of 2 to 5 carbon atoms, carboxy, sulfo, phosphato, Sulfato, hydroxy, phenyl, sulfophenyl, carboxyphenyl or dialkylamino, each having an alkyl of 1 to 4 carbon atoms, or
R¹ and R² together with the nitrogen atom and an alkylene of 3 to 8 C atoms or with a further hetero group and two alkylenes of 1 to 5 C atoms form the remainder of a 4- to 8-membered heterocyclic ring;
B is a radical of the general formula (2a) or (2b) in which
R³ is hydrogen, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms,
R⁴ is hydrogen, halogen, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms,
M has the meaning given above,
m stands for number zero or 1 and
n represents the number zero, 1 or 2;
Y is vinyl or is ethyl which contains a substituent in the β-position which can be eliminated by alkali to form the vinyl group;
a is a number from zero to 3,
b is a number from zero to 2 and
c is a number from 1 to 4,
where the sum of (a + b + c) is 1 to 4. 2. Phthalocyanine dye according to claim 1, characterized in that B is a radical of the general formula (2a) in which R³ is hydrogen, Is methyl or methoxy, R⁴ is hydrogen or methoxy and m is for the Number zero stands.   3. phthalocyanine dye according to claim 1 or 2, characterized in that b means the number zero. 4. Phthalocyanine dye according to claim 3, characterized in that a is a number from zero to 3 and c is a number from 1 to 2. 5. phthalocyanine dye according to at least one of claims 1 to 4, characterized in that Y is β-sulfatoethyl or vinyl. 6. A process for the preparation of a phthalocyanine dye of the general formula (1) of claim 1, characterized in that phthalocyanine sulfonyl chloride of the general formula (3) in which H₂Pc and M have the meanings given in claim 1, p is a number from zero to 3 and q is a number from 1 to 4, the sum of (p + q) being 1 to 4, in aqueous or not aqueous medium with an amine of the general formula (4) H₂N-B-SO₂-Y (4) in which B and Y have the meanings given in claim 1, and optionally with a further amine of the general formula H-NR¹R² with R¹ and R² the above meaning simultaneously or in any order and with simultaneous or subsequent partial hydrolysis of the sulfochloride groups to sulfo groups, and optionally in the case of Y equal to β-hydroxyethyl, the β-hydroxyethylsulfonyl group into a group of the formula -SO₂-Y, in which Y is an ethyl group substituted in the β-position by an ester group. 7. Use of a phthalocyanine dye from at least one of the Claims 1 to 5 or one produced according to claim 6 Phthalocyanine dye for dyeing hydroxy and / or material containing carbonamide groups, in particular fiber material. 8. Process for dyeing hydroxy and / or carbonamide groups Material, preferably fiber material, in which one uses a dye onto the material or into the material and the dye on or in the material by means of heat or with the help of an alkaline acting agent or fixed by both measures, thereby characterized in that a phthalocyanine dye of at least one of claims 1 to 5 or one of claim 6 used phthalocyanine dye used in the process.