CA2142742A1

CA2142742A1 - Reactive dye mixtures

Info

Publication number: CA2142742A1
Application number: CA002142742A
Authority: CA
Inventors: Werner H. Russ; Kurt Hussong; Manfred Schulze-Braucks; Michael Kunze
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1994-02-19
Filing date: 1995-02-17
Publication date: 1995-08-20
Also published as: EP0668328B1; DE59508235D1; EP0978544B1; EP0978543B1; JPH07304986A; BR9500672A; EP0668328A3; EP0982375A1; EP0976794B1; EP0668328A2; EP0976794A1; DE59509231D1; EP0982375B1; EP0969050A1; CN1114664A; EP0978544A1; DE59509326D1; CZ44095A3; EP0978543A1; PL307324A1

Abstract

Specific combinations of known reactive dyes are used for dyeing and printing of cellulose and polyamide fibers, especially for shading.52

Description

~ 4~742 _ HOECHST AKL~ SELLSCHAFT HOE 94/F 046 Dr.HU/PP

Description Reactive dye mixturee The present invention relates to novel mixtures of reactive dyes for dyeing and printing cellulose and/or polyamide fiber materials.

It is known (EP-A-0 525 805) to mix a plurality of reactive dyes together to obtain certain combination shades, for example beige. It i8 further known that, in trichromatic dyeing, dyes of the three primary colors blue, red and yellow are mixed with one another (US-A 5,071,442). Combination shades frequently show disadvantages in depth of shade, build-up, fastness properties, ease of wash-off and incomplete discharge-ability.

It is an object of the present invention to providesuitable dye mixtures for dyeing and printing, especially shading, cellulosic fiber materials and polyamide fibers which shall be highly complementary as regards bril-liance, phototropism, metamerism, substantivity andblocking effecte. It has been found that only specific dye combinations can achieve the stated object.

The present invention accordingly provides the below-defined reactive dye mixtures of types 1 to 17 in which the radicals in the formulae (l) to (27) have in each case independently of one another the following meAn~ngs:
D is phenyl-SO2-CH2CH2-Z where the phenyl radical can be substituted by l or 2 methyl, methoxy or sulfo groups; 0 Dl is D, naphthyl or naphthyl-SO2-CH2CH2-Z, where the naphthyl radical can in each case be substituted by up to 3 sulfo groups;
D2 is D or phenyl-SO3H;
D3 is Dl or phenyl-CONH-phenyl-SO2Y; 5 Y is -CH2CH2-Z or -CH=CH2;

~4~742 ..

Z iB -OSO3H, Cl or -SSO3H; and m iB from 1 to 3.

The novel dye mixtures of types 1 to 17 consist essen-tially of 90 to 99.99% by weight of a dye A, 0 to 10% by 5 weight of a further dye A', 0 to 10% by weight of a dye B, 0 to 10% by weight of a dye C, 0 to 10% by weight of a dye D and 0 to 10% by weight of a dye E, the percen-tages of the dyes adding up to 100% by weight in each case and the mixture containing at least two reactive 10 dyes.

Formula nl~bers for the dyes Type Hue A B C D E
1 yellow (1) (2) (3) 2 yellow (4) (5) (6) 3 yellow (7) (1) (2) 4 orange (2) (8) (1) (9) (10) red (11) (12) (2) (13) (22) 6 red (14) (13) (12) 7 violet (12) (14) (15) 8 blue (12) (10) 9 blue (16) (12) (17) blue (10) (18) (12) (25) 11 blue (19) (16) (4) 12 brown (23) (9) (15) (10) 13 dark blue (20) (16) (21) 14 navy (24) (1) (11) - -black (25) (9) (12) (16) 16 blue (26) (1) (8) ~14~742 -Formula n-~hers for the dyes Type Hue A B C D E
17 yellowish- (27) (1) (14) brown D3-N~N R1 ~ (1) H O N~N

R1 is CH3, COOH or CO-NH2;
OH
D-N; N~NH~ R2 ( 2 ) R2 is CH3 or phenyl;

21427~2 o D - N ~ N,~ ( 3 HO3S SO,H

O \~0 Z--o ~ N/~O ( 4 ) ~ R

R4 and R40 are each hydrogen, methyl or methoxy;

( S 0 3 H ) ~_ x N--~`N)~N

N_~,N~GN

\=/ - ( N H - D ) X

x i~ from 1 to 3, preferably 1 to 2: M is Ni;

~142742 s N~N
( H O 3 S ) n~ N ~N ~ J~J N--D

H N
)cO (6) R6 i B CH3 or NH2, n iB from 1 to 3, X iB Cl or F;

' SO3H ) ~

N-$ \R70 R7 and R70 are each hydrogen, C1- C4 - alkyl or CH2-CH2-OS03H, R71 iB Cl, NH-C0-CH3 or NH-CO-NH2;

a iB 0 or 1;
o OH H-Nj~R2 5 o~y H O,S

21~274~

~N~NH2 ( 9 ) HN
~0 R9 is methyl or -NH2;

( ) H O S ~,~ C u ~ ( 1 ) N~N 2 ,~ R
OH HN

D 3 - N; N ~ S O ~ H

~,N~NH~ 2 or CO-C113 or CO-phenyl;

Z~ ~2742 , O ~~~~O NH R
A-N~N ~ (12) H03S ~ S03H

A is a bivalent radical based on Dl, the two free valences being in the phenyl or naphthyl radical;

(H3S)m ~ ~N

H0 ~

~0 N~
~3~

21427~2 O OH HN~
D - N HJL~ N N ~1 O, H

~SO,H ( I 6 ) \ D

(17) correspond~ to the formula (5) but M i8 Cu.

_~ (18) H O N~N

(19) corre~ponds to the formula (5) but M is Cu or Ni.

~14~742 g ~cu\ o I-N N ~OH NH R2 H O ~ SJ~~N~S O ~ H

~c u \
N N~3 H O ~ S

( H O~ 5 )r ~N~N ~ H N N~35 R ~

c u\
o o A-N ~ N~IOH( S03H ) n ro2s R2~ OH NH2 ~0~SO2Y

R2-~N~N~N~N (24) ~S ~S~
H-O ~o \O-H

where the R24 radical~ are, independently of one another, hydrogen, ~ulfo or methoxy;

~14~742 -COOH

O--C u ( I I ) )~N~

R 2 ,~l~ ~N~Il ~ ( 2 s ) O~OH

O~NH (26) 5 0 2 Y C l ~N~O~H~ ~0 H

N O
CH~ 11 ,[3~(o ~ ( 2 7 ) A sulfo group is a group of the formula -SO3M, a carboxyl group is a group of the formula -COOM, a sulfato group is a group of the formula -OS03M, and a thiosulfato group is a group of the formula -S-SO3M.

214~742 ~ The dyes of the formulae (1) to (27) can have the same chromophore but differ in respect of the structure of the fiber-reactive groups -S02-Y. In particular, the dye mixtures can contain dyes of the same chromophore in which the fiber-reactive groups -S02-Y are partly vinyl-sulfonyl groups and partly ~-chloroethylsulfonyl or thiosulfatoethylsulfonyl or preferably ~-sulfatoethyl-sulfonyl groups. If the dye mixtures contain the res-pective dye components in the form of a vinylsulfonyl dye, the proportion of the respective vinylsulfonyl dye to the respective ~-chloro- or ~-thiosulfato- or sulfato-ethyl-sulfonyl dye will be up to about 30 %, based on the respective dye chromophore.

The dye mixtures of the invention can be prepared in solid or in liquid (dissolved) form. In solid form they generally contain the electrolyte salts customary in the case of water-soluble and in particular fiber-reactive dyes, such as sodium chloride, potassium chloride, lithium chloride, lithium sulfate and sodium sulfate, and also the assistants customary in commercial dyes, such as buffer substances capable of establishing a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogenphosphate and disodium hydrogenphosphate, small amounts of siccatives or, if they are present in liquid, aqueous ~olution (including the presence of thickeners of the type cu~tomary in print pastes), substances which ensure the permanence of these preparations, for example mold preventatives.

In general, the dye mixtures will take the form of dye powders containing from 10 to 70 % by weight, based on the dye powder or preparation, of a strength-stAn~Ardiz-ing colorless diluent electrolyte salt. These dye powders may in addition contain the abovementioned buffer sub-stances in a total amount of up to 5 %, based on the dyepowder. If the dye mixtures of the invention are present in aqueous solution, the total dye content of these 21~2742 -_ - 12 -~ aqueous solutions is up to about 50 % by weight, the electrolyte salt content of these aqueous solutions preferably being below 10 % by weight, based on the aqueous solution; the aqueous solutions can in general contain the abovementioned buffer substances in an amount of up to 5 % by weight, preferably up to 2 % by weight.

The dye mixtures of the invention can be prepared in a conventional manner, for instance by mechanically mixing the individual dyes in the required proportions. In this connection, variation of the dye proportions makes it possible to influence the shade in a specific manner.
Liquid preparations of the dye mixtures of the present invention can be prepared by dissolving the pulverulent individual components in water and mixing them together, or by ~;Y; ng together the aqueous solutions obta; ne~ in the synthesis of the individual components or adjusting the reaction solution of the dyes prepared in a stirred apparatus side by side to the desired strength (%
content) by diluting with water or by strength~n; ng (evaporating water). The streng~hen;ng can also be effected by mixing the pulverulent dye mixture into a low ~trength solution of the dye mixture. This makes it possible to obtain highly concentrated dye formulations.
Furthermore, known membrane processes can be used to reduce the salt content. The aqueous liquid dye com-position is adjusted to a pH from 3 to 6 using a mineral acid or a base. Similarly, a buffer, for example a carboxylic acid or phosphoric acid, and a surfactant can be included in the aqueous liquid dye composition.

The novel mixtures of the dyes of the formulae (1) to (27) dye hydroxyl- and/or carboxamido - conta i n i n g fiber materials by the application and fixing methods numerously described in the art for fiber-reactive dyes with good color build-up and good washoff in respect of unfixed dye portions. In addition, some of the dyeings obtained are readily dischargeable. The dye mixtures of the present invention are suitable not only for dyeing 2~ 42742 -cellulose by the batchwise exhaust method, for semi-continuous dyeing processes, in particular cold pad-batch processes or pad-steam, but also for printing.

The present invention therefore also provides for the use of the novel dye mixtures for dyeing (including printing) hydroxyl- and/or carboxamido-contA;n;ng fiber materials and processes for dyeing such fiber materials using a dye mixture according to the invention by applying the dye mixture to the substrate in dissolved form and fixing the dyes on the fiber by the action of an alkali or by heating or both.

Hydroxyl-containing materials are natural or synthetic hydroxyl-contA;n;ng 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 can also be other vegetable fibers, such as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are for example staple viscose and filament viscose.

Carboxamido-containing materials are for example synthet-ic and natural polyamides and polyurethanes, in particu-lar in the form of fibers, for example wool and other An; m~ 1 hairg, silk, leather, nylon-6.6, nylon-6, nylon-11 and nylon-4.

Application of the dye mixtures of the invention is by generally known processes for dyeing and printing fiber materials by the known application techniques for fiber-reactive dyes. Since the dyes of the dye mixtures accord-ing to the invention are highly compatible with one another, the dye mixtures of the invention are also advantageously useful in exhaust dyeing proces~es.
Applied in this way for example to cellulose fibers by exhaust methods from a long liquor at temperatures between 40 and 105C, optionally at temperatures up to 130C, and optionally in the presence of customary dyeing ~14~742 _ - 14 -- assistants with the use of acid-b; n~; ng agents and optionally neutral salts, such as sodium chloride or sodium sulfate, they produce dyeings in very good color yields with excellent color build-up and consistent shade. One possible procedure is to introduce the material into the warm bath, gradually heat the bath to the desired dyeing temperature, and complete the dyeing process at that temperature. The neutral salts which speed up the exhaustion of the dyes can also if desired not be added to the bath until the actual dyeing tempera-ture has been reached.

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 contA;n;ng sodium carbonate or some other acid-bin~;ng agent and the colorant and subsequent steaming at from 100 to 103C, or in two phases, for example by printing with a neutral or weakly acid print paste contA;n;ng the colorant and subsequent fixation either by passing the printed material through a hot electrolyte-containing alkaline bath or by overpA~;ng with an alkaline elec-trolyte-contA;n;ng padding liquor and subsequent batching of this treated material or subsequent steA~; ng 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 obtA;ne~ with the 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 200C. In addition to the customary steam at from 101 to 103C it is also possible to use superheated ste_m and high pressure steam at up to 160C.

Acid-b;n~;ng agents responsible for fixing the dyes to the cellulose fibers are for example water-soluble basic salts of alkali metals and of alkaline earth metals of 2~ 74 2 - 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-b; n~; ng agents are for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbon-ate, potassium carbonate, sodium formate, sodium hydro-genphosphate and disodium hydrogenphosphate.

Treating the dyes of the dye mixtures according to the invention with the acid-b;n~ing agents with or without heating bonds the dyes chemically to the cellulose fiber;
especially the dyeings on cellulose, after they have been given the usual aftertreatment of rinsing to remove unfixed dye portions, show excellent wet fastness proper-ties, in particular since the unfixed dye portions are readily washed off because of their good cold water solubility.

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 assistants, for example based on a reaction product of cyanuric chloride with three times the molar amount of an A~; nohenzenesulfonic acid or am;no~ph-thalenesulfonic 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 40C 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 a temperature between 60 and 98C. However, the dyeings can also be carried out at the boil or at temperatures of up to 120C (under superatmos-pheric pressure).

2~ 92742 ~ The Examples which follow illustrate the invention. Parts and percentages are by weight, unless otherwise stated.
The parts by weight bear the same relation to parts by volume as the kilogram to the liter.

Example 1 1000 g of the blue formazan dye of the formula (B 27) are mixed with 4 g of the dye of the formula (B 34) in a mechanical mixer. The dye mixture obtA; ne~ in an amount of 1004 g dyes cellulose in blue RhA~e~.

Example 2 1000 g of the dye of the formula (B 30) are mixed with 3.5 g of the dye of the formula (B 26) in a mechanical mixer. The dye mixture obtained in an amount of 1003.5 g dyes cellulose in green shades.

Example 3 1000 g of the dye (B 23) are mixed with 10 g of the dye of the formula (B 24) in a mechanical mixer. The dye mixture obtained in an amount of 1010 g dye~ cellulose in violet shades.

Example 4 1000 g of the dye (B 38) are mixed with 25 g of the dye of the formula (B 33) in a mechanical mixer. The dye mixture obtained in an amount of 1025 g dyes cellulose in navy shades.

Example 5 1000 g of the dye of the formula (B 33) are mixed with 6 g of the dye of the formula (B 23) in a mechanical mixer. The dye mixture obtained in an amount of 1006 g dyes cellulose in navy shades.

Example 6 lO00 g of the dye of the formula (B 28) are mixed with 5 g of the dye of the formula (B l) in a mechanical mixer. The dye mixture obtained in an amount of 1005 g ~142742 ~ dyes cellulose in green shades.

In the table below 1000 g in each case of the main component are mixed with the stated amount of the ~A~ing component.

Example Main Amount !~A~;ng Hue component [g] component 7 B1 0.2 B30 yellow 8 Bl 3 B7 yellow 9 Bl 3 BlO yellow B2 5 BlO yellow 11 B2 5 B27 yellow 12 B3 2.5 B12 yellow 13 B4 3 B14 yellow 14 B5 1 B14 yellow B6 2 B14 yellow 16 B7 27 B1 yellow 17 B7 2.3 B19 yellow 18 B8 4.8 B2 yellowish brown 19 B8 5.2 B20 yellowish brown B9 5.1 B4 golden yellow 21 B9 4 B14 golden yellow 22 B10 3 B4 golden yellow 23 B10 3 B14 golden yellow 24 B11 22.5 B4 golden yellow B11 5.5 B14 golden yellow ~27~2 Example Main Amount S~A~; ng Hue component [g~ component 26 B12 6.5 B3 golden orange 27 B12 4.7 B15 golden orange 28 B13 4.6 B18 orange 29 B13 3.8 B3 orange B14 4 B10 orange 3 Oa B13 9.5 B4 orange 31 B14 0.2 B18 orange 32 B14 4.1 B27 orange 33 B15 5.1 B2 red 34 B15 5.1 B18 red B16 7.6 B14 red 36 B16 3.6 B23 red 37 B17 2.7 B13 red 38 B17 5 B23 red 39 B18 2 B13 red B18 3.2 B23 red 41 B19 2.3 B7 red 42 B19 1.2 B23 red 43 B20 5 B2 red 44 B20 5.5 B23 red B21 4.5 B14 red 46 B21 4 B23 red 47 B22 5 B14 red 48 B22 3.5 B23 red 49 B23 4 B17 violet ~142742 Example Main Amount Shading Hue component ~g] component B23 11.8 B23 violet 51 B24 9.3 B23 blue 52 B24 4.8 B27 blue 53 B25 10 B23 blue 54 B25 7 B27 blue B26 6.2 B23 blue 56 B26 6.2 B28 blue 57 B27 3.3 B2 blue 58 B27 3.3 B24 blue 59 B28 2 B26 turquoise B28 8.2 B30 turquoise 61 B29 9.2 B26 turquoise 62 B29 9.2 B30 turquoise 63 B30 1.2 Bl green 64 B30 3 B28 green B31 3.1 B10 brown 66 B31 3.1 B17 brown 67 B31 3.2 B27 brown 68 B32 3.2 B26 dark blue 69 B33 2.6 B35 navy B33 1.9 B4 navy 71 B34 6.4 B10 blac~
72 B34 21.8 B26 black 73 B35 3.5 B17 black 74 B36 5 B37 blue %142~42 _ - 20 -Example Main Amount Sh~i n~ ~ue component [g] component 75 B36 5 ¦B18 blue B1 (DE-A-33 03 156) ,C H 3 \o N~ ~5 o S ~ C H 3 ~ \\ O
o C H 3 H O--S = O

B2 (DE-A-925 121) N CH3 O=S--OH

~ `~ HO ~

HO~ / HO--S=
//s~o O

2~ 742 - B3 (DE-A-12 82 213) ~S//
~ ~OH

H ON~

Il O
o ~OH ~ ,[3~N HO

o// ~O~\~ ~

B4 (CA-A-519 978) CH, O

~1~2742 B5 1:1 mixture (DE-A-2442553) CH, ,N~ ,C R, O / O H
CH~ O

O=S~ ~N~o~cH

H O--r o o B6 (DE-A-12 06 107) ~ N ~ ~ 5=0 HjO ~ ~0 H0 O=S--O O

~ 42742 o_5_~
HO~ ~ ~NH2 B8 (DE-A-25 33 250) S~o H 0~ /o~ ~0 ~S~

~14Z~42 B9 (CA-A-519 978) o=S~ C~

O" ~

\S~O
H O-- \

B10 (DE-A-31 34 357) o S-O H

o ,~/ N ~--\S~O
H O--~142742 Bll (DE-A-26 53 478) o\\~o O ~

~N ~

O , O

S ~
o O =j 0 ~1 B12 (DE-A-16 96 198) ~o s\
O OH

~1427~2 B13 (DE-A-l9 43 904) H3C~O

OH NH

O ~ HO

O=~=O N
N H O-S=O

S ~
o~ ~o B14 (CA-A-519 978) Il / H 3 C ~O

H O ~--oJ/ ~o ~ 4~7~2 ._ B15 (DE-A-16 44 240) =S - O H
~ ~J
~ ~ ~

\

O~

B16 (DE-A-29 49 034) o 0=5 - OH

~S/ OH l - l ~

~S~s HO ~o O / O H O

2~42~42 B17 (DE -A- 11 2 6 547 ) ~S~ H N J~

H O " O o/iS~o H O/ ~

B 18 (DE-A-l9 43 904) \ ~ //

O / O H O

~ ~2742 Bl9 O= O H
HO

$N H--(~
~H IOH H

~1 \S~s/i B20 (DE-A-14 69 990) \\S~\~O\S//

\\o HO ;~0 0--~

C U N~

H O~S//
o~S~o HO/ ~

2~ 427~2 . _ B21 (CA-A-519 978) f H3 CH3 ,~ O H H N~o ~ \\ HO~ ~3 H O _O
o B22 (DE-A-21 42 728) S o H N \\S\o~HO
HO~

O--~ O N ~
~ H O S- O
o B23 (DE-A-ll 26 542) o Il `O S OH

O

O
H ~S S//

O/ O HO

B24 (DE-A-ll 26 542) o - O H

O
~0 // ~ HO/ ~

~ ~2742 -_ - 32 -B25 (DE-A-20 10 656) o !--O H

OH ~S ~o ~ ~
H0~s S//0 0// ~0 H0 B26 (DE-A-24 12 964) ~ ~ I I--~142742 _ - 33 -B27 (DE-A-29 45 537) o = - OH

RO ~ ~0 B28 (DE-A-ll 79 317) ~ ~ ~3S02~C~2)20SO~N)n ~ ~ n 1.1 B29 (DE-A-12 33 963) corresponds to the formula B30 except that Ni iB replaced 5 by Cu.

~42742 B30 (DE-A-ll 79 317) N~ ~ (502N11~3502~C112)20SO~N),, N~ N~ _ ~503No)~ "
N Ni N
\ jkN N~ n ~ e o . 1 . 5 ~N~

B31 (DE-A-12 33 963) S

C~

/ S~ /~/ ~ N~o H O H

~ b ~N O H H N~o H O--j'=O H O~s~S//

2~ 42742 B33 (D~-A-31 13 885) O= O H

~/ )~o ,¢~\\o o/ ~, ~S S
// ~O H O/ ~

B34 (D~-A-15 44 538) O O H

/ ~ - O N

0// ~0 ~ 42792 B35 (CA-A-519 978) O= O H

\l3\N~N~II~ O ~o H ~5 s~f O~ O HO

0~ ~0 HO
~ HO

H~ ~ O~ ~'~
~OH C I O --- ''~H
O ~ O
\5/

0~ ~0 ~1 ~7742 \\ ~0 H-O~ \
O
N~N~
)=~( O - H
H-O N=N
~=0 - O =O
o ~ 42742 O Cu(l 1) 1 l \\, ,~5 H-O--5 0 o~ ~
\\ H - O ~ O
O

Claims

1. A yellow reactive dye mixture of at least two reactive dyes, consisting essentially of 90 to 99.99% by weight of a dye of the formula (1), 0 to 10% by weight of a dye of the formula (2) and 0 to 10% by weight of a dye of the formula (3) (1) (2) or 90 to 99.99% by weight of a dye of the formula (4), 0 to 10% by weight of a dye of the formula (5) and 0 to 10% by weight of a dye of the formula (6) (4) (5) (6) or of 90 to 99.99% by weight of a dye of the formula (7), 0 to 10% by weight of a dye of the formula (1) and 0 to 10% by weight of a dye of the formula (2) (7) where, in the formulae (1) to (7), D is phenyl-SO2-CH2CH2-Z, wherein the phenyl radical can be substituted by 1 or 2 methyl, methoxy or sulfo groups and Z is -OSO3H, -Cl or -SSO3H;
D3 is phenyl-CONH-phenyl-SO2Y, where Y is -CH2CH2-Z or -CH=CH2; D; or naphthyl or naphthyl-SO2-CH2CH2-Z, wherein the naphthyl radical can in each case be substituted by up to 3 sulfo groups;
R1 is CH3, COOH or CONH2 and R2 is CH3 or phenyl;
R4 and R40 are each H, CH3 or OCH3;
x is from 1 to 3;
M is nickel;
R6 is CH3 or NH2;
X is Cl or F;
n is from 1 to 3;
R7 and R70 are H, C1-C4-alkyl or CH2CH2-OSO3H;
R71 is Cl, NH-CO-CH3 or NH-CO-NH2;
and a is 0 or 1.

2. A blue reactive dye mixture of at least two reactive dyes, consisting essentially of 90 to 99.99% by weight of a dye of the formula (16), 0 to 10% by weight of a dye of the formula (12) and 0 to 10% by weight of a dye of the formula (17) (16) (12) (17) or of 90 to 99.99% by weight of a dye of the formula (10), 0 to 10% by weight of a dye of the formula (18), 0 to 10% by weight of a dye of the formula (12) and 0 to 10% by weight of a dye of the formula (25) (10) (18) (25) or of 90 to 99.99% by weight of a dye of the formula (19), 0 to 10% by weight of a dye of the formula (16) and 0 to 10% by weight of a dye of the formula (4) (19) corresponds to the formula (17) where M is Cu or Ni;

(4) or of 90 to 99.99% by weight of a dye of the formula (12) and 0 to 10% by weight of a dye of the formula (10);
or of 90 to 99.99% by weight of a dye of the formula (26), 0 to 10% by weight of a dye of the formula (1) and 0 to 10% by weight of a dye of the formula (8) (26) (1) (8) or of 90 to 99.99% by weight of a dye of the formula (20), 0 to 10% by weight of a dye of the formula (16) and 0 to 10% by weight of a dye of the formula (21) (20) (21) where, in the formulae mentioned, D is phenyl-SO2-CH2CH2-Z, wherein the phenyl radical can be substituted by 1 or 2 methyl, methoxy or sulfo groups and Z is -OSO3H, -Cl or -SSO3H;
D3 is phenyl-CONH-phenyl-SO2Y, where Y is -CH2CH2-Z or -CH=CH2; D; or naphthyl or naphthyl-SO2-CH2CH2-Z, wherein the naphthyl radical can in each case be substituted by up to 3 sulfo groups;
R1 is CH3, COOH or CONH2 and R2 is CH3 or phenyl;
R4 and R40 are each H, CH3 or OCH3;
x is from 1 to 3;
M is copper;
A is a bivalent radical based on D1 where D1 is D, naphthyl or naphthyl-SO2-CH2CH2Z wherein the naphthyl radical can in each case be substi-tuted by up to 3 sulfo groups and the two free valences are in the phenyl or naphthyl radical;
and R24 is H, SO3H or OCH3.

3. A navy reactive dye mixture of at least two reactive dyes, consisting essentially of 90 to 99.99% by weight of a dye of the formula (24), 0 to 10% by weight of a dye of the formula (1) and 0 to 10% by weight of a dye of the formula (11) (24) (1) (11) where, in the formulae (24), (1) and (11), D is phenyl-SO2-CH2CH2-Z, wherein the phenyl radical can be substituted by 1 or 2 methyl, methoxy or sulfo groups and Z is -OSO3H, -Cl or -SSO3H;
D3 is phenyl-CONH-phenyl-SO2Y, where Y is -CH2CH2-Z or -CH=CH2; D; or naphthyl or naphthyl-SO2-CH2CH2-Z, wherein the naphthyl radical can in each case be substituted by up to 3 sulfo groups;

R1 is CH3, COOH or CONH2 and R24 is H, SO3H or OCH3; and R11 is or CO-CH3 or CO-phenyl where D2 is phenyl-SO3H or D.

4. A red reactive dye mixture of at least two reactive dyes, consisting essentially of 90 to 99.99% by weight of a dye of the formula (11), 0 to 10% by weight of a dye of the formula (12), 0 to 10% by weight of a dye of the formula (2), 0 to 10% by weight of a dye of the formula (13) and 0 to 10% by weight of a dye of the formula (22) (11) (12) (2) (13) (22) or of 90 to 99.99% by weight of a dye of the formula (14), 0 to 10% by weight of a dye of the formula (13) and 0 to 10% by weight of a dye of the formula (12) (14) where in the formulae (11), (12), (2), (13), (22) and (14), D is phenyl-SO2-CH2CH2-Z, wherein the phenyl radical can be substituted by 1 or 2 methyl, methoxy or sulfo groups and Z is -OSO3H, -Cl or -SSO3H;
D3 is phenyl-CONH-phenyl-SO2Y, where Y is -CH2CH2-Z or -CH=CH2; D; or naphthyl or naphthyl-SO2-CH2CH2-Z, wherein the naphthyl radical can in each case be substituted by up to 3 sulfo groups;
R1 is CH3, COOH or CONH2 and R2 is CH3 or phenyl;
R11 is or CO-CH3 or CO-phenyl;

A is a bivalent radical based on D1 where D1 is D, naphthyl or naphthyl-SO2-CH2CH2Z where the naphthyl radical can in each case be substituted by up to 3 sulfo groups and the two free valences are in the phenyl or naphthyl radical;
m is from 1 to 3;
X is Cl or F, and R9 is CH3 or NH2.

5. A black reactive dye mixture of at least two reac-tive dyes, consisting essentially of 90 to 99.99% by weight of a dye of the formula (25), 0 to 10% by weight of a dye of the formula (9), 0 to 10% by weight of a dye of the formula (12) and 0 to 10% by weight of a dye of the formula (16) (25) (9) (12) (16) where, in the formulae (25), (9), (12) and (16), D is phenyl-SO2-CH2CH2-Z, wherein the phenyl radical can be substituted by 1 or 2 methyl, methoxy or sulfo groups and Z is -OSO3H, -Cl or -SSO3H;
Y is -CH2CH2-Z or -CH=CH2;
R24 is H, SO3H or OCH3;
R9 is CH3 or NH2;
R2 is CH3 or phenyl; and A is a bivalent radical based on D1 where D1 is D, naphthyl or naphthyl-SO2-CH2CH2Z where the naphthyl radical can in each case be substi-tuted by up to 3 sulfo groups and the two free valences are in the phenyl or naphthyl radical.

6. An orange reactive dye mixture of at least two reactive dyes, consisting essentially of 90 to 99.99% by weight of a dye of the formula (2), 0 to 10% by weight of a dye of the formula (8), 0 to 10% by weight of a dye of the formula (1), 0 to 10% by weight of a dye of the formula (9) and 0 to 10% by weight of a dye of the formula (10) (2) (8) (1) (9) (10) where in the formulae (1), (2), (8), (9) and (10), D is phenyl-SO2-CH2CH2-Z, wherein the phenyl rad-ical can be substituted by 1 or 2 methyl, methoxy or sulfo groups and Z is -OSO3H, -Cl or -SSO3H;
D3 is phenyl-CONH-phenyl-SO2Y, where Y is -CH2CH2-Z or -CH=CH2; D; or naphthyl or naphthyl-SO2-CH2CH2-Z, wherein the naphthyl radical can in each case be substituted by up to 3 sulfo groups;
R1 is CH3, COOH or CONH2;
R2 is CH3 or phenyl; and R9 is CH3 or NH2.

7. A violet reactive dye mixture of at least two reactive dyes, consisting essentially of 90 to 99.99% by weight of a dye of the formula (12), 0 to 10% by weight of a dye of the formula (14) and 0 to 10% by weight of a dye of the formula (15) (12) (14) where, in the formulae (12), (14) and (15), D is phenyl-SO2-CH2CH2-Z, wherein the phenyl radical can be substituted by 1 or 2 methyl, methoxy or sulfo groups and Z is -OSO3H, -Cl or -SSO3H;

R2 is CH3 or phenyl; and Y is -CH2CH2Z or -CH=CH2; and A is a bivalent radical based on D1 where D1 is D, naphthyl or naphthyl-SO2-CH2CH2Z where the naphthyl radical can in each case be substi-tuted by up to 3 sulfo groups and the two free valences are in the phenyl or naphthyl radical.

8. A brown reactive dye mixture of at least two reactive dyes, consisting essentially of 90 to 99.99% by weight of a dye of the formula (23), 0 to 10% by weight of a dye of the formula (9), 0 to 10% by weight of a dye of the formula (15) and 0 to 10% by weight of a dye of the formula (10) (23) (9) (15) (10) or 90 to 99.99% by weight of a dye of the formula (27), 0 to 10% by weight of a dye of the formula (1) and 0 to 10% by weight of a dye of the formula (14) (27) (1) (14) where, in the formulae (1), (9), (10), (14), (15), (23) and 27), D is phenyl-SO2-CH2CH2-Z, wherein the phenyl radical can be substituted by 1 or 2 methyl, methoxy or sulfo groups and Z is -OSO3H, -Cl or -SSO3H;
D3 is phenyl-CONH-phenyl-SO2Y, where Y is -CH2CH2-Z or -CH=CH2; D; or naphthyl or naphthyl-SO2-CH2CH2-Z, wherein the naphthyl radical can in each case be substituted by up to 3 sulfo groups;
R1 is CH3, COOH or CONH2 and R2 is CH3 or phenyl;
A is a bivalent radical based on D1 where D1 is D, naphthyl or naphthyl-SO2-CH2CH2Z where the naphthyl radical can in each case be substituted by up to 3 sulfo groups and the two free valencies are in the phenyl or naphthyl radical;
n is from 1 to 3; and R9 is CH3 or NH2.

9. The use of a reactive dye mixture as claimed in any one of claims 1 to 8 for dyeing and printing hydroxyl- and/or carboxamido-containing fiber materials.

10. A use as claimed in claim 9 wherefor the fiber material comprises cellulose fibers, preferably cotton, regenerated cellulose fibers, filament viscose, wool, silk or nylon-4.

11. A process for dyeing and printing hydroxyl- and/or carboxamido-containing fiber materials, which comprises applying a reactive dye mixture as claimed in any one of claims 1 to 8 to the fiber material in dissolved form and fixing the dyes on the fiber by the action of an alkaline agent or by heat or by both measures.