DE1419856C - Process for the production of reactive dyes - Google Patents

Description

The invention relates to reactive dyes, in particular new ones, for dyeing natural and artificial Textile materials valuable dyes.

According to the invention processes for the preparation of new dyes are proposed which have the general formula ^

Ν —Τ

have and where F is a known customary dye radical, »ι = 1,2 or 3, R is a hydrogen atom or a substituted or unsubstituted alkyl radical or a cycloalkyl radical and T a 1,3,5-triazine or pyrimidine ring, which is attached to the nitrogen atom N through a carbon atom of the ring is bound and at least one group of the formula amino, diethylamino, di - (/ i-hydroxyethyl) amino, Anilino, sulfoanilino, disulfoanilino, carboxyanilino and sulfonaphthylamino, dialkyldithiocarbamyl radicals, such as diethyldithiocarbamyl and N-methyl-N-ethyldithiocarbamyl, Nitro, cyano, rhodanide and sulfonic acid groups.

The substituted or unsubstituted alkyl radicals represented by R are preferably lower ones Alkyl radicals such as methyl, ethyl, propyl and butyl,

ίο which substituents, such as hydroxyl or methoxy groups, may contain. As an example of a cycloalkyl group represented by R, let Cyclohexyl radical mentioned.

According to the invention, a method for

'5 Production of the new dyes as defined above, proposed, wherein a dye compound which has the general formula III

Noun

N-T'R

contains, where Z ¹ denotes a sulfur or selenium atom and the benzene ring can carry a further substituent.

Each of the groups in the bracket of Formula I, as defined above, is one that is present in the dye Carbon atom bonded. This carbon atom can be part of one present in the dye Aryl radical or part of an alkyl chain, which is directly or via a bridging atom or a bridging group is bound to an aryl radical present in the dye, form. The dye residue F can be any residue of a known dye series and is preferably a dye residue of the azo series, which can be the monoazo or polyazo series, the nitro, anthraquinone or phthalocyanine series, which optionally at least one water-solubilizing group, such as an alkyl sulfone, a carboxylic acid or a sulfamyl group and preferably a sulfonic acid group. If desired, the dye can also be coordinated metal, such as coordinated copper, Chrome or cobalt.

As examples of substituents attached to the benzene ring in the group of formula II may be: methyl, nitro, chlorine, methoxy, ethoxy, acetylamino, benzoylamino, ureide, Sulfonic acid and carboxylic acid.

If the 1,3,5-triazine ring represented by T contains only one group of Formula II, it can carry another substituent, or if the pyrimidine ring represented by T is less than Contains three groups of the formula II, it can carry a further substituent. As examples of such Substituents which are bonded to a carbon atom or atoms of these rings may be mentioned: Halogen atoms, such as chlorine and bromine, mercapto and substituted mercapto groups, such as methyl mercapto, Carboxymethyl mercapto and phenyl mercapto groups, alkyl radicals such as methyl and ethyl, aryl radicals such as Phenyl and ToIyI, hydroxy and alkoxy radicals, such as methoxy, ethoxy, propoxy and butoxy, aryloxy radicals, such as phenoxy, sulfophenoxy and chlorophenoxy, amino and substituted amino groups such as methylamino, Contains ethylamino, / y-hydroxyethylamino, dimethyl, where R has the meaning given above and T 'denotes a 1,3,5-triazine or pyrimidine ring, which is bonded to the nitrogen atom N through a carbon atom of the ring and at least carries a halogen atom with a compound of the formula

S -W

in which Z ^{1 has} the meaning given above and the oenzene ring can carry further substituents and in which W denotes a hydrogen or metal atom. As examples of the metal atoms represented by W, there are mentioned: alkali metal atoms such as sodium and potassium.

As examples of the halogen atom or the halogen atoms attached to the 1,3,5-triazine or pyrimidine ring are bound, are mentioned: bromine and especially chlorine atoms.

This process according to the invention can conveniently be carried out by adding an aqueous solution of the suspension of the compound of the formula IV to a solution or suspension of the dye compound containing at least one group of the formula III in water or a water-miscible organic liquid, for example ethanol or acetone, or in a Mixture of water and a water-miscible organic liquid is, the mixture thus obtained, preferably at a temperature between 20 and 90 ⁰ C, stirs, if necessary, adding sodium carbonate to keep the pH of the mixture between 5 and 10 and the precipitated dye is filtered off . If desired, sodium chloride and / or water can be added to ensure complete precipitation of all of the dye.

If the 1,3,5-triazine or pyrimidine represented by T 'has more than one halogen atom, it is through a suitable choice of the reaction conditions, more than one of the halogen atoms is possible To replace groups of formula II. It is generally found that an excess is used of the compound of formula IV and an increase

i 419

j is the reaction temperature for replacing more than one of the halogen atoms with groups of the formula 11 leads.

As particular examples of the compounds of

Formula IV, which can be used in the process according to the invention, may be mentioned:

the sodium salt of 2-mercaptobenzothiazole, 2-mer-

\ capto-4-, -5-, -6- or -7-methylbenzthiazole, 2-mercapto - 6 - nitrobenzthiazole, 2 - mercapto - 5 or

- 6 - chlorobenzothiazole, 2 - mercaptobenzselenazole, 2-mercaptobenzothiazole-6-sulfonic acid, 2-mercapto- - methoxybenzthiazole, 2 - mercapto - 6 - ethoxybenzthiazole, 2 - mercapto - 6 - acetylaminobenzthiazole, 2-mercapto-6-benzoylaminobenzothiazole, 2-mercaptobenzothiazole - 5 - sulfonic acid and 2 - mercapto-6-ureidobenzothiazole.

The at least one group of the formula III used in this process according to the invention ι containing dye compounds can be obtained even j by having at least one

- NHR group-containing dye compound with a 1,3 containing at least 2 halogen atoms ^,! 5-triazine or pyrimidine converts.

\ I corresponds Examples of at least 2 halogen atoms: holding 1,3,5-triazine or pyrimidine, which can be used to obtain the dye compounds containing at least one halogen atom, used in the inventive method are mentioned:

Cyanuric chloride,

Cyanuric bromide,

2,4-dichloro-1,3,5-triazine,

2-methoxy-4,6-dichloro-1,3,5-triazine,
2-ethoxy-4,6-dichloro-1,3,5-triazine,

2-methyl-4,6-dibromo-1,3,5-triazine,
'2- phenyl ^ o-dichloro-1,3,5-triazine,

2-methylamino-4,6-dichloro-1,3,5-triazine,

2-ethylamino-4,6-dichloro-1,3,5-triazine,

2-phenoxy-4,6-dichloro-1,3,5-triazine,

2- (sulfophenoxy) -4,6-dichloro-1,3,5-triazine,

2-amino-4,6-dichloro-1,3,5-triazine,

2-aniline-2,6-dichloro-1,3,5-triazine,

2- (2'-, -3'- or -4'-sulfoaniline) -4,6-dichloro-1,3,5-triazine,

2- (3 ', 5' -disulfoanilineH ^ -dichloro-1,3,5-triazine,

2- (2'-, -3'- or ^ '- carboxyanilineH ^ -dichloro-1,3,5-triazine,

2-mercapto-4,6-dichloro-1,3,5-triazine,

2-hydroxy-4,6-dichloro-1,3,5-triazine,

2-methylmercapto-4,6-dichloro-1,3,5-triazine,

2- phenylmercapto ^ .o-dibromo-1,3,5-triazine,

2,4,6-trichloropyrimidine,

2,4,6-tribromopyrimidine,

2,4,5,6-tetrachloropyrimidine,

2,4,5,6-tetrabromopyrimidine,

2,4,6-trichloro-5-nitropyrimidine,

2,4-dichloro-5-nitro-6-methylpyrimidine,

2,4-dichloro-5-nitropyrimidine,

2,4,6-trichloro ^ 5-cyanopyrimidine,

5-cyano-2-methyl-4,6-dichloropyrimidine and

2-methyl-4,6-dichloro-5-nitropyrimidine.

Each of the -NHR groups present in the dye compound is directly attached to a carbon atom an aryl radical present in the dye compound, or any of the '- NHR groups is bonded to a carbon atom which forms part of an alkyl radical which is directly or by a bridging atom or group to an aryl radical present in the dye compound is bound. Examples of such connecting atoms or groups are:

o -

-SO ₇

and

S— —NH- -SO ₂ NH-

SO ₂ -N- alkyl

- N - alkyl CONH-

As examples of at least one - NHR group, as defined above, containing dye compounds, which can be used to produce the dye compounds containing at least one group of the formula III to obtain, the compounds of the following classes may be mentioned, but without the Restrict classes to those specifically described.

1. Monoazo compounds of the formula

D ₁ -N = N

HO ₃ S

NHR

wherein D _{1 is} at most dicyclic, from azo and

- NHR groups means free aryl radical, which

- NHR group is preferably attached to the 6-, 7- or 8-position of the naphthalene nucleus and the latter may contain a sulfonic acid group in the 5- or 6-position.

D ₁ can mean a radical of the naphthalene or benzene series free of azo substituents, for example a stilbene, diphenyl, benzthiazolylphenyl or diphenylamine radical. In this class, the related dyes should also be considered, in which the

- NHR group instead of being attached to the naphthalene nucleus to one of the 6-, 7- or 8-positions of the Naphthalene nucleus bound benzoylamino or anilino group is bound.

Particularly valuable dyes are obtained from those in which D _{1 is} a sulfonated phenyl or naphthyl radical, especially those which contain an —SO ₃ H group in ortho division to the azo bond; the phenyl radical can be further substituted, for example by halogen atoms, such as chlorine, alkyl radicals, such as methyl, acylamino groups, such as acetylamino, and alkoxy radicals, such as methoxy. 2. Disazo compounds of the formula V, in which D ₁ denotes a radical from the azobenzene, azonaphthalene or phenylazonaphthalene series and the naphthalene nucleus is substituted by the —NHR group and, if desired, by sulfonic acid, as in class 1.

3. Monoazo compounds of the formula

D, - N = N-

NHR

in which D _{1 is} an at most dicyclic aryl radical, as described for class 1, and is preferably a disulfonaphthyl or stilbene radical and the benzene nucleus is further substituents, such as halogen atoms or

May contain alkyl, alkoxy, carboxylic acid and acylamine groups. 4. Mono- or disazo compounds of the formula

H - N - D ₁ - N = N - K

VI

where D _{1 is} an arylene radical, such as a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series, or preferably an at most dicyclic arylene radical of the benzene or naphthalene series and K is the radical of a naphtholsulfonic acid or an enolized or enolizable ketomethylene compound (such as an acetoacetarylide or a 5 -Pyrazolon) with the OH group in ortho division to the azo group . D ₁ preferably denotes a radical of the benzene series containing a sulfonic acid group.
5. Mono- or disazo compounds of the formula

D ₁ - N = N - K ₂ - NR

VIl

O NHR

SO ₃ H

NH-Y-NHR

wherein the anthraquinone nucleus can contain a further sulfonic acid group in the 5-, 6-, 7- or 8-position and Y denotes a bridging group which is preferably a divalent radical of the benzene series, for example a phenylene, diphenylene or 4,4 ' -divalent stilbene or azobenzene radical. It is preferred that Y should contain one sulfonic acid group for each benzene nucleus present.
8. Phthalocyanine compounds of the formula

Pc

¹ ISO ₂ NH - Y - NHR) _1n

where Pc is the phthalocyanine nucleus, preferably of copper phthalocyanine, m —OH and / or —NH ₂ , Y is a bridging group, preferably an aliphatic, cycloaliphatic or aromatic bridging group, and μ and m are each 1, 2 or 3, and the latter is the same or can be different, provided that η + m is not greater than 4.

where D ₁ denotes a radical of the types defined above for D ₁ in classes 1 and 2 _{and K 2} denotes the radical of an enolizable ketomethylene compound (such as an acetoacetarylide or a 5-pyrazolone) with the OH group in -position to the azo group.

6. The metal complex compounds, e.g. B. the copper, chromium and cobalt complexes, of those dyes of the formulas V, VI and VII, wherein D ₁ , K and K _{2 have} all the meanings given, which have a metallizable group (for example a hydroxyl, lower alkoxy or Carboxylic acid group) in ortho division to the azo group in D ₁ .

7. Anthraquinone compounds of the formula

9. Nitro dyes of the formula

A - NH - B --NHR

775 308,
802 935,
826 405,
836 248,

where A and B are monocyclic aryl nuclei and the nitro group in A is ortho to the NH group stands.

Specific examples of the dye compounds containing at least one group of the formula III which can be used in this process according to the invention are given in British patents 209 723, 298 494, 467 815, 503 609, 772 030, 774 925, 780 591, 781 930, 784 221, 785 120, 785 222, 803 473, 805 565, 822 047, 822 948, 825 377, 828 353, 829 042, 832 400, 833 396, 834 304, 836 647, 837 035, 837 124, 837 953 , 837 985 and 837 990 and in Belgian patents 556 092, 558 801, 558 816, 558 817, 558 884, 558 957,

559 782, 559 945, 560 791, 560 792, 560 793, 560 794,

560 795, 563 439, 563 862, 569 115, 570 122, 570 343, 571 238, 571 523, 571 893, 571 942, 572 833, 572 967, 573 299, 573 300, 578 742, 578 932 and 581 401 and in U.S. Patent 2,258,977.

According to the invention, a modified process for the preparation of those new dyes which are azo dyes with at least one group of the formula I is given, wherein a primary amine or the corresponding sulfamic acid is diazotized and the diazo compound thus obtained is coupled with a coupling component, the primary amine and / or the coupling component contain at least one group [of the formula I] as it stands in the brackets [-].

This modified process according to the invention can expediently be carried out by adding sodium nitrite to a solution or suspension of the primary amine, which may be an aminoazo compound (or the corresponding sulfamic acid), in a dilute aqueous hydrochloric acid solution and the resulting solution or suspension of the diazo compound to a There is a solution of the coupling component and the precipitated azo dye is filtered off. If desired, sodium chloride can be added to ensure complete precipitation of all of the azo dyes.

The primary amine or the corresponding sulfamic acid used in this modified process according to the invention can be members of any of these be known series of diazotizable primary amines, but are preferably a primary amine of Benzene or naphthalene series, which optionally contains an arylazo group. The one used in this modified method according to the invention Coupling component can be any member of any known series of coupling components be, but is preferably a coupling component of the acylacetarylide, 5-pyrazolone, phenol, Naphthol or arylamine series.

Those primary amines or the corresponding sulfamic acids and the coupling components, which contain at least one group [of the formula I], as it stands in brackets [-] even by treating the corresponding primary amine or the sulfamic acid or the coupling component which has at least one —NHR group contain, with (a) a 1,3,5-triazine or pyrimidine, which at least one halogen atom and at least

carries a group of the formula II, or (b) a 1,3,5-triazine or pyrimidine, which at least Bears 2 halogen atoms, and are then obtained with a compound of the formula IV.

According to the invention, a modified process for the preparation of the new dyes, such as defined above, proposed, wherein a dye compound which at least one -NHR group contains, wherein R has the meaning given above, with a 1,3,5-triazine or pyrimidine, which at least a halogen atom and at least one group of the formula II, as defined above, is reacted will.

This modified process according to the invention can expediently be carried out by adding a solution or suspension of the 1,3,5-triazine or pyrimidine in water and a solution of the dye compound in water or a water-soluble organic liquid or a mixture of water and a water-soluble organic liquid / or a water-miscible organic liquid adding, the mixture, preferably at a temperature between 0 and 90 ⁰ C, stirred, sodium carbonate is added to keep the pH of the mixture is between 5 and IO and filtering off the precipitated dye. If necessary, water and / or sodium chloride can be added to ensure complete precipitation of all of the dye.

The 1,3,5-triazines bearing at least one halogen atom and at least one group of the formula II or pyrimidines themselves can be obtained by adding a 1,3,5-triazine or pyrimidine, which is at least carries two halogen atoms, reacted with a compound of formula IV.

According to the invention, a modified process for the preparation of those new dyes is also as defined above, wherein the 1,3,5-triazine or pyrimidine ring represented by T is a group of formula II and a hydroxy group, an alkoxy or aryloxy radical, a mercapto or alkyl or aryl-substituted mercapto group or a substituted or unsubstituted amino group or a Rhodanid- or sulfonic acid group suggested, being a new dye, which a group of formula II and contains a halogen atom attached to the 1,3,5-triazine or pyrimidine ring, with a Compound of the formula W - Q is reacted, wherein W is a hydrogen or metal atom and Q is Hydroxy group, an alkoxy or aryloxy radical, a mercapto or alkyl or aryl-substituted mercapto group or a substituted or unsubstituted amino group or a rhodanide or sulfonic acid group mean.

This modified method according to the invention can expediently be carried out by a mixture of the compound of the formula W - Q and the new dye, as defined above, in Water or in a water-miscible organic liquid or in a mixture of water and a water-soluble organic liquid, preferably at a temperature between 0 and 100 ° C, stir, add sodium carbonate to keep the pH of the mixture between 5 and 10, and the precipitated Dye filtered off. If necessary, sodium chloride can be used to completely precipitate the add all of the dye.

As examples of compounds of the formula W - Q, which in this modified form according to the invention Methods that can be used include: methanol, phenol, ammonia, methylamine, diethylamine, Aniline, orthanilic acid, metanilic acid, sulfanilic acid, sodium sulfite, potassium rhodanide, methyl mercaptan, Sodium hydroxide, phenyl mercaptan, aniline-3,5-disulfonic acid and anthranilic acid.

If desired, the new dyes, as defined above, can be obtained from the medium in which they are formed isolated and / or then dried in the presence of a buffering agent. When Examples of buffering agents that can be used for this purpose are: buffering agents derived from phosphates such as sodium dihydrogen phosphate and disodium hydrogen phosphate, Citrates, such as sodium citrate, borates and dialkylmetanilic acid (salts), such as sodium diethyl metanilate, which is preferably used in conjunction with sodium hydrogen sulfate is used.

A preferred class of the new dyes according to the invention are the water-soluble dyes, which at least one water-solubilizing group, preferably a sulfonic acid group, and one or two groups of the formula

contain, in which R and Z ^{1 have} the meanings given above, halogen is a bromine or preferably a chlorine atom and the benzene ring can contain further substituents.

A second preferred class of the new dyes according to the invention are the water-soluble dyes, which contain at least one water-solubilizing group, which is preferably a sulfonic acid group is and which is one or two groups of the formula

N
\

c-s-c

Il

contain, in which R and Z 'have the meanings given above and the benzene ring has more May contain substituents.

A third preferred class of the new dyes according to the invention are the water-soluble dyes, which at least one water-solubilizing

209 609/30

Group, preferably a sulfonic acid group and one or two groups of the formula

Group, preferably a sulfonic acid group and one or two groups of the formula

- N - C

- N

C-

C-CN

. _C i

s - c

contain, in which R and Z ^{1 have} the meanings given above and A is an amino or substituted amino group, preferably a sulfonated phenylamino group, such as a 2-sulfoanilino, 3-sulfoanilino, 4-sulfoanilino or 2,5- or 3, 5-disulfoanilino group and the benzene ring may contain further substituents.

A fourth preferred class of the new dyes according to the invention are the water-soluble dyes, which at least one water-solubilizing group, preferably a sulfonic acid group and one or two groups of the formula

contain, in which R and Z ^{1 have} the meanings given above and R _{1 is} an alkyl radical, preferably a methyl radical, and the benzene ring can contain further substituents.

A fifth preferred class of the new invention Dyes are the water-soluble dyes which have at least one water-solubilizing agent (i group, preferably a sulfonic acid group and one or two groups of the formula

S-C

R (halogen) ,,

contain, in which R and Z ^{1 have} the meanings given above, T is a pyrimidine ring, halogen is a chlorine or bromine atom and η is 1 or 2 and the benzene ring can contain further substituents. A sixth preferred class of the new dyes according to the invention are the water-soluble dyes, which have at least one water-solubilizing agent

contain, in which R and Z ^{1 have} the meanings given above and X is a hydrogen or Halo-> 5 gene atom and the benzene ring can contain further substituents.

As examples of the halogen atoms represented by X, bromine, and preferably chlorine, may be mentioned. The new dyes as defined above are valuable for coloring natural and artificial Textile materials, for example textile materials made of cotton, viscose rayon, regenerated cellulose, Wool, silk, cellulose acetate, polyamides, polyacrylonitrile, modified polyacrylonitrile and aromatic Polyester fibers. For this purpose the dyes can be applied to the textile materials by dyeing, padding or printing using printing pastes that contain the usual oil-in-water or thickening agents Containing water-in-oil emulsions, the textile materials in lively Tones with excellent fastness to light and wet treatments such as washing can be colored.

The new dyes, which have water-solubilizing groups, for example sulfonic acid and carboxylic acid groups, which make them soluble in water are particularly valuable for dyeing Cellulosic textile materials. For this purpose the dyes are applied to the cellulosic textile material, preferably in connection with a treatment with an acid-binding agent, for example sodium carbonate, Sodium metasilicate, trisodium phosphate or sodium hydroxide, which is applied to the Cellulosic textile material can be applied before, during or after the application of the dye. Instead, if the dyed textile material is then heated or steamed a substance such as sodium bicarbonate or sodium trichloroacetate should be used, which when heated or vapors release an acid-binding agent.

For example, the cellulose textile material can be dyed by treating it with an aqueous solution or suspension of the acid-binding agent and then ^{immersing the cellulose textile material treated in this way at a temperature of 0 to 100 °} C. in a dye bath containing a solution of one or more of the new dyes , as defined above, the dyed cellulosic fabric is removed from the dyebath, and if desired, the dyed cellulosic fabric is subjected to a treatment in a hot aqueous soap solution.

Those new dyes which do not have any water-solubilizing groups, for example sulfonic acid, Carboxylic acid, sulfonamide and acylsulfonamide groups, are generally on Textile materials applied in the form of an aqueous dispersion, which can be obtained by gravel grinding the dye with water in the presence of a dispersing agent

by means of, for example, the sodium salt of sulfonated Naphthalene-formaldehyde condensation products, sulfosuccinic acid esters, Turkish red oil, Alkylphenol / ethylene oxide condensation products, soap and similar surface-active materials, with or without protective colloids, such as dextrin, British gum and water-soluble proteins. If desired, the aqueous paste thus obtained can be dried to make it redispersible To form powder which is after any of those known for making non-dusting powders Process can be turned into a non-dusting powder.

The new dyes, as defined above, can be applied to nitrogen-containing textile materials, such as wool and polyamide textile materials can be applied from a slightly alkaline, neutral or acidic dye bath. The dyeing process can be carried out at a constant or substantially constant pH be, d. that is, the pH of the dyebath during the dyeing process will be the same or substantially the same remains the same; or, if desired, the pH of the dye bath can be adjusted at any stage of the dyeing process can be changed by adding acids or acidic salts or alkalis or alkaline salts. For example, dyeing can begin at a dyebath pH of about 3.5 to 5.5 and this to about 6.5 to 7.5 during the staining process

or higher, if desired, can be increased. The dyebath can also contain substances that are usual be used in the dyeing of nitrogen-containing textile materials. As examples of such substances are mentioned: ammonium acetate, sodium sulfate, ethyl tartrate, nonionic dispersants, such as Condensates of ethylene oxide with amines, fatty alcohols or phenols, surface-active cationic Agents such as quaternary ammonium salts, for example cetyltrimethylammonium bromide and cetylpyridinium bromide, and organic liquids such as n-butanol and benzyl alcohol.

In comparison with the dyes of German patent specification 959 748, which is a group of the formula

CH = CH

CH = C

CH ₂ - NH

Contained bound to the triazine ring, result in the dyes prepared according to the invention Cellulose textile fabrics dyeing with greater depth. The invention is illustrated, but not limited, by the following examples. Parts and Percentages are based on weight.

example 1

A solution of 2.6 parts of the sodium salt of 2-mercaptobenzothiazole in 40 parts of water is under Stir to a solution of 8.95 parts of the trisodium salt of 7- (2'-sulfophenylazo) -l- (4 ", 6" -dichlorl ", 3", 5 "-triazine-2" -ylamino) -8-naphthol -3,6-disulfone- acid (which can be obtained according to the procedure of Example 1 of British Patent 785 222) given in 350 parts of water, and the mixture obtained is 3 hours at a temperature between Stirred at 20 and 22 ° C. 60 parts of sodium chloride are then added, and the precipitated dye is filtered off. The filter cake obtained in this way is with 0.49 parts of disodium hydrogen phosphate and 1.0 Part of potassium dihydrogen phosphate is mixed, and the mixture is at a temperature of 20-25 ° C dried. According to the analysis, the dye contains five sulfur atoms and one organically bound Chlorine atom for each dye molecule.

When used on cellulosic textile materials in conjunction with a treatment with an acid-binding agent Medium the dye gives red shades with excellent wash fastness.

The following table gives further examples of the new dyes according to the invention which are obtained if you use the 8.95 parts of the trisodium salt of the aminoazo compound used in Example 1 replaced by equivalent amounts of the sodium salts of the monoazo compounds, which by condensation obtained from cyanuric chloride with the aminoazo compound listed in the second column of the table and / or the 2.6 parts of the sodium salt of 2-mercaptobenzothiazole by equivalent M narrow of the sodium salts of the heterocyclic compounds listed in the third column of the table will.

The fourth column of the table indicates the color shades that are obtained when the dyes are applied on cellulosic fabrics in connection with treatment with an acid-binding agent receives.

example Aminoazo compound Heterocyclic compound Color ion 2 Copper complex of l-amino-8,2'-dihydroxy 2-mercaptobenzothiazole violet 7- (phenyl-azo) -naphthalene-3,5 ', 6-trisulfonic acid 3 l-Amino-7- [4'-phenylazo) -2'-methoxy-5'-methyl- the same blue phenylazo] -8-naphthol-3,2 ", 6-trisulfonic acid 4th l- (3'-aminophenyl) -3-carboxy-4- (l ", 5" -disulfo- the same yellow naphth-2 "-ylazo) -5-pyrazolone 5 Copper complex of 2-amino-5,2'-dihydroxy the same ruby 6- (phenylazo) -naphthalene-l, 7,5'-trisulfonic acid 6th l-Benzoylamino-7- (3'-aminophenylazo) -8-naphthol- the same Red 3,6,6'-trisulfonic acid 7th the same 2- mercaptobenzselenazole Bluish red

continuation

example Amino acid bond Heterocyclic compound Carbon fiber 8th l-Benzoylamino-7- (3'-aminophenylazo) -8-naphthol- 2-mercapto-6-methoxybenz- Bluish red 3,6,6'-trisulfonic acid thiazole 9 the same 2-mercapto-6-nitrobenzothiazole Bluish red 10 l-amino-7- (2'-sulfophcnylazo) -8-naphthol- 2-mercapto-6-acetylamino Bluish red 3.6-disulfonic acid benzthiazole 1! the same 2-mercapto-5-methylbenz- Bluish red thiazole 12th the same 2-mercaptobenzothiazole Bluish red 5-sulfonic acid 13th the same 2-mercapto-6-chlorobenzothiazole Bluish red 14th the same 2-mercaptobenzothiazole Bluish red 5-carboxylic acid 15th the same 2-mercaptobenzothiazole Bluish red 6-sulfonic acid 16 l-Amino-7- (phenyIazo) -8-naphthol-3,6-disulfone- 2-mercaptobenzothiazole Bluish red acid 17th 2- (4'-Amino-2'-methylphenylazo) -naphthalene- the same yellow 4,8-disulfonic acid c 18th 2-amino-6- (2'-sulfophcnylazo) -5-naphthol- the same orange 7-sulfonic acid 19th 2-Amino-7- (2'-sulfophenyIazo) -8-naphthol- the same orange 6-sulfonic acid 20th l- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl- 2-mercaptobenzselenazole yellow 4- (3 "-amino-6" -sulfophenylazo) -5-pyrazolone 21 l- (2'-chloro-5'-sulfophenyl) -3-methyl-4- (3 "-amino- the same yellow 6 "-sulfophenylazo) -5-pyrazolone 22nd 2-amino-6- (2'-sulfo-4'-methoxyphenylazo) - the same Scarlet fever 5-naphthol-7-sulfonic acid Red 23 2-Amino-7- (2'-sulfo-4'-methoxyphenylazo) - 2-mercaptobenzothiazole Red 8-naphthol-6-sulfonic acid 24 2-methylamino-7- (2'-sülfo-4'-methoxyphenylazo) - the same Red 8-naphthol-6-sulfonic acid 25th 2-amino-5-hydroxy-6,2'-azonaphthalene the same orange 7, l \ 5'-trisulfonic acid 26th 2-methylamino-5-hydroxy-6,2'-azonaphthalene the same orange 7, l ', 5'-trisulfonic acid 27 1,2-chromium complex of 2-amino-6- (2'-carboxy- the same Brown phenyl-azo) -5-naphthol-7-sulfonic acid 28 the same 2-mercaptobenzselenazole Brown 29 the same 2-mercapto-6-methoxybenz- Brown thiazole 30th 4-nitro-4 '- (4 "-N-methylaminophenylazo) -stilbene- 2-mercaptobenzothiazole Reddish yellow 2,2'-disulfonic acid 31 1,2-chromium complex of 6-amino-1,2'-dihydroxy the same black 6'-nitro-2,1 '-azonaphthalene-3,4'-disulfonic acid 32 2- (3'-Amino-6'-sulfophenylazo) -l-naphthol- the same Reddish 3,6-disulfonic acid orange 33 2-amino-6- (3'-amino-6'-sulfophenylazo) -5-naphthol-
7-sulfonic acid p the same orange 34 2-Amino-6- [2'-sulfo-4 '- (4 "-sulfophenylazo) - the same Red phenylazo] -5-naphthol-7-sulfonic acid 35 2-amino-5-hydroxy-6,2'-azonaphthalene-7,4 ', 8'-tri- the same Scarlet fever sulfonic acid Red 36 2-amino-5-hydroxy-6,2'-azonaphthalene the same Scarlet fever 7,5 ', 7'-trisulfonic acid Red 37 2- (4'-Amino-3'-sulfophenylamine) -6- [2 "-sulfo- the same violet 4 "- (p-sulfophenylazo) -phenylazo] -5-naphthol- 7-sulfonic acid c

continuation

Example Aminoazo compound Heterocyclic compound hue 38 2-amino-7- (3'-amino-6'-sulfophenylazo) - 2-mercaptobenzothiazole Reddish 8-naphlhol-6-sulfonic acid orange 39 2-amino-8-hydroxy-7,2'-azonaphthalene the same Red 6,4 ', 8'-trisulfonic acid 40 2-amino-8-hydroxy-7,2'-azonaphthalene the same Red 6,1 ', 5'-irisulfonic acid 41 l-amino-7- (3'-sulfophenylazo) -8-naphthol- the same Bluish red 3,6-disulfonic acid 42 l-amino-7- (2'-sulfo-4'-chlorophcnylazo) -8-naphthol- the same Bluish red 3,6-disulfonic acid 43 l-Amino-7- (2'-sulfo-4'-methoxyphenylazo) - the same ruby 8-naphthol-3,6-disulfonic acid 44 l-amino-7- (3'-amino-6'-sulfophenylazo) - the same Bluish red 8-naphthol-3,6-disulfonic acid 45 l-amino-7- (2'-sulfophenylazo) -8-naphthol- the same Red 4,6-disulfonic acid 46 i-Amino-S-hydroxy ^ '- azonaphthalene- the same ruby 3,6,1'-trisulfonic acid 47 l-Amino-7- (4'-sulfophenyIazo) -8-naphthol • the same. Bluish red 4,6-disulfonic acid 48 2- (2'-Acetylamino-4'-aminophenyIazo) -naphthalene-
4 8-disulfonic acid * the same Reddish yellow 49 2- (2'-methyl-4'-aminophcnylazo) -naphthalene-5,7-di-
sulfonic acid the same Reddish yellow 50 2- [2'-methyl-4 '- (4 "-amino-2" -methylphenylazo) - the same Brownish phenylazo] naphthalene-4,8-disulfonic acid orange 51 1- (2'-sulfophenyl) -3-methyl-4- (3 "-amino- the same yellow 6 "-sulfophenylazo) -5-pyrazolone 52 1- (3'-aminophynyl) -3-methyl-4- (1 ", 5" -disulfo- the same yellow naphthyl-2 "-azo) -5-pyrazolone 53 1 - (4'-aminophenyl) -3-methyl-4- (1 ", 5" -disulfo- the same yellow naphthyl-2 "-azo) -5-pyrazolone 54 l- (3'-amino-4'-sulfophenyl) -3-methyl- the same yellow 4- (1 "-sulfonaphthyl-2" -azo) -5-pyrazolone 55 l- (4 ', 8'-disulfonaphth-2'-yl) -3-methyl- the same yellow 4- (3 "-amino-6" -sulfophenylazo) -5-pyrazolone 56 l- (3'-Amino-6'-sulfophenylazo) -2-naphthol-6-sulfone- the same orange acid 57 l- (3'-Amino-6'-sulfophenyIazo) -2-naphthol- . the same orange 6,8-disulfonic acid 58 2- (3'-Amino-6'-sulfophenylazo) -l-naphthol-
3-sulfonic acid the same orange 59 2- (3'-amino-6'-sulfophenylazo) -1,8-dihydroxy- the same Bluish red naphthalene-3,6-disulfonic acid c 60 l- (3'-Amino-6'-sulfophenylazo) -2-amino-8-naphthol-
fi-siilfoti ^ iiii rf * the same Red 61 l-acetylamino-7- (3'-amino-6'-sulfophenylazo) - the same Red 8-naphthol-3,6-disulfonic acid c 62 l-acetylamino-7- (3'-amino-6'-sulfophenylazo) - the same Red 8-naphthol-4,6-disulfonic acid 63 l-Benzoylamino-7- (3'-amino-6'-sulfophenylazo) - 2-mereaptobenzothiazole Red 8-naphthol-5,6-disulfonic acid 5-sulfonic acid 64 2-propionylamino-6- (3'-amino-6'-sulfophenylazo) - the same Yellowish red 5-naphthol-7-sulfonic acid 65 2-Benzoylamino-6- (3'-amino-6'-sulfophenylazo) - the same Yellowish 5-naphthol-7-sulfonic acid Red 66 2-amino-7- (3'-amino-6'-sulfoplienylazo) - the same Yellowish- 8-naphthol-6-suironic acid Red

17th

Continued 18

A m inoii / o connection

l- (4'-amino-2'-sulfophenyla / o) -2-naphthol-

8-sulfonic acid 2-acctylamino-6- (4'-amino-2'-su! Fophenylazo) -

5-naphthol-7-sulphonic acid 2-acetylamino-7- (4'-aniino-2'-sulfophenylazo) -

8-naphthol-6-sulfonic acid 1- (4'-amino-2'-sulfophynyllazo) -2-amino-

8-naphthol-6-sulfonic acid l-acetylamino-7- (4'-aniino-2'-sulfophcnylazo) -

8-naphthol-3,6-disulfonic acid l-benzoylamino-7- (4'-amino-2-sulfophenylazo) -

8-naphthol-4,6-disulfonic acid 1- (3'-aminophenyl) -3-methyl-4- (2 ", 5" -disulfo-

phenylazo) -5-pyrazolone 1- (3'-aminobenzoylamino) -7- (2 "-sulfophenylazo) -

8-naphthol-3,6-disulfonic acid 1- (4'-aminosulfonaphth-r-yla / o) -4- (8 "-sulfonaphth-

l "-ylazo) -naphthalenesulfonic acid l-amino-2- (4'-aminophenylazo) ~ 7- (4" -sulfo-

phenylazo) -8-naphthol-3.6-disulfonic acid 1- (4'-aminobenzoylamino) -7- (2 "-sulfophenylazo) -

8-naphthol-3,6-disulfonic acid 2-amino-6- [2'-methoxy-5'-methyl-4 '- (2 ", 5" -disulfophenylazo) -phenylazoJ-

5-naphthol-l, 7-disulfonic acid 2- (4'-sulfophenylamino) -7- (3 "-amino-

6 "-sulfophenylazo) -8-naphthol-6-sulfonic acid Copper complex of 2-amino-6- [2'-methoxy-5'-methyl-4 '- (2 ", 5" -disulfophenylazo) -phenylazo] -

5-naphthol-l, 7-disulfonic acid desgl.

the same

Copper complex of 2-amino-6- (2'-hydroxy-

5'-sulfophenylazo) -5-naphthol-7-sulfonic acid copper complex of 2-amino-6- (2'-hydroxy-3 \ 5'-disulfophenylazo) -5-naphthol-

1,7-disulfonic acid copper complex of l-amino-7- (2'-hydroxy-3'-chloro-5'-sulfophenylazo) -8-naphthol-

3,6-disulfonic acid copper complex of l- (3'-amino-4'-sulfophenyl) -3-methyl-4- (2 "-carboxy-4" -sulfophenylazo) -

5-pyrazolone copper complex of l- (3'-amino-4'-sulfophenyl) -3-methyl-4- (2 "-hydroxy-3", 5 "-disulfophehylazo) -

5-pyrazolone copper complex of l-phenylamino-7- (2'-hydroxy-3'-amino-5'-sulfophcnylazo) -8-naphthol-

3,6-disulfonic acid copper complex of l-phenylamino-7- (2'-carboxy-4'-aminophcnylazo) -8-naphlhol-3, ft-disulfonic acid

Ku |) l'erk <) i) iplex of 2- (4'-aniino-.V-stillOphenyl) -6- (2 "-hydroxy-3" -nitro-6 "-sullophenylazo) -

5-naphthol-7-sulfonic acid copper complex of 2- (4'-amino-3'-sullophenyl) -6- (2 "-carboxyphenylazo) -5-naphthol- 7-sulfonic acid heterocyclic compound

2-mercaplobenzthiazole-5-sulfonic acid the same

the same.

2-mercaptobenzothiazole like. like. like. like. like. like.

2-mercaptobenzothiazole-5-sulfonic acid desgl.

2-mercaptobenzothiazole 2-mercaptobenzselenazole 2-mereaptobenzothiazole like.

like. like. like. like.

the same.

the same

Color ion

Red

Yellowish red

Bluish red violet

Bordo

yellow

Red

Reddish brown

green

Red

Bluish purple

Brown

Navy blue

Navy blue

Navy blue ruby

Ruby purple

Greenish yellow

Reddish yellow

blue

Greenish blue

Bluish purple

ruby

continuation

Example Aminoazo compound Heterocyclic compound • the same hue 92 1,2-chromium complex of l- (3'-aminophenyl) - 2-mercaptobenzothiazole Reddish 3-methyl-4- (2 "-carboxy-4" -sulfophenylazo) - yellow 5-pyrazolone the same 93 1,2-chromium complex of 2-amino-6- (2'-hydroxy- the same Greenish 6'-nitro-4'-sulfonaphth-r-ylazo) -5-naphthol- black 7-sulfonic acid the same 94 Copper complex of 2-amino-6- (2'-hydroxy- the same Reddish 6'-nitro-4'-sulfonaphth-1 '-ylazo) -5-naphthol- blue 7-sulfonic acid the same 95 1,2-cobalt complex of 2-amino-6- (2'-hydroxy- the same Brown 6'-nitro-4'-sulfonaphth-1 '-ylazo) -5-naphthol- 7-sulfonic acid the same 96 Nickel complex of 2-amino-6- (2'-hydroxy- violet 6'-nitro-4'-sulfonaphth-1 '-yIazo) -5-naphthol- 7-sulfonic acid the same 97 1,2-chromium complex of 2-methylamino black 6- (2'-hydroxy-6'-nitro-4'-sulfonaphth-1'-ylazo) - 5-naphthol-7-sulfonic acid 98 1,2-chromium complex of l-amino-7- (2'-hydroxy- Greenish 6'-nitro-4'-sulfonaphth-r-ylazo) -8-naphthol- black 3,6-disulfonic acid 99 1,2-cobalt complex of l- (3'-aminophenyl) - Red 3-carboxy-4- (2 "-hydroxy-6" -nitro-4 "-sulfo- naphth-1 "-ylazo) -5-pyrazolone 100 1,2-chromium complex of 2- (4'-amino marine 3'-sulfophenylamino) -6- (2 "-hydroxy-3" -chlor- blue 5 "-sulfophenylazo) -5-naphthol-7-sulfonic acid 101 1,2-chromium complex of 2- (3'-sulfophenylamino) - Bluish 6- (2 "-hydroxy-4" -aminophenylazo) -5-naphthol- Gray 7-sulfonic acid

Example 102

A solution of 19.6 parts of the trisodium salt of l-amino-4- [4 '- (4 ", 6" -dichlor-1 ", 3", 5 "-triazine-2" -ylamino] -anilinoanthraquinone-2, 3 ', 5-trisulfonic acid (which can be obtained according to the procedure in Example 1 of British Patent 781 930) in 400 parts of water is stirred at 20 ° C and a solution of 5.2 parts of the sodium salt of 2-mercaptobenzothiazole in 50 parts of water is added over the course of 15 minutes. The mixture is ^{stirred at 20 °} C. until the end of the reaction, and then sodium chloride is added. The precipitated dye is then filtered off, washed with brine and dried ^{at 20 ° C.}

When applied to cellulosic textile materials in connection with a treatment with an acid-binding agent The medium gives the dye blue shades with excellent fastness to wet treatments.

Example 103

Instead of the 19.6 parts of the trisodium salt used in Example 102, 17.0 parts of the disodium salt are used of l-amino-4- [3 '- (4 ", 6" -dichloro-s-triazin-2 "-yl) -amino] -anilinoanthraquinone-2,4'-disulfone- acid (which are obtained according to the procedure in Example 2 of Belgian patent 556 092 can) used.

When applied to cellulosic textile materials in connection with a treatment with an acid-binding agent Medium gives the dye thus obtained reddish blue shades with excellent fastness to Wet treatments.

Example 104

The dihalotriazinylamino derivatives of metal phthalocyanines, which are prepared according to the procedure of the examples 1, 2, 3, 8 and 14 of British Patent 805 562 are obtained according to the procedure of Example 1 with the sodium salt of 2-mercaptobenzothiazole using one mole fraction of the sodium salt of 2-mercaptobenzothiazole for each dihalotriazinylamino group present in the metal phthalocyanines implemented. The dyes thus obtained give when applied to cellulosic textile materials in connection with a treatment with an acid-binding agent greenish-blue resp. turquoise-blue or greenish-blue, or greenish-blue or greenish-blue shades with excellent Fastness to wet treatments.

Example 105

A solution of 5.2 parts of the sodium salt of 2-mercaptobenzothiazole in 80 parts of water is under Stir to a solution of 8.95 parts of the trisodium salt of 7- (2'-sulfophenylazo) -l- (4 ", 6" -dichlor-1 ", 3", 5 "-triazine-2" -yIamino) -8 -naphthol-3,6-di- sulphonic acid (obtained according to the procedure of example 1 of British patent 785 222 can) given in 350 parts of water, and the obtained

Mixing is 20 hours at a temperature stirred between 25 and 30 C. The precipitated dye is then bottled and the filter cake thus obtained mixed with 0.49 parts of disodium hydrogen phosphate and 1.0 part of potassium dihydrogen phosphate and the mixture dried at a temperature between 20 and 25 (■ ". According to the analysis, the dye contains seven sulfur atoms for each dye molecule.

When used on cellulose textile materials in In connection with a treatment with an acid binding agent, the dye gives red tones excellent washing fastness.

The following table gives more examples of the new dyes that will come out when one

the 8.95 parts of the trisodium salt in Example 105 azo compound used is replaced by equivalent amounts of the sodium salts of the azo compounds, which by condensation of cyanuric chloride with those listed in the second column of the table Aminoazo compounds are obtained, and / or the 5.2 parts of the sodium salt of 2-mercaptobenzothiazole by equivalent amounts of the sodium salts listed in the third column of the table

ίο heterocyclic compounds are replaced.

The fourth column of the table indicates the color shades which are obtained when the dyes are applied to cellulosic textile materials in conjunction with treatment with an acid-binding agent.

example

Aminoazo compound Heterocyclic compound hue l-amino-7- (2'-sulfophcnylazo) -8-naphthol- 2-mercaptobenzclenazole Bluish 3.6-disulfonic acid c Red 2-methylamino-6- (I \ 5'-disulfonaphth-2'-ylazo) - 2-Mcrcaptobcnzlhiazole orange 5-naphthol-7-sulfonic acid 2-amino-6- (2'-sulfophcnyIazo) -5-naphthol- the same orange 7-sulfonic acid 2-amino-7- (2'-sulfophenylazo) -8-naphthol- the same orange 6-sulfonic acid l-amino-7- (3'-sulfophenylazo) -8-naphthol- the same Bluish 3,6-disulfonic acid Red l-amino-7- (2'-sulfo-4'-melhoxyphenylazo) - the same ruby 8-naphthol-3,6-disulfonic acid l-Amino-7- (3'-amino-6'-sulfophcnylazo) - the same Bluish- 8-naphthol-3,6-disulfonic acid Red l-amino-7- (2'-sulfophenylazo) -8-naphthol- the same Red 4,6-disulfonic acid c l-acetylamino-7- (3'-amino-6'-sulfophcnylazo) - the same Red 8-naphthol-3,6-disulfonic acid c 2-Amino-6- [2'-methoxy-5'-methyl-4 '- (2 ".5" -disulfo- the same Bluish- phcnylazo] -5-naphthol-1.7-disulfonic acid c violet Copper complex of 2-amino-6- [2'-methoxy- the same marine 5'-methyl-4 '- (2 ".5" -disulfophenylazo] - blue 5-riaphthol-1,7-disulfonic acid l-amino-7- (l'-sulfonaphth-2'-yIazo) -8-naphthol- the same Bluish 3,6-disulfonic acid Red l- (2'.5'-dichloro-4'-sulfophenyl) -3-methyl- the same yellow 4- (4'-amine, .o-2'-sulfopnenylazo) -5-pyrazolone Copper complex of l-amino-7- (2'-hydroxy- the same purple 3'-chloro-4'-sulfophenyIazo) -8-naphthol- 3.6-disulfonic acid

106
107
108
109
110
Ml
112
113
114
115
116

Example 120

7.73 parts of the trisodium salt of 2- [8'-hydroxy-7 '- (2 "-sulfophenylazo) -3', 6'-disulfonaphth-l'-ylami- no] -4-anilino-6-chloro-l, 3,5-triazine and 2.84 parts of the sodium salt of 2-mercaptobenzothiazole dissolved in 250 parts of water, and the pH of the solution is adjusted by adding aqueous sodium hydroxide solution set to 8 to 9. The solution is then 5 hours at 70 C and finally 4 hours at 90 "C. Then 37 parts of sodium chloride are added, the solution is cooled to 30" C, and the precipitated dye is filtered off, washed with acetone and dried.

According to analysis, the dye contains 32 carbon atoms, 8 nitrogen atoms and 5 sulfur atoms per dye molecule.

When the dye is used in conjunction with an acid-binding agent treatment on cotton is applied, the result is bluish-red shades with excellent washfastness.

Example 121

6.43 parts of the disodium salt of 2- [5'-hydroxy-6 '- (4 "-methoxy-2" -sulfophenylazo) -7'-sulfonaphthr-ylmethylamino] -4-methoxy-6-chloro-1,3, 5-triazine

and 3.78 parts of the sodium salt of 2-mercaptobenzothiazole are dissolved in 250 parts of water, and the pH of the solution is adjusted to 8 to 9 by adding aqueous sodium hydroxide solution. The solution is then stirred ^{at 50 ° C. for 12 hours.} 12.5 parts of sodium chloride are added, the solution is ^{cooled to 20 °} C., and the precipitated dye is filtered off, washed with acetone and dried.

According to the analysis, the dye contains 7 atoms of nitrogen and 4 atoms of sulfur per dye molecule.

If the dye is applied to cellulosic textile materials in the presence of an acid binding agent, it delivers lively scarlet tones with good washfastness.

Example 122

8.1 parts of the trisodium salt of 2- [8'-hydroxy-7 '- (2 "- sulfophenylazo) - 3', 6 '- disulfonaphth - Γ - ylamino] -4-diethylthiocarbamylthio-6-chloro-1,3, 5-tri- azine (obtainable by condensation of the trisodium salt of 2- [8'-hydroxy-7 '- (2 "-sulfophenylazo) -3', 6'-disulfonaphth-1 '-ylamino] -4,6-dich! or-1,3,5-triazine with sodium diethyldithiocarbamate in an aqueous medium) and 2.1 parts of the sodium salt of 2-mercaptobenzothiazole are dissolved in 250 parts of water, and the pH of the solution is adjusted to 8 to 9 by adding aqueous sodium hydroxide solution. The solution is stirred for 20 hours at 20 ^° C., and the precipitated dye is then filtered off and washed with acetone. The solid product thus obtained is mixed with part of a mixture (weight ratio 1: 1.77) of sodium hydrogen phosphate and potassium dihydrogen phosphate, and the product obtained is dried. According to analysis, the dye contains nitrogen atoms and 7 sulfur atoms per dye molecule.

If you use the dye in conjunction with a treatment with an acid-binding agent If cellulose textile materials are applied, bluish-red tones with good washfastness are obtained.

Example 123

8.48 parts of the dye of Example 1 and 2.14 parts of the sodium salt of aniline-3-sulfonic acid dissolved in 250 parts of water, and the solution is then stirred for 8 hours at 40 ° C. 37.5 parts of sodium chloride are added and the solution is cooled to 20 ° C. The precipitated dye is then filtered off, washed with acetone and dried.

According to analysis, the dye contains nitrogen atoms and 6 sulfur atoms per dye molecule.

If you use the dye in conjunction with a treatment with an acid-binding agent Applies cellulose textile materials, it gives bluish-red tones with good washfastness.

The following table gives further examples of the new dyes according to the invention which are obtained when adding the 8.48 parts of the dye of Example 1, which are used in Example 123, by equivalent amounts of the dyes listed in the second column of the table and / or the 2.14 parts of the sodium salt of the aniline-3-sulfonic acid used in Example 123 by equivalents Amount of sodium salts of the compounds listed in the third column of the table replaced. The fourth Column of the table indicates the color tones that are obtained when the dyes are combined with a Treatment with an acid-binding agent can be applied to cellulose.

example

129
130
131
132
133
134
135

dye

Dye from Example I.
Dye from Example 1

Dye from Example 3
Dye from Example 6
Dye of Example 24

Dye of
Dye of
Dye of
Dye of
Dye of
Dye of
Dye of

Example 25
Example 30
Example 33
Example 39
Example 40
Example 94
Example 99

connection phenol hue Bluish Aniline-3,5-disulfonic acid Red Bluish Aniline-4-sulfonic acid Red Aniline-3-carboxylic acid blue Aniline-3-sulfonic acid Red Bluish the same Red the same yellow 2-carboxyaniline-4-sulfonic acid c yellow Aniline-3-sulfonic acid orange the same yellow the same black the same ruby blue

The following table gives further examples of the new dyes according to the invention which are obtained if one uses the 7.73 parts of the trisodium salt of the azo compound used in Example 120 replaced by equivalent amounts of the azo compounds, which by condensation in the second Aminoazo compound listed in the column of the table with that listed in the third column of the table Triazine can be obtained. The fourth column of the table shows the color shades that are obtained when the Dyes in connection with an acid binding agent treatment on cellulosic textile materials be applied.

? 09 609 30

Hcispic

Aniinoazo compound

136 1-Amino-7- [4 '- (phcnylazo) -2'-methoxy-5'-methyl-phenylazo] -8-naphthol-3,2', 6-trisulfonic acid

137 l- (3'-aminophenyl) -3-carboxy-4- (l ", 5" -disulfo-

naphth-2 "-ylazo) -5-pyrazolone

138 l-Benzoylamino-7- (3'-aminophenylazo) -

8-naphthol-3,6,6'-trisulfonic acid

139 2- (4'-Amino-2'-methylphenylazo) -naphthaIine-

4,8-disilfonic acid c

140 l- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-

4- (3 "-amino-6" -sulfophenylazo) -5-pyrazolone

141 2-methylamino-5-hydroxy-6,2'-azonaphthalene

7, r, 5'-trisulfonic acid

142 4-Nitro-4 '- (4 "-N-methylaminophenylazo) -stilbene-

2,2'-disulfonic acid

143 l-amino-8-hydroxy-7,2'-azonaphthalene

3,6,1'-trisulfonic acid

144 I- (3'-Amino-6'-sulfophenylazo) -2-naphthol-

6,8-disulfonic acid

145 l-amino-2- (4'-aminophenylazo) -7- (4 "-sulfo-

phenylazo) -8-naphthol-3,6-disulfonic acid

146 2-Amino-6- (2'-sulfophenylazo) -5-naphthoI-

7-sulfonic acid

147 I-Amino-7- (2'-sulfophenylazo) -8-naphthol-

4,6-disulfonic acid

Example 148

A solution of 9.1 parts of the disodium salt of I-amino-8-naphthol-3,6-disulfonic acid in 100 parts of water is converted into a suspension of 4.65 parts of cyanuric chloride in a mixture of 30 parts of acetone and 50 parts for 30 minutes Added ice and 50 parts of water. The resulting mixture is stirred for 1 hour at a temperature between 0 and 5 "C, and a 10% aqueous sodium carbonate solution is then added until the pH of the mixture is 7. A solution of 4.75 parts of the sodium salt of 2-mercaptobenzothiazole in 30 Portions of water are then added and sodium carbonate is added until the pH of the mixture is between 8 and 9. The mixture is stirred for 1 hour at 35 ° C., then ^{cooled to 0} ° C., and an aqueous solution of diazotized orthanilic acid (obtained by Diazotization of 4.1 parts of orthanilic acid in the usual way) and 10 parts of sodium carbonate are added. The mixture is ^{stirred for 2 hours at 0} ° C., 40 parts of sodium chloride are added, and the dyestuff which has precipitated out is filtered off and dried. The dyestuff obtained in this way is identical with the dye of Example I.

Example 149

To a solution of 9.38 parts of 4- (4 ", 6" -Dichlor - 1 ", 3", 5 "- triazine - 2" - ylamino) - 2 '- hydroxy-5'-methylazobenzene (obtainable by condensation of cyanuric chloride with 4-amino-2'-hydroxy-5'-methylazobenzene) in 400 parts of dioxane is a solution of 5.24 parts of 2-mercaptobenzothiazole in a mixture of 50 parts of water, 13.75 parts of 2 N aqueous sodium hydroxide solution and 150 parts of dioxane given, and the mixture obtained is then stirred for 5 hours at 20 "C. Then 750 parts

Triizine hue 2-phenoxy-4,6-dichloro blue 1,3,5-triazine 2- (3'-sulfophenylamino) - yellow 4,6-dibromo-1,3,5-triazine 2- (3 ', 5'-disulfophenylamino) - Red 4,6-dichloro-1,3,5-triazine 2-methoxy-4,6-dichloro yellow 1,3,5-triazine 2-amino-4,6-dichloro yellow 1,3,5-triazine 2-methylamino-4,6-dichloro orange 1,3,5-triazine 2-dimethylamino-4,6-dichloro Reddish 1,3,5-triazine yellow 2- (4'-sulfoanilino) -4,6-dichloro- ruby 1,3,5-triazine 2-methyl-4,6-dichloro orange 1,3,5-triazine 2-methylthio-4,6-dichloro green 1,3,5-triazine 2-phenylthio-4,6-dichloro orange 1,3,5-triazine 2-phenyl-4,6-dichloro Red 1,3,5-triazine

Water is added and the precipitated dye is filtered off and dried.

When dispersed in an aqueous medium, the dye dyes polyamide textile materials in yellow tones with excellent fastness to wet treatments.

Example 150

A solution of 4.16 parts of the sodium salt of 2-mercaptobenzothiazole in 70 parts of water is added a solution of 19.74 parts of the tetrasodium salt of a mixture of l-amino-4- [4 '- (4 "- {4"', 6 "'- dichloro -1 '", 3"', 5 "'- triazine - 2'" - ylamino} - phenylvinyl) -anilino] -anthraquinone-2,5,3 ', 2 "- and -2,8,3 ', 2 "-tetrasulfonic acids (obtainable by condensation of cyanuric chloride with a technical mixture of Tetrasodium salts of l-amino-4- [4 '- (4 "-aminophenylvinyl) -anilino] -anthraquinone-2,5,3', 2" - and -2,8,3 ', 2 "-tetrasulfonic acids) in 300 parts of water, and the resulting mixture is 2 hours at a Temperature between 25 and 30 ° C stirred. Then 30 parts of sodium chloride are added, and the The precipitated dye is filtered off, washed with a 5% strength aqueous sodium chloride solution and dried.

According to the analysis, the dye contains 6 sulfur atoms and 1 atom of organically bound chlorine per Dye molecule.

The dye thus obtained provides when applied to cellulosic fabrics in conjunction with a Treatment with an acid-binding agent to bluish green tones with excellent fastness to Wet treatments.

The following table gives further examples of the new dyes according to the invention which are obtained if you add the 19.74 parts of the tetrasodium

salt of the anthraquinone compound used in Example 150 replaced by equivalent amounts of the sodium salts of the anthraquinone compounds, which by condensation of cyanuric chloride with the aminoanthraquinone listed in the second column of the table and / or the 4.16 parts of the sodium salt of that used in Example 150

2-mercaptobenzothiazoles by equivalent amounts of those listed in the third column of the table replaced heterocyclic compounds. The fourth column of the table indicates the color tones that you can use obtained when the dyes in conjunction with a treatment with an acid-binding agent Cellulosic textile materials are applied.

example Aminoanthraquinone Heterocyclic compound Color ion 151 l-Amino-4- [4 '- (4 "-aminophenylazo) -ani! ino] - 2-mercaptobenzothiazole Yellowish anthraquinone-2,5,2'-trisulfonic acid green 152 the same 2-mercaptobenzselenazole Yellowish green 153 l-amino-4- (4'-aminoanilino) anthraquinone 2-mercaptobenzothiazole blue 2,5,3'-trisulfonic acid 5-carboxylic acid 154 the same 2-mercaptobenzothiazole blue 6-sulfonic acid 155 l-amino-4- (3'-aminoaTiilino) -anthraquinone- the same Reddish 2,4'-disulfonic acid blue 156 the same 2-mercaptobenzselenazole Reddish
blue 157 the same 2-mercaptobenzothiazole Reddish 5-carboxylic acid blue

Example 158

19.7 parts of copper phthalocyanine-3-sulfone-N- (3'-aminophenyl) amidsulfonamidsulfonic acid (obtainable as described below) are suspended in 400 parts of water, and a 2 η aqueous sodium hydroxide solution is added until a clear solution is obtained and the pH of the solution is 7. The solution is cooled to 0-5 ° C and a solution of 3.88 parts of cyanuric chloride in 20 parts of acetone is added. The mixture is stirred for 30 minutes at a temperature between 0 and 5 ° C., while the pH of the mixture is kept between 6.5 and 7 by adding 2N aqueous sodium carbonate solution. A solution of 3.8 parts of the sodium salt of 2-mercaptobenzothiazole in 50 parts water is then added and the mixture heated slowly to a temperature of 40 ⁰ C and held for 2 hours at this temperature, while the pH of the mixture by adding 2n aqueous sodium carbonate solution is kept between 6.5 and 7.0. 150 parts of sodium chloride are then added and the precipitated dye is filtered off and dried.

When the dye is applied to cellulosic textile materials by a printing process greenish-blue prints with excellent fastness to wet treatments.

The copper phthalocyanine - 3 - sulfone - N - (3 '- aminopheny 1) - amidesulfonamidsulfonic acid used in the above example can be obtained as follows: 115.2 parts of copper phthalocyanine are slowly added to 540 parts of chlorosulfonic acid with stirring and the mixture is then added for 3 hours a temperature of 140 to 145 ° C stirred. The mixture is cooled to 8O ⁰ C, 100 parts of thionyl chloride are added and the mixture was then stirred for 2 hours at a temperature of 85 ° C. The mixture is cooled to 20 ⁰ C, poured onto ice, and the precipitated is filtered off and washed with Phthalocyaninsulfonchlorid 1000Teilen a cooled to 0 ⁰ C l% aqueous hydrochloric acid solution.

The solid sulfonic chloride thus obtained is stirred with 1000 parts of water, and 600 parts of ice and 30 parts of m-aminoacetanilide are then added. The pH of the mixture obtained is adjusted to 8 by adding 2N aqueous ammonium hydroxide solution and the temperature of the mixture is then increased to 50 ° C. over an hour, the pH of the mixture being kept at 8 by further additions of 2N aqueous ammonium hydroxide solution . The mixture is then stirred at a temperature of 50 ^° C. until no further additions of ammonium hydroxide solution are required in order to keep the pH at 8. Then 500 parts of concentrated aqueous hydrochloric acid are added and the mixture is ^{stirred at a temperature of 90 °} C. for 4 hours. The mixture is then cooled to 20 ° C. and the precipitated solid product is filtered off, washed with a 1% strength aqueous hydrochloric acid solution and dried.

Example 159

Instead of the 19.7 parts used in Example 158 Copper phthalocyanine - 3 - sulfone - N - (3 '- aminophenyl) amidesulfonamidesulfonic acid 19.7 parts of copper phthalocyanine-3-silicone-N- (4'-aminophenyl) amidesulfonamidesulfonic acid were obtained used to obtain a dye with similar properties.

The copper phthalocyanine-3-sulfone-N- (4'-aminophenyl) amidesulfonamidesulfonic acid used in the above example can be according to that described in Example 158 for the preparation of the isomeric compound Procedure except replacing 30 parts of m-aminoacetanilide with 30 parts of p-aminoacetanilide will be obtained.

Example 160

Instead of 19.7 parts of copper phthalocyanine-3-sulfone-N- (3'-aminophenyl) -amidsulfonamidsulfonic acid, which were used in Example 158, 19.7 parts of the copper phthalocyanine - 4 - sulfone

N- (3'-aminophenyl) amidesulfonamidsulfonic acid is used and thus obtained a similar dye.

The copper phthalocyanine-4-sulfone-N- (3'-aminophenyl) amidesulfonamidesulfonic acid used in the above example can be obtained as follows.

196.8 parts of the tetrasodium salt of copper phthalocyanine tetra -4-sulfonic acid become slow added with stirring to 970 parts of chlorosulfonic acid and then the mixture for 3 hours at one temperature Stirred between 115 and 120 "C. The mixture is cooled to 80 C, 100 parts of thionyl chloride are added, and the mixture is 2 hours stirred at a temperature between 115 and 120 "C. The mixture is then cooled to 20 ° C. and poured onto ice, along with the precipitated phthalocyanine sulfonyl chloride is filtered off, and with 1000 parts of a 10% aqueous hydrochloric acid solution cooled to 0 "C. washed.

The sulfonic chloride thus obtained is stirred with 1000 parts of water, and 600 parts of ice and 30 parts of m-aminoacetanilide are then added. The pH of the mixture obtained is adjusted to 8 by adding 2N aqueous ammonium hydroxide solution and the temperature of the mixture is then increased to 50 ° C. over an hour, the pH of the mixture being kept at 8 by further additions of 2N aqueous ammonium hydroxide solution . The mixture is then stirred at a temperature of 50 ^° C. until no further additions of the ammonium hydroxide solution are required in order to keep the pH at 8. 500 parts of concentrated aqueous hydrochloric acid are then added, and the mixture is ^{stirred at a temperature of 90 °} C. for 4 hours. The mixture is ^{cooled to 20 °} C. and the precipitated solid product is filtered off, washed with a 1% strength aqueous hydrochloric acid solution and dried.

Instead of the copper phthalocyanine-4-sulfone-N- (3'-aminophenyl) amidesulfonamidsulfonic acid used in the above example equivalent amounts of copper phthalocyanine-4-sulfone-N- [3'-amino-4 '- (methyl-, chloro- or methoxy) -phenyl] -amidsulfonamidsulfonsäu're used and thus obtained similar dyes.

The aforesaid copper phthalocyanines can be obtained as described above except that the 30 parts of m-aminoacetanilide by 32.8 parts of 3-amino-6-methylacetanilide or by 36.9 parts of 3-amino-6-chloroacetanilide or 36.0 parts of 3-amino-6-methoxyacetanilide be replaced.

Example 161

Instead of the solution of 3.8 parts of the sodium salt of 2-mercaptobenzothiazole in 50 parts of water used in Example 153, a solution of 7.6 parts of the sodium salt of 2-mercaptobenzothiazole in 75 parts of water is used, and instead of the reaction mixture for 2 hours To maintain a temperature of 40 ⁰ C, the reaction mixture is kept at a temperature of 90 ⁰ C for 12 hours and thus a similar dye is obtained.

Example 162

A solution of 5 parts of 2-mercaptobenzothiazole and 1.3 parts of sodium hydroxide in 50 parts of water is stirred into a solution of 7.13 parts of the disodium salt of 1- (2 ', 5'-dichloro-4'-sulfophenyl) -3 -methyl-4- [5 "- (dichloropyrimidyIamino) -2" -sul- fophenylazo] -5-pyrazolone (obtainable by condensation of a molar proportion of 2,4,6-trichloropyrimidine with a molar proportion of 1- (2 ', 5'- Dichloro-4'-sulfophenyI) -3-methyl-4- (5 "-amino-2" -sulfophenylazo) -5-pyrazolone) in 100 parts of water, and the resulting mixture is 19 hours at a temperature of 90 "C. A solution of 75 parts of potassium acetate in 90 parts of water is then added, the mixture is ^{cooled to 0 °} C. and the precipitated dye is filtered off. The dye is then dissolved in 150 parts of water, the solution is filtered and a solution of 25 Parts of potassium acetate in 30 parts of water are added to the filtrate, and the precipitated dye is then filtered off and dried.

According to the analysis, the dye thus obtained contains 8 nitrogen atoms, 4 sulfur atoms and 3 chlorine atoms per dye molecule.

If you use the dye in conjunction with a treatment with an acid-binding agent Applies cellulose textile materials, it delivers orange tones with excellent fastness to washing and light.

Example 163

A solution of 6.3 parts of 2-mercaptobenzothiazole and 1.6 parts of sodium hydroxide in 30 parts of water is stirred to a solution of 8.09 parts of the disodium salt of 2- [4'-Trichlor.pyrimidylamino) - 2 '- methylphenylazo] - naphthalene - 4,8 - disulfonic acid (obtainable by condensation of a Molar fraction of 2,4,5,6-tetrachloropyrimidine with a molar fraction of 2- (4'-amino-2'-methylphenylazo) -naphthalene-4,8-disulfonic acid) added in 100 parts of water, and the mixture thus obtained is 2 hours at a Temperature of 90 ° C stirred. The mixture is then filtered and a solution of 100 parts of potassium acetate in 50 parts of water added to the filtrate. The precipitated dye is then filtered off and dried.

According to the analysis, the dye thus obtained contains 6 nitrogen atoms, 4 sulfur atoms and 2 chlorine atoms per dye molecule.

When using cellulosic textile materials in connection with a treatment with an acid-binding agent Medium, the dye gives yellow shades with excellent fastness to washing and light.

Example 164

55 A solution of 4.3 parts of 2-mercaptobenzothiazole in 25 parts of 1 η-aqueous sodium hydroxide solution is stirred into a solution of 15.5 parts of the disodium salt of 4- (5-cyandichloropyrimidylamino) -2'-nitrodiphenylamine-3,4 ' -disulfonic acid (obtainable by condensation of a molar proportion of 5-cyano-2,4,6-trichloropyrimidine with a molar proportion of the disodium salt of 4-amino-2'-nitrodiphenylamine-3,4'-disulfonic acid) in 450 parts of water.

give, and the mixture obtained is _{stirred for 1/2} hour at a temperature between 30 and 35 ° C. 125 parts of potassium chloride are then added and the precipitated dye is filtered off and dried.

After analysis, the obtained dye contains

7 nitrogen atoms, 4 sulfur atoms and 1 chlorine atom per dye molecule.

If you use the dye in conjunction with a treatment with an acid-binding agent Applies cellulosic textile materials, it gives yellow tones with excellent fastness to wet treatments.

B e i s ρ i e 1 165

A solution of 9 parts of 2-mercaptobenzothiazole in 52 parts of a 1N aqueous sodium hydroxide solution is stirred into a solution of 15.5 parts of the disodium salt of 4- (5-cyandichloropyrimidylamino) -2'-nitrodiphenylamine-3,4'-disulfonic acid added in 450 parts of water, and the resulting mixture is stirred for 1 hour at a temperature of 60 ° C and then 15 minutes at 80 "C. the mixture is then cooled to 20 ⁰ C and the precipitated dye collected by filtration and dried.

After analysis, the obtained dye contains

8 nitrogen atoms and 6 sulfur atoms per dye molecule.

If you use the dye in conjunction with a treatment with an acid-binding agent If cellulose textile materials are applied, yellow shades with excellent fastness to wet treatments are obtained.

Example 166

17.0 parts of copper phthalocyanine-3-sulfone-N- (4'-aminophenyl) -amidsulfonamidsulfonic acid (obtainable as described below) are suspended in 800 parts of water, and a 2 η aqueous sodium hydroxide solution is added until a clear solution is obtained and the pH of the solution is 7. The solution is ^{cooled to 10 °} C., and a solution of 3.8 parts of 5-cyano-2,4,6-trichloropyrimidine in 80 parts of dioxane is then added. The mixture is stirred for 30 minutes at a temperature of 10 ° C., while the pH of the mixture is kept between 6.5 and 7 by adding a 1N aqueous sodium hydroxide solution. A solution of 3 parts of 2-mercaptobenzothiazole in 18 parts of a 2 η-aqueous sodium hydroxide solution is then added, and the mixture is slowly heated to a temperature of 6O ⁰ C and held for 4 hours at this temperature. 100 parts of sodium chloride are then added and the precipitated dye is filtered off and dried.

When the dye is applied to cellulosic textile materials by a printing process, results he vivid greenish blue prints with excellent fastness to wet treatments.

The copper phthalocyanine used in the above example - 3 - sulfone - N - (4 '- aminophenyl) - amidesulfonamidsulfonic acid can be obtained as follows: 115.2 parts of copper phthalocyanine are slowly added to 540 parts of chlorosulfonic acid with stirring, and the mixture is stirred for 3 hours at a temperature between 140 and 145 ° C. the The mixture is cooled to 80 ° C, 100 parts of thionyl chloride are added, and the mixture is then Stirred at a temperature of 85 ° C. for 2 hours. The mixture is cooled to 20 ° C, poured onto ice, and the precipitated Phthalocyaninsulfonchlo-Hd is filtered off and cooled to 0 "C with 1000 parts Washed 1% aqueous hydrochloric acid solution.

The solid sulfonic chloride obtained in this way is stirred with 1000 parts of water and 600 parts of ice, and 30 parts of p-aminoacetanilide are then added. The pH of the mixture obtained is adjusted to 8 by adding a 2N aqueous ammonium hydroxide solution set, and the temperature of the mixture is then increased to 50 "C over one hour, wherein the pH of the mixture was kept at 8 by further additions of 2N aqueous ammonium hydroxide solution will. The mixture is then kept at a temperature of 50 C until no further additions of ammonium hydroxide solution are required to keep the pH at 8. 500 parts concentrated aqueous hydrochloric acid are then added, and the mixture is 4 hours at a temperature of 90 "C. The mixture is then cooled to 20" C, and the precipitated solid product is filtered off, washed with a 1% aqueous hydrochloric acid solution and dried.

Example 167

Instead of the solution of 3 parts of 2-mercaptobenzothiazole in 18 parts used in Example 166 a 1N aqueous sodium hydroxide solution is a solution of 3.8 parts of 2-mercaptobenzothiazole-5-carboxylic acid used in 36 parts of a 1N aqueous sodium hydroxide solution and such a similar dye receive.

At spie I 168

A solution of 2.0 parts of 2-mercaptobenzothiazole and 0.48 parts of sodium hydroxide in 100 parts of water becomes a solution of 9.2 parts of the trisodium salt by reacting one molar fraction a technical mixture of l-amino-4- [4 '- (4 "- aminophenylazo) - anilino] - anthraquinone-2,2", 5- and -2.2 ", 8-trisulfonic acid with a molar proportion of 2,4,5,6-tetrachloropyrimidine obtained dye compound given, and the mixture obtained is stirred under reflux for 40 hours. The solution is then cooled to 20 "C, 90 parts of sodium chloride are added, and the precipitated The dye is filtered off, washed with a 15% strength aqueous sodium chloride solution and dried.

If you use the dye in conjunction with a treatment with an acid-binding agent Applying cellulosic textile materials, it gives olive green tones with excellent fastness to wet treatments.

The following table gives further examples of the new dyes according to the invention which are obtained if one uses the 9.2 parts of the trisodium salt of the dye compound used in Example 168 replaced by equivalent amounts of the sodium salts of the dye compounds, which by reaction the aminoanthraquinones listed in the second column of the table with those in the third Column of the table listed pyrimidines are obtained, and / or the 2.0 parts of mercaptobenzothiazole by equivalent amounts of the heterocyclic compounds listed in the fourth column of the table be replaced. The fifth column of the table shows the shades that you get when you use the Dyes in connection with an acid binding agent treatment on cellulosic textile materials brings up.

209 609 3

foispicl Aniinoanlhracliinone Pyrimidine Hydrocyclic compound hue 169 Mixture of I-amino 2,4,5,6-tetrachloro 2- / mercaptobenzothiazole green 4- [4 '-! / I- (4 "-aminophynyl) - pyrimidine vinyl} -anilino] -anthraquinone- 2.2 ", 3 ', 5- and 2.2", 3', 8-tetra- sulfonic acid c 170 the same the same 2-mercaptobenz green selenazole 171 the same 2,4,5,6-tetrabromo 2-mercaptobenzothiazole green pyrimidine 172 l-amino-4- (4'-aminoanilino) - 2.4.5,6-trachlor- the same blue anthraquinone-2,3,5-trisulfone- pyrimidine acid 173 the same 2,4,6-trichloropyrimidine the same blue 174 the same 2,4,6-tribromopyrimidine the same blue 175 the same 5-methyl-2,4,6-trichloro- the same blue pyrimidine 176 the same 2,4,5,6-tetrachloro 2-mercaptobenzothiazole blue pyrimidine 5-carboxylic acid 177 l-amino-4- (4'-aminoanilino) - 2,4,5,6-tetrachloro 2-mercaptobenzothiazole blue anthraquinone-2,3 ', 5-trisulfone- pyrimidine 6-sulfonic acid

acid

Example 178

A solution of 1.7 parts of 2-mercaptobenzothiazole and 0.42 parts of sodium hydroxide in 100 parts of water is added to a solution of 8.07 parts of the trisodium salt of l-amino-4- [4 '- (5 "-cyan-dichloropyrimidylamino) - anilino] - anthraquinone - 2,3 ', 5 - trisulfonic acid (obtainable by condensation of a molar proportion of the trisodium salt of 1- amino- 4 - [4' - aminoanilino] - anthraquinone - 2,3 ', 5 - trisulfone- is given acid with S-cyano ^ Ao-trichloropyrimidine) and the resulting mixture stirred for 4 hours at a temperature between 40 and 45 ° C. the solution is then cooled to 20 ⁰ C, 70 parts of sodium chloride are added and the precipitated dye then filtered off, washed with 10% aqueous sodium chloride solution and dried.

When applying the dye to cellulosic fabrics in conjunction with a treatment with a Applying acid-binding agents, it delivers blue tones with excellent fastness to wet treatments.

Example 179

Instead of the solution of 1.7 parts of 2-mercaptobenzothiazole and 0.42 parts of sodium hydroxide in 100 parts of water, which were used in Example 197, is a solution of 2.1 parts of 2-mercaptobenzothiazole-5-carboxylic acid and 0.8 part of sodium hydroxide in 100 parts of water or a solution of 2.5 parts of 2-mercaptobenzothiazole-6-sulfonic acid and 0.8 part of sodium hydroxide in 100 parts of water are used to obtain similar dyes.

Example 180

49.25 parts of copper phthalocyanine-3-sulfone-N- (3--aminophenyO amidsulfonamidsulfonsäure are suspended at a temperature between 55 and 60 ⁰ C in 350 parts of water, and a 2N aqueous sodium hydroxide solution is added until a clear solution and the pH of the solution. 7 A solution of 11 parts of 2,4,5,6-tetrachloropyrimidine in 40 parts of acetone is then added and the mixture stirred at 55 to 60 ⁰ C until no further additions of 2-η aqueous sodium hydroxide erforder to keep the pH of the mixture between 6.5 and 7.0 A solution of 8.3 parts of 2-mercaptobenzothiazole and 2.4 parts of sodium hydroxide in 250 parts of water is then added and the resulting mixture at 70 for 3 hours stirred ° C and then 1 hour at 80 ⁰ C. the mixture is then cooled to 25 ° C, 100 parts of sodium chloride are added and the precipitated dye is filtered and dried.

If you put the dye in conjunction with a

Applying a treatment with an acid-binding agent to cellulose textile materials, it delivers turquoise-blue tones with excellent fastness to wet treatments and light.

The copper phthalate used in the example above

cyanine-3-sulfone-N- (3'-aminophenyl) -amidsulfonamidsulfonsäure can according to the example 166 for the Preparation of the isomeric compound described method except that the 30 parts p-aminoacetanilide by 30 parts of m-aminoacetanilide be replaced.

Example 181

98.5 parts of copper phthalocyanine-3-sulfone-N- (3'-aminophenyl) amidesulfonamidsulfonic acid (available as water) described in Example 180 in 700 parts of suspended at a temperature of 55 to 6O ⁰ C, and a 2N aqueous sodium hydroxide solution is added until a clear solution of pH. 7 A solution of 18.4 parts of 2,4,6-trichloro pyrimidine in 80 parts of acetone is then added and stir the mixture at 55 to 60 ° C until none further additions of 2 η aqueous sodium hydroxide solution are required to keep the pH between 6.5 and 7.0 to hold. A solution of 16.7 parts of 2-mercapto benzthiazole in 4 parts sodium hydroxide in 500 parts len water is then added and the mixture obtained is stirred at 90 to 95 ° C. for 20 hours. then 40 parts of sodium chloride are added, the mi

The mixture is cooled to 25 ° C. and the dye obtained is filtered off and dried.

If you use the dye in conjunction with a treatment with an acid-binding agent When applying cellulose textile materials, it delivers greenish-blue tones with excellent light fastness and wet treatments.

Example 182

A mixture of 9.66 parts of the disodium salt of the 1,2-chromium complex of 2-dichloropyrimidylamino-6- (2'-carboxyphenylazo) -5-naphthol-7-sulfonic acid, 3.46 parts of the sodium salt of 2-mercaptobenzothiazole and 250 parts Water is stirred for 8 hours at a temperature between 80 and 85 ° C., the pH of the mixture being kept between 7 and 8 by adding a dilute aqueous sodium hydroxide solution. The solution obtained is then ^{cooled to 20 °} C., 50 parts of sodium chloride are added, and the precipitated dye is filtered off and dried.

According to the analysis, the dye contains 12 nitrogen atoms, 6 sulfur atoms and 2 chlorine atoms per dye molecule. When you put the dye in contact applied to cellulosic fabrics with an acid binding agent treatment he brown tones with excellent fastness to washing and light.

30th

Example 183

A mixture of 6.18 parts of the trisodium salt of l- (5-Cyandichlorpyrimidylamino) -7- (2'-sulfophenylazo) -8-naphthol-3,6-disulfonic acid, 1.73 parts of the sodium salt of 2-mercaptobenzothiazole and 120 parts of water is 4 hours at a Temperatur stirred between 80 and 85 ° C, the pH of the mixture by adding a dilute aqueous Sodium hydroxide solution is kept between 7 and 8. The resulting solution is then cooled to 20 ° C, the pH of the solution is adjusted to 5.5 by adding a dilute aqueous hydrochloric acid solution, 30 parts of sodium chloride are added and the precipitated dye is then filtered off with Washed 25% aqueous sodium chloride solution and dried.

According to the analysis, the dye contains 7 nitrogen atoms, 5 sulfur atoms and 1 chlorine atom per dye molecule. If you use the dye in conjunction with a treatment with an acid-binding agent Applies agent to cellulosic textile materials, it delivers bluish-red tones with excellent washing and washing properties Lightfastness.

Be is pie I 184

A mixture of 3.9 parts of the disodium salt of the copper complex of 2- [4'-trichloropyrimidylamino - 3 '- sulfopheny lamino] - 6 - (2 "- carboxyphenylazo) -5-naphthol-7-sulfonic acid, 2.0 parts of the sodium salt of 2-mercaptobenzothiazole and 220 parts of water is 8 hours at a temperature between 80 ° and 85 ° C., the pH of the mixture being adjusted by adding a dilute aqueous sodium hydroxide solution between 7 and 8 is held. Then 37.5 parts of salt are added, and the precipitated solid product is filtered off. The solid product thus obtained is dissolved in 250 parts of water and Acetic acid added until the pH is between 5 and 6. The solution is then warmed to 40 ° C, 6 parts of a 25% aqueous copper sulfate solution is added and the mixture is kept at 40 ° C. for 30 minutes stirred, the pH of the solution being kept between 5 and 6 by adding acetic acid. 25 parts Sodium chloride is then added and the precipitated dye is then filtered off and dried. If you use the dye in conjunction with a treatment with an acid-binding agent When applying cellulosic textile materials, it delivers ruby-red tones with excellent fastness to wet treatments.

The following table gives further examples of the new dyes according to the invention which are obtained if the sodium salts of the azo compounds used in Example 182 or 183 or the sodium salt of the copper complex of the azo compound used in Example 184 by equivalent amounts of the sodium salts of the azo compounds or the sodium salts of the copper complexes the azo compounds, which are obtained by condensation of the aminoazo compounds or the copper complexes of the azo compounds listed in the second column of the table with the pyrimidines listed in the third column of the table, and / or the sodium salt of 2-mercaptobenzothiazole by equivalent amounts of the sodium salts of the heterocyclic compounds listed in the fourth column of the table . The fifth column of the table gives the color tones which are obtained when the dyes are applied to cellulose textile materials in connection with a treatment with an acid-binding agent.

example Aminoazo compound Pyrimidines Heterocyclic compound hue 185 1 -amino-7- (phenylazo) - 2,4,6-trichloropyrimidine 2-mercaptobenzothiazole Red 8-naphthol-3,6-disulfonic acid 186 2-amino-6- (2'-sulfophenylazo) - 2,4,5,6-tetrachloro the same orange 5-naphthol-7-sulfonic acid pyrimidine 187 2-amino-7- (2'-sulfophenylazo) - the same the same orange 8-naphthol-6-sulfonic acid 188 1 - (2'-chloro-5'-sulfophenyl) - the same the same yellow 3-methyl-4- (3 "-amino- 6 "-sulfophenylazo-5-pyrazolone 189 2-amino-6- (2'-sulfo-4'-methoxy- the same the same Crowd phenylazo) -5-naphthol- laugh 7-sulfonic acid

37

Example 190

Aminoazo compound

2-amino-6- (2'-sulfo-4'-methoxyphenylazo) -5-naphthol-7-sulfonic acid

2-methylamino-7- (2'-silfo-4-mclhoxyphenylazo) -8-naphthol-6-sulfonic acid c the same

2-amino-5-hydroxy-6.2'-azo

naplnhalin-7, r, 5'-trisulfone-

acid 2-methylamino-5-hydroxy-

6.2'-azonaphthalene

7.1 ', S'-trisulfonic acid c 4-nitro-4 '- (4 "-N-methylamino-

phcny lazo) -st ilbcn-

2,2'-disulfonic acid 1,2-chromium complex from

6-ainino-1,2'-di-hydroxy-

6'-nitro-2.1'-azonaphthalene

3.4-disulfonic acid l-amino-8-hydroxy-7,2'-azo-

naphthalene-3.6.1'-trisulfone-

acid c

2- (2'-Acetylamino-4'-aminophycnylazoj-naphthalene-4,8-disulfonic acid c

l- (2'-sulfophenyl) -3-methyl-

4- (3 "-amino-6" -sulfophenyl-

azo) -5-pyrazolone 1- (3'-aminophynyl) -3-methyl-

4- (1 ", 5" -disulfonaphthyl-

2'-azo) -5-pyrazolone 1- (4 ', 8'-disuironaphth-2'-yl) -

3-methyl-4- (3 "-amino-

6 "-sulfophenylazo) -5-pyrazolone I- (3'-amino-6'-sulfophenylazo) -

2-naphthol-6,8-disulfonic acid l-acetylamino-7- (3'-amino-

6'-sulfophenylazo) -8-naphthol-

3.6-disulfonic acid c

-Bcnzoylamino-7- (3'-amino-6'-sulfophenylazo) -8-naphthol-3,6-disulfonic acid

- (3'-AminobenzoyIamino) -7- (2 "-sulfophenylazo) -8-naphthol-3,6-disulfonic acid

1- (4'-aminosulfonaphth-l'-ylazo) -4- (8 "-sulfonaphth-1 "-ylazo) naphthalenesulfonic acid

1-Amino-2- (4'-aminophenylazo) -7- (4 "-sulfophenylazo) -8-naphthol-3,6-disulfonic acid

Copper complex of 2-amino-6- (2'-hydroxy-5'-sulfophenyl-azo) -5-naphthol- 1,7-disulfonic acid

Copper complex of 1-amino- 7- (2'-hydroxy-5'-chloro-3-sulfophenylazo) -8-naphthol-3,6-disulfonic acid

Continuation of pyrimidines

38

5-methyl-2.4.6-trichloropyrimidine

5-cyano-2,4,6-trichloropyrimidine

the same.

the same

2.4,6-tribromopyrimidiii

the same

5-nitro-2,4,6-trichloropyrimidine

the same

2,4-dichloro-5-nitro-6-methylpyrimidine

the same

5-nitro-2,4-dichloropyrimidine

5-cyano-2-methyl-4,6-dichloropyrimidine

2,4,6-trichloropyrimidine-5-carboxylic acid

2,4,6-trichloropyrimidine-5-carboxylic acid

2,4,6-trichloropyrimidine

the same

the same

2,4,5,6-tetrachloropyrimidine

the same

Heterocyclic compound

2-mercaptobenzlhiazole the same

2-mcrcaptobenzsclenazole
the same

2-Mcrcaptobcnzthiazol the same.

like. like. like. like.

the same.

like. like. like. like.

the same

hue

Scarlet fever

Rol

RoI

orange

orange

Reddish yellow

black

ruby

Reddish yellow

yellow

Yellow yellow

Orange red

Red Red

Reddish brown

green

ruby

purple

39 1 419 856 40 hue Aminoazo compound continuation Heterocyclic compound purple Example Copper complex of 1-amino Pyrimidines 2-mercaplobenzothiazole 210 7- (2'-hydroxy-5'-chloro 5-cyan-2,4,6-tric! Ilor- 3'-sulfophenylazo) -8-naphthol- pyrimidine 3,6-disulfonic acid purple the same 2-Mercuptobenz- 211 the same sclcnazol Bluish 2-amino-6- [2'-methoxy- the same violet 212 5'-methyl-4 '- (2 ", 5" -disulfo- 5-cyano-2,4,6-trichloro- phenylazoj-phenylazo] - pyrimidine 5-naphthol-1,7-disulfonic acid c Bluish the same 2-mercaplobulin thiazole violet 213 2,4,5,6-tetrachloro marine Copper complex of 2-amino pyrimidine the same blue 214 6- [2'-methoxy-5'-methyl- the same 4 '- (2 ", 5" -disulfophcnylazo) - phenylazo] -5-naphthol- 1,7-disulfonic acid marine the same 2-mcrcaptobenz- blue ¹ 215 the same sclcnazol marine the same the same blue 216 5-cyano-2,4,6-trichloro- marine the same pyrimidine 2-mercaplobenzothiazole blue 217 the same

Example 218

100 parts of bleached cotton fabric are padded through an aqueous solution containing 1% of the dye of Example 1, 1% sodium bicarbonate and 0.2% of an alkylated phenol / ethylene oxide condensate at a temperature of 18 ° C, and the cotton fabric is then squeezed between rollers until its weight is 200 parts. The cotton fabric is ^{dried at 70 °} C. and then exposed to steam at a temperature of 102 ^{° C. for 1 minute.} The dyed cotton fabric is then rinsed in water, immersed in a 0.2% strength aqueous soap solution for 15 minutes, rinsed again in water and finally dried.

The cotton fabric is thus produced in a lively bluish-red shade with excellent washfastness colored.

Instead of the 1% of the dye from Example 1, which in Example above, 1% of the dye of Example 3 or 1% of the dye of Example 4 or 1% of the dye from Example 11 or 1% of the dye from Example 25 are used and so the cotton fabric in lively blue or lively yellow or lively bluish-red or lively yellow Shades dyed with excellent wash fastness.

Example 219

100 parts of bleached cotton yarn are immersed in a dyebath consisting of 2 parts of the dye from Example 1 and 90 parts of sodium chloride dissolved in 3000 parts of water, and the dyeing is carried out at a temperature of 20 ° C. for 30 minutes. 5 parts of trisodium phosphate are then added and dyeing is continued for 60 minutes at 20 ° C. The dyed cotton yarn is then removed from the dyebath, rinsed in water, immersed for 5 minutes in a 0.2% strength aqueous solution of a synthetic surface-active agent at a temperature of 100 ^° C., rinsed again in water and finally dried. The cotton yarn is dyed washable in a lively bluish-red shade.

Instead of the 2 parts of the dye from Example 1 used in the above example, 2 parts of the dye from Example 22 or 2 parts of the dye from Example 19 or 2 parts of the dye from 118 are used to give the cotton yarn in vivid scarlet or Dyed in lively orange or lively yellow shades with excellent wash fastness. _D. .

Example 220

100 parts of bleached cotton fabric are replaced by an aqueous solution containing 0.2% of the dye of Example Contains 1 and 2% sodium carbonate, padded, and the cotton fabric is then passed through rollers, until its weight is 200 parts. The cotton fabric is then rolled up and held at one temperature for 4 hours stored at 20 ° C. The cotton fabric is then rinsed in water for 5 minutes in a 0.2% strength

aqueous solution of a synthetic surfactant Means immersed at a temperature of 100 ° C ', rinsed again in water and dried. The cotton fabric is in a lively red tone with dyed excellent wash fastness.

Example 221

100 parts of wool are immersed in a dye bath, which is a solution of 1.5 parts of the dye of Example 30, 3.0 parts of ammonium acetate, 0.5 part of cetyltrimethylammonium bromide and part 1 contains a condensate of ethylene oxide with a fatty alcohol in 5000 parts of water, immersed, and the dyeing is carried out for 1 hour at a temperature of 100 "C. The dyed woolen fabric is

then removed from the dye bath, rinsed in water and dried. The wool is in one Scarlet shade dyed with excellent washfastness.

209 609 30

Example 222 nine printing paste, consisting of:

the dye of Example 5 3 parts

Urea 10 parts

Water 50.8 parts

Sodium bicarbonate 1.2 parts

4% aqueous sodium algae

bicarbonate solution 35 T rush

TÖÖ ~ parts

was applied to non-mercerized cotton fabric by machine printing. The printed cotton fabric is dried at a temperature of 70 ° C. and then ^{steamed for 6 minutes at a temperature of K) O 0} C. The printed cotton fabric is then rinsed in water for 10 minutes in a 0.3% strength aqueous solution of a synthetic Dipped surfactant at a temperature of 100 "C, rinsed again in water and finally dried.

The cotton fabric is thereby in a ruby red tone with excellent fastness against Wet treatments printed.

Instead of the non-mercerized cotton fabric used in the above example, mercerized Cotton sateen or rayon fabric can be used, with brown prints being excellent Maintains authenticity against wet treatments.

In place of the 3 parts of the dye from Example 5 used in the example above, use 3 parts of the dye of Example 1 or 3 parts of the dye of Example 81 or 3 parts of the dye of Example 112 or 3 parts of the dye of Example 102 or 3 parts of the dye of Example 118 were used and so red, navy blue and red, respectively or blue or yellow prints obtained with excellent wash fastness.

Example 223

40

100 parts of mercerized bleached cotton material are replaced by an aqueous solution containing 2.0% of the dye from Example 1.10% dimethylol dioxalmonourein, 1.0% N, N-di (/ i-hydroxyethyl) amine hydrochloride, 1.0% methylol stearamide and 0.5% sodium triisopropylnaphthalene sulfonate, and the cotton material is then squeezed between rollers until its weight is 200 parts. The cotton material is dried at a temperature of 70 ⁰ C and then baked for 3 minutes at a temperature of 155 ° C. The cotton material is then rinsed in water, immersed for 5 minutes in a boiling aqueous solution containing 0.5% sodium carbonate and 0.1% of a mixture of a condensate of alkylated phenol / ethylene oxide and a fatty acid alcohol, rinsed again in water and finally dried.

The cotton material comes in a vivid bluish red tone with excellent fastness against Light and wet treatments colored and is wrinkle resistant.

Example 224

100 parts of a bleached mercerized cotton poplin are replaced by an aqueous solution containing 1.0% of the dye from Example 107, 10% trimethylolmelamine, 1.5% N - (/ f-hydroxyethyl) -N - (/ f-hydroxyn-butyl) -amine hydrochloride, 1.0% methylol stearamide,

0.3% sodium triisopropylnaphthalene sulfonate and 0.3% sodium chloride, padded and the cotton poplin is then squeezed between rollers until its weight is 200 parts. The cotton poplin is dried at a temperature of 65 ° C and then baked for 3 minutes at a temperature of 150 ⁰ C. The cotton poplin is then rinsed in water, immersed for 5 minutes in a boiling aqueous solution containing 0.5% sodium carbonate and 0.1% of a mixture of a condensate of alkylated phenol / ethylene oxide and a fatty alcohol sulfate, rinsed again in water and finally dried .

The cotton poplin comes in a vivid orange shade with excellent fastness to light and Dyed wet treatments and is wrinkle resistant.

Claims (18)

Patent claims: 1. Process for the preparation of reactive dyes of the general formula I Ν —Τ R where F is a known customary dye radical and μ = 1, 2 or 3, R is a hydrogen atom or a substituted or unsubstituted alkyl or cycloalkyl radical and T a 1,3,5-triazine or Pyrimidine ring means which is attached to the nitrogen atom N through a carbon atom of the ring is bonded and at least one group of the formula II Noun contains, in which Z ¹ denotes a sulfur or selenium atom and the benzene ring of the formula II can carry a further substituent, characterized in that a dye compound of the general formula III F - N-T ' I.
R. III in which F, η and R have the meanings given above and T 'denotes a 1,3,5-triazine or pyrimidine ring which is connected to the nitrogen atom N through a carbon atom of the ring and carries at least one halogen atom, with a compound of the formula W — S —C Subst. IV wherein Z 'has the meaning given above and W is a hydrogen or metal atom, converts, it being possible for the benzene ring of the formula IV to carry a further substituent. 2. The method according to claim 1, characterized in that the dye compound Formula III one which has at least one water-solubilizing group and one or two Groups of the formula N-C C - halogen N N si halogen wherein R has the meaning given in claim 1 and halogen is chlorine or bromine, contains, is implemented. 3. The method according to claim 1, characterized in that the dye compound of the formula 111 is used which has at least one water-solubilizing group and one or two groups of the formula I / N-C C - halogen wherein R and halogen have the meanings given in claims 1 and 2 and A has one Amino or substituted amino group, especially a sulfoanilino or disulfoanilino group means contains. 4. The method according to claim 1, characterized in that the dye compound of the formula III one is used which has at least one water-solubilizing group and one or two groups of the formula R _N - N - C C - halogen I Il N N v / OR ₁ wherein R and halogen have the meanings given in claims 1 and 2 and R _{1 is} an alkyl radical, in particular a methyl radical, contains. 5. The method according to claim 1, characterized in that the dye compound of the formula III one is used which has at least one water-solubilizing group and one or two groups of the formula .-NT ₁ - (halogen) ", wherein R and halogen are as defined in claims 1 and 2 have given meanings and T _{1 is} a pyrimidine ring and m 2 or 3 contains. 6. The method according to claim 1, characterized in that the dye compound of the formula III one is used which has at least one water-solubilizing group and one or two groups of the formula -N -C Il C- C-CN C ' ■ Halogen X wherein R and halogen have the meanings given in claim 1 and 2 and X is a hydrogen or halogen atom contains. 7. The method according to any one of claims 1 to 6, characterized in that as a compound of Formula IV is a compound of the formula - S - W in which W has the meaning given in claim 1 and Z ^{1 is} a sulfur or selenium atom and the benzene ring can carry substituents is used. 8. A process for the preparation of those reactive dyes of the formula I according to Claim 1, which Azo dyes are and at least one group of the formula - Ν —Τ with the meaning defined in claim 1, characterized in that a primary amine or the corresponding sulfamic acid is used diazotized and the diazo compound thus obtained is coupled with a coupling component, wherein the primary amine and / or the coupling component is at least one group of the initially introduced given formula II included. 9. Process for the preparation of the reactive dyes of the formula I according to Claim 1, characterized characterized in that a dye compound which contains at least one —NHR group, wherein R has the meaning given in claim 1, with a 1,3,5-triazine or pyrimidine, which at least one halogen atom and at least one group of the formula II, in which Z is in claim 1 has given meaning, contains, is implemented. 10. A process for the preparation of the reactive dyes according to claim 1, wherein the by T reproduced 1,3,5-triazine or pyrimidine ring a group of the formula II, wherein Z is in claim 1 has the meaning given, and a hydroxyl group, an alkoxy or aryloxy group, a mercapto or alkyl or aryl substituted one Mercapto group or a substituted or unsubstituted one Amino group or a rhodanidodic group Sulfonic acid group, characterized in that that a new dye, which is a group of the formula IV and at T is a haloalom contains bound, with a compound of l-'ormcl W - Q, where W is a hydrogen or metal atom and Q is a hydroxy group. an alkoxy or aryloxy st. a mercapto or alkyl or aryl-substituted mercapto group or a substituted one or is an unsubstituted amino group or a sulfonic acid group. 11. Use of the according to one of the procedures 1 Up to 10 available dyes for dyeing 1 extilmatcrialien. 12. Use according to claim 11, characterized characterized in that the textile material in connection with a treatment with an acid binding agent Agent with an aqueous solution of a new dye-according to one of claims I. to 10 is treated. 13. Use according to claim II, characterized in that the acid-binding agent the textile material is applied before the treatment with the aqueous solution of the dye. 14. Use according to claim 11, characterized in that the acid-binding agent is applied to the textile material after treatment with the aqueous solution of the dye. 15. Use according to claim 11, characterized in that the acid-binding agent of aqueous solution of the dye is added. 16. Use according to any one of claims 12 to 15, characterized in that the aqueous Solution of the dye applied to the textile material by a dyeing or padding process will. 17. Use according to any one of claims 12 to 15, characterized in that the aqueous Solution of the dye containing a thickener and applied to the textile material by a printing process is applied. 18. Use according to claim 11, characterized in that the textile material with a aqueous solution is treated, which (1) a dye according to any one of claims 1 to 10, (2) a resinous composition of matter and (3) contains an acid catalyst, the treated textile material, if desired, dried and the Textile material is heated.