Black trisazo metal complex dyes

Details Black trisazo metal complex dyes Black trisazo metal complex dyes

2001-03-23

2004-06-15

Klemanski, Helene (Department: 1755)

Compositions: coating or plastic

Coating or plastic compositions

Marking

C106S031480, C106S031500, C534S708000, C534S715000

Reexamination Certificate

active

06749674

ABSTRACT:

CROSS-REFERENCES TO RELATED APPLICATIONS
The present invention is described in the German priority application No. 100 15 004.7, filed Mar. 25, 2000, which is hereby incorporated by reference as is fully disclosed herein.
FIELD OF THE INVENTION
The present invention describes black trisazo complex dyes, processes for preparing them and their use in recording fluids, especially for the inkjet printing process, and also as colorants for electrophotographic toners, powder coatings and color filters.
BACKGROUND OF THE INVENTION
The inkjet process is a contactless printing process, which generally speaking exists in two forms: drop-on-demand and continuous stream. The drop-on-demand principle is that the ink in the form of a droplet from a nozzle is placed in the right place at the right time, whereas in continuous stream the ink issues continuously and then either impinges on the receiving medium, for example paper, or is deflected into a collecting vessel. To obtain prints of high definition and resolution, the recording fluids and dyes present in them have to meet very stringent requirements, especially with regard to lightfastness, waterfastness, purity, freedom from particles, solubility, stability in storage, viscosity, surface tension, conductivity, color strength, hue and brilliance (EP-A-0 825 233 and U.S. Pat. No. 5,188,664).
The most important part in all this is played by the dyes used in the inks. Although a large number of dyes have been developed, there are only few which meet the requirements of a modern inkjet printing process.
Initially, traditional dyes from the food, textile and paper sectors were used after specific modification for the inkjet application. This may be illustrated with reference to C.I. Food Black 2 (1), which, as well as structurally similar compounds, was used as a black dye in inks (JP 59-093,766).
However, the prints it provides were not a clean black, but bluish black. In addition, the lightfastnesses are unsatisfactory. To minimize these disadvantages, the substituents on C.I. Food Black 2 are varied to obtain black dyes of the general formula (2) which provide a more neutral black and possess improved waterfastness (U.S. Pat. No. 5,053,495).
True, the introduction of the carboxyl groups did provide improved waterfastness, but at the same time had an adverse effect on crockfastness because the dye molecules form aggregates which penetrate into the receiving medium only to a very small extent, if at all.
Improved lightfastness was obtained by using metal complexes of disazo and tetraazo dyes such as C.I. Direct Black 62 (3) (DE-A-19831095).
Although it provides improved fastness properties, dye (3) does not meet all the requirements. For example, as well as having low stability in storage it is insufficiently soluble in the application medium.
SUMMARY OF THE INVENTION
There is accordingly a need for dyes which are superior to prior art blacks especially in ink lightfastness, waterfastness, solubility and stability in storage and at the same time possess the other properties needed for the inkjet sector. It has been found, surprisingly, that the stated requirements are fulfilled by water-soluble dyes defined hereinbelow.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention accordingly provides metal complexes of trisazo dyes of the general formula (4)
where
R
1
is aryl substituted by one or more, for example 2, 3, 4 or 5, substituents selected from the group consisting of OH, O(C
1
-C
6
)-alkyl, O(C
1
-C
6
)-alkyl-COOM, O(C
1
-C
6
)-alkyl-SO
3
M, O(hydroxy(C
1
-C
6
)-alkyl), (C
1
-C
6
)-alkyl, COOM, SO
3
M, SO
2
NH
2
, SO
2
N(hydroxy(C
1
-C
6
)-alkyl)
2
, SO
2
NH(C
1
-C
6
)-alkyl, SO
2
N((C
1
-C
6
)-alkyl)
2
, NH
2
, NH(C
1
-C
6
)-alkyl, NHacyl, NHaryl, N(hydroxy(C
1
-C
6
)-alkyl)
2
, N((C
1
-C
6
)-alkyl)
2
and halogen;
R
2
is OH, O(C
1
-C
6
)alkyl, COOM or SO
3
M;
R
3
, R
4
and R
5
are identical or different and are each selected from the group consisting of H, OH, O(C
1
-C
6
)-alkyl, O(C
1
-C
6
)-alkyl-COOM, O(C
1
-C
6
)-alkyl-SO
3
M, O(hydroxy(C
1
-C
6
)-alkyl), (C
1
-C
6
)-alkyl, COOM, SO
3
M, SO
2
NH
2
, SO
2
N(hydroxy(C
1
-C
6
)-alkyl)
2
, SO
2
NH(C
1
-C
6
)-alkyl, SO
2
N((C
1
-C
6
)-alkyl)
2
, NH
2
, NH(C
1
-C
6
)-alkyl, NHacyl, NHaryl, N(hydroxy(C
1
-C
6
)-alkyl)
2
, N((C
1
-C
6
)-alkyl)
2
, and halogen,
R
6
is a mono- or bicyclic carbocyclic or heterocyclic aromatic which is unsubstituted or substituted by one or more, for example 2, 3, 4 or 5, substituents selected from the group consisting of OH, O(C
1
-C
6
)-alkyl, O(C
1
-C
6
)-alkyl-COOM, O(C
1
-C
6
)-alkyl-SO
3
M, O(hydroxy(C
1
-C
6
)-alkyl), (C
1
-C
6
)-alkyl, COOM, SO
3
M, SO
2
NH
2
, CONH-phenyl, SO
2
NH-phenyl, SO
2
N(hydroxy(C
1
-C
6
)-alkyl)
2
, SO
2
NH(C
1
-C
6
)-alkyl, SO
2
N((C
1
-C
6
)-alkyl)
2
, NH
2
, NH(C
1
-C
6
)-alkyl, NHacyl, NHaryl, N(hydroxy(C
1
-C
6
)-alkyl)
2
, N((C
1
-C
6
)-alkyl)
2
, halogen and phenylsulfo, or is a similarly substituted pyrazole or pyridone radical; and
M is hydrogen, a monovalent metal cation, one equivalent of a polyvalent metal cation or an unsubstituted or alkyl-, alkoxyalkyl- or hydroxyalkyl-substituted ammonium ion.
Preference for the purposes of the present invention is given to those dyes of the formula (4) where the complexed metal atom is aluminum, chromium, iron, cobalt, nickel or copper.
In the above definitions, aryl is preferably phenyl or naphthyl and acyl is preferably formyl, acetyl or propionyl.
In the trisazo metal complex dyes of the invention, the metal atom is preferably bonded as depicted in the formula (4a)
where
M
1
is preferably Al, Cr, Fe, Co, Ni or Cu, especially Cu,
R
20
is C
1
-C
6
-alkyl,
n is 0 or 1, and
X is a chemical bond, —CO— or —SO
2
—.
Preferably R
1
is a phenyl or naphthalene radical substituted by 1, 2 or 3 substituents selected from the group consisting of OH, O(C
1
-C
6
)-alkyl, COOM, SO
3
M and NH
2
.
Preferably R
2
is OH or COOM.
Preferably R
3
is H, methyl or O(C
1
-C
6
)-alkyl.
Preferably R
4
and R
5
are each H, COOM or SO
3
M.
Preferably R
6
is a phenyl, naphthyl, pyridyl or pyrazole radical substituted by 1, 2 or 3 substituents selected from the group consisting of OH, O(C
1
-C
6
)-alkyl, COOM, SO
3
M, NH
2
, NHaryl, NHacyl and phenylsulfo.
Preferably M is H, Na, K, Li, Ca/2 or ammonium.
Particular preference is given to the copper complexes of the dyes of formula (4) where R
1
-R
6
and M each have the preferred meanings mentioned.
Particularly preferred dyes conform to the following formulae (5)-(13):
The present invention also provides a process for preparing a metal complex of a trisazo dye of the formula (4), which comprises diazotizing a naphtholamine of the formula (14)
and coupling the resultant diazonium salt with a compound of the formula (15)
H—R
6
  (15)
and coupling the resultant compound of the formula (16)
with the diazonium salt of the formula (17)
where X
⊖
is an anion, for example chloride or sulfate, and complexing with a metal salt solution.
It is also possible first to carry out a coupling of the compound of the formula (14) with the diazonium salt (17), then a diazotization and the coupling with the compound (15).
It is additionally possible under the same conditions to carry out a coupling of the diazonium salt (17) onto the building block (14), then another diazotization and the coupling with the compound (15). The final step is the metallization with a metal salt solution carried out either according to the same method or by the method indicated in example X.
The diazotization and coupling steps mentioned may be carried out according to customary methods.
The diazotizations are preferably carried out in aqueous solution or suspension with sodium nitrite at 0 to 10° C. and a pH between 1 and 3.
The azo couplings are preferably carried out in aqueous solution or suspension at 0 to 20° C. and a pH between 3 and 9.
The molar ratios between the particular diazonium salt and the particular coupling component are preferably 1:(0.8 to 2).
The complexing with metal M
1
is advantageously effected by adding an aqueous metal

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