CS195257B2 - Process for preparing azodyes reactive with fibres - Google Patents

Abstract

1405016 Reactive disazo dyes CIBA-GEIGY AG 2 Aug 1972 [4 Aug 1971] 36038/72 Heading C4P New reactive disazo dyes of formula wherein X is a direct bond or a C 1-6 alkylene, C 1-6 alkyleneoxy or C 1-6 alkylenemercapto group, one Y is H and the other is SO 3 H, Z is a halogen atom, R 1 and R 2 are H or C 1-6 alkyl and A is alkylene or arylene are prepared by condensation reactions between a cyanuric halide, a diamine and (1) an aminonaphtholsulphonic acid followed by coupling with a diazo component or (2) an appropriate aminoazo dye. The dyes are used to colour leather, silk, wool, synthetic polyamide or polyurethane fibres and in particular cellulose fibres, in red shades.

Description

The invention relates to a process for the preparation of fiber-reactive azo dyes of the formula I

in which

X represents a direct bond or an alkylene group, an alkylene mercapto group or an alkyleneoxy group having from 1 to 4 carbon atoms, one symbol

Y represents a hydrogen atom and the second symbol Y represents a sulfonic acid residue,

Z is halogen and u is amino of formula 2

I I I | fy fy 11 (1),

OF

Y in which

R1 and R2 are hydrogen or C1-C4alkyl;

A is C 2 -C 6 alkylene, phenylene optionally substituted with C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, nitro, carboxy and sulfo, diphenyl oxide, diphenylurea, diphenyloxetane or a stilbene radical optionally substituted by a sulfone group, a diphenylmethane radical, a diphenyl radical optionally substituted by methyl, methoxy, chlorine, carboxy and methoxycarbonyl, or a dinaphthyl radical optionally substituted by methyl, or wherein the group -N (R 1) ] —A — N (R2) is piperazino,

Z is halogen and ui is halogen, C1-C6 alkoxy, phenoxy, NH2 or the radical of formula 3

wherein X and Y are as defined above,

The linker X is preferably a short-chain aliphatic hydrocarbon, such as methylene, methylene mercapto or methyleneoxy, but in particular X represents a direct bond. Particularly valuable dyes of formula (1) are those in which the HOOC-X- group is not in the meta- or para-position to the azo group.

. Preferably, the symbol Y is hydrogen at the α-position and the sulfonic acid residue at the β-position. Halogen Z is preferably bromine or especially chlorine.

The substituent u may be a HsN group or a secondary or tertiary amino group such as methylamino, isopropylamino, isopropyloxypropylamino, NiN-dimethylamino, Ν-methyl-, N-ethylamino, NiN-dibutylamino, phenylamino, sulfophenylamino, sulfophenylamino, sulfophenylamino, sulfophenylamino, sulfophenylamino, sulfophenylamino, sulfophenylamino, sulfophenylamino, sulfophenylamino, such as plperidino, piperazino or morpholino.

In particular, however, u is a single amino group that confers little fiber affinity (such as morpholino or N-methylanilino) or an amino group of formula 2

Rf R ₂ NyN

Z in which

R 1 and R 2 are hydrogen or a lower alkyl radical having 1 to 4 carbon atoms,

A is C 2 -C 6 alkylene, phenylene optionally substituted with C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, nitro, carboxy and sulfo, diphenyl oxide, diphenylurea, diphenyloxetane or a stilbene radical optionally substituted by a sulfo group, a diphenylmethane radical, a diphenyl radical optionally substituted by a methyl, methoxy, chlorine, carboxy and methoxycarbonyl group, or a dinaphthyl radical optionally substituted by a methyl group, or wherein the —N (Rij) moiety —A — N (R2) is piperazino.

Lower alkyl radicals are alkyl radicals having up to 4 carbon atoms. A may be C 2 -C 6 alkylene, for example ethylene or hexylene, but preferably A is phenylene, especially m- or p-phenylene. With respect to the symbol Z, reference is made here to the above details of formula 1. The same applies to substituents ui when they represent a halogen atom. Suitable alkoxy groups are those of primary, secondary or tertiary alcohols, such as methoxy, ethoxy, propyloxy, isopropoxy or 1,1-dimethylethoxy, residues of etherified dialcohols such as ethoxyethoxy or methoxypropyloxy, unsaturated aliphatic residues alcohols such as alkyloxy or propargyloxy, or aliphatic alcohol residues containing cyclic groups such as benzyloxy, furfuryloxy or tetrahydrofurfuryloxy.

In a preferred embodiment of the process of the invention, the ui symbol in formula 2 is the same chromogenic dye residue of formula 1, i.e. the amino group of formula 3

-HN OH

in which

Y and X are as defined in Formula 1.

The dyes produced according to a preferred embodiment of the process according to the invention are symmetrical in terms of their basic structure and correspond to the general formula 4.

wherein X, Y and Z or R 1 and R 2 and A have the meanings given in Formula 1 or 2, respectively.

An important sub-group of these bis-reactive disazo dyes of Formula 4 are those of Formula 5

in which

A is a m- or p-phenylene moiety. The fiber-reactive azo dyes of the formula I are prepared according to the invention by producing the diazo components of the formula 6.

coupling components of the formula

trihalogen-s-trlazines of the formula

and diamines of formula 8

H (R 1) N - A - N (R 2) H [8] in which

X, Y, Z, R 1, R g and A have the meanings given in formulas 1 and 2, react with each other in any sequence of partial reactions to form fiber-reactive azo dyes 1 and before or after condensation of the trihalogen-s-triazine with diamine optionally, the halogen atom in the outer triazine residue is replaced by condensation with a C 1 -C 6 alcohol, phenol or ammonia corresponding to the residue.

If residue d in the dyes of formula 1 is a residue of formula 2, then the number of partial reactions feasible in any reaction order is increased, thereby also increasing the number of possible embodiments of the production process, especially if in the compound in question the substituent ui in residue 2 the rest of formula A3.

These dyes can be obtained by treating cyanurhalides with 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid to give compounds of formula 7

then the obtained compounds are condensed with amines of formula 8

H (R1) .N — A — N (R2) H (8) The condensation products obtained are reacted with di- or trihalogen-1,3,5-triazines, where, in the latter case, the halogen atom in the formed dihalogentriazine residue of condensa-

With ammonia, a C1-C6 alcohol or a phenol optionally with 1-amino-8-hydroxy-naphthalene-3,6- or -4,6-disulfonic acid or with the primary amine of the radical of formula (3) for the corresponding residues, and at any stage of the process, i.e. before or after the coupling, by coupling with the diazo compounds of the amines of formula (6), the corresponding and optionally disazo compounds are formed. The bis-reactive compounds of the invention are also obtained by using an acylating agent which already contains a fiber-reactive moiety, in particular a di- or trihalogen-1,3,5-triazine monoacylated diamine, in place of the diamine of formula 8 in the present process.

A further embodiment of the process of the invention consists in condensing 1-amino-8-hydroxynaphthalene-3,6- or '-4,6-disulfonic acid with a compound of formula 9

and combined with or between the amine diazo compounds of formula 6 before or after coupling.

The bisreactive azo compounds are also obtained by treating the azo compounds of formula 10

HOOC-X

(10) acts with an acylating agent comprising a fiber-reactive residue, in particular 4,6-dihalogen-1,3,5-triazines, which contain, in the 2-position, an ammonia, amine, alcohol, phenol or mercaptan residue, optionally a residue of formula 3.

However, the diazo compounds of formula 4 are preferably prepared by coupling the diazo compound from the amine of formula 6 to 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, acylating the obtained monoazo dye with cyanuric chloride and condensing the resulting mono-reactive monoazo dye with diamine 8 2 - 1.

In the above formulas 6 to 10, the symbols X, Y, Z, R 2, A and µ have the meanings given in formulas 1 and 2.

Suitable starting materials of the formula (6) are, for example, the following aminocarboxylic acids:

β- (2-aminophenyl) propionic acid, β- (3-aminophenyl) propionic acid, β- (4-aminophenyl) propionic acid, γ- (2-aminophenyl) butyric acid, β- (4-aminophenyl) butyric acid, ? - 3-aminophenyl) isobutyric acid,? - (2-aminophenoxy) butyric acid,? - (4-aminophenoxy) propionic acid,? - (4-aminophenoxy) butyric acid, in particular 2-, 3 or 4-aminobenzoic acid, 2-, 3- or 4-aminophenylacetic acid, 4-aminophenylmercaptoacetic acid, 2-, 3- or 4-aminophenoxyacetic acid.

The diazotization of these amines is carried out by conventional methods using, for example, sodium nitrite and mineral acids, and the coupling with 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid is also carried out according to methods known per se in the art. aqueous-alkaline environment.

Acylating agents include the following halogen-1,3,5-triazines:

2,4,6-trichloro (-tribromo- or -trifluoro-) -1,3,5-triazine- and 4,6-dichloro (dibromo- or -difluoro-) -1,3,5-triazines; which are substituted in the 2-position by an aryl or alkyl radical, for example a phenyl, methyl or ethyl radical or an aliphatic or aromatic radical bonded via a sulfur atom of a mercapto group or an oxygen atom of a bonded hydroxy compound or especially NH2 or a radical of an aliphatic, heterocyclic or aromatic amino group bonded via an atom nitrogen. Such compounds whose residues can be bound by reaction with trihalogentriazines at the 2-position on the triazine nucleus include, for example, the following: aliphatic or aromatic mercapto blacks or hydroxy compounds such as thioalcohols, thioglycolic acid, thiophenols, alkoxyalkanols, methyl, ethyl, isopropyl alcohol, glycolic acid, phenol, chlorine or nitrophenols, phenolecarboxylic and phenolsulfonic acids, naphthols, naphtholsulfonic acids, etc., in particular. ammonia and compounds containing acylated amino groups such as hydroxylamine, hydrazine, phenylhydrazine, phenylhydrazine sulfonic acids, monoalkyl glycol ethers, methyl-, ethyl-, isopropyl-, methoxyethyl-, methoxypropylamine, dimethylamine, diethylamine, methylphenylamine, ethylene-phenylamine, ethylene-phenylamine, ethanolamine, ethanolamine, ethanolamine, ethanolamine, ethanolamine benzylamine, cyclohexylamine, morpholine, piperidine, piperazine, aminocarbonic esters, ethyl aminoacetic acid ester, aminoethanesulfonic acid, N-methylaminoethanesulfonic acid, in particular aromatic amines such as aniline, N-methylaniline, toluidines, xylidines, chloranilines, p- or m-aminoacetil , aminophenols, anisidine, phenetidine, and in particular anilines containing an acid group, sulfanilic acid, methanilic acid, orthanilic acid, anilindisulfonic acid, aminobenzylsulfonic acid, aniline-methanesulfonic acid, aminobenzodicarboxylic acids, naphthylaminomona-, di- and di- -trisulfonic acid, aminobenzoic acids, such as 2-hydroxy-5-aminobenzoic acid, and also colored compounds, for example dye-like compounds, for example 4-nitro-4'-aminostilbendisuifonic acid, 2-nitro-4-aminodiphenylamino-4 - stilbendisulfonic acid, 2-nitro-4'-amino-diphenylamino-4,3'-disulfanic acid, and in particular aminoazo dyes which contain at least one reactive amino group.

The introduction of the substituents at the 2-position of the triazine moiety can be carried out as described also after acylation or coupling to the azo compound of formula I.

The acylations or condensations according to the invention are preferably carried out using an acid-binding agent such as sodium carbonate or sodium hydroxide and under such conditions that the halogen-replaceable halogen atoms remain in the final product, e.g. in organic solvents or at relatively low temperatures in aqueous agents.

Suitable starting materials of the formula (8) are amines having an acyclic or cyclic radical, in particular an aliphatic alkyl radical or an aromatic radical. Amines having an aliphatic alkyl radical include, for example, ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, and piperazine.

However, m- or p-diaminobenzenes which may be substituted by halogen atoms such as chlorine or bromine atoms, alkyl groups such as methyl, ethyl or isapropyl or carboxylic or sulfonic acid residues are particularly suitable as starting materials of formula 8. Examples include:

1,3- or 1,4-diaminobenzene,

2,4-diaminotoluene, 1,3- or 1,4-dlaminobenzene-2-carboxylic acid or sulfonic acid,

1,3-diamino-2,4,6-trimethyibenzene,

1,4-diamino-2,3,5,6-tetramethylbenzene,

1,3-diamino-4-methoxybenzene

1,3-diamine-4-chlorobenzene,

1.3- diaminot4-nitrobenzene, ^4.4, -diaminostilben, 4,4'-diaminodiphenylmethane, benzidine, ^3,3, tdimethyibenzidin, 3,3'-dimethoxybenzidine, 3,3'-dichlorobenzidine, _with 3'-3 dikarbαxybtnzidin 3 3'-dicarboxymethoxybenzidine, 2,2'-dimethylbenzidine, diphenylin, 3,3'-dimethylnaphthidine.

In the compounds of formula I obtained by the process of the present invention, the movable halogen atoms of one or the other of the fiber-reactive substituents can be readily replaced, for example by reaction with ternary amines or hydrazines (such as dimethylhydrazine) to produce fiber-reactive compounds. an ammonium or hydrazine group bonded to a carbon atom, in particular a heterocyclic radical.

The novel azo compounds of the formula I according to the invention can be used as dyes. They can be isolated and processed into useful dry dye preparations. The isolation is preferably carried out at as low a temperature as possible by salting out and filtration. The filtered dyes may optionally be dried after addition of the buffing agents and / or buffers, for example after addition of a mixture of equal proportions of mono- and disodium phosphate. Preferably, the drying is carried out at not too high temperatures and under reduced pressure. By spray-drying the entire mixture, in certain cases of the process according to the invention, dry preparations can be obtained directly, i.e. the dyes can be produced without intermediate insulation.

The novel dyes of the present invention are suitable for dyeing and printing a wide variety of materials such as silk, leather, wool, superpolyamide fibers and superpolyurethanes, but especially cellulosic fibrous materials such as flax, cellulose, regenerated cellulose, especially cotton. The dyes of formulas 4 and 5 are particularly suitable for dyeing cellulose by the pull-out process, wherein the dyed material is dyed for an extended period of time (about 100 to 120 minutes) in an alkaline solution of the salt-containing dye at elevated temperature and fixed. The methods provide dyeings and prints which are generally characterized by good light fastness, high degree of fixation and, above all, excellent wet fastness.

In the following examples, parts and percentages are by weight unless otherwise indicated, and temperatures are in degrees Celsius.

He did

46.7 parts of the monoazo dye obtained by coupling diazotized p-aminobenzoic acid to 1-amino-8-naphthol-3,6-disulphonic acid in an alkaline medium are dissolved in the sodium salt in 600 parts of water and this solution is added 18.5 parts of cyanuric chloride in an ice-cooled aqueous suspension. The mixture is stirred at a temperature between 0 and 5 ° and neutralized by the gradual addition of dilute sodium hydroxide solution. After completion of the condensation, a solution of 5.4 parts of m-phenylenediamine in 100 parts of water is allowed to flow in and the mixture is stirred for 1 hour at a temperature between 30-40 ° while maintaining a pH of 5-7 by dropwise addition of sodium hydroxide solution. the pH is adjusted to 8 by the addition of sodium carbonate and the disazo dye is precipitated by the addition of acetone, filtered off and dried. The disazo dye obtained is of the formula

dyes the cellulose fibers in a pull-out manner in the presence of alkaline bath electrolytes in intensely colored, pure bluish-reddish shades.

If p-phenylenediamine is used instead of m-phenylenediamine, a dye with similar properties is obtained. In this case, the colorant can also be salted out by adding sodium chloride or potassium chloride.

When 1,8-aminonaphthol-3,6-disulfonic acid is coupled with diazotized m-aminobenzoic acid or m-aminophenoxyacetic acid, according to the data in this example, dyes of similar properties are obtained.

The following table contains further examples of the dyes obtained according to Example 1, when the monoazo dyes listed in column I are reacted with the cyanuric chloride and the diamines listed in column II in a 2: 2: 1 ratio.

Table 1

Monoazobarviva I Diamin II Shade p-aminobenzoic acid 1,8-aminonaphthol-3,6-disulfonic acid 1,8-aminonaphtholic acid · · -> 2,4-diaminotoluene red -3,6-disulfonic acid 1,8-aminonaphthol- 2,4-diaminochlorobenzene red -3,6-disulfone 2,5-diaminotoluene red 1,8-aminonaphthol- p-phenylenediamine sulphate -3,6-disulfone new acid red m-aminobenzoic acid 1,8-aminonaphthol-3,6-disulfonic acid * p-phenylenediamine red m-aminobenzoic acid 1,8-ammonaphthal-3,6-disulfonic acid p-aminophenylacetic acid -> 4,4´-dlaminodiphenyl oxide red acid -> 1,8-aminonaphthal-3,6- red disulfonic acid p-phenylenediamine 1,8-aminonaphthol-3,6- 4,4’-diaminodiphenyiureido- disulfonic acid p-aminophenoxyacetic acid -2,2'-disulfonic acid red -> 1,8-aminonaphthol-3,6-disulfonic acid m-phenylenediamine strongly bluish red

Monoazobarviva I

1,8-aminonaphthal-3,6-disulfonic acid m-aminophenoxyacetic acid -

1,8-aminonaphthal-3,6-disulfonic acid aminoisophthalic acid 1.8-aminonaphthal-3,6-disulfinic acid 1-aminobenzene-3,4-dicarboxylic acid *

1,8-aminonaphthol-3,6-disulfonic acid p-aminobenzoic acid

1,8-aminonaphthol-3,6-disulfonic acid

Díamin II

1,4-diaminoethane 4,4'-diamineodiphenyloxyethane-2,2´-disulfonic acid m-phenylenediamine m-phenylenediamine

-> p-phenylenediaminocarboxylic acid

Shade strongly bluish red strongly bluish red heavily bluish red heavily bluish red heavily bluish red

Example 2

31.9 parts of 1,8-aminonaphthol-3,6-disulfonic acid are dissolved into neutral solution with the addition of sodium hydroxide and this solution is added to an ice-cooled aqueous suspension of 18.5 parts of cyanuric chloride. The mixture is stirred for 2 hours at a temperature between 0 and 5 ° and then neutralized with dilute sodium hydroxide solution so that the reaction remains weakly acidic to Congo red. After completion of the condensation, a diazonium salt solution prepared from 13.7 parts of anthranilic acid is added in the usual manner. About 50 parts by volume of 2 N sodium hydroxide solution are added dropwise over 1 to 2 minutes. After coupling, a solution of 5.4 parts of m-phenylenediamine in 100 parts of water was added, the mixture was heated to 35 ° C and maintained at this temperature for 2 hours. The reaction mixture is neutralized by the gradual addition of dilute sodium hydroxide solution. The resulting bis-dichlorotriazinylamine dye was salted out, filtered off and dried. The dye may also be precipitated by the addition of acetone or alcohol.

The dye obtained dyes the cellulosic fibers in a pull-out manner in constant intensive red shades.

Example 3

31.9 parts of 1,8-aminonaphthol-3,6-disulfonic acid were condensed with 18.5 parts of cyanuric chloride as described in Example 2. An aqueous solution of 5.4 parts of m-phenylenediamine is added to the obtained primary condensation solution solution over 10 minutes, the mixture is heated slowly to 30 ° and about 50 parts by volume of 2 N sodium hydroxide solution are added dropwise over 1 hour. the pH did not exceed 6. After completion of the condensation, a solution of 20 parts of anhydrous sodium carbonate was added, followed by a solution of the diazo compound from 13.7 parts of p-aminobenzoic acid at 5-10 °. Upon completion of the coupling, the dye precipitates upon the addition of acetone or alcohol, - filtered and dried. The dye obtained is identical to the dye prepared according to Example 1.

Example 4

46.7 parts of 7- (p-carboxyphenylazo) -1,8-aminonaphthol-3,6-disulfonic acid were condensed with 18.5 parts of cyanuric chloride according to the data in Example 1. A neutral aqueous solution of 8.8 parts of m-phenylenediamine sulphonic acid was added to the obtained condensation product, and the pH was adjusted to 6 with dilute sodium hydroxide solution at 30 ° over 1 hour. The reaction mixture was cooled to 5 ° and a fine aqueous solution was added. a suspension of 18.5 parts of cyanuric chloride, stirred for 1 to 2 hours while maintaining the pH by adding a sodium hydroxide solution between 5 and 6.

Upon completion of the condensation, 50 parts of a 10% ammonium hydroxide solution were added and the reaction mixture was maintained at 40 ° for 2 hours. The dye is then salted out, filtered and dried. The dye obtained dyes cotton with permanent red shades.

Example 1 a d 5

According to the data in Example 4, 18.5 parts of cyanuric chloride were first condensed with 46.7 parts of monoazo dye and 18.8 parts of m-phenylenediamine sulfonic acid. At 30 DEG C., 20 parts of 2,4-dichloro-6-isopropoxytriazine are added to the solution obtained, and the pH is maintained between 6 and 7 by dropwise addition of dilute sodium hydroxide solution. After the condensation has been completed, the dye is salted out, filtered and dried. The obtained dye dyes cotton in red - shades.

The following table gives additional examples of dyes which have been produced by condensing the monoazo dyes obtained from components I and II with cyanuric chloride and diamine III and III. finally, the reaction product is reacted with reactive components IV.

Diazosložki I

Coupling component II

Table 2 diamine III

Reactive component IV p-aminobenzoic acid 'p-aminobenzoic acid m-phenoxyacetic acid

1,8-aminonaphthol-3,6-disulfonic acid

1.8-8X11 ^ (^ 31: 301-3,6-disulfonic acid β-phenylenediamine sulfonic acid p-phenylenediamine sulfonic acid m-phenylenediamine sulfonic acid m-phenylenediamine sulfonic acid m-phenylenediamine sulfonic acid

2,4-dichloro-6-iminotriazine

2,4-dichloro-phenoxytriizine

Example 1 a d 6

Dissolve 33.2 parts of the reaction product from 18 parts of β-β-β-β-β-β-β-β-β-β-β-β-β-β-β and 18.8 parts m-phenylenediaminosulfonic acid to neutral solution in water. To this solution was added a neutral aqueous solution, which was obtained by condensing 46.7 parts of 7- (p-carboxyphenylizo) -1,8-aminonaphthol-1,6-disulfophonic acid with 18.5 parts of cyanuric chloride, and stirred at room temperature for several hours. The pH is maintained between 5 and 7 by the addition of aqueous sodium hydroxide solution. After the condensation has been completed, the dye is salted out, filtered and dried, which dyes the cellulose fibers in red shades.

Example 7

To a fine suspension of 18.5 parts of cyanuric chloride in 250 parts of ice water was added a neutral solution of 31.9 parts of 1-imino-8-hydroxynaphthalene-3,6-disulfonic acid. About 100 parts of 1 N sodium hydroxide solution are added dropwise over 1 hour. After completion of the reaction, a neutral solution obtained from 18.8 parts of m-phenylenediine sulfonic acid was added to the obtained solution, and the pH was maintained by dropwise addition of 1 N sodium hydroxide solution between 3.5 and 4.0. After completion of the condensation, the solution is neutralized. After addition of 15 parts of sodium bicarbonate, the diazo compound prepared in the usual manner from 17.3 parts of orthinilic acid is allowed to flow. Upon completion of the coupling, 23 parts of isopropoxydichlorotriazine and the reaction mixture were added to the dye solution, and the mixture was heated to 40-50 ° while maintaining a pH of between 6.5 and 7. The reaction solution was evaporated to dryness in vacuo.

Dye Code Dissolve 1 part of the dye in 100 parts of water with the addition of 0.5 part sodium m-nitrobenzenesulfonic acid salt. The obtained solution is impregnated with cotton tkinini, tik, after receiving the impregnation additionally by% of its weight, after which the fabric is dried.

The fabric is then impregnated with a 20 ° solution containing 5 grams of sodium hydroxide and 300 grams of sodium chloride per liter, and the tkinini is soaked off with an additional 75% of its original weight, steaming for 60 seconds at 100-101 °, rinse fabric, wash in soap solution for 1/4 hour in 0.3% boiling solution of non-ionic detergent, rinse and dry.

The prescription for printing the dye parts is poured into 100 parts of the basic dye with vigorous stirring, which contains 45 parts of 5% sodium alginate based, 32 parts of water, 20 parts of urea, 1 part sodium m-nitrobenzenesulfonic acid and 2 parts sodium hydrogen carbonate .

The printing paste thus obtained is printed on a cotton fabric in a printing roll machine and subjected to a steam treatment for 4 to 8 minutes at 100 [deg.] In saturated steam. The printed fabric is then rinsed thoroughly in cold and hot water, whereby the chemically non-fixed fractions can be easily removed from the fibers and then dried.

The dye formulation II parts of the dye obtained according to Example 1 are dissolved in 100 parts of water. The solution was added to 3900 parts cold water, 80 parts sodium chloride was added to the dye bath. 100 parts of cotton fabric are introduced.

The bath temperature is raised to 80 ° C over 45 minutes, after which 40 parts of sodium phosphate and 80 parts of sodium chloride are added after 30 minutes. The temperature is maintained for 30 minutes at 80 ° C, the fabric is rinsed and then washed for 15 minutes in a 0.3% boiling solution of non-ionic detergent, rinsed and dried again.

A bluish-red coloration which is stable in the light and underwear is obtained.

Claims (9)

A process for the production of fiber-reactive azo dyes of general formula 1 wherein: X represents a direct bond or an alkylene group, an alkylene mercapto group or an alkyleneoxy group having from 1 to 4 carbon atoms, one symbol Y represents a hydrogen atom and the second symbol Y represents a sulfonic acid residue, Z is a halogen atom and u is an amino group of formula 2 wherein X and Y are as defined above, characterized in that the diazo components of formula 6 HOOC-X '( ₆₎ wherein R1 and R2 are hydrogen or C1-C4alkyl, A is C 2 -C 6 alkylene, phenylene optionally substituted with C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, nitro, carboxy and sulfo, diphenyl oxide, diphenylurea, residue diphenyloxyethane or a stilbene radical optionally substituted by a sulfone group, a diphenylmethane radical, a diphenyl radical optionally substituted by methyl, methoxy, chlorine, carboxy and methoxycarbonyl, or a dinaphthyl radical optionally substituted by methyl, or wherein the group -N ( R1-A-N (R2) is piperazino, Z is halogen and ui is halogen, C1-C6 alkoxy, phenoxy, NH2 or the radical of formula 3 -HN OH coupling components of the formula trihalogen-s-triazines of the formula and diamines of the formula 8 H (R 1) N - A - N (R 2) H (8) wherein X, Y, Z, R 1, R 2 and A have the meanings given under 1 and 2, reacting in any sequence of partial reactions to form fiber-reactive azo dyes of formula 1, and optionally before or after condensation of the respective trihalogen-s-triazine with the diamine, optionally replace the halogen atom in the outer triazine residue with 6 carbon atoms, phenol, or ammonia, the corresponding radical. 2. The process of claim 1 wherein the cyanurhalides are condensed with 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid to form compounds of formula 7. -amino-8-hydroxynaphthalene-3,6- or 4,6-disulfonic acid to form a compound of formula 7, on the other hand, a diamine of formula NH 2 -N-NH 2 with halogen-s-triazine to give a compound of the formula wherein Z and Y are as defined in formula 1, the obtained compounds are condensed with amines of formula 8 H (R 1) N - A - N (R 2) H (8), the condensation products thus obtained are treated with di- or trihalogentriazines; in the latter case, the halogen atom of the dihalogentriazine residue formed is exchanged by condensation with ammonia, C 1 -C 6 alcohol carbon or phenol, optionally with 1-amino-8-hydroxynaphthalene-3,6 or -4,6-disulfonic acid or with the primary amine of the radical of formula 3 in which: Z, A and ui are as defined in formula 2, whereupon this compound is condensed with a compound of formula 7 and the product obtained is coupled with the diazo compounds of amines of formula 6. 3. A process according to claim 1, wherein the cyanurhalides are condensed with 1 in which Z, R 1, R 2, A, and ui are as defined in formula 2, this compound is condensed with 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid and 1-amino-8-hydroxynaphthalene- The 3,6- or -4,6-disulfonic acid is coupled with the diazo compounds of the amines of formula 6 before or after the above condensation. 4,6-dichloro-2-alkoxy-s-triazine to form a compound of formula i and wherein R represents an alkyl radical having 1 to 6 carbon atoms, whereupon both compounds obtained are condensed. 4. The process of claim 1, wherein the halogen-s-triazines are reacted by double condensation with a diamine of formula 8 to form a compound of the formula for the corresponding residues, and azo compounds are formed at any stage of the process, i.e. by coupling with diazo compounds from amines of formula 6 HOOC-X ·? - ⁷ (G) _z wherein R 1, R 2, A and X are as defined in formulas 1 and 8. 5. The process of claim 1, wherein the amine compound of formula 6, 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 2,4,6-trihalogen-s-triazine. and the diamine of formula 8 by coupling and double coupling to react to form a compound of formula HOOC-X in which X, Y, Z, R 1, R 2 and A are as described in point 2, and this compound is condensed with 4,6-dihalo-1,3,5-triazines containing at the 2-position an amino, alkoxy, phenoxy, alkylmercapto or arylmercapto group optionally a radical of formula 3. 6. The process of claim 1, wherein the diazo compound of p-aminobenzoic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, cyanuric chloride and 1,3-phenylenediamine is reacted by coupling and double condensation to form the compound. of the formula and this compound is condensed with 4,6-dichloro-1,3,5-triazine which in the 2-position contains an amino group or an alkyl radical of 1 to 6 carbon atoms which is bonded via an oxygen atom. 7. A process according to claim 6, wherein the compound of formula (6) is condensed with 4,6-dichloro-1,3,5-triazines containing at the 2-position methoxy, ethoxy, propyloxy or isopropoxy. 8. The process of item 1 for producing a fiber-reactive azo dye of the general formula HOOC in which R is an alkyl group having 1 to 6 carbon atoms, characterized in that p-aminobenzoic acid 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and cyanuric chloride are reacted by coupling and condensation to give a compound of formula HOOC -N = N- HO NH-C ^Cal sOaH and on the one hand, the 1,3-phenylenediamine is condensed 9. A process according to claim 8, wherein R is a methyl, ethyl, propyl or isopropyl group.