CH672136A5 - - Google Patents

Description

DESCRIPTION There are already e.g. from US Pat. No. 4,544,739 asymmetrical 1: 2 chromium complex dyes of two azo dyes, in which one is 2-amino-8-hydroxynaphthalene-6-sulfonic-5o acid and the other a phenol, β-naphthol or 1-phenylpyra -zol-5-one contains as a coupling component, known as intermediates for the production of reactive dyes.

The present invention relates to asymmetrical 1: 2 chromium complex dyes of the formula

55

60

65

y \

.2 / V /

° 3S \ A /

Y v "w-

0

> 0

2 Ka

©

(1)

vorin l nitrogen or a CH group,

an optionally further substituted residue of the benzene or naphthalene series which has a hydroxyl or carboxy group in the O position to the azo or azomethine group, 3 the residue of an acetoacetic acid amide or benzoylacetic acid anilide, if Z is nitrogen, the acetoacetic acid amide or benzoylacetic acid anilide in a- Position to the azo group which contains group X or the residue of an o-hydroxyalde hyd if Z represents the CH group,

X means oxygen

Y1 sulfo, chlorine, Q-Q-alkyl, S02-R2, where R2 is C1-C4-alkyl, or -SO2-NRR3, where R3 is independently hydrogen or Cj-Q-alkyl,

Y2 is hydrogen, sulfo, chlorine or Ci-C4-alkyl,

R1 is hydrogen or a group of the formula -SO2-Q or -C0- (0) nQ, where n is zero or 1 and Q is C1-C5-alkyl or phenyl, the phenyl group being nitro, halogen, C1-C5-alkyl or -alkoxy can be substituted, p 0 or 1 and Ka® is a cation.

The dyes according to the invention are asymmetrical 1: 2 chromium complexes. If X is oxygen, Z is nitrogen and p is 0, the diazo component A and the coupling component B must not be identical to the diazo and coupling component of the other azo dye at the same time.

In the chromium complex dyes of the formula (1) according to the invention, the radical A can also carry one or more further substituents, e.g. low molecular weight alkyl or alkoxy, halogen, e.g. Chlorine or bromine, nitro, cyano, sulfo, carboxy, phosphono, alkylsulfonyl, e.g. Methylsulfonyl, sulfamides such as e.g. Sulfamide or N-methylsulfamide, acylamino, phenylazo, sulfophenylazo or methoxyphenylazo. In this application, low molecular weight alkyl or alkoxy groups are generally to be understood as meaning those having 1 to 6, preferably 1 to 2, carbon atoms and “acylamino” means low molecular weight alkanoylamino, alkylsulfonylamino and alkoxycarbonylamino residues as well as aroylamino, aryloxycarbonylamino and arylsulfo -nylamino residues.

The radical A is derived, for example, from the following amines: anthranilic acid, 4- or 5-chloroantrhanilic acid, 4- or 5-sul-foanthranilic acid, 2-amino-3-naphthoic acid, 2-amino-1-hydroxybenzene, 4-chloro- and 4,6-dichloro-2-amino-1-hydroxybenzene, 4- or 5-nitro-2-amino-l-hydroxybenzene, 4-chloro, 4-methyl and 4-acetylamino-6-nitro- 2-amino-1-hydroxybenzene, 6-acetylamino and 6-chloro-4-nitro-2-amino-l-hydroxybenzene, 4-cyano-2-amino-1-hydroxybenzene, 4-sulfonamido-2-amino- 1-hydroxybenzene, 1-hydroxy-2-aminobenzene-4-sulfoanthranilide, 4-methoxy-2-amino-1-hydroxybenzene, 4-methoxy-5-chloro-2-amino-I-hydroxybenzene, 4-methyl-2- amino-1-hydroxybenzene, 4-chloro and 4-methyl-5-nitro-2-amino-1-hydroxybenzene, 3,4,6-trichloro-2-amino-1-hydroxybenzene, 6-acetylamino-4-chloro -2-amino-1-hydroxybenzene, 4,6-dinitro-2-amino-1-hydroxybenzene, 2-amino-l-hydroxybenzene-4- or -5-sulfonic acid, 4-nitro-2-amino-1-hydroxybenzene -6-sulfonic acid, 6-nitro-2-amino-1-hydroxybenzene-4-sulfonic acid, 4-chloro-2-amino-1-hydroxyb enzole-6-sulfonic acid, l-amino-2-hydroxynaphthalene-4-sulfonic acid, 1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid, 1-amino-2-hydroxy-6-chloronaphthalene-4-sulfonic acid, l-amino-2-hydroxy-naphthalene-4,6-disulfonic acid, 2-amino-l-hydroxybenzene-4,6-disulfonic acid.

Instead of the amines with hydroxyl groups mentioned above, corresponding methoxy compounds or corresponding compounds whose hydroxyl group has been tosylated, such as anisidine, 4- or 5-chloroanisidine, 4- or 5-nitroanisidine, anisidine-4- or -5- sulfonic acid, or tosylated l-hydroxy-2-aminobenzene, the methoxy or O-tosyl

3,672,136

Group is converted into an OH group before or during the metallization. Compounds with these groups are used especially when the corresponding 1-hydroxy-2-amino compounds couple poorly.

5 In preferred dyes of the formula (1), A is the residue of an l-hydroxy-2-aminobenzene, which is optionally substituted by halogen, nitro, sulfo or low molecular weight alkyl or alkoxy, or the residue of an l-amino-2-hydroxy- 4-sulfonaphthalene, which is optionally substituted in the 6-position 10 by halogen, such as bromine or in particular chlorine, nitro or sulfo.

Dyes of the formula (1) in which A denotes the residue of an 1-hydroxy-2-aminophenol which is substituted by a nitrograppe and optionally by a sulfo group are particularly preferred. The radical B is preferably derived from the following group of coupling components: acetoacetic acid amides, especially acetoacetic acid anilides, and benzoyl acetic acid anilides, which are optionally substituted in the anilide core with chlorine, bromine, nitro, C 1 -C 4 -alkyl or alkoxy or sulfo groups Can be 20.

Examples of such coupling components are: acetoacet-anilide, acetoacetanilide-4-sulfonic acid, acetoacet-o-anisidide, aceto-aceto-toluidide, acetoacet-o-chloroanilide, acetoacet-m-xylidide.

Coupling component B is preferably an acetes-25-acetic anilide, it being possible for the phenyl group to be substituted by Ci-C4-alkyl, Q-Q-alkoxy, chlorine, nitro or sulfo.

If Z is the CH group, B represents the residue of a 0-hydroxyaldehyde, preferably an o-hydroxybenzaldehyde or o-hydroxynaphthaldehyde, which is substituted by low molecular weight alkyl, halogen, sulfo, phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo can be. Examples of suitable aldehydes are: 2-hydroxy-1-naphthaldehyde, 1-hydroxy-2-naphthaldehyde, 2-hydroxy-benzaldehyde, 3- and 5-methyl-2-hydroxybenzaldehyde, 3,5-dimethyl-2-hydroxybenzal-35 dehyde, 5-butyl-2-hydroxybenzaldehyde, 5-chloro or 5-bromo

2-hydroxybenzaldehyde, 3-chloro-2-hydroxybenzaldehyde, 3,5-dichloro-2-hydroxybenzaldehyde, 5-sulfo-2-hydroxybenzaldehyde,

3-methyl-5-chloro-2-hydroxybenzaldehyde, 5- (phenylazo) -2-hydroxybenzaldehyde, 5- (2'-, 3'- or 4'-sulfophenylazo) -2-

40 hydroxybenzaldehyde, 5- (6'-sulfonaphthyl-l'-azo) -2-hydroxybenzaldehyde or 5- (4 "-sulfo-4'-phenylazo) phenylazo-2-hydroxy-benzaldehyde.

Ka® represents a cation, for example an alkali application, such as lithium, potassium or preferably sodium. Furthermore, 45 Ka® can be an ammonium cation or the ammonium salt of an organic amine.

Suitable radicals R1 in the dyes of the formula (1) are, for example:

Is hydrogen, acetyl, propionyl, Butyiyl, isobutyryl, Valeiyl, 50 Isovaleiyl, pivaloyl, Capronyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-pentoxycarbonyl, methylsulfonyl, Ethylsulfo-nyl, butylsulfonyl, phenylsulfonyl, benzoyl or Phenoxycarbo-nyl, where the phenyl groups in the three latter compounds may be substituted, for example by nitro, halogen, such as 55 bromine or especially chlorine, Q-C4-alkyl or alkoxy.

R1 is preferably hydrogen, acetyl, methoxycarbonyl, benzoyl, phenylsulfonyl or methylphenylsulfonyl and in particular hydrogen, methoxycarbonyl or acetyl.

Preferred radicals Y1 are sulfo, chlorine, methyl, sulfonamide, 60 N-methylsulfonamide and methylsulfonyl, sulfo being particularly preferred.

Preferred radicals Y2 are hydrogen, sulfo, chlorine or methyl, especially hydrogen.

Particularly preferred dyes according to the invention correspond to the formula

672 136

4th

^ V w

A -N = Z -B

3 Ka

© (2)

wherein

R2

Z A1

B1

Hydrogen, acetyl, methoxycarobnyl, benzoyl, phenylsulfonyl or methylphenylsulfonyl,

Nitrogen or a CH group,

the remainder of an l-hydroxy-2-aminobenzene, which is optionally substituted by halogen, nitro, sulfo or low molecular weight alkyl or alkoxy, or the remainder of an l-amino-2-hdroxy-4-sulfonaphthalene, which is optionally substituted in 6- Position is substituted by halogen, such as bromine or in particular chlorine, nitro or sulfo,

if Z is nitrogen, an acetoacetic anilide, where the phenyl group can be substituted by Ci-C4-alkyl, Ci-C4-alkoxy, chlorine, nitro or sulfo, or, if Z is the CH group, the rest of an o-hydroxybenzaldehyde or o-hydroxynaphthaldehyde, which can be substituted by low molecular weight alkyl, halogen, sulfo, phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo, and

Ka® means a cation.

Among these, those are particularly preferred in which R2 is hydrogen, methoxycarbonyl or acetyl, A 'the residue of 4-nitro-2-amino-1-hydroxybenzene, 4-nitro-2-amino-1-hydroxy-benzene-6-sulfonic acid or l-amino-2-hydroxy-4-sulfo-6-nitro-naphthalene, B1, if Z is nitrogen, the remainder of an acetic acetic anilide, where the phenyl group can be substituted by chlorine or sulfo, or, if Z is CH Group is the residue of o-hydroxybenzaldehyde which is unsubstituted or substituted in the p-position by phenylazo, sulfoiphenylazo, naphthylazo or sulfonaphtylazo, and Ka® means a cation.

The dyes of the formula (1) according to the invention can be prepared by methods known per se, for example by using the 1: 1 chromium complex of the azo dye of the formula

? H? H

- Q to the 1 '.2 chromium complex, or by the 1: 1-

Chromium complex of a dye of formula (4) and then reacted with the dye of formula (3).

A, B, Z, X, Y1, Y2, R1 and p have the meaning given under the formula (T s.

The dyes of the formulas (3) and (4) are known or are prepared in a manner known in principle.

The new chromium complex dyes of the formula (1) obtainable by the above process are isolated and suitable in the form of their salts, in particular alkali metal salts, especially sodium, potassium or lithium salts, or also ammonium salts or salts of organic amines with a positively charged nitrogen atom for dyeing and printing various materials, if necessary] in the presence of a leveling agent, but especially for dyeing and printing materials containing nitrogen, such as silk, wool, and also for synthetic fibers made of polyamides or polyurethanes, and especially for leather.

Olive dyeings with good fastness properties are obtained, in particular light and wet fastness properties.

The preferred use of the dyes according to the invention is in the dyeing of wool, polyamide and in particular of furs or leather, all types of leather being suitable, e.g. Chrome leather, retanned leather or suede from goat, beef, sheep or pork. Above all, the dyes according to the invention are suitable for dyeing leather with dye mixtures, in particular in a mixture with one or more suitable 1: 2 metal complex dyes.

The following examples serve to illustrate the invention without restricting it. Parts mean 30 parts by weight and percentages by weight. The temperatures are given in degrees Celsius.

example 1

35

40

45

y.

'i * "

% / *

•

J.l

■ n = n-.

ho3s

^ v ^ /

IN THE

/% / \ y

, nhr

(3)

50

produces and then this with the dye of the formula A - N = Z - B

f °:

° 3S \ f \ / \ • • •

I! I.

• -N = N- *

V / VVNm

I / I 2

o /

V

Ä0 "

^ / À = N-

? ° 3 • •

I I!

V / #

0

4Na

©

(CO) I I 0H

XH

(4)

or a mixture of the amine of the formula

A - Nll "

(Ç0) 011

p and the aldehyde of the formula

HO-B-CHO

(5)

(6)

The 1: 1 chromium complex, which contains 43.9 parts of the dye from diazotized 2-amino-1-hydroxybenzene-4-sulfonic acid and 2-amino-8-hydroxynaphthalene-6-sulfonic acid and 5.2 parts of chroi, is converted into 500 Parts of water are added and 15.4 parts of 60 4-nitro-2-amino-1-hydroxybenzene and 30.6 parts of the monoazo dye from diazotized 2-aminobenzenesulfonic acid and salicylic aldehyde are added. The reaction mixture is then heated to 80 to 85 °, adjusted to pH 7 to 7.5 with sodium hydroxide and kept at this temperature and constant pH until the starting products are no longer detectable. After the addition reaction has ended, the dye is isolated by evaporation. A dark powder is obtained which dissolves in water with an olive green color and dyes leather in real olive tones.

5

672 136

Example 2

° 3S \ A /%

I * I "II *

V y - N = N- «v» / *.

\ y; V V V

l = $ - / x, r

^ / L

e

4 na

. ©

Example 3

? ° 3

/ ^

I *

I.

II I I

•. y— N = N- «. - -

Y / Y V \ "2

JT Cr-tL

: f% -N = CH - »^ X.

\ / ita.

V

ii. »Y / V

ti i \

L

Q

4Na,

©

heated to 80 to 85 °, adjusted to pH 7 to 7.5 with sodium hydroxide and held at this temperature and constant pH until the starting products can no longer be detected. After the addition reaction has ended, the dye is isolated by 5 evaporation. After drying, a dark powder is obtained, which dissolves in water with a green olive color and dyes leather in real olive tones.

Example 4

20th

48.9 parts of the complex chromium compound of the 1 atom chromium type: 1 molecule of dye, which contains 5.2 parts of chromium and 43.9 parts of monoazo dye from diazotized 2-amino-1-hydroxybenzene-4-sulfonic acid, are suspended in 500 parts of water and 2-amino-8-hydroxynaphthalene-6-sulfonic acid, with 15.4 parts of 4-nitro-2-amino-1-hydroxybenzene and 30.6 parts of the monoazo dye from diazotized 3-aminobenzenesulfonic acid and salicylaldehyde. The reaction mixture is then heated to 80 to 85 °, the pH is adjusted to 7 to 7.5 with 5N sodium hydroxide solution and the reaction mixture is kept at this temperature and constant pH until the starting products are no longer detectable. After the addition reaction has ended, the dye is isolated by spray drying. A dark powder is obtained which dissolves in water with an olive green color and dyes leather in real olive tones.

25th

30th

° 3S \ A /%

©

5Na

The 1: 1 chromium complex, which contains 43.9 parts of the dye from diazotized 2-amino-l-hydroxybenzene-4-sulfonic acid and 2-35 amino-8-hydroxynaphthalene-6-sulfonic acid and 5.2 parts of chromium, is in 500 parts of water were added and 23.4 parts of 4-nitro-2-amino-l-hydroxybenzene-6-sulfonic acid and 35.6 parts of the monoazo dye from diazotized 1-aminonaphthalene-6-sulfonic acid and salicylaldehyde were added. The reaction mixture 40 is then heated to 80 to 85 °, adjusted to pH 6.5 to 7 with 5N sodium hydroxide and kept at this temperature and constant pH until the starting products have disappeared. The dye obtained is then isolated by evaporation. After drying, a dark powder is obtained which dissolves in water with an olive green color and dyes leather in very real olive tones.

Examples 5 to 42

the procedure is as described in Examples 1 to 4, but uses the 1: 1 chromium complex of the azo dye listed in column 2 in the following table and sets this with the azomethine dye listed in column 3 or with the amine and aldehyde forming it um, 55 1: 2 chromium complexes are obtained, which have the shade listed in column 4 and dye leather with good fastness properties.

60

The 1: 1 chromium complex, which contains 43.9 parts of the dye from diazotized 2-amino-l-hydroxybenzene-4-sulfonic acid and 2-amino-8-hydroxynaphthalene-6-sulfonic acid and 5.2 parts of chromium, is converted into 600 Parts of water are added and 15.4 parts of 4-nitro-2-amino-1-hydroxybenzene and 35.6 parts of the coupling product of diazotized l-aminonaphthalene-6-sulfonic acid and salicylaldehyde are added. The reaction mixture is thereupon

672 136

6

N °

Azo dye

Azomethine dye

nuance

5

OH OH

A 'AA / n *

r. r "»; • • • • •

HO S7 V

K

3rd

<j) H (j) H

A A 5 Y »- ™ Y s 5n"

\ /% /? 3 • • •

ào2 À = N-.7 \

V

olive

6

(j) H (j) H

A N M AA / h2

il rN = N "i m î • • • • •

X ^ un Q / ^ X ^ • HO S • •

OH OH

H03s \ .A N CH A

• • —N = CH- * •

11 1 I II

•. • §v •

• • •

Äo2 I! I = N - «/ N

V

olive

•

1 "

7

OH OU • v • • NH

• «-N = N-» • •

ii 1 1 ii 1

•, # • •

\ * HO </ ^ 7 X ^ • HO S • •

SO3H

(pH <j) H

/ VN, clI - / \ • • • •

W ^ / • •

Ào2

olive

8th

do

(j) H (j) H

/ y ».cH- / xj •. • • •

\ S ^ / • •

Ä02 tUlj!

A

• m i n% / *

•

olive

9

do

<j> H <j) H

• y0 * v •

\ ^ ^ /

1 1 4 \ no2 n = n- ».

V \ o3

olive

H

10th

do

<pH <j) H

{N-b - chY \

\ S% / f00 "• • •

N02 iUN- ^ \ • •

V

brown-tinged olive

11

do

(pH

• • •

\ S% / • • •

i t <? \ N02 N = N-y.

'V \ u olive

7

672 136

N °

Azo dye

Azome tli in dye £

nuance

12

<j) H (pH

A NN A A / h2

. .-N = N_. . .

\ To SA / \ s'

• HO S • •

ÔO3H

(pil (pu ho3s \ A NrH A

Il rN = CH "î II \ /% / *

• •

ÀO À = Ij]

A A • • •

1 II 1 • • •

\ \ S • •

^ O3H

olive

13

do

<pH <pH N = CH - «^

V v ". F3"

AO2 À = N- / Y N

% / \ / • •

äOjH

olive

14

Oli (pH •. * • nh

/ yN = Ny y yïo VHOAV ^

é03H

OH OH

"° 3S \ A n>" CH3

n r ~ N = N ~ c \

\ / co ~ f ho J

2 1 II% / *

•

olive

15

<pH <pH

/% „„ AA / f s »r ço och

• HO S • • 3

SO3H j do do

16

OH OH • • • NH

7 ^ M M / N X ^ A

Il i-N = N "î 11 î CO • • • • •

N ^ un </ ^ X ^ Ì

L H 3 "'S X * s -j 1 ii

#v *

V

do do

17th

OH OH

A NN AA;

• • -N = N- «• • i

Il 1 1 I! I S0o

• • • • • ï Z

N ^ un c; / ^ / \ ^ A • HO. S • •? \

îo h î n

V

èH3

CpH Cj> H

/ ^ s \

li | -N = CH "T m

\ /% / * • •

ÀO À = Iji

A • •

in % /'

•

do

65

672 136

8th

N °

AzoCarbstofC

Azomethine color shade E

nuance

18th

OH OH

• • • NH

{Yn = nY Y Yjf °

• • • * • (V H

\ ^ Hn </ ^ / \ ^ 2 5

• HO S • •

SO H

OH OH H03S \ A / "" 'B

. YN = N-C (

\ s c ° - ^

L

2 1 II • •

•

do

19th

<j> H <j) H

A M NT A / NH2

. .-N = N-. . . • • • • •

\ S / \ \ S HO S x. V

S03H

OH OH

î'V-'C'V

\ / CO-KH - 7 y io2 V

brown-tinged olive

20th

do

OH OH

A ^ "ch3

. X.-N = N-C; J - •

io2 »H2 V

olive

Dyeing instructions for leather

100 parts of suede clothing (dry weight) are rolled on at 50 ° in a solution of 1000 parts by volume of water and 2 parts of ammonia 24% for 2 hours and then at 60 ° in a solution of 1000 parts of water, 2 parts of ammonia 24% and 6 parts Dye from Example 1 colored for 1 hour. Then a solution of 40 parts by volume of water and 4 parts of 85% formic acid is added and the dyeing is continued for a further 30 minutes. Then the leather is rinsed well and optionally treated with 2 parts of a dicyandiamide formaldehyde condensation product for 30 minutes at 50 °.

Other suede and glove leather can be dyed in the same way.

The olive dyeings obtained in this way are distinguished by good fastness properties and good hiding power.

30 Coloring instructions for polyamide

100 parts of polyamide knitting yarn are introduced at 50 ° into a dyebath which contains 2 parts of the dye of Example 14.4 parts of ammonium sulfate and 2 parts of a leveling agent per 4000 parts of water. The liquor is brought to the boil over the course of 45 minutes and kept at the boiling temperature for a further 45 minutes. The paint is then removed, rinsed thoroughly with cold water and dried. An olive-colored polyamide with good fastness properties is obtained.

40

Color specification for wool

100 parts of wool knitting yarn are introduced at 50 ° into a dyebath containing 2 parts of dye of Example 14.4 parts of 80% acetic acid and 2 parts of a leveling aid 45 per 4000 parts of water. The hotte is brought to the boil over the course of 45 minutes and held at the boiling temperature for 45 minutes. The material to be dyed is then removed, thoroughly rinsed with cold water and dried.

An olive-colored wool with good fastness properties is obtained.

G

Claims (11)

672136 1 11 M M '11 1 • • —n = n— • • • y / y v w 0. / 0 .e (1) B X Y1 Y2 R1 2. Dyes according to claim 1, wherein A is the residue of an l-hydroxy-2-aminobenzene, which is optionally substituted by halogen, nitro, sulfo or low molecular weight alkyl or alkoxy, or the residue of an l-amino-2-hydroxy-4- sulfonaphthalene, which is optionally substituted in the 6-position by halogen, such as bromine or in particular chlorine, nitro or sulfo. (2) bliss R2 wherein Z nitrogen or a CH group, A is an optionally further substituted radical of the benzene or naphthalene series which is in the o-position to the azo or Azomething group carries a hydroxyl or carboxy group, the rest of an acetoacetic acid amide or benzoylacetic acid anilide if Z is nitrogen, the acetoacetic acid amide or benzoylacetic acid anilide containing group X in the a-position to the azo group, or the rest of an o-hydroxyalde hydrate if Z represents the CH group, Oxygen means Sulfo, chlorine, C1-C4-alkyl, S02-R2, where R2 is Ci-C4-alkyl, or S02-NRR3, where R3 are each independently hydrogen or Q-Q-alkyl, Hydrogen, sulfo, chlorine or Q-Q-alkyl, Hydrogen or a group of the formula -S02Q or - C0- (0) "- Q means, where n is zero or 1 and Q Ci-C5- Is alkyl or phenyl, the phenyl group being replaced by nitro, Halogen, Cj-Cs alkyl or alkoxy may be substituted, p is zero or 1 and Ka® is a cation. 2 Ka © , 2 / v / / y VW , 0 2nd PATENT CLAIMS 1. Unsymmetrical 1: 2 chromium complex dyes of the formula A ° 3SN A A • m • • • i «-N = N-« v Ï Ì 3. Dyes according to claim 2, wherein A is the residue of an l-hydroxy-2-aminobenzene, which is substituted by a nitro group and optionally by a sulfo group. 3 Ka ? ° 3 A ° 3S \ S '\ /% 4. Dyes according to any one of claims 1 to 3, wherein B is an acetoacetic anilide, wherein the phenyl group can be substituted by Ci-Gt-alkyl, Cj-Gt-alkoxy, chlorine, nitro or sulfo, and wherein Z is nitrogen. 5. Dyes according to any one of claims 1 to 3, wherein B represents the residue of an o-hydroxybenzaldehyde or o-hydroxynaphthalene dehyde which can be substituted by low molecular weight alkyl, halogen, sulfo, phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo, and in which Z is the -CH group. 6. Dyes according to one of claims 1 to 5, wherein R1 is hydrogen, acetyl, methoxycarbonyl, benzoyl, phenylsulfonyl or methylphenylsulfonyl. 7. Dyes according to claim 6, wherein R1 is hydrogen, methoxycarbonyl or acetyl. 8. Dyes according to one of claims 1 to 7, wherein Y1 is sulfo, chlorine, methyl, sulfonamide, N-methylsulfonamide or methylsulfonyl. 9. Dyes according to one of claims 1 to 8, wherein Y2 is hydrogen, sulfo, chlorine or methyl. 10. Dyes according to claim 1 of the formula Z A1 Bl Hydrogen, acetyl, methoxycarbonyl, benzoyl, phenylsulfonyl or methylphenylsulfonyl, Nitrogen or a CH group, the remainder of an l-hydroxy-2-aminobenzene, which may be halogen, nitro, sulfo or low molecular weight. res alkyl or alkoxy is substituted, or the residue of an l-amino-2-hydroxy-4-sulfonaphthalene, which is optionally substituted in the 6-position by halogen, such as bromine or in particular chlorine, nitro or sulfo, if Z is nitrogen, an acetoacetic anilide, where the phenyl group can be substituted by Ci-C4-alkyl, Ci-C4-alkoxy, chlorine, nitro or sulfo, or if Z is the Is CH group, the residue of an o-hydroxybenzaldehyde or o-hydroxynaphthaldehyde, which can be substituted by low molecular weight alkyl, halogen, sulfo, phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo, 3o and Ka® means a cation. 11. Dyes according to claim 10, wherein R2 is hydrogen, methoxycarbonyl or acetyl, A1 is the rest of 4-nitro-2-amino-1-hydroxybenzene, 4-nitro-2-amino-l-hydroxybenzene-6-sulfone-35 acid or l-amino-2-hydroxy-4-sulfo-6-nitronaphthalene, B1, if Z is nitrogen, the residue of an acetoacetic anilide, where the phenyl group can be substituted by chlorine or sulfo, or, if Z is the CH group, the residue of o-hydroxy-benzaldehyde, which is unsubstituted or in the p-position by 40 Phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo is substituted, and Ka® means a cation.