WO2003099937A1

WO2003099937A1 - Bisazo and trisazo copper complex dyestuffs

Info

Publication number: WO2003099937A1
Application number: PCT/IB2003/002154
Authority: WO
Inventors: Dominique Pflieger
Original assignee: Clariant International Ltd
Priority date: 2002-05-28
Filing date: 2003-05-23
Publication date: 2003-12-04
Also published as: AU2003228044A1; TW200401010A; GB0212216D0

Abstract

This invention relates to coppered bis- or trisazo dyestuffs containing at least two (for bisazo) and at least three (for trisazo) alkyl-, alkoxy- or aryl- ammonium sulfonate groups or sulfonate groups with Rhodamine B type or Rosinamine D type counterions. The invention also relates to various intermediates used in the preparation of the metallized dyes, to compositions, and to processes for preparing the metallized dyestuffs. The compounds are particularly suited for the application in lacquers.

Description

BISAZO AND TRISAZO COPPER COMPLEX DYESTUFFS

This invention relates to coppered bisazo and trisazo dyestuffs containing at least two (for bisazo) or at least three (for trisazo) alkyl-, alkox - or aryl- ammonium sulfonate groups or sulfonate groups with hodamine B type or Rosinamine D type counterions. The invention also relates to various intermediate dyestuffs used in the preparation of the metallized dyes, to compositions, and to processes for preparing the metallized dyestuffs.

One class of solvent soluble dyes known in the art are chromium based complex dyes which are highly soluble in solvents such as alcohols or ketons and are practically insoluble in water. On the one hand chromium based solvent soluble dyes have very advantageous properties, in particular a high lightfastness, but on the other hand chromium based dyes are increasingly under concern due to environmental reasons. Therefore there is a need for suitable non chromium based solvent soluble dyes.

Solvent soluble dyes as described in this application are defined as being highly soluble in solvents such as alcohols or ketones, and being practically insoluble in water. A test well established in the art for solvent soluble dyes is the so called "water fastness".

Bisazo compounds and in particular trisazo, tetrakisazo and higher azo compounds are well known in the art for being potentially useful as black dyestuffs. For the coupling reactions a multitude of combinations of known diazo compounds and coupling components are possible and the components utilised in industrial azo coupling are mainly selected due to accessibility and price. A crucial issue in the synthesis of trisazo and higher azo compounds is the solubility of the components and intermediates throughout the entire process.

In the Japanese Patent Application No. 5-311085 copper complex dyes based on bisazo, trisazo or tetrakisazo dye compounds are disclosed wherein the first, phenyl type, diazo component is described to be optionally substituted by inter alia Cι- alkyl sulfonamido groups. Further the first diazo component as well as the first, phenyl type, coupling component may be substituted by halogen, Cι-₄alkyl, Cι- alkoxy, sulpho or carboxy groups. The second, naphthol type, coupling component is described as being optionally substituted by 0 to 2 sulfonic acid groups, which in the example (compound III) is present as an internal amine sulfonate salt. The coupling product is optionally converted into a copper complex, an inner salt, an acid addition salt, an alkali metal salt or an amine salt. The obtained dyestuffs are characterised as black dyes with strong dyeing power which are useful for colouring paper, fibres and leather, for surface dyeing and printing.

Suφrisingly, it has now been found that starting from non-sulfonamido substituted diazo compounds and coupling components coppered bis- and trisazo dyestuffs are accessible which are characterised as coloured or black dyestuffs with high dyeing power, high weather and lightfastness and which are particularly useful as solvent soluble dyes.

This invention relates to coppered bis-and trisazo dyestuffs containing at least two (for bisazo) and at least three (for trisazo) alkyl-, alkoxy- or aryl- ammonium sulfonate groups or sulfonate groups with Rhoda ine B type or Rosinamine D type counterions. The compounds of the invention are particularly suited for the application in solvent based laquers and solvent based resin systems as well as in non-aqueous printing and ink-jet applications.

A bis- or trisazo 1 : 1 copper complex dye compound comprising the residue of a bis- or trisazo dye compound according to general formula (I)

D- -N=N— K_n- -N=N- -κ_n (I) wherein

n is 1 or 2

D is the residue of a diazo component D' selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphtyl, K° is the residue of K⁰' being selected from the group consisting of substituted or unsubstituted phenol, substituted or unsubstituted naphtol, substituted or unsubstituted l-phenyl-5-pyrazolone, substituted or unsubstituted l-naphtyl-5-pyrazolone,

K^l is the residue of K¹' being selected from the group consisting of substituted or unsubstituted phenol, substituted or unsubstituted naphtol,

K² is the residue of K²' being selected from the group consisting of substituted or unsubstituted phenol, substituted or unsubstituted naphtol,

with the substituents of the phenyl, naphtyl, phenol, naphtol, l-phenyl-5-pyrazolone and l-napthyl-5-pyrazolone in D, K°, K¹ and/or K² being hydroxy, methyl, methoxy or halogen, preferably chloro,

and at least n+1 of the components D, K , K and K are substituted with at least one alkyl-, alkoxy- or aryl ammonium sulfonate group or with a sulfonate group having a Rhodamine B type or Rosinamine D type counterion.

A bisazo 1:1 copper complex dye compound according to the invention comprises a bisazo dye compound according to general formula (la)

D — N=N — K:J — N=N K₀ (la)

wherein D, K° and K¹ are defined as above.

A trisazo 1: 1 copper complex dye compound according to the invention comprises a trisazo dye compound according to general formula (lb)

D— N=N— K₂ N=N-K^ N=N K_{0 ([b})

wherein D, K , ¹ and K² are defined as above. The counterions to the sulfonate groups are selected from ⁺NH₄__m(C ι -ι 2alkyl)_m, ⁺NH₄. _m(Cι-ι₂alkoxy)_m,

(with m being an integer from 1 to 4), Rhodamine B type or Rosinamine D type cations.

Preferred counterions are alkylammonium and alkoxyammonium ions wherein m is 1 and in particular ^ΗΗ^l, 1-di-n-propylhexylene) or its isomers and ⁺NH₃(2'-ethyl- hexyloxy-n-propylene). Preferred Rhodamine B type or Rosinamine D type cations are of the following formulae:

One preferred aspect of the invention are bisazo 1:1 copper complex dyestuffs wherein n is 1,

D is the residue of a diazo component D' being naphtyl, K° is the residue of a component K⁰' being methyl substituted l-phenyl-5-pyrazolone,

K¹ is the residue of a component K¹' being unsubstituted phenol, and at least two of the components D, K° and/or K¹ are substituted with at least one alkyl-, alkoxy or aryl ammonium sulfonate group or with a sulfonate group having a Rhodamine B type or Rosinamine D type counterion.

Another preferred aspect of the invention are trisazo 1:1 copper complex dyestuffs wherein n is 2,

D is the residue of a diazo component D' being unsubstituted naphtyl,

K is the residue of a component K⁰' being selected from the group consisting of amino substituted or unsubstituted naphtol, substituted or unsubstituted l-phenyl-5- pyrazolone, K¹ is the residue of a component K¹' being unsubstituted naphtol,

K² is the residue of a component ' being selected from the group consisting of methoxy substituted or unsubstituted phenol, and at least three of the components D, K , K¹ and/or K² are substituted with at least one alkyl-, alkoxy or aryl ammonium sulfonate group or with a sulfonate group having a Rhodamine B type or Rosinamine D type counterion.

In particular the phenol or naphtol residue K₂' may be further substituted by methyl or methoxy.

The metallized dyestuffs of the present invention can be readily prepared by treating the corresponding unmetallized, o,o'-dihydroxy azo dyestuff or o-methoxy-o'-hydroxy azo dyestuff with a cooper salt in an aqueous or nonaqueous medium by known methods, such as reaction of the azo dyestuff with copper sulphate in the presence of water and sodium acetate or ammonia, or with cupric nitrate in the presence of soda ash and an appropriate solvent near the reflux temperature of the system until the reaction is complete.

The unmetallized bisazo dyestuffs may be prepared by diazotizing an aminobenzene compound of the formula (II) or a naphtylamine of the formula (III) in a first step.

wherein X is hydrogen, hydroxy or methoxy in ortho-position to the amino group.

In a second step the diazotized compound is coupled to a phenolic, methoxyphenolic or naptholic amino compound with the aminogroup optionally being protected.

In a third step the further diazotized compound is coupled to a naphtol or phenylpyrazolone compound by well-known methods. The unmetallized trisazo dyestuffs may be prepared by diazotizing an aminobenzene compound of the formula (II) or a naphtylamine of the formula (III) in a first step.

wherein X is hydrogen, hydroxy or methoxy in ortho-position to the amino group.

In a second step the diazotized compound is coupled to a ortho-aminophenolic compound having an optionally protected aminogroup for further diazotation.

In a third step, the aminogroup is deprotected, diazotized and coupled to a phenolic or naptholic amino compound.

In a fourth step the further diazotized compound is coupled to a naphtol or phenylpyrazolone compound by well-known methods.

Alternatively the coupling can be done in reverse order by combining a diazotized ortho-aminohydroxy- or ortho-aminomethoxynaphtalene compound with phenolic compounds of the formula (IV), methoxyphenolic compounds or naphtolic compounds of the formula (V)

wherein the hydroxy group is in 1- or 2-position and the sulfo group is attached in any position other than 1 or 2.

Diazo components of formula (II) or (III) and couplers of formula (IV) or (V) above are known compounds and can be prepared by methods well known to those skilled in the art. A synthesis of bisazo compounds of the invention is given by the reaction scheme below:

wherein R is hydrogen, methyl or methoxy and k and r are 1 or 2.

For the first coupling a protective group on the amine is optional. If the substituent R (see formula (VIII) below) is hydrogen or methyl a protective group is required. If R is methoxy or a sulfonate group, no protective group is required. The protective group is preferably an omega-methylene sulfonic acid group.

A synthesis of the trisazo compounds is given by the reaction scheme below:

3) Deprotection

4) Diazotisation

5) 2^nd coupling

wherein R is hydrogen, methyl or methoxy and k and r are 1 or 2. Preferred compounds for the first diazotation are of the formula (VI) or (VII):

(VI) (VII)

Particularly preferred coupling components for the first coupling in the synthesis are compounds according to formula (VIII) with R being hydrogen.

(VIII)

Particularly preferred coupling components for the second coupling are compounds known as gamma-acid (formula IX), j-acid (formula X) or h-acid (formula XI)

(IX) (X) (XI)

The new soluble dye compounds according to the invention are suitable for dyeing (especially dyeing in the mass) of plastics including solvent- free and solvent containing plastics masses and solvent-free or solvent containing plastics resins. Further they are suitable for finishes, oil or water based paints, for lacquers, for spin dyeing of viscose or cellulose acetate, for dyeing of natural or synthetic polyamides, polyester, polyethylene, polystyrene, polyvinylchloride, rubber or synthetic leather. The new compounds can also be used for printing of graphic material, including textiles and paper, for dyeing of paper masses and for coating of textile and leather.

Dyeings with the new compounds have good properties, for example high light fastness, good heat withstanding properties, good weathering properties, good chemical resistance, good migration properties, low blooming, good overcoating properties, good fastness in solvents, high tinting strength and good application properties (e.g. flocculation fastness).

The dye compounds according to the invention are suitable as colorants in solvent based ink-jet inks, for printing paper or papery substrates, textile fibre materials, plastic films and plastic transparencies.

The dye compounds according to the invention are also suitable as colorants in electrophotographic toners and developers, such as one- or two-component powder toners (also called one- or two-component developers), magnetic toners, liquid toners, polymerisation toners and speciality toners.

The dye compounds according to the invention are further suitable as charge control agents.

The following examples illustrate the invention. Unless otherwise specified, parts and percentages used in the examples are on a weight to weight basis.

Example 1

a) 22.9 parts of 4-(6,8-disulfonaphthalene-2-ylazo)-2-methoxyaniline are stirred into a mixture of 300 parts of water and 12.9 parts of 30% HC1. After the addition of 30 parts of ice, the amine is diazotised by the addition of 12.0 parts by volume of 4N NaNO₂ solution. The resulting suspension is stirred for 1 hours at 5°C and then slowly poured into a solution of 1 1.4 parts of 2-amino-8- hydroxynaphthalene-6-sulfonic acid (gamma acid) in 33 parts of water and 6.4 parts of 30% NaOH. By the simultaneous addition of a further 10.6 parts of 30% NaOH, the pH is brought to 9.5- 10. The resulting mixture is then stirred at room temperature for 8 hours and brought to pH 1.5 by the addition of 30% HCl. 120 parts of sodium chloride are added and the resulting precipitate build-up is filtered and dried.

b) 16.4 parts of the bisazo dyestuffs of part a) above are stirred into a mixture of 150 parts of water, 5.3. parts of 30% NaOH and 6.2 parts by volume of 4N NaNO₂ solution. The resulting solution is slowly poured into 50 parts of ice and 18.8 parts of 30% HCl resulting in a suspension of diazonium salt that is stirred for 2 hours at 5°C. This slurry is slowly poured into a solution of 3.4 parts of 2- naphthol-8-sulfonic acid in 12 parts of water and 3.2 parts of 30% NaOH. By the simultaneous addition of a further 26.6 parts of 30% NaOH, the pH is brought to 9.5-10. The resulting mixture is then stirred at room temperature for 3 hours and brought to pH 1.5 by the addition of 30% HCl. 160.0 parts of solid sodium chloride are then added, resulting in an voluminous precipitate build-up that is filtered and dried.

c) 19.9 parts of the trisazo dyestuffs of part b) above are suspended in 100 parts of water, 10.0 parts of dipropylene glycol monomethyl ether and 4.8 parts of sodium acetate. After warming at 96°C for over one hour, 5.9 parts of copper sulphate are added in small portions for over one hour, followed by 20.0 parts of 25%> ammonia. The mixture is heated to reflux for 12 hours whereupon a voluminous suspension of the copper complex results. The temperature is allowed to fall to 45°C over 2 hours (while stirring well) and the suspension is slowly reacted with a solution of 13.3 parts of 3-[(2-efhylhexyl)oxy]-l- propanamine in 70 parts of water and 8.3 parts of 30% HCl. The resulting precipitate is stirred a further hour at room temperature, filtered and the residue is washed salt free and dried. A compound of formula

wherein R is methoxy, is obtained.

Example 2

a) 33.5 parts of 6-aminonaphthalene-2-sulfonic acid are stirred into a mixture of 150.0 parts of water and 24.7 parts of 30% HCl. After the addition of 100.0 parts of ice, the amine is diazotised by the addition of 41.0 parts by volume of 4N NaNO₂ solution. The resulting suspension is stirred for 1 hours at 5°C, the excess of sodium nitrite is destroyed with aminosulfonic acid and the pH is brought to 4.5 by adding 3.5 parts of NaHCO₃. 32.6 parts of [(2-methoxyphenyl)amino]- methanesulfonic acid is added in small portions while the pH is adjusted to 4.3- 4.5 by the simultaneous addition of 8.0 parts of NaHCO₃. The resulting mixture is then stirred at room temperature for 4 hours and the pH is brought to 9.5 by the addition of 150.0 parts of 30% NaOH. The resulting mixture is then heated up to 85°C for 5 hours. 210 parts of sodium chloride are added and the resulting orange precipitate build-up is filtered and dried.

b) 38.0 parts of the monoazo dyestuffs of part a) above are stirred into a mixture of

150 parts of water and 28.2 parts of 30% HCl. 100.0 parts of ice are added, followed by 29.0 parts by volume of 4N NaNO₂ solution. The resulting brown slurry is stirred for 2 hours at 5°C before destroying the excess of sodium nitrite with aminosulfonic acid. The suspension of diazonium salt is then slowly poured into a solution of 25.4 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid

(gamma acid) in 280 parts of water and 19.0 parts of 30% NaOH. By the simultaneous addition of 26.5 parts of Na2CO₃, the pH is brought to 8.5-9.0. The resulting mixture is then stirred at room temperature for 3 hours and brought to pH 1.0 by the addition of 58.7 parts of 30% HCl, resulting in a brown precipitate that is filtered and dried. c) 24.3 parts of the bisazo dyestuffs of part b) above are stirred into a mixture of 70 parts of water and 12.2 parts of 30%o HCl. 50.0 parts of ice are added, followed by 1 1.0 parts by volume of 4N NaNO₂ solution. The resulting dark brown suspension is stirred for 2 hours at 5°C before destroying the excess of sodium nitrite with aminosulfonic acid. The suspension of diazonium salt is then slowly poured into a solution of 13.6 parts of l-amino-8-hydroxynaphthalene-3,6- disulfonic acid (H acid) in 50 parts of water and 4.7 parts of 30%> NaOH. By the simultaneous addition of 21.7 parts of sodium acetate, the pH is brought to 4.5- 5.0. The resulting mixture is then stirred at room temperature for 3 hours resulting in a dark violet suspension. The trisazo dyestuff is recovered by filtration and dried.

d) 37.5 parts of the trisazo dyestuffs of part c) above are stirred into 60 parts of water, 9.7 parts of diethanolamine and 27.2 parts of sodium acetate. It is heated to 98°C before slowly adding a slurry made from 10.0 parts of copper sulphate,

16 parts of water and 16.0 parts of 25% ammonia heated to 60°C. The reaction mixture is heated to reflux for 12 hours whereupon a black solution of the copper complex results. The temperature is allowed to fall to 25 °C over 2 hours (while stirring well) and the suspension is slowly reacted with a solution of 21.1 parts of 2-ethylhexylamine in 85 parts of water and 18.8 parts of 30% HCl. The resulting precipitate is stirred for one hour, filtered and the residue is washed salt free with deionized water and dried. A compound (46.0g) of formula

is obtained. Example 3

a) 78.1 parts of 6-aminonaphfhalene-2-sulfonic acid are stirred into a mixture of 750.0 parts of water and 54.1 parts of 30% HCl. After the addition of 300.0 parts of ice, the amine is diazotised by the addition of 88.0 parts by volume of 4N

NaNO₂ solution. The resulting suspension is stirred for 1 hours at 5°C and the excess of sodium nitrite is destroyed with aminosulfonic acid. The suspension of diazonium salt is then slowly poured into a solution of 55.3 parts of 2,5- dimethoxyaniline in 300 parts of water. The pH is brought to 4.3-4.5 by the simultaneous addition of 29.7 parts of NaHCO₃. The resulting mixture is then stirred at room temperature for 4 hours and the resulting orange precipitate buildup is filtered and dried.

b) 23.0 parts parts of the monoazo dyestuffs of part a) above are stirred into a mixture of 100.0 parts of water, 6.5. parts of 30% NaOH and 15.0 parts by volume of 4N NaNO₂ solution. This solution is slowly poured into 100 parts of ice and 51.7 parts of 30%> HCl resulting in a suspension of diazonium salt that is stirred for 2 hours at 5°C. The excess of sodium nitrite is then destroyed with aminosulfonic acid.. This slurry is slowly poured into a solution of 13.2 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid (gamma acid) in 20 parts of water and 7.4 parts of 30% NaOH. By the simultaneous addition of 55.5 parts of Na₂CO₃, the pH is brought to 8.5-9.0. The resulting mixture is then stirred at room temperature for 3 hours and brought to pH 1.0 by the addition of 91.7 parts of 30%) HCl, resulting in a dark violet precipitate build-up that is filtered and dried.

c) 21.1 parts of the bisazo dyestuffs of part b) above are stirred into a mixture of 100.0 parts of water, 15.0 parts of 30% NaOH and 9.0 parts by volume of 4N NaNO₂ solution. This solution is slowly poured into 50 parts of ice and 30.6 parts of 30%) HCl resulting in a suspension of diazonium salt that is stirred for 2 hours at 5°C. The excess of sodium nitrite is then destroyed with aminosulfonic acid.This slurry is slowly poured into a solution of 9.4 parts of l-(4'- sulfophenyl)-3-carboxy-5-pyrazolone in 40 parts of water and 6.3 parts of 30% NaOH. By the simultaneous addition of 33.3 parts of sodium acetate, the pH is brought to 4.3-4.5 resulting in a dark violet suspension. The resulting mixture is stirred at room temperature for 3 hours and brought to pH 1.5 by the addition of 30%) HCl. 60.0 parts of solid sodium chloride are then added, resulting in an voluminous precipitate build-up of trisazo dyestuff that is filtered and dried.

d) 24.7 parts of the trisazo dyestuffs of part c) above are stirred into 200 parts of water, 8.0 parts of diethanolamine and 24.9 parts of sodium acetate. It is heated in an autoclave to 98°C before slowly adding a slurry made from 8.3 parts of copper sulphate, 13 parts of water and 13.0 parts of 25% ammonia heated to

60°C. The reaction mixture is then heated to 125-130°C for 16 hours whereupon a black solution of the copper complex results. The temperature is allowed to fall to 25°C and the suspension is slowly reacted with a solution of 19.8 parts of Cπ- Cι₄ tert.-Alkylamine (e.g. commercial product known as "Primene 81R") in 50 parts of water and 12.9 parts of 30% HCl. The resulting precipitate is stirred for one hour, filtered and the residue is washed salt free with deionized water and dried. A compound (45.6g) of formula

is obtained.

Example 4

a) 24.2 parts of 1,3-Naphthalenedisulfonic acid, 7-[(4-amino-3- methoxyphenyl)azo]-, disodium salt (CAS Registry Number 65151 -26-0) are stirred into a mixture of 300 parts of water and 14.1 parts of 30%> HCl. After the addition of 100 parts of ice, the amine is diazotised by the addition of 13.0 parts by volume of 4N NaNO₂ solution. The resulting solution of diazonium salt is stirred for 1 hours at 5°C and the excess of sodium nitrite is destroyed with aminosulfonic acid. The orange solution is then slowly poured into a solution of 12.7 parts of l-(4'-sulfophenyl)-3-methyl-5-pyrazolone in 50 parts of water and 4.0 parts of 30%> NaOH. By the simultaneous addition of a further 15.0 parts of sodium acetate, the pH is brought to 4.3-4.5. The resulting mixture is then stirred at room temperature for 3 hours and brought to pH 1.5 by the addition of 30%

HCl. 50 parts of sodium chloride are added and the resulting orange precipitate build-up is filtered and dried.

b) 19.9 parts of the bisazo dyestuffs of part a) above are stirred into 120 parts of water and 1 1.3 parts of diethanolamine. It is heated to 98°C before slowly adding a slurry made from 11.7 parts of copper sulphate, 19 parts of water and

19.0 parts of 25%) ammonia heated to 60°C. The reaction mixture is heated to reflux for 4 hours whereupon a dark red solution of the copper complex results.

The reaction mixture is cooled down to 25°C and is reacted with a solution of 36.6 parts of 9-(2-carboxyphenyl)-3,6-bis(diethylamino)xanthylium chloride (a dyestuff known as "Rhodamine B") in 240 parts of water heated to 60°C. A solution of 21.5 parts of hydroabietylamine (a commercial product known as

"Amine D", CASRN 61790-47-4) in 50 parts of water and 5.0 parts of acetic acid is slowly added resulting in a voluminous violet precipitate build up. The pH of the resulting mixture is then brought to 3.0-3.5 by the addition of 30%

HCl and the bluish red dyestuff is filtered and dried. A compound (77.6g) of formula

is obtained.

Claims

1. A bis- or trisazo 1: 1 copper complex dye compound comprising the residue of a bis- or trisazo dye compound according to general formula (I)

D- N=N— K_n- N=N K₀ (I) wherein n is 1 or 2,

D is the residue of a diazo component D' selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphtyl,

K° is the residue of a component K⁰' being selected from the group consisting of substituted or unsubstituted phenol, substituted or unsubstituted naphtol, substituted or unsubstituted l-phenyl-5-pyrazolone, substituted or unsubstituted l-naphtyl-5-pyrazolone,

K¹ is the residue of a component K¹' being selected from the group consisting of substituted or unsubstituted phenol, substituted or unsubstituted naphtol,

9

K is the residue of a component K ' being selected from the group consisting of substituted or unsubstituted phenol, substituted or unsubstituted naphtol,

with the substituents of the phenyl, naphtyl, phenol, naphtol, l-phenyl-5- pyrazolone and l-napthyl-5-pyrazolone being hydroxy, methyl, methoxy or halogen,

and at least n+1 of the components D, K°, K¹ and/or K² are substituted with at least one alkyl-, alkoxy or aryl ammonium sulfonate group or with a sulfonate group having a Rhodamine B type or Rosinamine D type counterion. A bis- or trisazo 1:1 copper complex dye compound according to claim 1 characterised in that the counterions to the sulfonate groups are selected from

⁺NH4-m(Cι.ι₂alkyl)_πι

⁺NH ._m(C₆.ι₀aryl)_m

Rhodamine B type cations or Rosinamine D type cations,

with m being an integer from 1 to 4, preferably m being 1.

A bis- or trisazo 1:1 copper complex dye compound according to claims 1 and 2 characterised in that the counterions to the sulfonate groups are selected from

⁺ H₃( 1 , 1 -di-n-propylhexylene), ⁺NH₃(2'-ethyl-hexyloxy-n-propylene),

or

4. A bisazo 1:1 copper complex dye compound according to claims 1 to 3 characterised in that n is 1,

D is the residue of a diazo component D' being naphtyl, K° is the residue of a component K⁰' being methyl substituted l-phenyl-5- pyrazolone,

5. A bisazo 1: 1 copper complex dye compound according to claims 1 to 4 characterised in that

n is 1,

D is substituted by at least one sulfonate group with

as counterion and

K° is substituted by at least one sulfonate group

as counterion.

6. A trisazo 1 : 1 copper complex dye compound according to claims 1 to 3 characterised in that n is 2,

D is the residue of a diazo component D' being unsubstituted naphtyl,

5 K° is the residue of a component K⁰' being selected from the group consisting of amino substituted qr unsubstituted naphtol, substituted or unsubstituted 1- phenyl-5-pyrazolone,

K¹ is the residue of a component K¹' being unsubstituted naphtol,

K² is the residue of a component K²' being selected from the group consisting o of methoxy substituted or unsubstituted phenol,

and at least three of the components D, K°, K¹ and/or K² are substituted with at least one alkyl-, alkoxy or aryl ammonium sulfonate group or with a sulfonate group having a Rhodamine B type or Rosinamine D type 5 counterion.

7. A trisazo 1: 1 copper complex dye compound according to claims 1 to 3 and 6 characterised in that 0 n is 2,

D is substituted by one mono-(Cι-ι₂alkyl)-ammonium sulfonate

5 K° is substituted by at least one mono-(Cι-ι₂alkyl)-ammonium sulfonate

K¹ is substituted by one mono-(Cι-ι₂alkyl)-ammonium sulfonate.

8. Process for the preparation of bis- or trisazo 1 : 1 copper complex dye compounds according to claims 1 to 7 characterised in that a bis- or trisazo dye compound according to general formula (I)

_D_|__N=:_N__Kn-|__{N = N} K₀ (I)

wherein n, D, K°, K¹ and K² are defined as in claim 1 ,

is metallized with a copper salt, reacted with the respective alkyl-, alkoxy- or aryl-amine or with Rhodamine B or

Rosinamine D and precipitated from the acidified aqueous or non-aqueous suspension.

9. Use of a bis- or trisazo 1 : 1 copper complex dye compound according to claims 1 to 7 as dyestuff in lacquers.

10. Use of a bis- or trisazo 1:1 copper complex dye compound according to claims 1 to 7 as dyestuff or charge control agent in ink-jet inks or electrographic toners.