Dyestuffs containing chromophores linked via diethylenetriamine are known from literature and are described for example in JP 50107277.

The inventors of the present invention have surprisingly found that dyestuffs of the general formula (I) or dyestuffs of the general formula (II) and especially mixtures of dyestuff (I) and dyestuff (II) providing exceptionally strong and economic dyes and exhibiting excellent fastness properties, can be obtained if diethylenetriamine and analogues are used to link two or three chromophores each selected from a specific range of chromophores as defined below.

The present invention claims mixtures of fibre reactive dyes comprising one or more dyestuffs of the formula (I) and one or more dyestuffs of the formula (II)

and especially mixtures of dyestuffs (I) and (II) where (I) and (II) are water soluble reactive dyes and chromophores of formula D have the general structure where Ar1 and Ar2 are optionally substituted aryl groups, especially phenyl or naphthyl ; V and W are hydroxy or amino and V and W are not the same; R is hydrogen, optionally substituted C1-C4 alkyl or optionally substituted phenyl ; M is H or alkali metal, especially sodium, G is nitrogen or a sp2-carbon atom substituted by H, Cl, F, CN or NO2 ; m and n are independently 2 to 6; Y is a halogen radical such as fluoro, chloro or bromo or a quaternary ammonium unit; X is a a group R-carbonyl-or a heterocyclic fibre reactive group where R is an optionally substituted alkyl group, or optionally substituted phenyl, or optionally substituted vinyl and X may be coloured or colourless and of the form

where A, A'and A"independently are fluorine or chlorine, Q is hydrogen, fluorine, chlorine, cyano or nitro and B denotes oxyalkyl of the formula OR'°, thioalkyl of the formula SR"or amino NR12R13 where R10, R", R12 is hydrogen, optionally substituted C,-C4 alkyl or optionally substituted phenyl and R'3 is hydrogen, optionally substituted alkyl or optionally substituted aryl or is nitrile. The group R'3 can be coloured or colourless and may consist of an azo chromophore, but NR12R13 cannot be a chromophore of formula D.

Alkyl groups may be straight-chain or branched and are preferably (C1-C4)-alkyl groups, for example methyl, ethyl, n-propyl, i-propyl or n-butyl. Substituted alkyl groups are preferably substituted by hydroxyl, (C,-C4)-alkoxy, halogen or carboxyl groups and acylated amino (NR'COR2) Substituents for aryl groups are preferably (C,-C4)-alkoxy, halogen, carboxyl, carbonamide, optionally substituted C,-C4-alkyl, nitrile, sulpho, sulphonamide and acylated amino (NR1COR2) wherein R'is H, (C1-C4)-alkyl optionally substituted with hydroxyl, (C,-C4)-alkoxy, halogen or carboxyl groups and R2 is H, (C1-C4)-alkyl optionally substituted with hydroxyl, (C,-C4)-alkoxy, halogen or carboxyl groups, a vinyl group optionally substituted with (C,-C4)- alkyl, an aryl group optionally substituted with sulpho, (C l-C4)-alkoxy, halogen or

carboxyl groups.

Preferred embodiments of the invention are where in m and n are 2 or'3 or 6, especially preferred 2; Y is chloro or fluoro, or 3-or 4-carboxypyridinium, especially chloro ; X is alkylcarbonyl, vinylcarbonyl or a heterocyclic fibre reactive group (Z)

where A is as defined above and is preferably chloro R12 is hydrogen or optionally substituted C, to C4 alkyl R13 is hydrogen or an aromatic or aliphatic radical optionally sulphonated, and maybe coloured or colourless, such as ß- hydroxyethyl, sulfophenyl, or a group of formula Z-3

Z-3 wherein M is as defined above; and the chromophoric units. D are based on the chromophore of formula (III) or especially preferably based on the chromophore of formula (IV)

wherein Ar is a phenyl or naphthyl unit, substituted by one or more sulpho groups, and optionally substituted by one or more C, to C4 alkyd units, halogen such as fluoro, chloro or bromo, or methoxy; V and W are independently hydroxy or amino under the proviso that V is different to W and M is preferably H, an alkaline meta !, such as sodium, potassium or lithium and is especially preferably sodium.

Especially preferred dyestuff mixtures of the invention comprise (1-1)

wherein Ar, V, W, X, Y and M are as defined above.

The dyes of formulae (I) and (II) where m=n=2 are derived from cheap diethylenetriamine according to formula (1).

NH2CH2CH2NHCH2CH2NH2 (1) The dyestuffs of the present invention can be present as a preparation in solid or liquid (dissolved) form. In solid form they generally contain the electrolyte salts customary in the case of water-soluble and in particular fibre-reactive dyes, such as sodium chloride, potassium chloride and sodium sulfate, and also the auxiliaries customary in commercial dyes, such as buffer substances capable of establishing a pH in aqueous solution between 3 and 8, such as sodium acetate, sodium borate, sodium bicarbonate, sodium citrate, sodium dihydrogenphosphate and disodium hydrogenphosphate, small amounts of siccatives or, if they are present in liquid, aqueous solution (including the presence of thickeners of the type customary in print pastes), substances which ensure the permanence of these preparations, for example mold preventatives.

The azo dyestuffs of the formula (I) are contained in the mixture in quantity of 10-50% by weight and the azo dyestuffs of the formula (II) are contained in the

mixture in a mixing ratio of 10-50% by weight, preferably in a mixing ration of 20% by weight to 40% by weight.

In general, the dyestuffs of the present invention are present as dye powders containing 10 to 80% by weight, based on the dye powder or preparation, of a strength-standardizing colorless diluent electrolyte salt, such as those mentioned above. These dye powders may additionally include the aforementioned buffer substances in a total amount of up to 10%, based on the dye powder. If the dye mixtures of the present invention are present in aqueous solution, the total t dye content of these aqueous solutions is up to about 50 % by weight, for example between 5 and 50% by weight, and the electrolyte salt content of these aqueous solutions will preferably be below 10% by weight, based on the aqueous solutions. The aqueous solutions (liquid preparations) may include the aforementioned buffer substances in an amount which is generally up to 10% by weight, for example 0.1 to 10% by weight, preference being given to up to 4% by weight, especially 2 to 4% by weight.

A dyestuff mixture comprising dyestuff of the formula (I) and dyestuff of the formula (II) may for example be prepared by reacting dialkylenetriamine with dichlorotriazinyl dyes of formula (V) (V) followed by reaction with X-CI or X-OCOR.

The compounds of the formula (V) based on the radicals (III) and (IV) can be prepared for example by means of customary diazotization and coupling reactions in a manner familiar to those skilled in the art.

Thus reaction of diethylenetriamine with a solution of the navy dichlorotriazinyl dye (V-1)

followed by addition of acetic anhydride to the reaction mixture gives an approximate 1: 1 ratio of dyestuffs of the general formula (1-1) and dyestuffs of the general formula (II-1) where Y is chloro and X is acetyl.

The dyestuffs and dyestuff mixtures of the instant invention are reactive dyestuffs suitable for dyeing and printing hydroxy-and/or carboxamido- containing fibre materials by the application and fixing methods numerously described in the art for fibre-reactive dyes. They provide exceptionally strong and economic shades. Such dyes especially when used for exhaust dyeing of cellulosic materials can exhibit excellent properties including build-up, aqueous solubility, light-fastness, wash off and robustness to process variables. They are also wholly compatible with similar dyes designed for high temperature (80- 100° C) application to cellulosic textiles, and thus lead to highly reproducible application processes, with short application times.

The present invention therefore also provides for use of the inventive dyestuffs for dyeing and printing hydroxy-and/or carboxamido-containing fibre materials and processes for dyeing and printing such materials using a dyestuff according to the invention. Usually the dyestuff is applied to the substrate in dissolved form and fixed on the fibre by the action of an alkali or by heating or both.

Hydroxy-containing materials are natural or synthetic hydroxy-containing materials, for example cellulose fiber materials, including in the form of paper, or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton but also other natural vegetable fibers, such as linen, hemp, jute and ramie fibres. Regenerated cellulose fibers are for example staple viscose and filament viscose.

Carboxamido-containing materials are for example synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6, 6, nylon-6, nylon-11, and nylon-4.

Application of the inventive dyestuffs is by generally known processes for dyeing and printing fiber materials by the known application techniques for fibre- reactive dyes. The dyestuffs according to the invention are highly compatible with similar dyes designed for high temperature (80-100° C) applications and are advantageously useful in exhaust dyeing processes.

Similarly, the conventional printing processes for cellulose fibers, which can either be carried out in single-phase, for example by printing with a print paste containing sodium bicarbonate or some other acid-binding agent and the colorant, and subsequent steaming at appropriate temperatures, or in two phases, for example by printing with a neutral or weakly acid print paste containing the colorant and subsequent fixation either by passing the printed material through a hot electrolyte-containing alkaline bath or by overpadding with an alkaline electrolyte-containing padding liquor and subsequent batching of this treated material or subsequent steaming or subsequent treatment with dry heat, produce strong prints with well defined contours and a clear white ground.

Changing fixing conditions has only little effect on the outcome of the prints.

Not only in dyeing but also in printing the degrees of fixation obtained with dye mixtures of the invention are very high. The hot air used in dry heat fixing by the customary thermofix processes has a temperature of from 120 to 200°C. In addition to the customary steam at from 101 to 103°C, it is also possible to use superheated steam and high pressure steam at up to 160°C.

The inventive dyestuffs can in addition be used to produce inks useful for printing the substrates described above, for example textiles, especially cellulosic textiles, and paper. Such inks can be used in all technologies, for example conventional printing, ink-jet printing or bubble-jet printing (for

information on such printing technologies see for example Text. Chem. Color, Volume 19 (8), pages 23 ff and Volume 21, pages 27 ff).

Acid-binding agents responsible for fixing the dyes to cellulose fibers are for example water-soluble basic salts of alkali metals and of alkaline earth metals of inorganic or organic acids, and compounds, which release alkali when hot. Of particular suitability are the alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids, the preferred alkali metal compounds being the sodium and potassium compounds. These acid-binding agents are for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate and disodium hydrogenphosphate.

Treating the dyestuffs according to the invention with the acid-binding agents, with or without heating, bonds the dyes chemically to the cellulose fibers.

Especially the dyeings on cellulose, after they have been given the usual aftertreatment of rinsing to remove unfixed dye portions, show excellent properties.

The dyeings of polyurethane and polyamide fibers are customarily carried out from an acid medium. The dyebath may contain for example acetic acid and/or ammonium sulfate and/or acetic acid and ammonium acetate or sodium acetate to bring it to the desired pH. To obtain a dyeing of acceptable levelness it is advisable to add customary leveling auxiliaries, for example based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic acid or aminbnaphthalenesulfonic acid or based on a reaction product of for example stearylamine with ethylene oxide. In general the material to be dyed is introduced into the bath at a temperature of about 40°C and agitated therein for some time, the dyebath is then adjusted to the desired weakly acid, preferably weakly acetic acid, pH, and the actual dyeing is carried out at temperature between 60 and 98°C. However, the dyeings can also be carried out at the boil or at temperatures up to 1 20°C (under superatmospheric pressure).

The examples herein below serve to illustrate the invention. Parts and percentages are by weight, unless otherwise stated. Parts by weight relate to A parts by volume as the kilogram relates to the liter. The compounds described in the examples in terms of a formula are indicated in the form of the free sulphonic acids, but as in general they are prepared and isolated in the form of their alkali metal salts, such as lithium, sodium or potassium salts, and used for dyeing in the form of these salts. The starting compounds and components mentioned in the form of the free acid in the examples hereinbelow may be used in the synthesis as such or similarly in the form of their salts, preferably alkali metal salts.

Example 1 Diethylenetriamine (0.74g, 0.007 mol) was added in one portion to a stirred solution of the navy dichlorotriazinyl dye (VI) (0.007 mol) in water (400 ml) at ambient temperature and pH8. 5. The pH was then maintained at 8.5 with sodium carbonate solution for 30 minutes. More navy dichorotriazine dye (0. 007mol) in water (400 ml) was then added to the reaction mixture over 6 hrs maintaining the solution at pH 8.5 and ambient temperature. The pH was adjusted and maintained at 9 whilst an excess of acetic anhydride was added.

Subsequent chromatography indicated complete reaction to yield an approximate 1: 1 ratio of the two products (Vil) and (VIII). The reaction mixture was adjusted to pH 6 with 2N HCI and the dye precipitated by the addition of methylated spirits.

The precipitated dye was filtered off, and dried (Amax = 624. 5nm).

Following exactly analogous procedures the following dyes (examples 2-27) were synthesized giving 1: 1 mixtures of the respective dyestuff (IX) and (X)

Example D x kmax 2ciso, H"p 617, 5 NN S3H OH NHZ i i CI oH 3 cl lSO3H-COCH-CH2 623, 5 NAP CC 3 OH NH2 < 3 H H03S S03H WO. sISO . H so. 3crso, H--COCH=CH2623, 5 N i I 3 OH NHZ i i w w N'N w H S03H HO3SJSO3H 3 HO, S-SO, H ° Cl SO3H-COCH-CH2 620, 5 N'IN 3OH NH, N NaN N-C ; 6 N) N, 5aso, H'-COCH=CH2620, 5 OH NHZ * N N N'N 'N \ 3H S03H 'HOSO 6 cl sl 03H-COCH2CI 620, 0 N N N-IN N'N J i v I : N N,. w * N N N N 3H S03H HO3S <SO3H 3 7 ci SO H CH3-COCH3 613, 5 *JNN W I N.. N W Wz N.. N W I H ,, S03N HO3S+SO3H 3 HO, S-SO, H SO'HNH2 OH N12 C 3 NH2 OH < /NiN I N : N w w N.. N w W I 9 OH 623 HO, SOCH 3 has 9 X NH2 OH * H 623 N=N N=N N, N HO3S S03H 10 N OH 624 HO ; HO 3s So3H HO3S/ NH OH N=N N=N HO35 WSO3H HO. SSOH Example D x kmax H, c"061 ! 3 1 1 HO, O 613 * \ NHZ OH N=N N=N I Ho 3s S03H 12 SSO3H HO3S gH 62 1 HO, s \ NH OH HO3SJ\ßASO3H N SS N 3 Ho3s I i i So3H N Y N t 13/SSO3H HO3SYQ 61 9 Ho3s \ NHZ OH gp3H CI N=N N=N N 'N HOSO J H H 14 S03 H ci. 622 Ha s NH2 OH N=N, N=N H03S S03H 622 1 5 622 OH =\C ! 622 NH2 OH N=N N=N H03S I//S HOS-'SOgH 16'S03H H03S/-COCH3 619 HN>-NH2 OH/* N=N N=N HO3S4\H\SO3H 7-COCH = CH2 615 H3C S03H H03S \ NHZ OH <* N=N N=N HO3S SO3H Example D X , max 18 H3c 0 614 SO3H HO3S < NH2 OH > * wOH N=N N=N o H03S S03H S03H H03S -COCH3 614 19 NH2 OH < * N=N N=N HO 3s S03H 20 S03H H03S 0 614 2 OH N=N N=N I HO3S < SO3H O 21 H3c O 616 ''S03H H03S \ NHZ OH * N=N N=N o H03S S03H 22HgC-614 S03H H03S 2 2 < SO3H HO3S < 614 n7 NH2 OH-COCH2CH3 N=N < N=N H03S S03H Compounds derived from H2N(CH2)2NH(CH2)3NH2 Example D x Xmax 23aso, H"-GOCHs623, 0 N)"N 3 OH NH *NH w N., N I N,. N w w H HO 3s S03H S03H HO3S<so3H. HO, SSO, H 24 Cl SO3H-COCH2CI 622t5 Soh *NN N'N w W N'N w H ,' SOyH HO3S SO3H 3 Example D x kmax 25aso-COCH=CHC02H622, 5 "il SO H *N I N'-N w w N'N w 'H ,, So3H Hots 3 26 ci-COCH3 614, 5 N S03H pN NHZ/Me *NN \ HO3S +so H SO3H 27 ci S03H M e-COCH2C'615, 0 SO H Me N NaN N''N'q I : t,, H //S03H H03S S03H