Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...
Reexamination Certificate
2000-05-15
2002-12-03
Sanders, Kriellion A. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Processes of preparing a desired or intentional composition...
C524S100000, C524S140000, C524S157000, C524S158000, C524S167000, C524S230000, C524S248000, C524S368000
Reexamination Certificate
active
06489382
ABSTRACT:
BACKGROUND OF THE INVENTION
The invention relates to preparations of solids containing graft copolymers, to their preparation, and to formulations comprising them and to their use for pigmenting natural and synthetic materials.
Aqueous and non-aqueous coating compositions (emulsion paints, other paints), for example aqueous coating materials for fabric and paper, paper pulp, building materials, especially concrete, plasters, mortar and asphalt, natural and synthetic polymers, and aqueous and non-aqueous inks, especially inkjet inks, are nowadays pigmented using particulate solids, especially organic and inorganic pigments, together with dispersants, in the form of preparations. The function of the dispersants is the physical stabilization of the fine-particled solids (primary particles) in the preparation and/or in the application medium against reaggregation, reagglomeration or flocculation. They further serve for disaggregation and stabilization of the powder pigments or solids, which are generally in the form of aggregates or agglomerates, while the preparations are being prepared, and in particular in connection with the synthesis of organic colour pigments, as auxiliaries for controlling the morphology, crystallization and surface properties.
The dispersants used are generally nonionic, anionic, cationic or amphoteric compounds having molar masses of in general from 500 to 500,000 g/mol. In many cases, ionic dispersants are polyelectrolytes, which are usually used for aqueous applications and which stabilize the fine-particled solids by electrostatic repulsion alone or in conjunction with steric stabilization. Nonionic dispersants stabilize the particles by means of steric effects and are characterized by groups with affinity for the pigment and groups which have affinity or are soluble in the dispersion medium or application medium, e.g. binder. Electrostatic, hydrophobic and hydrogen-bond forces are primarily responsible for the interaction between dispersants and particulate solids.
Ionic dispersants have the disadvantage that their stabilizing action is heavily dependent on the electrolyte concentration of the dispersion medium or application medium.
With many particulate solids, especially organic and inorganic pigments, hydrophobic interactions with the dispersants cannot be utilized to a sufficient extent owing to the predominantly hydrophilic nature of the particle surfaces. In addition to the resultant inadequate stabilization of the particles, the preparations often have further disadvantages, such as increased foaming in conjunction with nonionic wetting agents and/or dispersants and polyelectrolytes, excessive dispersant concentrations, poor product properties such as poor colour yield in the case of organic and inorganic colour pigments, and also incompatibilities in the application media, such as flocculation or even separation of the components.
There is therefore a need for preparations of solids, especially pigment preparations or water-insoluble dye or brightener preparations, having improved properties relative to the prior art.
SUMMARY OF THE INVENTION
Preparations of solids have now been found comprising
a) a particulate solid, especially an organic or inorganic pigment, carbon black, extender pigment or metal pigment, water-insoluble or sparingly water-soluble dye or optical brightener and
b) a water-dispersible graft copolymer built up from at least one hydrophobic, ethylenically unsaturated monomer, optionally one or more ethylenically unsaturated hydrophilic monomers, and at least one natural protective colloid or protective colloid obtained from a natural protective colloid by derivatization or thermal, enzymatic, oxidative, hydrolytic or bacteriological degradation having an average molar mass of M
n
>500g/mol.
DETAILED DESCRIPTION OF THE INVENETION
Particulate Solids of Component a)
By particulate solids are meant organic or inorganic solids which are insoluble or sparingly soluble in water and organic solvents, sparing solubility in water meaning a solubility of less than 100 mg/l at 20° C., and which have a primary particle size of less than 100 &mgr;m, in particular less than 10 &mgr;m. They can be polymeric, amorphous or crystalline in nature and may possess lyophilic, lyophobic or amphiphilic properties, in particular lyophilic or amphiphilic, and especially hydrophilic, properties.
For the purposes of the invention they are not subject to any restriction. Particular preference is given to organic and inorganic pigments, water-insoluble dyes and optical brighteners, carbon blacks, and also metal pigments and extender pigments.
Suitable pigments and fillers are those known from the prior art as documented, for example, by Lückert, Pigment+Fullstoff Tabellen, 5
th
Edition, Laatzen, 1994.
Inorganic white pigments that may be mentioned include especially oxides, such as titanium dioxide, zinc oxide (ZnO, zinc white), zirconium oxide, carbonates such as lead white, for example, sulphates, such as lead sulphate, for example, and sulphites such as zinc sulphite, for example, and lithopones; titanium dioxide is particularly preferred.
Inorganic colour pigments that may be mentioned include those from the group of the oxides and hydroxides in the form of their inorganic single compounds or mixed phases, especially iron oxide pigments, chromium oxide pigments and mixed-phase oxide pigments with a rutile or spinel structure, and also bismuth vanadate, cadmium, cerium sulphide, chromate, ultramarine and iron blue pigments.
Examples of iron oxide pigments are Colour Index Pigment Yellow 42, Pigment Red 101, Pigment Blue 11, Pigment Brown 6, and transparent iron oxide pigments. Examples of chromium oxide pigments are Colour Index Pigment Green 17 and Pigment Green 18. Examples of mixed-phase oxide pigments are nickel titanium yellow and chromium titanium yellow, cobalt green and cobalt blue, zinc iron brown and chromium iron brown, and also iron manganese black and spinel black.
Examples of inorganic black pigments that may be mentioned include those already described above together with the inorganic colour pigments, especially iron oxide black, spinel black, and black mixed-phase oxide pigments.
Furthermore, depending on the field of use, the inorganic pigments may have been organically or inorganically aftertreated.
Extenders are, in particular, substances different from the abovementioned pigments, are primarily light in colour, and are inert with respect to the binder of component b). With particular preference, the extenders are distinguished by an optical refractive index which is lower than that of the abovementioned white pigments.
Examples of inorganic extenders that may be mentioned include carbonates, such as chalk, calcite or dolomite, silicon dioxide (quartz flour), natural or synthetic silicas, silicates, such as talc, kaolin or mica, and sulphates such as heavy spar or barium sulphate (blanc fixe).
Examples of organic extenders that may be mentioned are polymeric powders and so-called hollow spheres.
Also suitable are nanoscale pigments of non-oxide ceramics, especially those from the group of the carbides, nitrides, borides and suicides of the elements Ti, Zr, Hf, Si, Ge and Sn having an average primary particle size of from 0.1 to 50 nm.
Suitable organic pigments are, for example, those of the monoazo, disazo, laked azo, &bgr;-naphthol, Napthol AS, benzimidazolone, disazo condensation, azo metal complex, azo-methine 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 suitable are laked dyes, such as Ca, Mg and Al lakes of dyes containing sulphonic acid 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 2
nd
Edition of the Colour Index.
Mention may be made in particular of acidic to alkaline carbon blacks
Giesecke Heinz
Hauschel Bernd
Nyssen Peter-Roger
Pfützenreuter Dirk
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