CH619480A5 - Process for preparing phthalocyanine-azo dyes - Google Patents

Description

The present invention relates to a process for the preparation of valuable water-soluble green phthalocyanine azo dyes, which can have fiber-reactive properties, of the formula

• <S03H) lc

R.

pc

(so2-n

\

r,

(I)

s ° 2-n ar

«3

coor

~ rn what

A = the group - NH—, -CO-NH -, - S02-NH— or

-so2-,

B = the residue of an optionally substituted mono- or dinuclear aromatic hydrocarbon,

X = the vinyl, β-hydroxyethyl or an ethyl group substituted in the β position by a group which can be split off by means of alkalis, such as an acyl or acyloxyethyl radical, for example a β- (arylsulfonyloxy) -, such as phenylsulfonyloxy-, ß- (3 -Carboxyphenylsulfonyloxy) -, ß- (alkylsulfonyloxy) -, such as ß- (methylsulfonyloxy) -, ß- (aryl- or ß- (alkylsulfonyloxy) -, such as ß-acetoxy-, ß- (3-sulfo-benzoyloxy) -, a ß-chloro-, ß-thiosul-fato-, ß-sulfato-, ß-phosphato-, ß-phenoxy-, ß- [di- (lower alkyl) amino] - or a ß- [tri- (lower Alkyl) ammonium halide] ethyl radical, but preferably the vinyl, β-chloroethyl, β-thiosulfatoethyl, β-dialkylaminoethyl group with 1 to 4 carbon atoms in each alkyl radical, for example the β-dimethylaminoethyl and β -Diethylaminoethyl group, or the ß-sulfato-ethyl group or the ß-phosphatoethyl group or ß-hydroxy-ethyl group.

Pc = the remainder of a metal-containing or metal-free phthalocyanine ar = the remainder of an optionally substituted mono- or dinuclear aromatic or araliphatic hydrocarbon, the alkylene chain of which is bonded to the SO2-N group

55

I.

R,

is

R! = Hydrogen, optionally substituted alkyl with 1-6 C atoms, phenalkyl or naphthalkyl with 1-3 C atoms in the aliphatic chain, phenyl or naphthyl, where the aromatic nuclei can optionally carry further substituents,

R2 = hydrogen, optionally substituted alkyl with 1-6 C atoms or unsubstituted alkyl with 7-20 C atoms,

R3 = hydrogen, optionally substituted alkyl having 1-6 C atoms,

R4 = hydrogen or optionally substituted alkyl

5

619 480

with 1-6 C atoms or unsubstituted alkyl with 7-18 C atoms,

k = for the numbers 0,1, 2 or 3,

1 = for 0.1 or 2,

m = for 1,2,3 or 4,

n = 0 or 1 and p = 0.1 or 2 and the sum of k, I and m is 2, 3 or 4, preferably 3 or 4, and their salts, in particular alkali metal, such as sodium or potassium -, The ammonium or the alkaline earth metal, such as calcium salts. This process according to the invention is characterized in that an amine of a phthalocyanine compound of the formula

(S03H) k

R5-OOC-CH2-C H-COOR'4 I

CO-Z

III

wherein

R'4 = optionally substituted alkyl with 1-6 C atoms or unsubstituted alkyl with 7-18 C atoms,

R5 = optionally substituted alkyl having 1-6 carbon atoms or unsubstituted alkyl having 7-18 carbon atoms and

Z = hydrogen, an optionally substituted alkyl radical having 1-10 carbon atoms, an optionally substituted phenyl radical or alkoxycarbonyl having 2-6 carbon atoms, couples, and the hydrazones of the formula obtained

(so3H) k pc

(so2-n

/ ri iv

1 R5 ° C / CH2

(S02-N-ar-NH-N-C

COOH

m in which the amino group is bonded to an aromatic C atom of the radical ar and in which Pc, ar, Rb R2, R3, k, 1 and m have the abovementioned meanings, diazotized and in an aqueous medium at a pH from 3-8 with a succinic acid derivative of the formula in which Pc, ar, Rls R2, R3, R'4, R5, k, I and m have the meanings given above, by the action of alkalis in pyrazo-ions of the formula

S ° 3H) k pc

(s0o-n '

Ri

X 1

«• r,

(V)

s0o-n

I.

r,

ar coor i />

U 1

h oh m

wherein

Pc, ar, Rb R2, R3, R4, k, 1 and m have the meanings given above, and these with the diazonium compound of an amine of the formula

H2N- (.

-B- (CH2) p-so2x

(VI)

wherein

A, B, X, n and p have the meanings given above, couples.

Since the phthalocyanine pyrazolones of the formula V which occur as intermediates in the production process were hitherto unknown, there is no relevant prior art. B is preferred

the remainder of a mono- or dinuclear aromatic hydrocarbon which is substituted by a substituent from the group alkyl with 1-4 C-atoms, alkoxy with 1-4 C-atoms, halogen, as in

619 480

6

for example chlorine or bromine, carboxy, hydroxy, nitro, phenylamino or sulfo can be substituted.

In the formulas mentioned above, including in the amines of the phthalocyanine series of the formula II to be used according to the invention, 5 denotes in particular

Pc the rest of a metal-containing phthalocyanine, such as copper, cobalt or nickel phthalocyanine,

ar is the remainder of a mono- or dinuclear aromatic or araliphatic hydrocarbon which is optionally substituted by a -S03H group and which is formed per core by a sub-i <> substituent from the group alkoxy having 1 to 4 carbon atoms, -S02-R6 or an additional —SO3H group, by one or two identical or different substituents ”from the halogen group,

r'i

-S02-N 15

r'2

or -COOH may be substituted, or ar means phenylene, which may optionally be substituted by a —SO3H group and additionally by one to three identical or different alkyl radicals having 1 to 4 carbon atoms, 20

Ri and R '! independently of one another hydrogen, methyl, carboxymethyl, sulfomethyl, one optionally by Cl, Br, OH, alkoxy with 1-6 C atoms, alkanoylamino with 1-6 C atoms, preferably acetylamino, benzoylamino, alkanoyloxy with 1-6 C atoms , preferably acetyloxy, -COOH or 25 -SO3H substituted alkyl radical having 2-6 C atoms, a phenalkyl or naphthalkyl radical having 1-3 C atoms in the aliphatic chain, phenyl or naphthyl, the aromatic nuclei being represented by Cl, Br , OH, alkyl and / or alkoxy with 1-6 C atoms, alkanoylamino with 1-6 C atoms, 3 (1

-COOH or -S03H can be substituted,

R2 and R'2 independently of one another hydrogen, methyl, carboxymethyl, sulfomethyl, one optionally by Cl, Br, OH, alkoxy with 1-6 C atoms, alkanoylamino with 1-6 C atoms, benzoylamino, alkanoyloxy with 1-6 C -Atoms, 35 -COOH or -SO3H-substituted alkyl radical having 2-6 C atoms or an unsubstituted alkyl radical having 6-20 C atoms,

R3 = hydrogen, methyl, carboxymethyl, sulfomethyl,

an alkyl radical optionally substituted by Cl, Br, OH, alkoxy with 1-6 C- 40 atoms, alkanoylamino with 1-6 C atoms, benzoylamino, alkanoyloxy with 1-6 C atoms, -COOH or-S03H with 2-6 Carbon atoms, and

R6 = methyl, carboxymethyl, alkyl with 2 or 3 carbon atoms, benzyl or phenyl, it being possible for the aromatic nuclei to be substituted once or twice by -COOH or -SO3H.

The symbol k stands for the numbers 0,1,2 or 3,

1 for 0.1 or 2 and m for 1.2, 3 or 4

and the sum of k, 1 and m is 3 or 4.

Preferred amines of the formula II to be used according to the invention are those in which Pc denotes the rest of a metal-containing phthalocyanine such as, for example, cobalt or copper phthalocyanine, but in particular the rest of the nickel phthalocyanine.

Ar standing for aliphatic radicals are always bound with an aromatic nucleus to the —NH2 groups, thus in formula I to the pyrazolone nucleus. Mononuclear aromatic or araliphatic radicals which can stand for ar are the optionally substituted radicals phenylene and mono- or poly-phenylene of the general formula

- (cVb

<y in which b is an integer from 1 to 10.

Binuclear aromatic or araliphatic radicals which can represent ar are the optionally substituted radicals naphthylene, mono- or polymethylene-naphthylene of the formula

<CH2) b in which b is an integer from 1 to 3, and the optionally substituted radicals of the formulas

XÎ> C0 <y And

Examples of mono- or dinuclear aromatic or araliphenylene (1,3), 2-carboxy-5-sulfophenylene (1,4,), 2-carboxy-6-

phatic hydrocarbon radicals which are present in the amines of forsulfophenylene (1,4), 3-carboxy-6-sulfophenylene (1,4,), 6-carbo-

mel II for ar can be: 65 oxy-4-sulfophenylene (1,3), 5-carboxy-2-sulfophenylene (1,3),

Phenylene (1,4), phenylene (1,3), 2-sulfophenylene (1,4), 3-sul-2,5-dicarboxyphenylene (1,4), 4,6-dicarboxyphenylene (1,3), 2 -

fophenylene (1,4), 4- or 5-sulfophenylene (1,3), 2-carboxy-chloro-5-sulfophenylene (1,4), 2-chloro-6-sulfophenylene (1,4), 3-

nylene (l, 4), 3-carboxyphenylene (l, 4), 4-, 5- or 6-carboxy-chloro-6-sulfophenylene (l, 4), 6-chloro-4-sulfophenylene (l, 3), 2-

619 480

Chloro-5-carboxyphenylene (1,4), 2,6-disulfophenylene (1,4), 2,5-disulfopylene (1,4), 4,6-disulfophenylene (1,3), 3-chloro-6- carboxyphenylene (l, 4), 6-chloro-4-carboxyphenylene (l, 3), 4-chloro-5-carboxyphenylene (l, 3), 2-methyl-5-carboxyphenylene (l, 4), 2- Ethyl-6-carboxyphenylene (l, 4), 3-ethyl-6-sulfophenylene (l, 4), 6-ethyl-4-carboxyphenylene (l, 3), 6-propyl-4-suIfo-phenylene (l , 3), 5-isopropyl-4-sulfophenylene (1,3), 5-isopropyl-6-carboxyphenylene (1,3,), 4-n-butylene-6-sulfophenylene (1,3), 3-n-butyl -6-sulfophenylene (1,4), 4-tert-butyl-6-sulfophenylene (1,3), 3-isobutyl-6-sulfophenylene (1,4), 2,5-diisopropyl-6-i sulfophenylene (l, 4), 2,4-diethyI-5-carboxyphenylene (l, 3), 2,4,6-trimethyl-5-sulfophenyIen (l, 3), 2-cyanophenylene (l, 4), 4- Cyanophenylene (1,3), 2-cyan-5-sulfophenylene (1,4), 2-tri-fluoromethylphenylene (1,4), 2-methylsulfonylphenylene (1,4), 2-ethylsulfonylphenylene (1,4 4), 4-sulfonaphthylene (1,5), 8-sulfonaphthylene (1,5), 4-sulfonaphthylene (2,6), 2-carboxynaphthylene (1,4), 2-carboxynaphthylene (1,5 5), 5-carboxynaphthy -len (l, 4), 3-carboxynaphthylene (l, 8), 3-carboxynaphthylene (l, 5), 4-carboxynaphthylene (2.6), 4-carboxynaphthylene (2.7), l- Sulfonaphthylene (2,6), 8-sulfonaphthylene (1,3), 4,8-; Disulfonaphthylene (2,6), 3,7-disulfonaphthylene (1,5), 1-sulfo-4-chloronaphthylene (2,6), l-chloro-5-sulfonaphthylene (2,6), 1-chloro-7- sulfonaphthyleii (2,6), 2-chloro-6-sulfonaphthylene (1,4), 1-methyl-4-sulfonaphthylene (2,6), 2-methyl-7-sulfonaphthylene (1,4). The hydrazone group is in the 1-position 2 of the phenyl nucleus or in the 1- or 2-position of the naphthalene nucleus. The following list contains examples of compounds from which further divalent radicals which stand for ar are derived. The positions of the two bonds with which the divalent radicals are on the one hand in the 1-position of the pyrazole (first position specification) and on the other hand to the group -N - (second position specification) of the preparation according to the invention

R3

ren dyes are shown in the second column of the table.

35

Connection from which -ar- is derived

Dipheriyl

2,2 '-dimethyl-diphenyl

Position of the bindings of -ar—

4.4 '

4.4 '

Connection from which position the

-ar— derives. -Ar-'s Bindings

3,3'-dimethoxy-diphenyl 4,4 '

3,3'-dichloro-diphenyl 4,4 '

3,3'-dimethyl-diphenyl 4,4 '

2,2'-disulfodiphenyl 4,4 '

Diphenylethane 4,4 '

Diphenyl ether 4,4 '

2,2'-disulfodiphenylmethane 4,4 '

2,2'-disulfodiphenylethane 4,4 '

3,3'-disulfodiphenylethane 4,4 '

2,2'-disulfo-diphenyl ether 4,4 '

2-sulfamido-diphenylethane 4,4 '

2,2'-disulfamido-diphenylethane 4,4 '

2,2'-di-ß-hydroxyethylsulfamido-4,4 'diphenylethane

Stilbene-2,2'-disulfonic acid 4,4 '

Methyl-phenyl 4, co

1-methyl-phenyl-3-sulfonic acid 4, co

1-ethyl-phenyl-2-sulfonic acid 4, co

1-PropyI-phenyI-3-sulfonic acid 4, co

5-methyl 1-naphthalene-1 sulfonic acid 2, co diphenylamine 4,4 '

6-methoxy-diphenylamine-2'-sulfonic acid 3,4 '4-methyl-diphenylamine-2'-sulfonic acid 3,4' diphenylketone-5,5 '-disulfonic acid 3,3' diphenylketone-3 '-sulfonic acid 3,4' Diphenylsulfone 4,4 '4,4'-dichloro-diphenylsulfone 3,3' 4,4'-disulfo-diphenylsulfone 3,3 '4-methyl-5-sulfo-diphenylsulfone 3,3'

Preferred in the amines of the formula II to be used according to the invention for ar are the optionally substituted radicals phenylene, naphthylene,

-ch

2 "0

-ch "-ch

-ch,

and

The optionally substituted mono- or dinuclear aromatic or araliphatic hydrocarbon radical which ar in the amines of the formula II to be used according to the invention advantageously contains at least one sulfo group or carboxyl group, but also with radicals of the general definition of ar which do not contain an acidic, water-solubilizing group to obtain valuable dyes according to the invention. In addition, ar per core can be replaced by a substituent from the group -OH, alkoxy with 1-4 C atoms, -CN, -CF3, -S02R6 or an additional -S03H group by one or two identical or different

yR> i j /

dene substituents of the groups halogen, -S02 ~ N

\

55

or -COOH may be substituted. If ar is derived from a phenylene residue, it can be added to an existing one

-S03H group can be substituted by one to three identical or different alkyl radicals with 1-4 C atoms.

Amines of the formula II in which ar is phenylene or phenylene substituted by one or two carboxyl groups or by one or two sulfo groups or a naphthylene residue substituted by one or two sulfo groups or a stilbenyl residue substituted by two sulfo groups are particularly preferred, and in particular those in which ar is a residue of the formula

619 480

S ° 3H

SO

s ° 3h or

■ O

s03h

/,, \ h h. .

/ Vc = c- / ^

• <3-

so3h

1i0..s

15

-0-

s'o3M

S0.il s is, the position shown here corresponds to the position in formula I.

Of the amines of the formula II, which ar a / R'i

—S02 — N \ group, those in r'2 are preferred

which Rj and R't independently of one another are hydrogen, an alkyl radical with 2 or 3 C atoms, methyl, carboxymethyl or sulfomethyl, which is optionally substituted by OH, alkoxy with 1-3 C atoms, -COOH or —S03H, and also those in which R2 and R'2 independently of one another are an alkyl radical with 2 or 3 carbon atoms which is optionally substituted by OH, alkoxy with 1-3 C atoms -COOH or SO3H or an unsubstituted alkyl radical with 1-20 C atoms, but especially hydrogen, Is methyl, carboxymethyl or an alkyl radical which is optionally substituted by OH and has 2 or 3 carbon atoms.

Particularly preferred meanings for Rj and R2 are hydrogen, methyl or β-hydroxyethyl. Likewise, hydrogen, methyl and β-hydroxyethyl are particularly preferred meanings of R 'j and R'2.

Amines of the formula II are particularly preferred which carry no further substituents in the divalent radical ar apart from carbon and sulfonic acid radicals.

Further preferred groups of amines of the formula II to be used according to the invention are characterized in that R3 is hydrogen, methyl, carboxymethyl, sulfomethyl or an ethyl radical which is optionally substituted by Cl, OH, alkoxy with 1 or 2 C atoms, -COOH or -SO3H, in particular hydrogen or Methyl means.

Of the amines of formula II which contain a —SO2 — R6 group in ar, preferred are those in which R6 is methyl, ethyl, phenyl or carboxymethyl.

Those amines of the formula II to be used according to the invention in which 1 = 0, k = 2 or 3 and m = 1 or 2 and the sum k + m = 4 are particularly preferred.

The substituents indicated in formula II can be in the 3 or 4 positions of the phthalocyanine. The 3-position of the stated substituents is preferred. 3 positions are the 3, 3 ', 3 "and 3"' positions, 4 positions are the 4,4 ', 4 "and 4"' positions of the phthalocyanine.

The amines of the formula II required for the preparation of the dyes of the formula I according to the invention are obtained in the event that 1 is 0 by reaction of phthalocyanine-3-or -4-di-, tri- or preferably tetrasulfochlorides with amines of the formula

HN -ar-NH,

R,

wherein R3 and ar have the meanings given above. Instead of the amines of formula X, mono-acylated amines, e.g. B. acetylated amines of the formula

H

HN -ar-N-C -CH,

Xa

R,

O

30th

be used. In this case, the condensation product formed is then saponified with phthalocyanine sulfochloride.

If 1 in formula I or IV stands for the number 1, the phthalocyanine-3- or -4-sulfochloride is obtained in any order with an amine of the formula to obtain the amines of the formula II

/ Rl

\ r.

HN:

XI

45

50

in which Rt and R2 have the meanings given above and reacted with an amine of the formula X.

In addition, however, it is also possible to start from the beginning with a mixture of the amines of the formulas X and XI. The reaction of the phthalocyanine sulfochloride with the amines mentioned is carried out in a manner known per se by adding the amines either in succession or in a mixture to give a concentrated aqueous suspension of the sulfochlorides in water or a mixture of water with organic, water-miscible solvents. However, it can also be carried out alone in organic solvents. The temperature of the reaction mixture is kept at 0 to 35 ° C. and the pH, which constantly shifts into the acidic range during the reaction, is kept between 4 and 10, preferably between 6 and 8, by the gradual addition of alkali. The usual alkaline substances such as 60 sodium hydroxide solution, soda, potash, trisodium phosphate come into consideration as alkali. Sodium hydroxide solution is preferred. To accelerate the reaction, a tertiary amine such as e.g. Added pyridine in catalytic amounts. It is possible to further process the amines of the formula II directly in the aqueous solution in which they are obtained, but it is generally advantageous to isolate them in order to separate them from any remaining unreacted amine Exempt formula X and / or XI.

9

619 480

The following may be mentioned as amines of the formula XI which can be used to prepare the amines of the formula II:

Ammonia methylamine dimethylamine ethylamine diethylamine ß-hydroxyethylamine ß-methoxyethylamine bis-ß-hydroxyethylamine aminoacetic acid taurine

N-methyl taurine

Butylamine

Caprylamine

Laurylamine

aniline

Toluidine

Chloraniline

Aniline-o-, m- or p-sulfonic acid Aniline-o-, m- or p-carboxylic acid N-methylaniline

N-ethylaniline o, m or p-sulfonic acid

Aniline-ro-methane-sulfonic acid

Benzylamine

N-β-hydroxyethyl-benzylamine

Benzylamine sulfonic acid

ß-acetylaminoethylamine

The following may be mentioned as examples of amines of the formula X which can also be used in the form of the monoacyl compound:

p-phenylenediamine N-methyl-p-phenylenediamine N-carboxymethyl-p-phenylenediamine m-phenylenediamine

N-β-hydroxyethyl-m-phenylenediamine l, 4-phenylenediamine-2-sulfonic acid l-amino-4-N-sulfomethylamino-phenylene-2-sulfonic acid l, 4-phenylenediamine-2,5- or 2,6-disulfonic acid l -Amino-4-N-methylamino-phenylene-2,6-disulfonic acid l, 3-phenylenediamine-4-sulfonic acid

1,3-phenylenediamine-4,6-disulfonic acid

2,4-diamino-toluene-5- or 6-sulfonic acid 2,6-diamino-toluene-4-sulfonic acid

2,5-diamino-1,3,5-trimethylbenzene-4-sulfonic acid

2,6-diamino-l, 3-diethylbenzene-4-sulfonic acid

2,4-diamino-l-chlorobenzene-6-sulfonic acid

2,4-diamino-l-tert-butyl-benzene-6-sulfonic acid

2,4-diaminotoluene 5- or 6-sulfamide

2,6-diaminotoluene-4-ethanol or diethanolsulfamide l, 4-diaminophenylene-2-dimethylsulfamide l, 3-diaminophenylene-4-sulfanilide l, 3-diaminophenylene-4-ß-hydroxyethylsulfone

N-ethyl-p-phenylenediamine

N-propyl-p-phenylenediamine

N-butyl-p-phenylenediamine

N-pentyl-p-phenylenediamine

N -hexyl-p-phenylenediamine

N-ß-hydroxypropyl-p-phenylenediamine

N-β-carboxypropyl-p-phenylenediamine

N-y-chloro-butyl-p-phenylenediamine

N-ô-methoxyl-butyl-p-phenylenediamine

N-ô-propoxy-butyl-p-phenylenediamine

N-ß-acetylamino-ethyl-p-phenylenediamine

N-ß-Butyrylamino-ethyl-p-phenylenediamine

N-Benzoylamino-ethyl-p-phenylenediamine 1-N-methyl-3-amino-benzene-4-sulfonic acid 1-N-butyl-4-amino-benzene-3-sulfonic acid

2,4-diamino-phenol-6-sulfonic acid

2,4-diamino-l-methoxybenzene-5-sulfonic acid

1,5-diaminonaphthalene

1,5-diaminonaphthalene-3-sulfonic acid l, 5-diaminonaphthalene-4-sulfonic acid

1,5-diaminonaphthalene-2-sulfonic acid

1,6-diaminonaphthalene-4-sulfonic acid l, 4-diaminonaphthalene-2-sulfonic acid 1,4-diaminonaphthalene-5-sulfonic acid

1,4-diaminonaphthalene-7-sulfonic acid 1,8-diaminonaphthalene-4-sulfonic acid 2,6-diaminonaphthalene-8-sulfonic acid 2,6-diaminonaphthalene-4,8-disulfonic acid

1,5-diaminonaphthalene-3,7-disulfonic acid 1,4-diaminonaphthalene-5-carboxylic acid l, 4-diaminonaphthalene-2-carboxylic acid l, 8-diaminonaphthalene-3-carboxylic acid 4,4'-diaminodiphenyl 2,2'-dimethyl-4 , 4'-diaminodiphenyl 3,3'-dichloro-4,4'-diaminodiphenyl 4,4'-diaminodiphenyI-2,2'-disulfonic acid 3,3'-dimethoxy-4,4'-diaminodiphenyl

1-Amino-4-aminomethyl-benzene l-amino-4-aminomethyl-benzene.-3-sulfonic acid l-amino-4-ß-aminoethyl-benzene-2-sulfonic acid

1-amino-4-y-aminopropyl-benzene-3-sulfonic acid

2-amino-5-aminomethyl-naphthalene-l-sulfonic acid 4,4'-diamino-diphenylmethane-2,2'-disulfonic acid 4,4'-diamino-diphenylethane-2,2'-disulfonic acid 4,4'-diamino- diphenylethane monosulfamide 4,4'-diamino-diphenylethane disulfamide

4,4'-diaminostilbene-2,2'-disulfonic acid 4,4'-diamino-diphenylmethane

4,4'-diamino-diphenylethane-di-β-hydroxyethylsulfamide

4,4'-diamino-diphenylamine-3-sulfonic acid

3,4'-diamino-6-methoxy-diphenylamine-2'-sulfonic acid

3,4'-diamino-4-methyl-diphenylamine-2'-sulfonic acid

3,3'-diaminobenzophenone-5,5'-disulfonic acid

3,4'-diaminobenzophenone-3 'sulfonic acid

4,4'-diamino-diphenyl sulfone

4,4'-dichloro-3,3'-diamino-diphenyl sulfone

3,3'-diamino-4-methyl-diphenylsulfone-5-sulfonic acid

3,3'-diamino-diphenylsulfone-4,4'-disulfonic acid

In the preparation of the dyes of the formula I according to the invention, an amine of the phthalocyanine series of the formula II is first used, the free amino group being bonded to an aromatic C atom of the rest ar

(so3H) k Pc r (so -N z "1 \ 11

\ N "4

and wherein Pc, ar, R1; R2, R3, k, 1 and m have the meanings given above, diazotized and in an aqueous medium at a pH of 3-8 with a succinic acid derivative of the formula

5

10th

15

2t)

25th

30th

35

40

45

50

55

60

65

619 480

10th

Rs-OOC-OL-C H-C00R'4 I

CO-Z

III

where R'4 and R5 have the meanings given above and? Z is hydrogen, an alkyl radical which is optionally substituted by alkoxy with 1-4 C atoms, alkoxycarbonyl with 2-6 C atoms and has 1-10 C atoms, and is optionally substituted by Cl, Br, alkyl or alkoxy with 1-4 C atoms Substituted phenyl radical or alkoxycarbonyl with 2-6 C atoms means coupled in.

Preferred succinic acid derivatives of the formula III are those in which R'4 is an alkyl radical which is substituted by Cl, OH, alkoxy with 1-4, preferably 1-2 C atoms and has 2-6, preferably 2 C atoms or an unsubstituted Alkyl radical with 1-18, preferably 1-6 C atoms, R5 is an ethyl radical substituted by Cl, OH, alkoxy with 1-2 C atoms or an unsubstituted alkyl radical with 1-18 C atoms and Z is hydrogen, alkyl with 1- 3 carbon atoms, phenyl, methyl, () phenyl or alkoxycarbonyl with 2 or 3 carbon atoms.

Succinic acid derivatives of the formula III are particularly preferred, in which R'4 and R5 are identical and denote methyl or ethyl and Z represents a methyl group.

The diazotization of the amines of the formula II can be carried out in a manner known per se in an aqueous acidic medium by reaction with nitrous acid or an agent which splits off nitrous acid. A salt of nitrous acid, in particular an alkali metal salt such as sodium or potassium nitrite, is generally used as the agent which splits off nitrous acid in a mineral acid medium. In a preferred embodiment, the neutral aqueous solution of 1 mole of an amine of the formula II is mixed with a solution of sodium nitrite in a molar ratio of 1: m and this mixture is then present in at least 2.5 moles, preferably 3 moles per mole, with stirring Allow approximately 5-15% hydrochloric acid diluted in amino group at temperatures between -5 and + 25 ° C, preferably -2 to + 5 ° C. The diazo suspension thus obtained is then reacted with a succinic acid derivative of the formula III at a pH of 3-8, preferably between 4.5 and 5.5, by, for example, B. the succinic acid derivative to the acid suspension of the diazonium compounds and then the pH by adding alkali, for. B. sodium hydroxide, soda, sodium hydrogen carbonate, sodium acetate, potassium carbonate or sodium phosphate, to the desired value. After stirring for 1-3 hours, the diazotized amine is no longer detectable and the formation of the hydrazone is complete. Salting out, i.e. by adding a neutral water-soluble salt, such as sodium or potassium chloride, from the solution. However, the deposition is by no means necessary for further processing of the hydrazones, rather it is expedient and advantageous to directly use the reaction solutions obtained in the coupling for further processing.

The aqueous medium in which the coupling reaction of the diazotized amines of the formula II with the succinic acid derivatives of the formula III is carried out can also contain organic water-miscible solvents, in particular lower aliphatic alcohols, such as, for example, methanol, ethanol or isopropanol. Likewise, known coupling accelerators, such as urea or pyridine, may be present in the coupling reaction.

The second reaction step of the production process according to the invention, the cyclization of the hydrazone IV to the pyrazolone V, is carried out very easily by alkaline treatment f, 5 of the aqueous solution of the hydrazone of the formula IV at temperatures between 0 and 100 ° C., preferably 15 to 30 ° C. a pH of 8-14 with elimination of the alcohol

Formula R5OH. The cyclization can be coupled with saponification of the group -COOR4 of the resulting pyrazolone to form the free carboxyl group. It is only necessary to work in the vicinity of the upper limit of the specified pH range, for example at pH values from 10 to 14. The cyclization is expediently carried out directly in the reaction solution of the hydrazone of the formula IV which is obtained during the coupling by increasing its pH to 10 to 14, room temperature being generally sufficient. The solution of pyrazolone V thus obtained is expediently a diazo solution of an amine of the formula without isolation of the pyrazolone after cooling to temperatures between −5 and + 35 ° C., preferably +5 to + 20 ° C.

A—) B- (CH2) p - S02 - X

(VI)

in which A, B, X, p and n have the abovementioned meanings, is added and, if necessary, is stirred with cooling at temperatures between -5 and + 25 ° C., preferably +5 to + 15 ° C., until the coupling reaction has ended. During the course of the coupling reaction, which generally ends after only a few minutes, the pH is maintained at values of 3 to 8, preferably 5 to 6, by the successive addition of a buffer substance or an alkali.

The amines of the formula VI are diazotized in a manner known per se in an aqueous medium by reaction with 1 mol of nitrous acid or an agent which splits off nitrous acid in the presence of at least 2 equivalents, preferably about 2.5 equivalents, of a strong acid, based on 1 Mole of amine. A salt of nitrous acid, in particular an alkali metal salt such as sodium or potassium nitrite, is generally used as the nitrous acid-releasing agent in a mineral acid medium.

If the diazonium compound of an amine of the formula VI is coupled to the pyrazolone V in the preparation process according to the invention, the preparation according to the invention of the water-soluble, fiber-reactive phthalocyanine azo dyes is ended after the coupling reaction has ended. This embodiment of the method according to the invention is preferred.

The dye can then be isolated from the aqueous solutions of the phthalocyanine azo dyestuffs obtained by salting out or it can be obtained in the form of a solid dye preparation by spray drying the solutions.

The water-soluble fiber-reactive phthalocyanine dyes which can be prepared according to the invention are outstandingly suitable for dyeing and printing cellulose materials, cellulose-free materials and natural and synthetic polyamide materials. They are characterized by a high fixation yield, especially in printing processes and fixation by dry heat and good washability of the unfixed dye component, and they provide yellow to bluish green dyeings and prints of high brilliance and color strength with very good lightfastness, good wet fastness properties such as washing at 60 ° C and 95 ° C, sea water fastness, sweat fastness acidic and alkaline, chlorine bath water fastness, peroxide fastness, flue gas fastness.

Mixtures of dyes which can be prepared according to the invention, in particular those in which the meanings of k and / or 1 and / or m in the individual components are different, are outstandingly suitable for dyeing and printing cellulosic materials and have the same advantageous properties as the individual dyes. Mixtures of this type are obtained, for example, when starting from the amines of the formula II in the preparation of mixtures according to the invention,

11

619 480

whose individual components differ from one another with regard to the meanings of k and / or 1 and / or m. Mixtures of amines of the formula II, in which one component generally predominates, are normally obtained in their preparation by reacting phthalocyanine sulfo chlorides with amines.

example 1

281 g of 4-aminophenyl-ß-sulfatoethyl-sulfone are dissolved neutral in about 6000 ml of water. The neutral solution is with

70 g of sodium nitrite were added and the mixture was then stirred into 250 ml of 10N hydrochloric acid at 0-3 ° C. When the diazotization is complete, the diazo suspension is added to a solution of N- [3 '- (3-carboxy-5-hydroxy-1-pyrazolyl) -4' -sulfo-phenyl] -Ni-trisulfo-phthalocy-aninylsulfonamide, to which 100 g of sodium bicarbonate had previously been added. The coupling is finished in a few minutes.

The resulting green phthalocyanine azo dye can be isolated by salting out or spray drying. It has the following constitution:

NiPc

(so3h) 3

HO

SOQ-NH_ ^ s ^

XX

»O s02-ch2-ch2-0s03h

COOH

so3H

The phthalocyanine pyrazole solution required for coupling can be obtained in the following way: - s

1060 g of 3- (3-amino-4-sulfo-phenyl) amino-sulfonyl-nickel-phthalocyanine-3 ', 3 ", 3"' - trisulfonic acid, which in the usual way by condensation of nickel phthalocyanine sulfochloride with 1,3-diaminobenzene -4-sulfonic acid had been prepared, stirred with 7000 ml of water and dissolved by adding 400 ml of 1.1 lOn sodium hydroxide solution. This solution is mixed with 72 g of sodium nitrite and then concentrated over a period of 30 minutes in a mixture of 2000 g of ice and 300 ml. Hydrochloric acid stirred in. A temperature of 0 to 5 ° C is maintained by adding another 2000 g of ice. After a short time, any excess of nitrite is destroyed by adding aminosulfonic acid. 21 g of dimethyl acetylsuccinate are poured into the diazo suspension thus obtained. Subsequently, the pH is first sprinkled from about 13 g of soda to 5.5 and then with about 21 g of sodium bicarbonate at 5 to 6 4 (1

held. The mixture is then stirred for about 1 hour. The end of the reaction can be recognized by the fact that the pH remains constant and that no color change occurs when a sample is mixed with a solution of H-acid in 2N soda. 45

The solution of the dimethyl oxaloacetate-3- (nickel-trisulfo-phthalocyaninylsulfonylamino) -6-sulfophenylhydrazone thus obtained is mixed with 350 ml 10 l alkali, whereby the pH rises to values from 12 to 13. Stir for a few hours 50, preferably overnight, at room temperature. The rearrangement to N- [3- (3-carboxy-5-hydroxy-l-pyrazolyl) -4-sulfo-phenyl] -nickel-trisulfo-phthalocyaninyl-sulfonamide is then complete; the pH is reset to 8 with a little hydrochloric acid and the crude solution obtained is used directly for coupling 55.

Dyes with similar properties are obtained

if instead of the 4-aminophenyl-ß-sulfatoethyl-sulfone equivalent amounts of the following amines are used: 3-aminophenyl-ß-sulfatoethyl-sulfone, m

3-amino-4-methoxyphenyl-ß-sulfatoethyl-sulfone,

4-amino-3-methoxyphenyl-ß-sulfatoethyl-sulfone, 3-amino-4-methylphenyl-ß-sulfatoethyl-sulfone,

3-amino-4-sulfophenyl-ß-sulfatoethyl-sulfone,

4-amino-3-bromophenyl-ß-sulfatoethyl-sulfone, h $ 4-amino-3,5-dichlorophenyl-ß-sulfatoethyl-sulfone, 3-amino-4-carboxyphenyl-ß-sulfatoethyl-sulfone, 3-amino- 4-hydroxyphenyl-ß-sulfatoethyl-sulfone,

4-amino-3-hydroxyphenyl-β-sulfatoethyl sulfone,

4-amino-2,5-dimethoxyphenyI-ß-suIfatoäthyIsulfon,

4-amino-2-methyl-5-methoxyphenyl-ß-sulfatoethyl-suIfon,

4-aminophenyl-β- (N, N-dimethylamino) ethyl sulfone,

4-aminophenyl-β- (N, N-diethylamino) ethyl suIfon,

4-aminophenyl-ß-phosphatoethylsulfone,

4-aminophenyI-β-thiosulfatoethylsulfone,

4-aminophenyl-ß-chloroethylsulfone,

3-aminophenyl-ß-chloroethylsulfone,

4-aminophenyl vinyl sulfone,

4-amino-3-chloro-5-methylphenyl-ß-sulfatoethyl-sulfone,

3-aminobenzyl-ß-sulfatoethylsulfone,

ß- (4-aminophenyl) ethyl-ß-sulfatoethylsulfone,

3-nitro-4- (4'-aminophenyl) -aminophenyI-ß-sulfatoethyl-sulfone,

2-phenylamino-5-aminophenyl-β-sulfatoethylsulfone,

4- (4'-aminophenylsulfonyl) phenyI-ß-sulfatoethylsulfone,

3- (4'-aminobenzoyl) -aminophenyl-β-sulfatoethyIsulfone,

3- (3'-aminophenylsulfonyl) aminophenyl-β-sulfatoethyI-sulfone,

4-aminonaphthyl- (l) -ß-sulfatoethylsulfone,

5-aminonaphthyl- (l) -ß-sulfatoethyIsuIfon,

6-aminonaphthyl- (l) -ß-sulfatoethylsulfone, 6-aminonaphthyl- (2) -ß-sulfatoethylsulfone, 6-amino-l-sulfonaphthyI- (2) -ß-sulfatoethylsulfone, 8-amino-naphthyl- (2) - ß-sulfatoethylsulfone, 8-amino-6-sulfo-naphthyl- (2) -ß-sulfatoethylsulfone.

If the condensation product of nickel phthalocyanine sulfochloride and 1,3-diaminobenzenesulfonic acid is used to produce the coupling component instead of the above-mentioned condensation product of nickel kelphthalocyanine sulfochloride and 1,3-diaminobenzenesulfonic acid and one of the amines mentioned below, and the procedure is as described, valuable green compounds are also obtained Reactive dyes: 1,4-phenylenediamine-2-sulfonic acid

1,3-phenylenediamine-4,6-disulfonic acid

1,4-phenylenediamine-2,5-disulfonic acid l, 4-phenylenediamine-2,6-disulfonic acid 2,4-diaminotoluene-6-sulfonic acid 2,6-diaminotoluene-4-sulfonic acid

2,4-diamino-l, 3,5-trimethylbenzene-6-sulfonic acid, 2,6-diaminonaphthalene-4,8-disulfonic acid

1,5-diaminonaphthalene-2-sulfonic acid

2,6-diaminonaphthalene-8-sulfonic acid

619 480

12

1-amino-4-aminomethyl-benzene-3-sulfonic acid

2-amino-5-aminomethyl-naphthalene-1 -sulfonic acid 4,4'-diamino-diphenylamine-3-sulfonic acid 3,3'-diamino-4-methyl-diphenylsulfone-5-sulfonic acid

1,3-phenylenediamine (acetyl derivative, then saponified)

2,4-diaminotoluene (acetyl derivative, then saponified)

1,4-phenylenediamine (acetyl derivative, then saponified)

4,4'-diamino-diphenylethane-2,2'-disulfonic acid

4,4'-diamino-diphenylethane-mono-suifamide

4,4'-diamino-diphenylethane disulfamide

4,4'-diaminostilbene-2-2'-disulfonic acid

4,4'-diamino-diphenylamine-3-sulfonic acid

3,4'-diamino-6-methoxy-diphenylamine-2'-sulfonic acid

3,4'-diamino-4-methyl-diphenylamine-2'-sulfonic acid

3,3'-diaminobenzophenone-5-5'-disulfonic acid

3,4'-diaminobenzophenone-3'-sulfonic acid

4,4'-diamino-diphenyl sulfone

4,4'-dichloro-3-3'-diamino-diphenyl isulfone

3,3 '-Diamino-4-methyl-1-diphenylsulfone-5-sulfonic acid

3,3'-diamino-diphenylsulfone-4-4'-disulfonic acid

Example 2

281 g4-aminophenyl-ß-sulfatoethyl-sulfone are dissolved neutral in about 6000 ml of water. After the addition of 70 g of sodium nitrite, the solution is allowed to flow into 250 ml of 10N hydrochloric acid, and the diazo suspension thus obtained is then added, as described in Example 1, to a solution of the 535 g of 3,3'- described as described below. Bis - [(4-aminophenyl) amino sulfonyl] nickel phthalocyanine-3 ", 3 '" disulfonic acid prepared bispyrazolones. The pH is then adjusted to 7-7.2 with 4N sodium carbonate solution and the resulting green dye is isolated by salting out or spray drying. The dye has the following constitution:

NiPc '

- (so3h)?

= n ^^ So2-ch2-CH2-oso3H),

The bispyrazolone () used as the coupling component was prepared in the following way:

535 g of 3,3'-bis [64-aminophenyI) -amino-suIfonyl] -nickel-phthalocyanine-3 ", 3 '" - disulfonic acid, prepared in the usual way by condensation of 0.5 mol of nickel phthalocyanine-trasulfochloride with 1 mol of acetyl -p-phenylenediamine and saponification of the condensation product, are stirred with 3500 ml of water and dissolved by adding 200 ml of 10N sodium hydroxide solution. This solution is mixed with 70 g of sodium nitrite and then concentrated over a period of about 30 minutes in a mixture of 2000 g of ice and 300 ml. HCl stirred in. By adding a further 40 100 g of ice, the temperature is kept between 0 and 5 ° C. The mixture is stirred for about 10 minutes and then a small excess of nitrite with amidosulfonic acid is removed. 135 g of diethyl acetylberosuccinate are added to the diazo suspension thus obtained. With about 250 g of soda, the pH is adjusted to 45 about 6 and held at this value until the diazo compound is no longer detectable. This gives a solution of the turquoise-colored 3,3'-bis [4- (1,2-bis-ethoxycarbonyl-ethyl-den) -hydrazino-phenyl-aminosu] fonyl-] nickel'phthalocyanine-3 ", 3" '- disulfonic acid, which is converted into the corresponding bispyrazolone directly by the action of alkali in 50, by adding about 400 ml of 10N sodium hydroxide solution and stirring for about 4 hours at room temperature.

If the corresponding 4,4 ') 4 ", 4"' derivative is used instead of the amine used above, valuable phthalocyanine hydrazones are also obtained.

If, instead of the amine used above, as the diazo component for the pyrazolone stage, the condensation product of nickel phthalocyanine sulfochloride with two moles of one of the amines listed in the table below and 60 is used as described above, green phthalocyanine azo dyes are also obtained.

1,3-phenylenediamine (acetyl derivative, then saponified)

2,4-diaminotoluene (acetyl derivative, then saponified) 2,4-diaminoanisole (acetyl derivative, then saponified) 1,4-phenylenediamine-2-sulfonic acid 2,4-diaminotoluene-6-sulfonic acid

4-amino-benzylamine (4-acetyl derivative, then saponified)

55

4,4'-diaminostilbene disulfonic acid

4,4'-diaminomethane disulfonic acid

4,4'-diamino-diphenylamine-3-sulfonic acid

If the ethyl acetylsuccinate used as the coupling component for the pyrazolone stage is replaced by one of the following derivatives of succinic acid, arylhydrazones are also obtained, which according to the invention can be processed into valuable azophthalocyanine dyes

Rs-OOC-CH7-CH-COO-R'4

I.

C-Z

II

II

O

r5

R'4

e.g.

-ch3

-ch3

-H

-ch3

-CjRtCl

-ch3

-ch3

-i-C3H4

-ch3

-ch3

-I-C4H9

-COO-CH3

-ch3

-i-C5Hu

-coo-c2h5

-ch3

-CÄ-oh

-ch3

-ch3

-c3h6-och3

-coo-c3h4

-ch3

-qhJ

-coo-c3h4

-c3h7

-c2h5

-c3h7

-C5Hn

-approx

-ch2-c6h5

-c9h19

-QH5

-coo-ch3

~ Ci6H33

-qh5

-cfihs

-qh4-o-

-c2h5 -c2h5

-c6h4- € h3

65

Example 3

If, instead of the amine given in Example 1, 3 - [(3-amino-4-sulfo-phenyl) amino-sulfonyl-] nickel-phthalocyanine-3 ', 3 ", 3"' - trisulfonic acid, the molar amount of one of the mentioned in the following table

13

619 480

Amines and otherwise operates as indicated there, esters are obtained, which can also be used to convert the correspondingly substituted pyrazolones to valuable hydrazones of methyl oxaloacetate pc

, <S03H) k

(so2-n

R,

(S02-g-ar-NH2) m

R.-h

-H

-H

-H

-H

-H

-H

-H

-H

-h r2

-ch3

-ch2-cooh «

-c2h4-so3h

-c2h4ci

-c2h4oh

R,

h h

ch,

h c, h <

ar k 1 m

-c2h4-o-c2h5 c2h5

-c4h8-nh-coch3 h

-c6h10-nh-coc6h5 h s03h 2 1 1

/ ^

o f ~ \

-Q-ch3

0

sogh ho3s

so3h ho3s s0..h h035

, - <'s03h

-c2h4-so3h

-c3h6-cooh

-c2h4-o-c2h5

-C6H12N-C-CH3 ~ CH2 H II

o o

2 1 1

1 1 2

2 1 1

2 1 1

2 1 1

2 1 1

2 1 1

2 1 1

2 1 1

619 480 Ì4

R] R2 R3 ar k 1 m

- ^^ - SO, F

-H -C9H19 H J VS00H 2 1 1

H -C6H, 3 H ^ "SU3 2 1 1

s ° 3H

-H -C, cH ,, -C4Ho -Il \ v 2 11

\ = / 3

<i

S03E S ° 3h

-h -c20h41 h - \ r 2 1 1

S03H

SO ^ H

-h -c4h9 h _ch2 - / \ 2 1 1

s ° 3h

-h -c3h7 h _ch2- ^ y 2 1 1

so.h

-h -c2h5 h o 2 1 1

ho3s s ° 3h

-ch3 -c2h5 h -fr 2ii ho3s

-c2h5 -c2h5 ch3 Jf \ v 2 11

<s so3h

-c3h7 -c2h5 -ch2-so3h - </ xv 2 11

Q

S03h so3h so3h so3h

-C2H4Br -C2H5 -CH2-S03H J (\ 2 11

O

s03h

O

-c2h4-o-ch3 -c2h5 -ch2ch2-cooh <y 211

-c, ™ -ch, -ch, c "2-cooh -q

m

1

1

1

1

2nd

1

1

1

3rd

2nd

2nd

3rd

4th

1

15

R, R-i ar kl

-c, h, -ch, y 2 1

-c2h5 -ch3 - / \ vc1 2 1

-c2h4oh -ch3 Vßr 2 î

-c2h4oh h 1 1

-c, h4oh h 11

SO,.

T7

-c2h4-s03h h j 1 2

h ° 3s c2h4-so3h h - / y il

O

-c2h4oh h 1 2

h ° °

O

C2H5 - / \ 0CHo 1 0

3rd

S03H

-ch2-cooh h ~ f \ ch 1 1

\ _ / "3

<3

S0jH

H -TV * 10

h - <\ 0 0

SOoH

/ d

W hó3s

Claims (10)

619 480 1-4 carbon atoms substituted phenyl radical or alkoxycarbonyl with 2-6 carbon atoms. 1 R3 is Rj = hydrogen, optionally substituted alkyl with 1-6 C atoms, phenalkyl or naphthalkyl with 1-3 C atoms 55 in the aliphatic chain, phenyl or naphthyl, where the aromatic nuclei can optionally carry further substituents, R2 'is hydrogen, optionally substituted alkyl having 60 1-6 C atoms or unsubstituted alkyl having 7-20 C atoms, R3 = hydrogen, optionally substituted alkyl having 1-6 C atoms and R4 = hydrogen or optionally substituted alkyl with 1-6 C atoms or unsubstituted alkyl with 7-18 C- 6S atoms, and their salts, characterized in that an amine of the formula (S03H) k in which the amino group is bonded to an aromatic carbon atom of the radical ar, diazotized and in an aqueous medium at a pH of 3-8 with a succinic acid derivative of the formula Rs - OOC - CH2 - C H - C00R'4 I. (III) co-z where R'4 = optionally substituted alkyl with 1-6 C atoms or unsubstituted alkyl with 7-18 C atoms, R5 = optionally substituted alkyl with 1-6 C atoms or unsubstituted alkyl with 7-18 C atoms and Z = hydrogen, an optionally substituted alkyl radical with 1-10 C atoms, an optionally substituted phenyl radical or alkoxycarbonyl with 2-6 C atoms, couples and the resulting hydrazones of the formula 619 480 • <S03H) k \ r50-c-çh2 \ COOR l 1 = for 0,1 or 2, 40 m = for 1,2,3 or 4, n = 0 or 1 and p = 0.1 or 2 and the sum of k, 1 and m is 2, 3 or 4, Pc = the remainder of a metal-containing or metal-free phtha-45 locyanin ar = the remainder of an optionally substituted mono- or dinuclear aromatic or araliphatic hydrocarbon, the alkylene chain of which is attached to the S02-N group 2. The method according to claim 1, characterized in that an amine of the phthalocyanine series of the formula II is diazotized, in which Pc = the rest of a metal-containing or metal-free phtha-locyanin, ar = the residue of a mono- or dinuclear aromatic or araliphatic hydrocarbon optionally substituted by a -S03h group, which is per nucleus; by a substituent from the group alkoxy with 1-4 C atoms, -S02R6 or an additional -S03H group, by one or two identical or different substituents of the Group halogen, -so2-n or -COOH can be substituted, or ar means phenylene, which can optionally be substituted by a -S03H group and additionally by one to three identical or different alkyl radicals with 1-4 C atoms, Rt and R'x = independently of one another hydrogen, methyl, carboxymethyl, sulfomethyl, one optionally by Cl, Br, OH, alkoxy with 1-6 C-atoms alkanoylamino with 1-6 C-atoms, preferably acetylamino, benzoylamino, alkanoyl-oxy with 1-6 C-atoms, preferably acetyloxy, -COOH or -S03H substituted alkyl radical with 2- 6 carbon atoms, a phenalkyl or naphthalkyl radical with 1-3 carbon atoms in the aliphatic chain, phenyl or naphthyl, the aromatic nuclei by Cl, Br, OH, alkyl and / or alkoxy with 1-6 carbon atoms , Alkanoylamino can be substituted with 1-6 C atoms, -COOH or-S03H, R2 and R'2 = independently of one another hydrogen, methyl, carboxymethyl, sulfomethyl, one optionally by Cl, Br, OH, alkoxy with 1-6 C atoms, alkanoylamino with 1-6 C atoms, benzoylamino, alkanoyloxy with 1-6 C atoms, -COOH or —S03H-substituted alkyl radical having 2-6 C atoms or an unsubstituted alkyl radical having 6-20 C atoms, R3 = hydrogen, methyl, carboxymethyl, sulfomethyl, one optionally by Cl, Br, OH, alkoxy with 1-6 C atoms, alkanoylamino with 1-6 C atoms, benzoylamino, alkanoyloxy with 1-6 C atoms, -COOH or-S03H substituted alkyl radical with 2-6 C atoms, R6 = methyl, carboxymethyl, alkyl with 2 or 3 carbon atoms, benzyl or phenyl, where the aromatic nuclei can be substituted once or twice by -COOH or -S03H, mean, k = for the numbers 0,1,2 or 3, 619 480 2nd PATENT CLAIMS 1. Process for the preparation of phthalocyanine azo dyes of the formula 35 wherein A = the group -NH—, -CO-NH—, -SQ2-NH— or —so2—, B = the residue of an optionally substituted mono- or dinuclear aromatic hydrocarbon, X = the vinyl, β-hydroxyethyl or an ethyl group substituted in the β position by a group which can be split off by means of alkalis, k = for the numbers 0,1,2 or 3 3. The method according to claim Î or 2, characterized in that an amine of the phthalocyanine series of the formula II is diazotized, wherein Pc means the rest of the cobalt, copper or nickel phthalocyanine. 4. The method according to any one of claims 1 to 3, characterized in that an amine of the phthalocyanine series of formula II is diazotized, wherein 1 = 0, k = 2 or 3 and m = 1 or 2 and the sum k + m = 4 is. 4th I = for 0,1 or 2 and m = for 1,2,3 or 4, stand, and the sum of k, 1 and m is 3 or 4. 5. The method according to claim 1, characterized in that an amine of the phthalocyanine series of the formula II is diazotized, in which the substituents on the Pc radical are in the 3 or 4 positions of the phthalocyanine. 6. The method according to claim 1, characterized in that the diazotized amine of formula II is coupled with a succinic acid derivative of formula III, wherein R'4 and R5 is an alkyl radical substituted by Cl, Br, OH, alkoxy with 1-4 C atoms with 2-6 C atoms or an unsubstituted alkyl radical with 1-18 C atoms and Z is hydrogen, an alkyl radical with 1-10 C- which is optionally substituted by alkoxy with 1-4 C atoms, alkoxycarbonyl with 2-6 C atoms Atoms, one optionally by Cl, Br, alkyl or alkoxy 7. The method according to claim 1, characterized in that the Diazoniumverbin- on the pyrazolone of formula V ? coupling of an amine of formula VI, wherein n and p = 0. 7 (iv) m by the action of alkalis in pyrazolones of the formula S03H) k pc (so2-n- »R. so - n I. R, ar t coor. (v) oh m transferred, and this with the diazonium compound of an amine of the formula h2n - (- A -) B (CH2) p-S02x (vi) couples. 8. The method according to claim 1, characterized in that the diazonium compound of an amine of the formula VI is coupled to the pyrazolone of the formula V, in which B is a phenylene or naphthylene radical. m 9. The method according to claim 1, characterized in that the diazonium compound of an amine of the formula VI is coupled to the pyrazolone of the formula V, where X is the β-sulfatoethyl group. 10. 15 phthalocyanine azo dyes of the formula I prepared by the process according to claim 1