Solid pigment preparations

Compositions: coating or plastic – Materials or ingredients – Pigment – filler – or aggregate compositions – e.g. – stone,...

Reexamination Certificate

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C106S402000, C106S420000, C106S429000, C106S440000, C106S441000, C106S447000, C106S453000, C106S460000, C106S465000, C106S471000, C106S476000, C106S479000, C106S487000, C106S491000, C106S493000, C106S494000, C106S495000, C106S496000, C106S497000, C106S498000, C106S501100, C106S503000

Reexamination Certificate

active

06596073

ABSTRACT:

The invention relates to solid pigment preparations, to processes for preparing them and to their use for pigmenting natural and synthetic materials, especially for pigmenting and colouring building materials such as concrete, plasters, mortar, asphalt, for example, aqueous coating compositions, varnishes and emulsion paints, aqueous coating compositions for fabric and paper, paper in the pulp, and polymers, e.g. synthetic or semisynthetic fibre materials.
For pigmenting in the abovementioned applications it is nowadays customary to use aqueous or aqueous/organic pigment preparations. Such preparations are disclosed, for example, in DE-A 195 11 624. In the course of preparing the preparations, dispersants or emulsifiers are used which stabilize the pigment particles physically in their finely divided form in an aqueous or aqueous/organic medium. Also critical to the selection of the dispersants is their compatibility in the various application media. For example, the preparations should be easy to incorporate into the application medium without flocculation or reaggregation of the pigment particles.
Customarily, anionic, cationic, nonionic or amphoteric dispersants, in polymeric form as well where appropriate, are employed.
In many cases, aqueous pigment preparations contain so-called dryout preventatives or agents for enhancing the freeze resistance, in the form for example of volatile organic solvents such as glycols or nonvolatile polyetherpolyols (polyglycols), for example.
These additives are of particular importance for the storage of such liquid preparations, but not for the application per se.
Whereas volatile organic solvent additives possess ecological disadvantages in the application, polymeric nonvolatile additives often have the disadvantages that, for example, they impair the rheology of the preparations or they greatly complicate the microbiological preservation of the preparations, or else that they remain in the application medium and impair, for example, the drying properties (e.g. in emulsion paints).
There is therefore a need for new pigment preparations which are comparable with or superior to liquid preparations in terms of their application properties and which do not possess the disadvantages described. There is also a need for pigment preparations which may be used universally in different aqueous application systems, i.e. which are highly compatible with a large number of binders.
DE 19 523 204 describes pulverulent pigment formulations comprising not only organic or inorganic pigment but also specific dispersants from the group of the novolaks or alkoxylated fatty acid derivatives and, as further component, a water-soluble mixture of polyvinyl alcohol and vinyl alcohol or vinyl alcohol copolymers, and which can be used to pigment plasters and architectural coating dispersions. In particular, the solid products of DE-A 195 23 204 further require the addition of so-called dedusters in order to be able to be referred to as low-dust products.
DE 3 839 865 describes polyvinyl alcohols adsorbed on pigments, which may be used as binders in paper coating slips and paper coatings and which are notable for improved low-temperature solubility of the polyvinyl alcohols.
In both cases, the application possibilities of the products obtained are limited.
Both references describe products whose particle sizes are dependent on the particle size of the pigment suspension used; as a result, in the case of very finely divided colour pigments having average particle diameters of <1 &mgr;m, low-dust products are already unlikely per se.
The pigment formulations specified in DE 19 523 204 are also in need of improvement with regard to universal usefulness, such as compatibility with a modern aqueous binder system (ready miscibility, flocculation stability, colour acceptance, high colour yield, and colour stability over time after tinting) in, for example, white emulsion paints based on silicone, PU, alkyd or acrylic dispersion binders, especially those with a pigment volume concentration (PVC) above the critical pigment volume concentration (CPVC).
It is an object of the present invention, therefore, to provide solid pigment preparations which do not possess the abovementioned disadvantages.
The invention accordingly provides solid pigment preparations comprising
a) at least one pigment,
b) at least one optionally ionically modified phenol-styrene-polyglycol ether and
c) at least one organic thickener.
By pigments are meant preferably particulate solids having an average primary particle size of from 0.01 to 100 &mgr;m, preferably from 0.01 to 10 &mgr;m. In the context of this specification, pigments also preferably include those particulate solids having a solubility in water at 20° C. of <100 mg/l; in particular, they are insoluble in water or aqueous-organic media.
The pigments that are present in the preparations of the invention are not subject to any restriction.
Suitable inorganic pigments are, for example, oxide pigments such as iron oxides, titanium dioxides, chromium oxides, zinc oxides, manganese iron oxides, nickel and chromium titanium dioxides, rutile mixed-phase pigments. Further inorganic pigments are zinc sulphides, ultramarine, sulphides of the rare earths, and bismuth vanadate.
Suitable inorganic fillers which are likewise understood as pigments in the context of this invention are, for example, inorganic compounds with a low colouring power, such as natural iron oxides, zinc sulphide, aluminium oxide, heavy spar, siliceous earth, silicates (mica, clay, talc), calcium carbonate and calcium sulphate.
Furthermore, depending on the field of use, the inorganic pigments may also have been organically or inorganically aftertreated.
Suitable organic pigments are, for example, those of the monoazo, disazo, laked azo, &bgr;-naphthol, Naphtol AS, benzimidazolone, disazo condensation, azo metal complex, isoindolinone and isoindoline series, and also polycyclic pigments of, for example, the phthalocyanine, quinacridone, perylene, perinone, thioindigo, anthraquinone, dioxazine, quinophthalone and diketopyrrolopyrrole series.
Also included are laked dyes such as Ca, Mg and Al lakes of dyes containing sulphonic acid groups and/or carboxylic acid groups, and also carbon blacks, which for the purposes of this specification are taken to be pigments and of which a large number are known, for example, from the Colour Index, 2nd edition.
As carbon blacks, mention may be made, for example, of the following: acidic to alkaline blacks from the gas black or furnace black process, and also chemically surface-modified blacks, examples being sulpho- or carboxyl-containing blacks.
Also suitable are mixed crystallizations (solid solutions) of the abovementioned organic pigments, mixtures of organic and/or inorganic pigments, metal pigments coated with inorganic pigments or carbon black, mica pigments or talc pigments, e.g. mica coated with iron oxide by CVD processes, and also mixtures of the abovementioned pigments with one another.
Optionally ionically modified phenol-styrene polyglycol ethers of component b) are known, for example, from DE-A-19 644 077.
Preferred compounds of component b) have an HLB of from 10 to 20, in particular from 12 to 18.
Preferred alkoxylation products of styrene-phenol condensates are those of the formula (X)
in which
R
15
denotes hydrogen or C
1
-C
4
-alkyl,
R
16
represents hydrogen or CH
3
,
R
17
denotes hydrogen, C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-alkoxycarbonyl or phenyl,
m denotes a number from 1 to 4,
n denotes a number from 6 to 120,
R
18
is identical or different for each unit indicated by n and represents hydrogen, CH
3
or phenyl, and, where CH
3
is present in the various —(—CH
2
—CH(R
18
)—O—)— groups, R
18
represents CH
3
in from 0 to 60% of the total value of n and R
18
represents hydrogen in from 100 to 40% of the total value of n, and, where phenyl is present in the various —(—CH
2
—CH(R
18
)—O—)— groups, R
18
represents phenyl in from 0 to 40% of the total value of n and R
18
represents hydrogen in from 100 to

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