DE2444883A1 - PIGMENT COMPLEXES AND THE PROCESS FOR THEIR PRODUCTION - Google Patents

Description

Dr. F. Zumsteln sen. - Dr. Ξ. Carrion Dr. R. Koenlgsberger - Dipl.-Phys. R. Hotebauer - Dr. F. ZumsteSn] un.

PATENT LAWYERS

TELEPHONE: COLLECTIVE NO. 226341

TELEX 529979

TELEGRAMS: ZUMPAT CHECK ACCOUNT: MUNICH 91139

BANK ACCOUNT: BANK H. HOUSES

8 MUNICH 2.

BRÄÜHAUSSTRASSE 4 / III

97 / N

Case 3-9002 / 9003 / ma 1561

CIBA-GEIGY AG, Basel / Switzerland

Pigment complexes and processes for their preparation

The invention relates to new pigments and, more particularly, to new metallazo pigments and methods of making these pigments.

According to the invention, a metal complex of the formula

-Τι

5098U / 1037

or

R ^!

III

provided in which

A is an aryl or heterocyclic radical,

B is an aliphatic, aryl or heterocyclic radical,

R denotes an alkyl, cycloalkyl, aryl, aralkyl or heterocyclic radical or R represents the atoms which together with the radical B are necessary to complete a heterocyclic radical,

R ¹ and R "each represent a carbon chain which may form part of an aromatic or heterocyclic ring, R 'having 2 to 3 carbon atoms between the nitrogen atom and the substituent Y and R" having 1 to 3 carbon atoms between the substituents X and Y having,

X and Y, which may be the same or different, each represent 0, S, N, COp or N-R, where R is the above Has meaning

M represents a Cu, Zn or Ni metal atom, ρ represents the number 1 or 2,

and if ρ is 1, '

C represents a hydrogen atom which is attached to one of the radicals A, B, R or R 'or R "is bonded,

and if ρ is 2,

5098H / 1037

C represents either a direct bond or an alkylene, arylene or aralkylene radical which ^{connect or link two radicals A, B, R or R 1} or R ″ to one another.

A preferred group of metal complexes according to formula I. has the formula

wherein X and M have the above meanings and V, Z and Q, which can be identical or different, are each hydrogen, the nitro group or alkyl or alkoxy radicals having 1 to 4 carbon atoms represent.

If A and / or B represent an aryl radical, the latter preferably contains 6 to 14 carbon atoms and can be composed of an aromatic Ring or two or more condensed aromatic rings. The aryl radical can be unsubstituted or with one or more groups which do not give the complex compound of the formula I, II or III any water solubility, be substituted, e.g., with alkyl, alkoxy, carboxyalkyl or alkylcarbamoyl groups, each having 1 to 4 carbon atoms in the alkyl part, arylcarboxyarylamide, arylcarbamoyl groups, Nitro groups or halogen atoms. Preferred examples of the aryl radicals A and / or B are the phenyl and naphthyl radicals,

If A and / or B represent a heterocyclic radical, this can either be unsubstituted or by one or more the aforementioned, non-water-solubilizing groups be substituted. Preferred heterocyclic radicals A and / B are the pyrazol-5-one radicals.

5098U / 1037

When B represents an aliphatic radical, this can be the radical of any aliphatic coupling component which is used for Coupling with a diazonium salt is capable of being. The preferred aliphatic radical B is the 1-methyl-2- (anilinocarbonyl) ethylene radical or a derivative thereof.

R is a monovalent group and can be: an alkyl radical with 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, such as a methyl, ethyl, propyl, butyl, hexyl, Octyl, decyl or dodecyl radical; a cycloalkyl radical with 5 or 6 carbon atoms; an aryl radical with 6 to 14 carbon atoms, such as a phenyl or naphthyl radical; an aralkyl radical with 7 to 12 carbon atoms, in particular a benzyl radical, or a heterocyclic radical, such as a pyrazol-5-one radical.

R ¹ is a divalent group and can be saturated or unsaturated. R 'can be, for example, a 1,2-ethylene, 1,2- or 1,3-propylene, allyl or methallyl radical. Alternatively, R ^{1 can} form part of an aromatic or heterocyclic ring, for example R 'and the substituent Y can each form part of a quinoline ring.

R "is a divalent group and can be saturated or unsaturated be. R "can, for example, be a methylene, 1,2-ethylene, 1,2- or 1,3-propylene, allyl, methallyl, 1,2-, 1,3- or 1,4-phenylene or a 4,4'-biphenylene radical.

Preferably ρ 1 and C is a hydrogen atom which is bonded to one of the radicals A, B, R and R ¹ or R ″, respectively.

If, however, ρ is 2, C is either a direct bond which connects two radicals, for example phenylene or biphenylene radicals A, B, R or R 'or R ", to one another, or C is alkylene, arylene or Aralkylene radical which connects or links two radicals A, B, R or R ¹ or R ″ to one another.

A preferred group of metal complexes of the formula III are those of the formula

509814/1037

or

wherein Y 0 or S, R "'1,2-phenylene, R phenyl or ethyl and V and Z, which can be identical or different, are each hydrogen, the nitro group or alkyl or represent alkoxy of 1 to 4 carbon atoms.

Typical classes of compounds of formula, I or II that are of particular interest are those of the Formulas:

. 5 09814/1037

class 1

N = N

——— jvj, ■ ■ IN

R ■ _J

2nd grade

X-

M N

R _l

Class 3·

N = N

N M N

60981.4 / i 03?

ORIGINAL INSPECTED

Examples of subgroups of compounds within class 1 are those of the formula:

V Z

χ—

N ^

.N X-

.N

ir I

CONHC.Hc / 6

. 5098U / 1037

X-M-NI C ₂ H ₅

An example of a subgroup of compounds within Class 2 is that of the formula:

509814/1037

An example of a subgroup of compounds within Class 3 is that of the formula:

Typical classes of compounds of Formula III that are of particular interest are those of the formula:

50-9 8 14/103?

r- 10 -

509814/1037

In each of the above formulas, A, B, R, R ¹ , X, Y, M, C, ρ and η are as defined above.

The invention further provides a process for the preparation of a compound of formula I, II or III, which is characterized is that one "is a compound of the formula

τ t ι

IV

or

-JP

_ • P. R.

509814 / 10.37

wherein A, B, R, R ', R ", X, C, ρ and Y have the above meanings and R ¹ " represents hydrogen or a methyl radical, metallized.

The metallization of the compound IV, V or VI can be carried out directly in the reaction medium that is used to prepare the compound IV, V or VI was used. Alternatively, the compound of formula IV, V or VI can be selected from its crude Separated reaction mixture and washed free of impurities and before the metallization in one Solvent are suspended with any solvent that is used for the preparation of the compound IV, V or VI used, identical or different.

The metallization can be carried out using a solution or suspension of any suitable salt or complex Metal M take place. For example, if the metallization is a copper plating process can be a suspension of a copper salt in an organic solvent or an aqueous solution of a copper salt such as copper acetate, cuprammonium sulfate or sodium cuprotartrate, can be used. In case of Metallization with zinc can be aqueous or organic Solution of a zinc salt such as zinc sulfate can be used. When the metallization using nickel is carried out, it is advisable to use a solution of nickel acetate tetrahydrate in methyl cellosolve.

Many of the compounds of the formula IV, V and VI are novel compounds per se and can be prepared according to methods known per se can be obtained.

For example, the compounds of Formula IV and V can be prepared thereby be that the diazo compound of an amine of the formula

509814/1037

VII.

with a compound, the formula

^B VIII

R HN

or the formula:

B IX

R'_YR '«I.

where A, B, X ,. Y, R, R 'and R ¹¹ V di "e have the preceding meaning, couples.

The compounds of the formula VI can be prepared, for example, by adding a diazo compound of an amine of the formula:

R "-XR

^UI

509814/1037

with a compound of the formula:

XI

wherein A, B, R, R ", X and Y have the above meaning and R ¹ " represents hydrogen or a methyl radical, couples,

The starting materials of the formulas X and XI are known per se.

The reaction is suitably carried out under known coupling conditions.

The starting materials of formulas VII and VIII are per se known.

The coupling components of the formula VIII, which are used according to the invention Uses include:

N-phenyl-ß-naphthylamine N- (2-thiophenyl) -ß-naphthylamine N- (2-ethylaminophenyl) -ß-naphthylamine N-phenyl-3- (anilino) -but-2-enoic acid amide l-phenyl-3-methyl-5-anilino-pyrazole N-phenyl-3-ethyl-but-2-enoic acid amide N- (8-quinolinyl) -β-naphthylamine N, N'-di- (2-naphthyl) -o-phenylenediamine

Suitable coupling components of the formula X which can be used according to the invention include:

N-phenyl-ß-naphthylamine

N-methyl-ß-naphthylamine

N-ethyl-ß-naphthylamine

N- (n-propyl) -β-naphthylamine

N- (η-butyl) -ß-naphthylamine

N- (4-chlorophenyl) -β-naphthylamine

609814/1037

Examples of suitable amines which can be used according to the invention of formula VII include:

Anthranilic acid '2-hydroxyaniline 2-methoxyaniline 2-hydroxy-5-chloroaniline, 2-methoxy-5-chloroaniline, 2-hydroxy-4-nitroaniline 2 ~ methoxy-4-nitroaniline 2-methoxy-4-nitro-5-methylaniline 8-aminoquinoline

Lactam of 2- (carboxymethoxy) -5-chloroaniline Lactam of 2- (carboxymethylthio) -aniline Lactam of 2- (carboxymethoxy) aniline

Examples of suitable amines of the formula XI which can be used according to the invention are:

5-chloro-2- (carboxymethoxy) -aniline (or its lactam) 2- (carboxymethoxy) -aniline (or its lactam) 2- (carboxymethylthio) aniline (or its lactam) 2- (1-hydroxyphenyloxy) aniline

Due to their insolubility in the reaction medium, the Compounds of formula I, II and III can easily be isolated from the reaction mixture by filtration.

The compounds of the formula I, II and III can be used as pigments directly after preparation; i.e., after they are filtered off from the crude reaction liquids and dried became. Alternatively, they can first be carried out using known wet or dry conditioning techniques, like grinding, either alone or in the presence of a water-soluble one Salt or another medium, which then can be easily removed, for example by washing, processed.

609814/1037

Accordingly, the invention further provides a method of coloring organic materials which can be used therein consists of incorporating a small proportion of a compound of the formula I, II or III into the organic material. The present invention also includes the organic material thus colored.

The proportion of the compound I, II or III used according to the invention to color the organic material can be within can be varied further limits, but is normally in the range from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, based on the total weight of the organic material to be colored.

Organic materials that can be colored according to the present invention include high molecular organic material, for example Cellulose ethers and cellulose esters, such as ethyl cellulose, acetyl cellulose and nitrocellulose, polyamides, polyurethanes and polyesters, natural and synthetic resins such as aminoplasts, especially urea-formaldehyde and melamine-formaldehyde resins, Alkyd resins, phenoplasts, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, Polypropylene, polyacrylonitrile, polyacrylic acid ester, rubber, casein, silicone and silicone resins, individually or in a mixture. It does not matter whether these high molecular weight compounds are in the form of plastic masses or melts or in the form of Spinning solutions are present. However, the compounds of the formula I, II and III are of particular interest for coloring Lacquers, paints and printing inks or inks.

Depending on the final use, it may be advantageous to use the compounds of formula I, II or III as clear organic To use dye (toner) or in the form of a pigment preparation.

As a rule, the compounds of the formula I, II and III characterized by excellent light and solvent fastness properties and high color intensity.

609814/1037

In addition, the compounds of the formula I and II excellent weather resistance or resistance.

In the following examples, parts and percentages relate to on weight.

Production of ligands example 1

41.1 parts of anthranilic acid were cold into a mixture of 91.4 parts of concentrated hydrochloric acid and 100 parts Stir in water. The mixture was cooled to 0-5 ° C and held at that temperature while a solution of 20.7 parts of sodium nitrite in 40 parts of water was added to the mixture. The diazonium solution thus obtained was within 15 minutes to a cold solution of 65.7 parts of N-phenyl-ß-naphthylamine added in 633 parts of ethanol. During the coupling, 600 parts of water were mixed with 475 parts Ethanol, added to prevent the suspension from becoming too thick. The red suspension was stirred for 1 hour, filtered off, the solid was washed with aqueous ethanol and dried at 55.degree. In this way, 96.1 parts became one red-orange solid with an F of 224.5 ° C of the following Get structure:

509814/1037

Analysis: C-oH ^ N-jOp

Calculated: C 75.20 H 4.63 N 11.44% Found: 74.75 4.80 11.09%

18.4 parts of the product obtained above as a paste before drying were added to 400 parts of cold water containing 0.15 parts of Solumin FIOS (sodium salt of sulfonated! Alkylphenoxypolyäthoxyäthanol), stirred in. Then 20.4 parts of sodium acetate trihydrate, followed by 13.74 parts of copper sulfate pentahydrate, dissolved in 50 parts of water, added. The temperature of the suspension was raised to 95 ° C by injecting steam, and it was kept at this temperature for 3 hours with stirring. The suspension obtained was filtered hot, with Washed sulfate free in hot water and dried at 70 ° C. This gave 20.2 parts of a maroon solid with an F of over 300 C.

Example 2

44.7 parts of 2-aminophenylglycolic acid lactam were heated under reflux for 1 hour in 300 parts of a 20% strength sodium hydroxide solution and then cooled to 0-5.degree. 20.7 parts of sodium nitrite in 40 parts of water were added to this solution. The resulting solution was added to 210 parts of concentrated hydrochloric acid, which was ^{stirred at 0} ° C., over the course of 15 minutes.

65 parts of N-phenyl-ß-naphthylamine were hot in 800 parts Dissolved ethanol and allowed to cool to room temperature. The diazo solution then became the ethanol solution within Added for 20 minutes, and stirring was then continued for 1 hour. The suspension obtained was filtered with 500 parts. len a 50% aqueous ethanol solution and then with 500 parts cold water and the filter cake was dried at 55 ° C. There were thus 111.6 parts (93.7%) of a compound obtained from F = 157 to 158 ° C of the following structure:

5098U / 1037

Examples 3 to 19

Using the procedure described in Example 1 or 2, those listed in Table I below were made Amines and coupling components reacted to obtain the corresponding coupled compound.

S098U / 1037

- 20 Table I

example

Coupling component

⁰ C the end
prey 188-90 66 227-0 71 249-50 87 283-5 96 151-2 95 150-1 95 186-7 80

NH,

CH, • COOH. 3

O ₂ N COOH ⁰ A / ^M 2 COOH ΓοΤ

CH,

NH ₀ I. I NH, COOH COOH

NH,

OH

NH,

OCH ₃

Cl NH,

OH

(ΧΓϋ

NHn

-NHv

'NH- • Il

509814/103?

- 21 Table I (continued)

example

Amine

Coupling component

yield

Cl KIL

OH

NH,

OCH

. OCH.

NH,

NH,

OCH

Cl NH,

OH

.0

174-5

NH _n

■ NHs 212-3

^ JU * 'W

202-3

-NH-

158-60

258-9

98-9

H ι

149-50

$ -As9 vs! 93

96

84

88

61

80

Β098Ί4. / 1037

Table I (continued)

example

Amine

Coupling component

F, ° C

yield

182-83

90

144-45

86

Manufacture of metal complexes Example 20

73.4 parts of the product from Example 1 were dissolved in 1400 parts of hot methyl cellosolve, and a solution of
40 parts of copper (II) acetate monohydrate, dissolved in 572 parts of dimethylformamide, and then 1,400 parts of methyl cellosolve were added. The resulting red suspension was refluxed for 4 hours, filtered hot, and the solid was washed with 500 parts of hot methyl cellosolve and then with ethanol
washed and then dried. There have been 68.5 parts a maroon solid with a F exceeding
300 C obtained from the following formula:

509814/1037

Example 21

79.4 parts of the product from Example 2 were dissolved in 800 parts of methyl cellosolve, and 40.0 parts of copper acetate monohydrate in 400 parts of dimethylformamide were added to this solution, and the mixture was refluxed for 6 hours. The resulting precipitate was filtered, washed with 400 parts of hot methyl cellosolve and then with 500 parts of ethanol and then dried in the oven at 55.degree. There were thus obtained 72.44 parts (79 % yield) of a maroon solid with an F of not less than 300 ° C of the following formula:

Examples 22 to 61

Using the procedure described in Example 20 or 21 the compounds listed in Table II were obtained from the corresponding ligands also listed in Table II manufactured.

509814/1037

- 24 Table II

example

Ligand

product

Color in a lacquer

22nd

23

24

25th

HC

NH

HC

(/ Sffl [

NH

0,

(/ S) H.

O ₂ N

0 ^ ° ^N 0H

NH

Bordeaux

V N

green

Maroon

θ ' Ν

black

■ Ν-

5098U / 1037

- 25 Table II (continued)

example

Ligand

product

Color in a 'paint

26 27

28

Red

green

Red

809814/1037

Table II (continued)

example

Ligand product

Color in
a varnish

cn o to co

29

30th

Bright purple.

■ chestnut brown

- 27 Table II (continued)

example

Ligand • product

Color in ■ one lacquer

31

32

34

Cl

OH

Cl

Maroon

Deep purple

Light purple

Red

5098U71037

- 28 Table II (continued)

7AAAB83

example

Ligand

product

Color in a lacquer

35

36

Eq

violet

Red

Red

5098U / 1037

- 29 Table II (continued)

!Example

Ligand product

Color in a ladder

38 39 40

41

blue

Deep purple

blue

blue

S098U / 1037

- 30 Table II (continued)

example

Ligand product

Color in one

paint

42

43

44

45

Deep blue

blue

Deep blue

Luminous, blue-red

509814/1037

- 31 Table II (continued)

example

Ligand product

Colour"

in a lacquer

46

48

49

green

Red

(easy

bluish)

purple

Dark red

509814/1037

- 32 Table "II (continued)

example

Ligand product

Color in a lacquer

52

53

.

Dark red

Bordeaux

Red

Bluish red

5098U / 1037

- 33 Table II (continued)

example

Ligand product

Color in a lacquer

54

55 56 57

Cl

Cl

Red

Plum blue

Blue red

Bright red

509814/1037

- 34 Table II (continued)

example

Ligand product

Color in a lacquer

58

59 60 61

Maroon

Light
Maroon

Red

Light purple

509814/1037

Example 62

a) 20.55 parts of anthranilic acid were stirred into 65 parts of water at room temperature over the course of 5 minutes. There were 37.5 parts of concentrated hydrochloric acid were added dropwise to give a thick slurry was taken another 5 minutes before the addition of 25 parts of ice to pre-set the temperature with the help of external cooling the addition of 10.35 parts of sodium nitrite dissolved in 25 parts of water to lower to 0 C within 5 minutes, stirred became. The volume of the diazo solution was adjusted to 250 parts with water.

34.5 parts of N-phenyl-ß-naphthylamine were in 40O parts Ethylene glycol containing 1.73 parts of Lissapol NX (a commercially available surfactant) was stirred in. Another 100 parts of ethylene glycol were added and the suspension was 30 minutes at room temperature stirred and then heated to 40 ° C using steam. The diazo solution was added to this suspension within 15 minutes were added, and the suspension was stirred at 40 ° C. for a further 2 hours.

To the red suspension, 18 parts of sodium hydroxide in 50 parts of water were added, and it was 30 minutes stirred, a dark red solution was obtained, which was then used to remove unreacted N-phenyl-ß-naphthylamine was filtered, after which the filtrate was washed with a solution of 20 parts of sodium hydroxide in 50 parts of water became. The volume of the filtrate was adjusted to 1,500 parts using water.

This solution of the ligand could now be metallized using one of the methods described below or the ligand itself could be isolated by acidification, filtering off, washing and drying and then to formation of the metal complex can be used.

509814/1037

- 36 -. 2U4883

b) 2.78 parts of the sodium salt of a naphthalenesulfonic acid-formaldehyde condensate were added to the solution of the ligand obtained under a) above, and the solution was "using a Silverson stirrer with high Speed. Stirred. 15 parts of glacial acetic acid in 15 parts of water were added to the solution over the course of 10 minutes. a thick red slurry was obtained. 40.8 parts of sodium acetate trihydrate dissolved in 50 parts of water were added to the suspension, and it was added Stirred for 10 minutes. Then 3 7.5 parts of copper sulfate pentahydrate, dissolved in 100 parts of water, added over 5 minutes, and the temperature was then raised using increased by steam to 95 ° C within 20 minutes. The temperature of 95 ° C was maintained for 90 minutes, and then boiled for 30 minutes. The resulting maroon slurry was filtered hot, free washed from sulfate and dried at 50 to 60 ° C. There were so 64.3 parts of a maroon solid with obtained an F of not less than 360 ° C.

Example 63

To the solution obtained in Example 62 a), 2.78 parts of the sodium salt of a naphthalenesulfonic acid-formaldehyde condensate were added and the solution was stirred at high speed using a Silverson stirrer. To this solution 3 7.5 parts of copper sulfate pentahydrate, dissolved in 100 parts of water, and 39 parts of concentrated ammonium hydroxide (D = 0.88) were added. The mixture was stirred for 10 minutes and then 15 parts of glacial acetic acid in parts of water were added over the course of 10 minutes. The red suspension was then heated to 95 ° C. over the course of 20 minutes and this temperature was maintained for 90 minutes, after which the mixture was boiled for a further 30 minutes. The thick maroon slurry was filtered hot, washed sulfate free and dried, leaving 61.5 parts of a maroon solid:
became.

Obtain solid with an F of not less than 360 ° C

S098U / 1037

Example 64

20.55 parts of anthranilic acid were stirred into 65 parts of water and 23 parts of concentrated sulfuric acid were added dropwise using external cooling to bring the temperature to ⁰ ° C. before the addition of 10.35 parts of sodium nitrate dissolved in 25 parts of water. within 10 to 15 minutes, the brown solution obtained being treated with activated charcoal and filtered through Supercel. The volume of the solution was adjusted to 450 parts.

34.5 parts of N-phenyl-β-naphthylamine became 113 parts of a 80% aqueous acetic acid was added, and 31.8 parts of concentrated sulfuric acid was added dropwise with a dark brown solution at 40 to 50 ° C. was obtained. This temperature is increased during the addition of the coupling component solution simultaneously with the diazonium salt solution to a coupling bath containing 25.8 parts of Nansa SSA (a commercially available Dodecylbenzenesulfonic acid) dissolved in 3000 parts of water at 40 to 50 ° C. After finished Addition, the red slurry is stirred for a further 1 hour. The slurry was then prepared using the in Example 49 or 50 described method for the preparation of metal complexes used.

509814/1037

Claims (1)

Claims 1. Metal complex of the formula M- C (D N = N C (H) or Rn_ ν - Λ • (III) 5098H / 1037 wherein A is an aryl or heterocyclic radical, B is an aliphatic, aryl or heterocyclic radical means, R is an alkyl, cycloalkyl, aryl, aralkyl or heterocyclic Radical or R represents the atoms which together to complete a heterocyclic radical with the remainder B are required, R ¹ and R "each represent a carbon chain which may form part of an aromatic or heterocyclic ring, R ¹ having 2 to 3 carbon atoms between the nitrogen atom and the substituent Y and R" having 1 to 3 carbon atoms between the X and Y substituents , X and Y, which may be the same or different, each represent 0, S, N, COp or N-R, where R is the above Has meaning M denotes a Cu, Zn or Ni metal atom, ρ represents the numbers 1 or 2, and when ρ is 1, C represents a hydrogen atom attached to one of the radicals A, B, R or R 'or R "is bonded, and if ρ is 2, C either a direct bond or an alkylene, arylene or aralkylene radical represents the two radicals A, B, R or R 'or R "are linked to one another. -2. Metal complex according to claim 1, characterized in that ρ is 1 and C represents a hydrogen atom ^{which is bonded to one of the radicals A, B, R or R 1} or R ". 3 '. Metal complex of the formula I according to claim 1 of the formula S098U / 1037 wherein X and M have the meaning given in claim 1 and V, Z and Q, which can be identical or different, are each hydrogen, the nitro group or alkyl or alkoxy radicals with 1 to 4 carbon atoms. 4. Metal complex ge, äß claim 1, wherein A and / or B is a Represent phenyl, naphthyl or pyrazol-5-one radical. 5. Metal! Complex of the formula I according to claim 3 of the formula 6. Metal complex of the formula I according to claim I of the formula 5098U / 1037 wherein X and M have the meaning given in claim 1 and V and Z have the meaning given in claim 3. 7. Metal complex of the formula I according to claim 1 of the formula CONHCUl ,. O D 509814/1037 • in which X and M have the meaning given in claim 1 and V, Z and Q have the meaning given in claim 3, 8. Metal complex of the formula I according to claim 1 of the formula CH, wherein X and M have the meanings given in claim 1 and V, Z and Q have the meanings given in claim 3. 9. Metal complex of the formula I according to claim 1 of the formula. wherein X and M have the meaning given in claim 1 and V and Z have the meaning given in claim 3. 10. Metal complex of the formula I according to claim 1 of the formula 509814/1037 CONHC, H 6 wherein X and M have the meaning given in claim 1 and V and Z have the meaning given in claim 3. 11. Metal complex of the formula II according to claim 1 of the formula wherein X and M have the meaning given in claim 1 and V and Z have the meaning given in claim 3. 12. Metal complex of the formula II according to claim 1 of the formula ■ f - ^M -, R R 509814/1037 wherein A, B, M, C, ρ and R have the meaning given in claim 1. 13. Metal complex of the formula III according to claim 1 according to the formula wherein M has the meaning given in claim 1, Y Represents 0 or S, R "represents the 1,2-phenylene radical, R denotes the phenyl or ethyl radical and V and Z, which can be identical or different, are each hydrogen, the nitro group or an alkyl or alkoxy radical with to 4 carbon atoms. 14. Metal complex of the formula III according to claim 1 according to the formula wherein M is in claim 1 and R, V and 2 are in claim have given meaning. 509814/1037 15. Metal complex of the formula III according to claim 14 of the formula wherein M is as defined in claim 1 and V and Z are as defined in claim 13 and Q is hydrogen, the nitro group or an alkyl or alkoxy radical having 1 to 4 carbon atoms represents. 16. Metal complex of the formula III according to claim 14 of the formula wherein M has the meaning given in claim 1 and V, Z and Q have the meaning given in claim 1 and 15- 17. Metal complex of the formula III according to claim 13 of the formula 509814/1037 wherein M has the meaning given in claim 1 and V, Z and Q have the meaning given in claims 13 and 15. 18. Process for the preparation of a metal complex of the formula (D (II) 509814/1037 or (III) worm A represents an aryl or heterocyclic radical, B is an aliphatic, aryl or heterocyclic radical represents represents an alkyl, cycloalkyl, aryl, aralkyl or heterocyclic radical, or R represents the required atoms represents to 'complete a heterocyclic radical together with the radical B, R ¹ and R "each represent a carbon chain which may form part of an aromatic or heterocyclic ring, R ¹ having 2 to 3 carbon atoms between the nitrogen atom and the substituent Y and R" having 1 to 3 carbon atoms between the X and Y substituents , X and Y, which can be the same or different, each represent 0, S, N, CO 2 or N-R, where R is the above Has meaning M represents a Cu, Zn or Ni metal atom and ρ means the numbers 1 or 2, and when ρ is 1, C represents a hydrogen atom which is bonded to one of the radicals A, B, R or R ¹ or R ", 5098U / 1037 and if ρ is 2, C represents either a direct bond or an alkylene, arylene or aralkylene radical, the two radicals A, B, R or R ¹ . or R "connect with each other, characterized in that a compound of the formula ^A AH 11 or R ¹¹¹ Y R "XR" « (IV) (V) C (VI) -ip 509814/1037 -49- 24U883 wherein R ¹ 'represents hydrogen or a methyl radical, metallized. 19. The method according to claim 18, characterized in that metallization using a solution or suspension of any suitable salt or complex of the metal M is performed. 20. The method according to claim 19, characterized in that a suspension of a copper, zinc or nickel salt in an organic solvent or an aqueous solution of a copper, zinc or nickel salt is used. 21. The method according to claim 20, characterized in that an aqueous solution of copper acetate, cuprammonium sulfate . or sodium cuprotartrate is used. 22. The method according to claim 20, characterized in that the zinc salt is zinc sulfate. 23. The method according to claim 20, characterized in that a nickel acetate tetrahydrate solution in methyleellosolve is used. 24. A method for dyeing organic material, characterized in that that it contains a small proportion of a metal complex of the formula I, II or III according to claim incorporated. 25. The method according to claim 24, characterized in that the proportion of the metal complex of the formula I, II or III in the range from 0.1 to 10% by weight based on the total weight of the organic material. 26. The method according to claim 25, characterized in that the proportion of the metal complex of the formula I, II or III in the range from 0.5 to 5% by weight, based on the total weight of the organic material. 509814/1037 - ⁵⁰ - 24U883 27. The method according to claim 24, characterized in that the organic material is a varnish, a paint or is a printing ink. 28. Organic material obtained by the method according to claim 24. 609814/1037