Compositions: coating or plastic – Coating or plastic compositions – Marking
Reexamination Certificate
2000-03-15
2002-08-13
Klemanski, Helene (Department: 1755)
Compositions: coating or plastic
Coating or plastic compositions
Marking
C534S803000
Reexamination Certificate
active
06432185
ABSTRACT:
CROSS REFERENCES TO RELATED APPLICATIONS
The present invention relates to water-soluble acid dyes, to processes for preparing them, to their use for dyeing and printing natural and synthetic fiber materials, and to recording liquids, especially for the inkjet process, and liquid formulations for the pulp dyeing of paper, which comprise the dyes of the invention.
BACKGROUND OF THE INVENTION
The inkjet process constitutes a contactless printing process in which droplets of the recording liquid are guided from one or more nozzles onto the substrate that is to be printed. In order to obtain prints of high definition and resolution, the recording liquids and the dyes present in them must meet very stringent requirements in terms, in particular, of purity, freedom from particles, sclubility storage stability, viscosity, surface tension, and conductivity.
Very stringent requirements are imposed in particular on color strength, shade, brightness and fastness properties such as, for example, fastness to light, fastness to water and fastness to rubbing. High lightfastness in particular is of great importance for inkjet applications in exterior regions and for the production of inkjet prints of photographic quality. In some cases, these properties are obtained by using mixtures of various dyes having different properties. This is described, for example, in EP 0 825 233 A2 and U.S. Pat. No. 5,188,664.
The development of water-soluble magenta dyes having the desired combination of shade, high brightness and color strength, high lightfastness and good waterfastness, has to date proven very difficult (see, for example, P. Gregory, High-Technology Applications of Organic Colorants, Plenum Press, New York (1991), pp.197-201.
Water-soluble reactive dyes which can be used to dye or print cotton fibers are known. Furthermore, these dyes can also be used to produce inks for inkjet printing (Surface Coatings International 77 (1994) 36-41). However, the known reactive dyes have disadvantages in connection with the production of recording liquids for the inkjet process, especially in terms of the storage stability of inks and recording liquids and the lightfastness of the resulting prints.
SUMMARY OF THE INVENTION
There is therefore a need for water-soluble dyes which are superior to the known magenta dyes in terms in particular of shade, storage stability of the inks, and waterfastness and which at the same time meet the other properties required in the inkjet sector.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
It has surprisingly been found that the requirements imposed are met by water-soluble acid dyes defined hereinbelow.
The present invention provides acid dyes of the formula (I)
in which
R
1
is A—X—COOM, A—X—SO
3
M, OR
4
or NR
5
R
6
,
A is NR
7
or S,
X is a straight-chain or branched (C
1
-C
16
)-alkylene radical, a straight-chain or branched, hydroxyl-, carboxyl- or amino-substituted (C
1
-C
16
)-alkylene radical, an arylene radical or a hydroxyl-, carboxyl- or sulfo-substituted arylene radical;
R
4
, R
5
and R
6
independently of one another are hydrogen or (C
1
-C
4
)-alkyl or are (C
1
-C
4
)-alkyl substituted by one or more—e.g., 2, 3 or 4-hydroxyl, 2-hydroxyethoxy, (C
1
-C
4
)-alkoxy or amino groups,
R
7
is hydrogen, methyl or ethyl;
M is a monovalent cation or one equivalent of a polyvalent cation, and
n is 0 or 1.
Preference is given to compounds of the formula (I) in which X is a straight-chain or branched (C
1
-C
6
)-alkylene radical, a straight-chain or branched, hydroxyl-, carboxyl- or amino-substituted (C
1
-C
6
)-alkylene radical, a phenylene radical or a hydroxyl-, carboxyl- or sulfo-substituted phenylene radical. With particular preference X is a (C
1
-C
4
)-alkylene or phenylene radical. X is, for example, methylene, ethylene, ethane-1,1-diyl, propane-1,1-diyl, 1,2-propylene, 1,3-propylene, 1,6-hexylene, 2-methylpropane-1,1-diyl, 3-methylbutane-1,1-diyl, 2-methylbutane-1,1-diyl, 2-hydroxyethane-1,1-diyl, 2-carboxyethane-1,1-diyl, 3-carboxypropane-1,1-diyl, 5-aminopentane-1,1-diyl, 3-aminopropane-1,1-diyl or 4-aminobutane-1,1-diyl.
R
4
, R
5
and R
6
are for example hydrogen, methyl, ethyl, hydroxymethyl, hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, methoxyethyl or ethoxyethyl, preference being given to hydrogen, hydroxyethyl end hydroxypropyl.
R
7
is preferably hydrogen.
M is preferably hydrogen or a lithium, sodium, potassium or ammonium ion of formula (II)
R
8
R
9
R
10
R
11
N
+
(II)
in which R
8
, R
9
, R
10
and R
11
independently of one another are hydrogen, unsubstituted (C
1
-C
4
)-alkyl or (C
1
-C
4
)-alkyl substituted by one or more—e.g., 2, 3 or 4-hydroxyl or 2-hydroxyethoxy groups.
M, furthermore, is preferably a mixture of said cations.
In preferred water-soluble acid dyes of the formula (I), the radical R
1
is A—X—COOM and A—X—SO
3
M.
In particularly preferred dyes of the formula (I) of the invention, the radical R
1
is A—X—SO
3
M.
The acid dyes of the formula (I) of the invention can be prepared, for example, by reacting the reactive dye of the formula (III)
in which M and n are as already defined and X
1
is a halogen atom, preferably a chlorine or bromine atom, with one or more—e.g., 1, 2 or 3-compounds of the formulae (IV), (V), (VI) and/or (VII)
The reactions are normally conducted in an aqueous medium at a pH of from 3 to 14, preferably from 7.5 to 12, and at temperatures from 10° C. to 100° C., preferably from 40 to 80° C. The compounds of the formula (IV)-(VII) are judiciously used in from 1 to 2.5 times the molar amount per radical X
1
.
The compounds of the formula (III) can be prepared in a manner known per se, as described, for example, in EP-A-0 755 985, EP-A-0 832 940 or DE-A-196 07 851.
Examples of carboxylic acids of the formula (IV) that can be used are the following: glycine, N-methylglycine, 2-aminopropionic acid, 3-aminopropionic acid, 2-aminobutyric acid, 3-aminobutyric acid, 6-aminohexanecarboxylic acid, valine, leucine, isoleucine, serine, aspartic acid, glutamic acid, lysine, 1,3-diaminobutyric acid, 1,4-diaminopentanecarboxylic acid, 2-aminobenzenecarboxylic acid, 3-aminobenzenecarboxylic acid, 4-aminobenzenecarboxylic acid, 5-aminobenzene-1,3-dicarboxylic acid, thioglycolic acid and 3-mercaptopropanecarboxylic acid.
Examples of suitable sulfonic acids of the formula (V) are the following: aminomethanesulfonic acid, taurine, 2-aminopropanesulfonic acid, 3-amino-propanesulfonic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-mercaptopropanesulfonic acid and 4-amino-benzene-1,3-disulfonic acid.
Examples of hydroxy compounds of the formula (VI) that can be used include water, methanol, ethanol, isopropanol, n-butanol, isobutanol, glycol, propylene glycol, glycol monomethyl ether, glycol monoethyl ether and glycol monobutyl ether.
Examples of suitable amines of the formula (VII) include ammonia, methylamine, ethylamine, propylamine, hexylamine, ethanolamine, diethanolamine, 2-aminopropanol, 3-aminopropanol, dipropylamine, N-methylethanol, 3-dimethylaminopropylamine and 3-diethylaminopropylamine.
The acid dyes of the formula (I) of the invention can be isolated from the preferably aqueous reaction mixtures obtained initially by means of customary methods of working up: for example, by salting out, filtration or spray drying, directly or following partial or complete demineralization by means of membrane filtration. Alternatively, isolation can be dispensed with and the reaction mixture comprising dyes of the formula (I) of the invention can be converted directly into concentrated dye solutions by adding organic and/or inorganic bases and/or humectants and, if desired, after partial or complete demineralization by means of membrane filtration.
Examples of suitable inorganic bases are lithium hydroxide, lithium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate and ammonia. Examples of suitable organic bases are monoethanolamine, diethanolamine, triethanolamine, 2-aminopropanol, 3-aminopropanol, dipropanolamine, tripropanolam
Bauer Wolfgang
Geisenberger Josef
Menzel Heidemarie
Pedrazzi Reinhard
Clariant GmbH
Hanf Scott E.
Jackson Susan S.
Klemanski Helene
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