Mixed color pigment precursors and their use

Details Mixed color pigment precursors and their use Mixed color pigment precursors and their use

2000-03-22

2002-07-23

Raymond, Richard L. (Department: 1624)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C540S135000, C540S140000

Reexamination Certificate

active

06423839

ABSTRACT:

The present invention relates to substituted azophthalocyanine pigment precursors which produce uniform mixed colours when their solubilising groups are splitted off.
Mixed colour pigmentations are usually produced by the combination of differently coloured pigments. In contrast to more complicated colourants, simple colourants have narrow absorption bands so that their mixtures have high colour saturations at high tinctorial strength when standard pigment dispersion methods are used, for example those customarily used for paint systems and printing inks.
Surprisingly, however, it has been found that the use of known pigment precursors of the phthalocyanine class in admixture with pigment precursors of different colour yields results which are not entirely satisfactory. The shades obtained are markedly duller than expected and depend to an undesirable degree on the elimination conditions. During the formation of the pigments, a substantial proportion of the mass of the molecule is eliminated, which must be disposed of or which may result in changes of the matrix properties, for example in loss of solidity or in inhomogeneities.
Quite unexpectedly, the same mixture yields pigmentations which, depending on the substrate, have different shades, such as for example a shade which is markedly different on wood than on leather, plastics, aluminium oxide, boron nitride or silicium nitride, or which even differs in different photo-sensitive compositions. Correspondingly, composite materials have non-uniform shades. This is a problem in particular for world companies interested in having so-called corporate colours which they may even use as trademarks or in advertising (for example well-known big producers of beverages).
For improvement, substantial expenditure is thus necessary in order to achieve a result on a specific material which is still not fully satisfactory, the advantages of the pigment precursor technology thus being virtually counterbalanced. In addition, the solubility of known pigment precursor mixtures is unsatisfactory so that only partially satisfying tinctorial strengths can be obtained.
WO 98/45756 discloses mixtures of copper phthalocyaninetetrakis(N-tert-butoxycarbonyl)-sulfonic acid hydrazide with an at least equimolar amount of N-substituted Pigment Yellow 109 or Pigment Violet 37. However, these mixtures yield only pigmentations having a less than satisfactory colour saturation and fastness properties, since a not clearly defined, inferior product mixture is obtained instead of the desired copper phthalocyaninetetrasulfonic acid hydrazide.
U.S. Pat. No. 2,351,119 discloses violet and green colourants of the phthalocyanine series which are substituted by azo groups and which may be used in paint systems or printing inks. According to JP 60/67949, analogous products are suitable as photoreceptors and, according to JP 60/260674, as infrared absorbers and, according to JP 63/293090, as optical recording materials.
JP-A-63/293090 discloses optical recording materials containing compounds, some of which contain 3-hydroxy-2-naphtoic acid amide as partial structure. However, these materials can only be used in the infrared range as their sensitivity to a visible laser beam (400-700 nm) is too low and as furthermore the reflectivity of the solid does not change enough during irradiation.
Although these sparingly soluble colourants of the phthalocyanine series have been known for several decades, they have to date neither been converted into a useful pigmentary form nor have they been used as pigments in practice.
Surprisingly, it has now been found that novel compounds containing this chromophore can be excellently used as pigment precursors for mixed colour pigmentations. The pigmentations obtainable therefrom are surprisingly more uniformly coloured, even on different materials or on composite materials, and also have a higher colour saturation than pigmentations starting from known mixtures of pigment precursors of different colours.
The novel compounds are additionally also distinguished by a surprisingly high solubility in customary solvents. In spite of the higher molecular weight, fewer and/or smaller solubilising groups are required than in the case of the pigment precursor mixtures known so far. Because of this, it is advantageous if less mass is eliminated per weight unit to obtain the pigment, and it is also possible to obtain pigmentations of higher tinctorial strength.
Mixed colours are understood to mean coloured pigments which have absorption maxima in two of the three spectral ranges 400-500 nm, 500-600 nm and 600-700 nm, and the maximum transmission of which is in the third of these spectral ranges. Owing to the structure of the novel compounds there is usually at least one absorption maximum at 600-700 nm and a maximum transmission in the range of 400-600 nm. Preferred mixed colours are green, violet and brown, particularly preferably green.
Accordingly, this invention relates to a compound of formula
m, n and p are each independently of one another 0 or 1,
R
1
, R
2
, R
3
and R
4
are each independently of one another a group of formula
R
5
is C
1
-C
12
alkyl, C
1
-C
12
alkoxy, cyano or
R
6
, R
7
and R
q
are H, E
5
, C
1
-C
12
alkyl,
R
8
is H, halogen, C
1
-C
12
alkyl or C
1
-C
12
alkoxy,
R
10
, R
11
, R
12
, R
13
and R
14
are each independently of one another H, C
1
-C
12
alkyl, C
1
-C
12
-alkoxy, trifluoromethyl, nitro, halogen or
R
15
is C
1
-C
12
alkyl, or C
6
-C
10
aryl which is unsubstituted or substituted by 1 to 3 substituents selected from the group consisting of C
1
-C
12
alkyl, C
1
-C
12
alkoxy, trifluoromethyl, nitro and halogen,
M is two hydrogen atoms or a divalent metal, oxometal, halogenometal or hydroxymetal, where the divalent metal may be additionally coordinated at one or two identical or different neutral ligands, and
E
1
, E
2
, E
3
, E
4
, E
5
, E
6
and E
7
are each independently of one another hydrogen or a group of formula
 where at least one group E
1
, E
2
, E
3
, E
4
, E
5
, E
6
or E
7
in a group R
1
, R
2
, R
3
or R
4
is not hydrogen, and L is any group suitable for solubilising.
Divalent metals are, for example, Cu(II), Zn(II), Fe(II), Ni(II), Ru(II), Rh(II), Pd(II), Pt(II), Mn(II), Mg(II), Be(II), Ca(II), Ba(II), Cd(II), Hg(II), Sn(II), Co(II) or Pb(II). Divalent oxometals are, for example, V(IV)O, Mn(IV)O, Zr(IV)O or Ti(IV)O. Divalent halogenometals are, for example, Fe(III)Cl, In(IIl)Cl or Ce(III)Cl. Divalent hydroxymetals are, for example, Al(III)OH, Cr(III)OH, Bi(III)OH or Zr(IV)(OH)
2
.
Neutral ligands are understood to mean molecules containing at least one heteroatom selected from the group consisting of N, O, P and S. Ligands suitable for metal phthalocyanines are known.
In tautomers, E
1
, E
2
, E
3
, E
4
, E
5
, E
6
and/or E
7
are bound to another N— or O-atom, which entails the shifting of double bonds.
m, n and p are preferably all 1.
R
1
, R
2
, R
3
and R
4
are each preferably a group of formula
 particularly preferably a group of formula
R
5
is preferably C
1
-C
12
alkyl, more preferably methyl.
R
6
is preferably H, E
5
, methyl, ethyl, branched C
3
-C
8
alkyl,
 particularly preferably H, methyl, tertiary C
4
-C
8
alkyl or phenyl.
R
7
is preferably methyl, tertiary C
4
-C
8
alkyl or, particularly preferably,
R
8
is preferably H or methoxy, particularly preferably H.
R
10
, R
11
, R
12
, R
13
and R
14
are preferably H, C
1
-C
4
alkyl, C
1
-C
4
alkoxy, nitro or halogen, particularly preferably H.
R
15
is preferably C
1
-C
4
alkyl, or phenyl which is unsubstituted or substituted by C
1
-C
4
alkyl,
C
1
-C
4
alkoxy, nitro or halogen; methyl or phenyl are particularly preferred.
M is preferably H
2
, Cu(II), Zn(II), Fe(II), Ni(II), Pd(II), Mn(II), Mg(II), Co(II), Pb(II) or Al(III)OH, particularly preferably H
2
, Cu(II), Zn(II), Fe(II), Ni(II), Pd(II), Co(II) or Pb(II), very particularly preferably Cu(II) or Ni(II), most preferably Cu(II). The divalent metal is preferably not coordinated with any additional ligand.
L is preferably a group of formula
 wherei

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