Aqueous carbon black dispersions

Compositions: coating or plastic – Coating or plastic compositions – Marking

Reexamination Certificate

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C106S031890, C106S031900, C524S156000, C524S217000

Reexamination Certificate

active

06685769

ABSTRACT:

CROSS-REFERENCE TO RELATED APPLICATION
This application relates to German Application DE 199 34 282.2, filed Jul. 21, 1999, which disclosure is incorporated herein by reference.
FIELD OF THE INVENTION
The invention concerns aqueous, cationically
on-ionically stabilized carbon black dispersions, a method for their production and their use.
BACKGROUND OF THE INVENTION
Aqueous carbon black dispersions are used in formulations for printing inks and also directly as inks, for example, in inkjet printers.
The inkjet printing method is a known reproducing technology in which the printing ink is transferred without pressure, that is, without contact of the print head with the print medium. Droplets of ink are sprayed from a jet or nozzle onto a receiving material during which deflection of the droplets can be electronically controlled. This technology, also known as pressureless printing, is particularly suitable for printing products having irregular surfaces and packaging because there is a certain distance between the print head and the printed material. The printing method is very flexible and relatively economical and is therefore also used in computer printing, for example, as a workplace printer. The inkjet method is also increasingly used in the industrial field, for example, in outside advertising. In outside advertising, the ink must meet special requirements of light-fastness and water resistance. In addition, the color components must be very finely divided to prevent printing jets from clogging. Both dyes as well as, more recently, pigments have been used as coloring substances. Pigments have the advantage over dyes that the light-fastness of pigments is very high and that pigments are water-resistant. Pigments have a disadvantage in comparison to dyes, namely that they only form stable dispersions with a long storage life when treated with surface-active substances (surfactants). Pigment particles are not present in the form of primary particles but rather in the form of aggregates. Pigment aggregates are larger than soluble dyes. If pigment aggregates are not sufficiently finely dispersed, they clog the jets of printing heads. Moreover, large aggregates alter the light absorption properties of the pigment black. The result is a graying of the print and a loss of covering power.
Early patents that disclose the use of carbon blacks as pigment blacks in inkjet inks are U.S. Pat. No. 5,085,698 and U.S. Pat. No. 5,320,668. The use of water-soluble acrylates for pigment stabilization is described therein.
The production of aqueous carbon black dispersions with carbon blacks having an average primary particle size of not greater than 30 nm and a DBP No. of at least 75 ml/100 g is known from U.S. Pat. No. 5,538,548.
The production of aqueous carbon black dispersions using water-soluble organic solvents and water-soluble acrylic resins is also known (U.S. Pat. No. 5,609,671).
A disadvantage of the known aqueous carbon black dispersions is running or bleeding after they have been sprayed onto a carrier. Commercial dispersions have zeta potentials <0 mV. A purposeful flocculation of the dispersion during or after its application onto the carrier can be readily achieved by positive surface charging of the dispersed particles (zeta potentials >0 mV), which counteracts bleeding.
SUMMARY OF THE INVENTION
Therefore, it is an object of the invention to produce carbon black dispersions that do not have the disadvantages mentioned above and that, in addition, are stable during storage.
The invention has as its subject matter aqueous carbon black dispersions containing the following components in addition to water relative to the total dispersion:
Carbon black: 1 to 45% by weight, preferably 5 to 25% by weight;
Cationic surfactant: 1 to 40% by weight, preferably 5 to 25% by weight; and
Non-ionic surfactant: 0.5 to 10% by weight, preferably 2 to 10% by weight.
At least one compound from the following group can be used as cationic surfactant:
R
1
—COOH: ricinoleic acid
R
2
, R
3
, R
4
: can be identical or different and consist of C
1
to C
5
alkyl groups or
R
5
: C
1
to C
5
alkyl groups,
n: natural number 1-5,
Akypoquat 132 (cationic fatty ester (CTFA: Lauroyl PG-trimonium chloride)) of the Kao Chemicals GmbH Company, Bayowet FT 738 VP AC 2023 (quaternary fluoroalkyl ammonium iodide) of the Bayer AG Company, DP2-7949 (aqueous solution of cationic homopolymers) of the Ciba Geigy Chemicals Company, DP 7-7961 (aqueous solution of cationic polymers) of the Ciba Geigy Chemicals Company, DP 7-7962 (aqueous solution of cationic polymers) of the Ciba Geigy Chemicals Company, DP 7-7963 (aqueous solution of cationic polymers) of the Ciba Geigy Chemicals Company, Epikuron 200 (phosphatidyl choline) of the Lukas Meyer Company, ethoxamine SF11 (ethoxylated fatty amine with 11 moles ethylene oxide) of the Witco Company, ethoxamine SF 15 (ethoxylated fatty amine with 15 moles ethylene oxide) of the Witco Company, Forbest 13 (neutral compound, acidic polyester and fatty alcohol) of the Lukas Meyer Company, Forbest 610 (carboxylic acid-diamine preparation) of the Lukas Meyer Company, Magnafloc 1797 (aqueous solution of cationic cross-linked condensation resins) of the Ciba Specialty Chemicals Company, Protectol KLC 50 (dimethyl-C 12/14-alkylbenzyl ammonium chloride in water (approximately 50%)) of the BASF Company, Rewoquat CPEM (coconut ethoxymethyl- ammoniumthiosulfate) of the Witco Surfactants GmbH Company, Rewoquat RTM 50 (ricinoleic acid propylamidotrimethylammonium methosulfate) of the Witco Surfactants GmbH Company, Sochamines 35 (alkylimidazoline) of the Witco Surfactants GmbH Company.
In one embodiment the cationic surfactant can be a wetting agent combination or a mixture of at least two cationic wetting agents.
At least one compound from the group of cross-linked polyoxyethylene acrylic acid, fatty alcohol oxyethylates, nonylphenolpolyglycol ether, polyvinylpyrrolidone, glycerol fatty acid ester, propyleneglycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, tetraoleic acid, polyoxyethylene sorbitol, polyoxyethylene alkyl ether, polyoxyethylenealkylphenyl ether, polyoxyethylenepolyoxypropylene glycol, polyoxyethylenepolyoxypropylene alkyl ether, polyethyleneglycol fatty acid ester, higher fatty acid alcoholic esters and polyhydric alcoholic fatty acid esters can be used as non-ionic surfactants.
The dispersion can contain a mixture of at least two non-ionic wetting agents in a preferred embodiment.
Pigment blacks with an average primary particle size of 8 to 80 nm, preferably 10 to 35 nm and a DBP number of 40 to 200 ml/100 g, preferably 60 to 150 ml/100 g can be used as the carbon black. Pigment blacks produced by means of furnace black methods, gas black methods, channel black methods or flame black methods can be used as the carbon blacks. Examples thereof are color black FW 200, color black FW 2, color black FW 2 V, color black FW 1, color black FW 18, color black S 170, color black S 160, special black 6, special black 5, special black 4, special black 4A, Printex 150 T, Printex U, Printex V, Printex 140 U, Printex 140 V, Printex 95, Printex 90, Printex 85, Printex 80, Printex 75, Printex 55, Printex 45, Printex 40, Printex P, Printex 60, Printex XE 2, Printex L 6, Printex L, Printex 300, Printex 30, Printex 3, Printex 35, Printex 25, Printex 200, Printex A, Printex G. special black 550, special black 350, special black 250, special black 100, manufactured by Degussa Hüls AG, Germany. In a preferred embodiment of the invention gas blacks are used.
In a further embodiment, carbon blacks containing Si and known from DE 19613796, WO 96/37447 and WO 96/37547 and metal-containing carbon blacks known from WO 98/42778 can be used.
The carbon black dispersed in the dispersion can have an average particle size of 50 to 250 nm in an embodiment of the invention.
Further subject matter of the invention is constituted by a method of producing the aqueous carbon black dispersion that is characterized in that carbon black is dispersed together with the

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