Pigments

The present invention relates to interference pigments based on multiply coated platelet-shaped substrates.

Luster or effect pigments are used in many areas of technology, particularly in the field of automotive coatings, decorative coatings, plastics, paints, printing inks and in cosmetic formulations.

Interference pigments based on platelet-shaped particles having an inner layer structure. The thicknesses of the layers are in the order of visible light so that interference phenomena occur on the layers that produce the intense shine and the colors. The pigment particles are typically made of a plate-like central support which is coated with one or more oxide layers. The occupancy with several oxide layers leading to so-called multilayer pigments which particularly high angular dependence of the hue and / or intense colors distinguished by special effects such. B..

Typical multi-layer pigments of this type consist of an alternating series of oxides having different refractive indices which are applied to the substrate.

As examples, here in the <patcit><text>WO 98/53011</text></patcit> and <patcit><text>WO 99/20695</text></patcit> known products described. A specific embodiment of a SnO₂is in the intermediate layer <patcit><text>CN101289580 A</text></patcit> described. The program envisages the preparation of a gold-colored interference pigment by coating mica with four successive layers of TiO₂, TiO₂/ Fe₂O₃, SnO₂ and TiO₂ described.

The from the <patcit><text>CN101289580 A</text></patcit> but known Gold pigments based on mica flakes have the disadvantage that they C * have a relatively low color intensity for a multilayer pigment.

Object of the present invention is therefore to provide intensely colored interference pigments with high color intensity and a high gloss, the same can be produced in a simple manner are distinguished by their advantageous application properties and.

It interference pigments have now surprisingly having at least two absorbent in the visible wavelength range layers found based on platelet-like substrates whose color intensity (chroma) goes well beyond the known from the prior art pigments interference type.

Object of the present invention are interference pigments based on multiply coated platelet-shaped substrates, on the surface of the substrate a layer sequence of <ul list-style="bullet"><li>(A0) optionally a high-index coating consisting of a layer of TiO₂.</li><li>(A) a high-index coating consisting of a mixture of TiO₂ and Fe₂O₃, Which may be optionally doped with one or more other oxides,</li><li>(B) a high refractive index layer consisting of SnO₂.</li><li>(C) a high-refractive-absorbing in the visible wavelength range coating, and optional</li><li>(D) an outer protective layer exhibit.</li></ul>

The multilayer pigments of the invention are distinguished from the interference pigments from the prior art by a higher color strength and show intense and brilliant colors in gold and red range.

The color strength of the pigments of the invention is dependent on the particle size distribution. The smaller the particle size, the more opaque is the pigment of the invention in the respective application, for example in a car paint, and the higher the color strength.

The pigments of the invention are the multilayered pigments from the prior art not only in terms of their optical properties, such as gloss and color strength, but auc clearly superior h in their application properties, such. As the mechanical stability and photostability.

&lt;?page 3?&gt;The invention relates to the use of the novel pigments in paints, coatings, especially automotive coatings, powder coatings, printing inks, security printing inks, plastics, ceramic materials, glasses, paper, in toners for electrophotographic printing processes, in seed, in greenhouse sheeting and tarpaulins, as absorbers in the laser marking of paper and plastics, in cosmetic formulations. Furthermore, the pigments of the invention for the production of pigment pastes with water, organic and / or aqueous solvents, pigment preparations and for producing dry preparations, such as, for example, granules, chips, pellets, briquettes, etc., are suitable. The dry preparations are particularly suitable for printing inks and in cosmetics.

Suitable base substrates for the pigments of the invention are colorless or selectively or non-selectively absorbing platelet-shaped substrates. Suitable substrates are, in particular sheet silicates such as natural or synthetic mica, talc, kaolin, platelet-shaped iron or aluminum, glass, SiO₂-, TiO₂-, Graphite platelets, synthetic support-free flakes, titanium nitride, titanium silicide, Liquid crystal polymers (LCPs), holographic pigments, BiOCl and platy mixed oxides or mixtures thereof. Particularly preferred substrates are glass flakes, natural or synthetic mica flakes and Al₂O₃Platelets.

The size of the base substrates is not crucial per se and can be matched to the particular application. In general, the platelet-shaped substrates have a thickness from 0.005 to 10 .mu.m, in particular between 0.05 and 1 micron. The extension in the other two dimensions is usually 1-500 microns, preferably 2-300 microns and especially 20-200 microns. Preferred smaller particle sizes are furthermore those in the range of 1-100 microns, particularly 5-60 microns and 1-15 microns.

Suitable base substrates are substrates in particular by synthesis due to their smooth surfaces: Particularly preferred synthetic substrates are glass flakes, mica flakes and Al₂O₃Platelets. Particularly preferred are Al₂O₃Platelets.

Suitable glasses for the glass flakes synthetically produced are all known to the expert glasses, such as silicate glasses, such as soda-lime glass, borosilicate glass, aluminosilicate glass, lead crystal glass, E-, A-, C-, ECR glass, Duran glass, window glass, laboratory glass, etc. Such glasses are of sand, lime, alumina, boron, potash, soda, etc. melted and molded in a state allowed to solidify. Suitable glass flakes preferably consist of C, E, ECR, or borosilicate glass. It is of course also mixtures of different glass plates are used, which differ only in the glass composition. Particularly preferred substrate flakes of calcium Aluminiumborosilikat or ECR glass.

The addition of inorganic colorants, the glass flakes in the preparation can be selectively colored. Suitable colorants are those that do not degrade at the melting temperature of the glass. The colorant is generally added in amounts of 0.1-50 wt .-%, particularly from 0.2 to 25 wt .-% and most preferably of 0.5-10 wt .-%, the glass melt.

Suitable coloring agents are, in particular Cu, the cations or anions of the complex elements, Cr, Mn, Fe and Co and / or combinations thereof. The addition of ions intense blue, green, yellow, orange or red colors can be obtained. Suitable colorants are furthermore TiO₂ or elemental metals.

The refractive index of suitable glass flakes is preferably 1.45 to 1.80, in particular at 1.50-1.70.

Often it is advisable to the surface of the glass flakes prior to occupancy with the layers (A0) - (C) or (A) - (C) with a SiO₂Layer to provide. The chemical composition of the glass flakes due to the occupancy of the SiO₂Layer (layer (S)), however, is of secondary importance for the further coatings and the resulting performance properties of the pigments. By SiO₂Occupation rules will protect the glass surface against chemical modification, such as swelling, leaching of glass constituents or dissolution in the aggressive acidic coating solutions.

Particularly preferred are glass flakes with an average thickness of &lt;2 microns. Thicker plates can not be used in the current printing methods and sophisticated finishes normally. Preferably, the glass flakes mean thicknesses of greater of &lt;1 .mu.m, in particular of &lt;0.9 microns. Especially preferred are glass flakes having thicknesses of 200-1000 nm. The diameter of the&lt;?page 4?&gt;Glass flakes is preferably 5-300 microns, especially preferably 10-300 microns. Glass flakes having these dimensions are available commercially.

Especially preferred interference pigments based on Al₂O₃Platelets. Preferably, the Al possess₂O₃Platelets following particle size distributions: D₁₀: 6-12 D₅₀: 15-23 D₉₀: 28-45.

The thickness of the Al₂O₃Platelets is preferably 50-500 nm. The form factor (ratio of diameter / thickness) of Al₂O₃Platelets is preferably 50-300.

The characterization of the particle size distribution will take place in this patent application by laser diffraction. In the present application, the particle size distribution with the Malvern Mastersizer is determined 2000th

The thickness of the individual layers of high refractive index, eg. As TiO₂, SnO₂, Fe₂O₃, Pseudobrookit, TiO₂/ Fe₂O₃ on the base substrate is essential for the optical properties of the pigment. For a pigment with intensive interference colors, the thickness of the individual layers must be set precisely to one another. It has been shown that the sum of all layers on the substrate has a thickness of ≤ 300 nm, preferably ≤ 250 nm should not exceed.

The interference pigments according to the invention contain at least three high-index layers (A) - (C). If the said substrates are coated with the layer (A0), interference pigments of the invention possess four high-index layers.

The high refractive index layer (A0) has a refractive index n ≥ 2.0, preferably n ≥ 2.1 and a TiO₂-Layer. The thickness of the coating (A) is preferably 10-550 nm, especially 15-400 nm and most preferably 20-350 nm.

The layer (A) consists of a mixture of TiO₂ and Fe₂O₃, The mixing ratio of TiO₂ to Fe₂O₃ is preferably from 10: 1 to 1: 3, especially 3: 1 to 1: 2.5. The thickness of the coating (A) is preferably 10-550 nm, especially 15-400 nm and most preferably 20-350 nm.

Often it is advisable to increase the color intensity of the layer (A) and / or the layer (C) the TiO₂/ Fe₂O₃Mixture, one or more oxides such. B. Al₂O₃, Ce₂O₃, B₂O₃, ZrO₂, SnO₂To mix. The wt .-% - Share of other oxides in addition to the Fe₂O₃/ TiO₂Mixture should be in the layer (A) and layer (C) not more than 20 wt .-%, preferably not more than 10 wt .-%, respectively. Preferably, a metal oxide is added, such. As Al₂O₃, ZrO₂ or SnO₂,

The layer (B) consists of SnO₂ and preferably has layer thicknesses of 0.5-50 nm, more particularly 1-30 nm and most preferably of 1-25 nm.

The high refractive index coating (C) has a refractive index n ≥ 2.0, preferably n ≥ 2.1, and may consist of one or more layers. Preferably it is in the coating (C)<ul list-style="bullet"><li>- A TiO₂Layer followed by a Fe₂O₃-Layer</li><li>- A Fe₂O₃-Layer</li><li>- A layer consisting of a mixture of TiO₂ and Fe₂O₃,</li></ul>

If it is a mixture of TiO₂ and Fe₂O₃ is, the mixing ratio of TiO₂ to Fe₂O₃ preferably 10: 1 to 1: 3, especially 3: 1 to 1: 2.5. The thickness of the coating (D) is preferably 10-550 nm, especially 15-400 nm and most preferably 20-350 nm.

The titanium dioxide may be in the high refractive index layer (A0) or if present in the coating (C) can be in the rutile or anatase modification. The process for the preparation of rutile are described for example in the prior art in the<patcit><text>US 5,433,779</text></patcit>. <patcit><text>US 4,038,099</text></patcit>. <patcit><text>US 6,626,989</text></patcit>. <patcit><text>DE 25 22 572 C2</text></patcit>. <patcit><text>EP 271 767 B1 0</text></patcit>, Preferably before the TiO₂-Auffällung On coated or uncoated substrate wafer a thin tin dioxide layer (&lt;10 nm) is applied, which serves as an additive to the TiO₂ to obtain as rutile.

&lt;?page 5?&gt;The thickness of the layers (A0) to (C) or (A) to (C) depends on the desired interference color.

Particularly preferred interference pigments have the following layer sequences on the platelet-shaped substrate: Substrate + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂/ Fe₂O₃Substrate + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + TiO₂/ Fe₂O₃Substrate + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + Fe₂O₃Substrate + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + Fe₂O₃Substrate + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + Fe₃O₄Substrate + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + carmine Substrate + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + Prussian blue Substrate + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂/ Fe₂O₃Substrate + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + TiO₂/ Fe₂O₃Substrate + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + Fe₂O₃Substrate + TiO₂/ Fe₂O₃ + SnO₂ + Fe₂O₃Substrate + TiO₂/ Fe₂O₃ + SnO₂ + Fe₃O₄Substrate + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + carmine Substrate + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + Prussian blue.

Very particularly preferred interference pigments have the following layer sequence: Substrate + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂/ Fe₂O₃,

The term "TiO₂/ Fe₂O₃"Means that here TiO₂ and Fe₂O₃ be applied mixed. The mixing ratio of TiO₂ to Fe₂O₃ is preferably from 10: 1 to 1: 3, especially 3: 1 to 1: 2.5.

Unless both the layer (A) and the coating (C) each made of a mixture of TiO₂ and Fe₂O₃ exist, the composition of the TiO₂/ Fe₂O₃Solvent mixture be identical or different.

Among the preferred multilayer pigments, the pigments are based on Al₂O₃Flakes, further, particularly preferably on glass slides. Very particularly preferred multilayer pigments of the present invention are mentioned below:synthetic mica platelets + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂/ Fe₂O₃synthetic mica platelets + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + TiO₂/ Fe₂O₃synthetic mica platelets + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + Fe₂O₃synthetic mica platelets + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + Fe₂O₃, synthetic mica platelets + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂/ Fe₂O₃synthetic mica platelets + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + TiO₂/ Fe₂O₃synthetic mica platelets + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + Fe₂O₃synthetic mica platelets + TiO₂/ Fe₂O₃ + SnO₂ + Fe₂O₃, Glass flake + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂/ Fe₂O₃Glass flake + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + TiO₂/ Fe₂O₃Glass flake + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + Fe₂O₃Glass flake + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + Fe₂O₃, Glass flake + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂/ Fe₂O₃Glass flake + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + TiO₂/ Fe₂O₃Glass flake + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + Fe₂O₃Glass flake + TiO₂/ Fe₂O₃ + SnO₂ + Fe₂O₃, Al₂O₃Flakes + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂/ Fe₂O₃Al₂O₃Flakes + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + TiO₂/ Fe₂O₃Al₂O₃Flakes + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + Fe₂O₃Al₂O₃Flakes + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + Fe₂O₃, Al₂O₃Flakes + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂/ Fe₂O₃Al₂O₃Flakes + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + TiO₂/ Fe₂O₃Al₂O₃Flakes + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂ + Fe₂O₃Al₂O₃Flakes + TiO₂/ Fe₂O₃ + SnO₂ + Fe₂O₃,

Among high refractive index coatings are those with n &lt;1.8 to be understood in this application layers with a refractive index of ≥ 1.8, taking low-refractive-index layers.

The multilayer pigments of the invention are relatively easy to manufacture, as a rule.

&lt;?page 6?&gt;In the wet coating, the substrate wafer that the SiO are suspended in water, optionally mixed with a water glass solution, and then with one or more hydrolysable metal salts at a suitable for hydrolysis pH, which is selected to₂If present, preferably in the availability of glass flakes, and or the metal oxide (s) or metal oxide (s) simultaneously or sequentially, precipitated directly onto the platelets without secondary precipitations. The pH is usually kept constant by simultaneous addition of a base and / or acid. The pigments are subsequently separated off, washed and dried at 50-150 ° C for 6-18 h dried and optionally calcined for 0.5-3 h, the annealing temperature can be optimized with respect to the particular coating present. In general, the calcination temperatures are in the range of 600-1100 ° C, preferably 700-1000 ° C. When using glass flakes as a substrate, preferably, the annealing temperature is in the range of 500-800 ° C. Finally, the pigment is sieved. If desired, the pigments can be separated off after application of individual coatings, dried and optionally calcined and then re-suspended for precipitation of the further layers.

Furthermore, the coating can also take place in a fluidized bed reactor by gas-phase coating, z. B. in <patcit><text>EP 0045851</text></patcit> and <patcit><text>EP 0106235</text></patcit> can be used correspondingly for the preparation of pearlescent pigments proposed method.

The gold or red color of the multilayer pigments can be varied within very wide limits by selecting different covering amounts or the layer thicknesses resulting therefrom. The fine tuning for a certain hue can be achieved beyond the pure choice of amount by visual or measurement technology control approaching the desired color.

To increase the light, water and weather stability it is frequently advisable, depending on the field of application, to subject the finished pigment to post or post-treatment. Suitable post or post-treatments, for example, in the<patcit><text>DE-PS 22 15 191</text></patcit>. <patcit><text>DE-OS 31 51 354</text></patcit>. <patcit><text>DE-OS 32 35 017</text></patcit> or <patcit><text>DE-OS 33 34 598</text></patcit> described method in question. This post (layer D), the chemical and photochemical stability is further increased or the handling of the pigment, especially its incorporation into various media facilitated. To improve the wettability, dispersibility and / or compatibility with the user media may functional coatings of Al₂O₃ or ZrO₂ or mixtures thereof are applied to the pigment surface. Furthermore, organic post are possible, eg. As with silanes such as described in the<patcit><text>EP 0090259</text></patcit>. <patcit><text>EP 0634459</text></patcit>. <patcit><text>WO 99/57204</text></patcit>. <patcit><text>WO 96/32446</text></patcit>. <patcit><text>WO 99/57204</text></patcit>. <patcit><text>US No. 5,759,255</text></patcit>. <patcit><text>US 5,571,851</text></patcit>. <patcit><text>WO 01/92425</text></patcit> or in <nplcit><text>JJ Ponjeé, Philips Technical Review, Vol. 44, No. 3, 81 ff., And PH Harding JC Berg, J. Adhesion Sci. Technol. Vol. 11 No. 4, pp 471-493</text></nplcit>, The layer (D) preferably has a thickness of 0.1-100 nm, in particular from 0.1 to 50 nm and most preferably of 0.1-30 nm.

In a preferred embodiment, the layer (D) consists of a SiO₂-Layer. This layer can be both calcined and non-calcined. Preferably, a calcined SiO₂-Layer.

Since multilayer pigments of the invention combine a high gloss with intense interference colors and an appealing powder paint can be with them particularly effective effects in the various application media achieve such. As in cosmetic formulations, such as. For example, nail varnishes, lipsticks, compact powders, gels, lotions, soaps, toothpastes, in paints such. as automotive coatings, industrial coatings and powder coatings, and in printing inks, coloring seed, plastics and in ceramics.

The concentration of the pigment according to the invention to be pigmented application system is generally between 0.1 and 100 wt .-%, preferably between 0.1 and 70 wt .-% and in particular between 0.5 and 10 wt .-%, based on the total solids content of the system. It depends on the specific application, usually.

It goes without saying that for the various applications, the multilayer pigments of the invention also advantageously in admixture with one or more colorants, z. B. Effect pigments selected from the group consisting of pearlescent pigments, interference pigments, goniochromatic pigments, BiOCl flakes, multilayered pigments, metal pigments, luster pigments , and / or organic dyes and / or organic color pigments and other pigments, such as. for example, transparent and opaque white, colored and black pigments, and with platelet-holographic pigments, LCPs (liquid crystal polymers) and conventional transparent, colored and black luster pigments based on metal oxide-coated mica and SiO₂Flakes, etc., can be used. The&lt;?page 7?&gt;Multilayer pigments of the invention can be mixed in any ratio with a colorant. The weight ratio of multi-layer pigment colorant may vary depending on color development 1:99 to 99: 1.

Colorants especially pearlescent pigments, in particular based on natural or synthetic mica, SiO₂Flakes, Fe₂O₃Flakes, glass flakes or Al₂O₃Platelets, which are coated with one or more metal, metallic effect pigments (Al flakes, bronzes), optically variable pigments (OVP's), liquid crystal polymer pigments (LCPs) or holographic pigments.

In addition to the effect pigments in admixture are in particular also predominantly non-glossy, conventional colorants in question, such. As TiO₂, Colored SiO₂, CaSO₄, Iron oxides, chromium oxides, carbon black, organic color pigments, such as. For example, anthraquinone pigments, quinacridone pigments, diketopyrrolo-pyrrole pigments, phthalocyanine pigments, azo pigments, isoindoline pigments. Also suitable are, for example BiOCl pigments, colored glass fibers, α-FeOOH, organic colored pigments, such. As azo pigments, β-phthalocyanine Cl Blue 15.3, Cromophtalgelb 8GN (Ciba-Geigy), Irgalith® Blue PD56 (BASF), Azomethinkupferkomplex Cl Yellow 129, Irgazingelb 5GT (BASF) or a mixture of said colorant. The colorant may be either natural or synthetic origin.

The multilayer pigments of the invention can of course be mixed together with fillers in any weight ratio and can be used. Fillers such. As may be mentioned synthetic organic polymers, polymethyl methacrylate, methyl methacrylate cross-polymer, natural and synthetic mica, nylon powder, pure or filled melamine resins, talc, SiO₂, Glass powder, glass beads, kaolin, oxides or hydroxides of aluminum, magnesium, calcium, zinc, BiOCl, barium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, basic alkaline earth metal carbonates, such as. For example, calcium or magnesium carbonate, carbon, and physical or chemical combinations of these substances. With respect to the particle shape of the fillers, there are no restrictions. You can be the requirements of z. B. irregular, flake-form, spherical or needle-shaped.

Similarly, finely divided, especially nanoscale, dielectrics, in particular in cosmetic formulations to improve the skin feel, the multilayer pigments are mixed. Examples of such admixtures are Al₂O₃, SiO₂, ZnO or TiO₂Which are usually added in amounts of 0.01-15 wt .-% of the formulation.

The multilayer pigments of the invention are compatible with a multiplicity of color systems, preferably from the area of ​​paints, coatings and printing inks. For the production of printing inks for, for. Example, gravure printing, flexographic printing, offset printing, offset overprint varnishing, a multiplicity of binders, in particular water-soluble grades, is suitable as such. B., by BASF, Marabu, Pröll, Sericol, Hartmann Gebr. Schmidt, SICPA, Aarberg, Siegberg, GSB-Wahl, Follmann, Ruco or Coates Screen INKS GmbH are sold. The printing inks can be water-based or solvent-based. Furthermore, multilayer pigments of the invention are also suitable for the laser marking of paper and plastics, and for applications in the agricultural sector, for. Example for greenhouse sheeting, and,. As for the coloring of tarpaulins, suitable.

In the pigmentation of binder systems, for. Example for paints and printing inks for gravure, offset or screen printing, or as a precursor for printing inks, has the use of the multilayer pigments of the invention in the form of highly pigmented pastes, granules, pellets, etc., to be particularly suitable proved. The novel pigment is incorporated into the rule in the printing ink in amounts of 2-35 wt .-%, preferably 5-25 wt .-% and in particular 8-20 wt .-%. Offset printing inks, the pigments in a proportion of up to 40 wt .-% and contain more. The precursors for printing inks, for. Example, in the form of granules, pellets, briquettes, etc., in addition to the binder and the additives contain up to 98 wt .-% of the pigment of the invention. Printing inks, which contain multi-layer pigment of the invention, generally exhibit purer hues as printing inks with conventional effect pigments.

The multilayer pigments of the invention are furthermore suitable for the preparation of flowable pigment compositions and dry preparations, especially for printing inks, comprising one or more pigments, binders and optionally one or more additives according to the invention.

In plastics, containing multi-layer pigment of the invention, preferably in amounts of from 0.01 to 50 wt .-%, preferably 0.1 to 7 wt .-%, particularly pronounced color effects can be achieved.

&lt;?page 8?&gt;In the coatings sector, particularly in the automotive paints, the multilayered pigment, for 2- and 3-layer constructions in amounts of 0.1-20 wt .-%, preferably 1 to 10 wt .-%, are used. Typically, the decorative painting of cars is done in 2 layers: first is the primer a decorative, ie containing the color-determining pigments layer sprayed. Thereafter, the coating is carried out with a clear coat layer, whereby the color intensified and the gloss is increased. The clear coat also contributes significantly to the weather stability and durability of the paint.

Furthermore, the pigment according to the invention for the finishing of foods, eg. Example mass coloring and / or coatings of boiled sweets, wine gums can such. As gummy bears, chocolates, licorice, candy, candy canes, puddings, fizzy drinks, soft drinks, etc., be used or as a coating, eg. as in dragees and tablets in the pharmaceutical industry.

The multi-layer pigment of the invention can also advantageously be employed in decorative and care cosmetics. The concentration ranges from 0.01 wt .-% in shampoo to 100 wt .-% at loose powders. When a mixture of pigments of the invention with fillers, preferably with spherical fillers, such as. For example, SiO₂, The concentration may range from 0.01 to 70 wt .-% in the cosmetic formulation. The cosmetic products, such. As nail varnishes, compact powders, shampoos, loose powders and gels, are distinguished by particularly interesting color effects and a high gloss.

The concentrations of the multilayer pigments of the invention in the formulation are no limits. You can - depending on the application - between 0.001 (rinse-off products, for example shower gels.) And 100% (for example luster-effect articles for particular applications.) Are.

Due to the good skin Feelings and the very good skin adhesion pigments of the invention are suitable for personal care applications, such. As body lotions, emulsions, shampoos, soaps, etc., and in particular for decorative cosmetics.

Of course, multilayer pigments of the invention can be combined in the formulations with any type of raw and auxiliary materials and active ingredients. These include water, alcohols, polyols, polar and nonpolar oils, fats, waxes, film formers, polymers, co-polymers, surfactants, radical scavengers, antioxidants, such. As vitamin C or vitamin E, stabilizers, odor amplifier, silicone oils, emulsifiers , perfumes, solvents such., ethanol, ethyl acetate or butyl acetate, a preservative and generally determine applicational properties adjuvants such. for example, thickeners and rheological additives, such as bentonite, hectorites, silicon dioxides, Ca silicates, gelatine, high-molecular-weight carbohydrates and / or surface-active assistants, etc.

Suitable active ingredients are, for. Example, insect repellents, inorganic UV filters, such. As TiO₂, UV A / BC protection filters (z. B. OMC, B3, MBC), in encapsulated form, anti-aging active ingredients, vitamins and derivatives thereof (eg. As vitamin A, C, E, etc.), Self (z. B. DHA, erythrulose, inter alia) and further cosmetic active ingredients, such as. for example, bisabolol, LPO, VTA, ectoine, emblica, allantoin, bioflavonoids and derivatives thereof.

Organic UV filters are generally incorporated usually in an amount of 0.5 to 10 wt .-%, preferably 1 to 8 wt .-%, and inorganic filters from 0.1 to 30 wt .-% in cosmetic formulations.

The multilayer pigments of the invention can, for example, lipsticks, lip gloss, blush, eyeliner, eyeshadow, (volume) mascara, nail varnishes, day creams, night creams, body lotions, cleansing milk, body powders, hair gels, hair masks, hair conditioners, hair shampoos, shower gels, shower oils, bath oils, sunscreen, pre -Sun- and after-sun preparations, tanning lotions, tanning sprays, make-up, lotions, soaps, bath salts, toothpaste, facial masks, compact powders, loose powders and gels, etc., are used. The aforesaid products are manufactured in a manner as is known to those skilled in the art.

The invention relates in particular formulations, in addition to the multi-layer pigment of the invention at least one component selected from the group of absorbents, astringents, antimicrobial substances, antioxidants, antiperspirants, antifoams, antidandruff active compounds, antistatics, binders, biological additives, bleaching agents, chelating agents, deodorants, emollients that, emulsifiers, emulsion stabilizers, dyes, humectants, film formers, fillers, fragrances, flavors, insect repellents, preservatives, corrosion inhibitors, cosmetic oils, solvents, oxidants, vegetable constituents, buffer substances, &lt;?page 9?&gt;Reducing agents, surfactants, propellant gases, opacifiers, UV filters and UV absorbers, denaturing agents, viscosity regulators, perfume and vitamins.

The invention is further the use of the pigments in formulations such as paints, coatings, industrial coatings, coil coatings, automotive coatings, automotive refinish coatings, automotive coatings, powder coatings, printing inks, security printing inks, plastics, ceramic materials, glasses, paper, in toners for electrophotographic printing processes, in seed, in greenhouse sheeting and tarpaulins, as absorbers in the laser marking of paper and plastics, in cosmetic formulations, for the preparation of pigment pastes with water, organic and / or aqueous solvents, for the production of pigment preparations and dry preparations, such as. for example, granules, pellets , chips, briquettes, for mass coloration of food, for coloring coatings of food products and pharmaceutical products, eg. as a coating for pills and tablets.

the use of the multilayer pigments of the invention in surface coatings is particularly preferred, such. as automotive coatings and industrial coatings, powder coatings, coil coatings and printing inks.

Typically, the decorative painting of cars is done in 2 layers: first is the primer a decorative, ie containing the color-determining pigments layer sprayed. Thereafter, the coating is carried out with a clear coat layer, whereby the color intensified and the gloss is increased. The clear coat also contributes significantly to the weather stability and durability of the paint.

The following examples illustrate the invention in more detail without restricting to.

Examples:

Example 1: Al₂O₃Flakes + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂/ Fe₂O₃)

100 g Al₂O₃Flakes of particle size 5-40 microns are heated in 1.5 liters of demineralised water at 75 ° C. After reaching this temperature, with vigorous stirring 460 g of a mixed solution of 167 g TiCl₄Solution (30 wt .-% TiCl₄), 222 g FeCl₃Solution (14% Fe), 6.6 g of AlCl₃ × 6H₂O and 111 g of demineralized water was slowly metered in. The pH is maintained with 32% strength sodium hydroxide solution constant at pH 2.6. After addition of this solution the pH is hydrochloric acid (18% HCl) is lowered to pH = 1.8 and a stabilized at this pH value within 300 minutes 805 g of concentrated hydrochloric acid with SnCl₄Solution (2 wt .-% SnCl₄) Are metered. Thereafter, the pH-value is increased with 32% sodium hydroxide to 2.6 and 835 g of a mixed solution of 306 g of TiCl₄Solution (30 wt .-% TiCl₄), 399 g FeCl₃Solution (14% Fe), 11.8 g of AlCl₃ × 6H₂O and 224 g of demineralized water was slowly metered in. The pH value with 32% sodium hydroxide solution is maintained constant. Then the pH with 32% sodium hydroxide solution is raised to pH = 5.0 and stirred for 15 minutes.

The pigment is filtered, washed with demineralised water and dried at 110 ° C for 16 h. 15 g of the product are annealed at 820 ° C for 30 min..

This gives a pale greenish gold pigment having an intense color, high hiding power and strong luster.

Example 2: Al₂O₃Flakes + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂/ Fe₂O₃)

100 g Al₂O₃Flakes of particle size 5-40 microns are heated in 1.5 liters of demineralised water at 75 ° C. After reaching this temperature, with vigorous stirring 460 g of a mixed solution of 167 g TiCl₄Solution (30 wt .-% TiCl₄), 222 g FeCl₃Solution (14% Fe), 6.6 g of AlCl₃ × 6H₂O and 101 g of demineralized water was slowly metered in. The pH is maintained with 32% strength sodium hydroxide solution constant at pH 2.6. After addition of this solution the pH is hydrochloric acid (18% HCl) is lowered to pH = 1.8 and a stabilized at this pH value within 300 minutes 805 g of concentrated hydrochloric acid with SnCl₄Solution (2 wt .-% SnCl₄) Are metered. Thereafter, the pH-value is increased with 32% sodium hydroxide to 2.6 and 760 g of a mixed solution of 306 g of TiCl₄Solution (30 wt .-% TiCl₄), 399 g FeCl₃Solution (14% Fe), 11.8 g of AlCl₃ × 6H₂O and 224 g of demineralized water was slowly metered in. The pH value with 32% sodium hydroxide solution is maintained constant. Then the pH with 32% sodium hydroxide solution is raised to pH = 5.0 and stirred for 15 minutes.

&lt;?page 10?&gt;The pigment is filtered, washed with demineralised water and dried at 110 ° C for 16 h. 15 g of the product are annealed at 850 ° C for 30 min..

This gives a strong greenish gold pigment having an intense color, high hiding power and strong luster.

Example 3: glass flake + SiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂/ Fe₂O₃)

150 g Calciumaluminiumborosilikat-platelet particle size of 20-200 microns are heated in 1.5 liters of demineralised water at 75 ° C. After reaching this temperature the pH is adjusted to pH 9.0 and under vigorous stirring 110.8 g Na₂SiO₃Solution (13.75% SiO₂) Are metered in over the course of 50 minutes. The pH is held constant using hydrochloric acid (18% HCl). Thereafter, the pH is lowered to 2.6 and 250 g of a mixture of 197 g of FeCl₃Solution (14.2% Fe), 148 g of TiCl₄Solution (32% TiCl₄) And 6.1 g of AlCl₃Solution (29% AlCl₃) Are metered in over the course of 60 minutes. Subsequently, the pH is lowered 1.8 and a mixture of 25.9 g of SnCl₄Solution, 66 g of hydrochloric acid (37% HCl) and 500 g of deionized water over the course of 200 min. Metered. Subsequently, the pH is raised to 2.6 and 285 ml of a mixture of 197 g of FeCl₃Solution (14.2% Fe), 148 g of TiCl₄Soln. (32% TiCl₄) And 6.1 g of AlCl₃Solution (29% AlCl₃) Are metered in the course of 350 minutes. The pH value is kept constant in each case with sodium hydroxide solution (32%). Then the pH with 32% sodium hydroxide solution is raised to pH = 5.0 and stirred for 15 minutes.

The pigment is filtered, washed with demineralised water and dried at 110 ° C for 16 h. 15 g of the product are annealed at 650 ° C for 30 min.. Giving a gold pigment having an intense color and strong glitter effect.

Example 4: SiO₂Flakes + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂/ Fe₂O₃

100 g SiO₂Flakes of particle size of 10-60 microns are heated in 2 liters of demineralized water at 75 ° C. After reaching this temperature, with vigorous stirring 415 g of a mixed solution of 178 g TiCl₄Solution (30 wt .-% TiCl₄), 237 g FeCl₃Solution (14% Fe), 7.0 g of AlCl₃ × 6H₂O and 117 g of demineralized water was slowly metered in. The pH is maintained with 32% strength sodium hydroxide solution constant at pH 2.6. After addition of this solution the pH is hydrochloric acid (18% HCl) is lowered to pH = 1.8 and a stabilized at this pH value within 300 minutes 750 g of concentrated hydrochloric acid with SnCl₄Solution (2 w .-% SnCl₄) Are metered. Thereafter, the pH is raised with 32% sodium hydroxide to 2.6 and 660 g of a mixed solution of 218 g TiCl₄Solution (30 wt .-% TiCl₄), 289 g FeCl₃Solution (14% Fe), 8.6 g of AlCl₃ × 6H₂O and 145 g of demineralized water was slowly metered in. The pH value with 32% sodium hydroxide solution is maintained constant. Then the pH with 32% sodium hydroxide solution is raised to pH = 5.0 and stirred for 15 minutes. The pigment is filtered, washed with demineralised water and dried at 110 ° C for 16 h. 15 g of the product are annealed at 850 ° C for 30 min.. Giving a gold pigment having an intense color and high gloss.

Example 5: (mica platelets + TiO₂ + TiO₂/ Fe₂O₃ + SnO₂ + TiO₂/ Fe₂O₃)

100 g mica flakes (thickness: 100-500 nm, D₅₀ = 15-30 microns) are heated in 1.5 liters of demineralised water at 75 ° C. After reaching this temperature the pH is adjusted with hydrochloric acid (18% HCl) to pH 2,2 and with vigorous stirring 22 g of TiC₄Solution (32% TiCl₄) Added over 20 minutes. The pH is held constant using hydrochloric acid (18% HCl). Thereafter, the pH with sodium hydroxide solution (32% NaOH) is raised to 2.6 and 552 g of a mixture of 236 g of FeCl₃Solution (14.2% Fe), 178 g of TiCl₄Solution (32% TiCl₄) And 7.3 g of AlCl₃Solution (29% AlCl₃) Over the course of 250 min. Metered. Subsequently, the pH is lowered 1.8 and a mixture of 34.6 g of SnCl₄Solution (50% SnCl₄), 90 g of hydrochloric acid (37% HCl) and 680 g of DI water over 200 minutes added. Subsequently, the pH with hydrochloric acid (18% HCl) is raised back to 2.6 and 342 ml of a mixture of 236 g of FeCl₃Solution (14.2% Fe), 178 g of TiCl₄Solution (32% TiCl₄) And 7.3 g of AlCl₃Solution (29% AlCl₃) Over the course of 160 min. Metered. The pH value is kept constant in each case with sodium hydroxide solution (32%). Then the pH with 32% sodium hydroxide solution is raised to pH = 5.0 and stirred for 15 minutes.

The pigment is filtered, washed with demineralised water and dried at 110 ° C for 16 h. 15 g of the product are annealed at 820 ° C for 30 min.. Giving a gold pigment having an intense color and strong glitter effect.

&lt;?page 11?&gt;Comparative Example:

As in Example 1 of <patcit><text>CN 101289580A</text></patcit>), 100 g of synthetic mica + TiO₂ + Fe₂O₃/ TiO₂ + SnO₂ + TiO₂ coated.

100 g fluoro phlogopite platelets of particle size 10-40 .mu.m are heated in 1.6 liters of demineralised water at 85 ° C. After reaching this temperature the pH is adjusted with hydrochloric acid (18 w .-% HCl) is lowered to 2.3 and under vigorous stirring 541.4 g of 32% TiCl₄Solution in the course of 290 min. Metered. Here, the pH is adjusted with sodium hydroxide solution (20w .-%) is kept constant.

Subsequently, the pH is raised with sodium hydroxide to 4.0 and a mixture of 172 g of FeCl₃Solution (14.2% Fe) 34.9 g TiCl₄Solution (32% TiCl₄) And 118 g of deionized water over the course of 75 min. Are metered. The pH is maintained with 20% strength sodium hydroxide solution constant at pH 4.0. Subsequently, the pH value is with hydrochloric acid (18% HCl) is lowered to pH = 1.2 and then raised with sodium hydroxide solution (20%) to pH 1.5. At this pH value, a solution of 32.1 g of SnCl₄ (50 w .-% SnCl₄) And 82.4 g hydrochloric acid (32% HCl) is added in 622.4 g of deionized water over the course of 240 minutes. Thereafter, the pH value with 32% sodium hydroxide solution is raised to 2.3 and in the course of 300 minutes 482 g of TiCl₄Solution (32% TiCl₄) Are metered. The pH value with 32% sodium hydroxide solution is maintained constant. Then the pH with 32% sodium hydroxide solution is raised to pH = 5 and stirred for 15 minutes.

The product is filtered, washed with deionized water and at 110 ° C for 10 h dried. 15 g of the product are annealed at 820 ° C for 30 min.. A bronze-colored powder.

Color measurements:

The following table shows the values ​​determined by color measurement lab values, and C are listed * values ​​(CIE L * a * b * -Normfarbwertsystem). The C * value is a direct measure of the intensity of color. The measurements with the ETA-photometer (manufacturer: STEAG ETA-OPTIK GmbH) performed. Table 1:<tables num=""><table frame="all"><tgroup cols="5" colsep="1" rowsep="1"><colspec colname="col1" colnum="1" colwidth="1*" /><colspec colname="col2" colnum="2" colwidth="1*" /><colspec colname="col3" colnum="3" colwidth="0.5*" /><colspec colname="col4" colnum="4" colwidth="1*" /><colspec colname="col5" colnum="5" colwidth="1*" /><tbody><row><entry colname="col1">pigment</entry><entry nameend="col4" namest="col2">75 ° / 95 ° black underground</entry><entry colname="col5">color intensity</entry></row><row><entry colname="col1" /><entry colname="col2">L *</entry><entry colname="col3">a *</entry><entry colname="col4">b *</entry><entry colname="col5">C *</entry></row><row><entry colname="col1">example 1</entry><entry colname="col2">142.9</entry><entry colname="col3">-2.0</entry><entry colname="col4">117.0</entry><entry colname="col5">117.0</entry></row><row><entry colname="col1">example 2</entry><entry colname="col2">144.5</entry><entry colname="col3">-16.8</entry><entry colname="col4">104.6</entry><entry colname="col5">105.9</entry></row><row><entry colname="col1">Comparative Example (<patcit><text>CN 101289580 A</text></patcit>)</entry><entry colname="col2">131.1</entry><entry colname="col3">15.9</entry><entry colname="col4">49.8</entry><entry colname="col5">52.3</entry></row></tbody></tgroup></table></tables>

The pigments of the invention according to the Examples 1 and 2 exhibit higher C * value in comparison to the comparative example.

application examples

Example A1: car paint

The pigment powder can be readily incorporated into automotive paints. For this, the base paint is added while stirring the pigment. The stirring process is continued until the pigment has uniformly distributed in the paint. The colored lacquer is sprayed onto black and white coated aluminum test.

Preparation of the coating plates:

<ul list-style="bullet"><li>Paint: Herberts basecoat 419982</li><li>Pigmentation: 5% of pigment from Example 1</li><li>Dry film thickness: 15 microns</li><li>Airbrush: Sprimag S 233, nozzle diameter 1.5 mm</li><li>Injection pressure: 4 bar</li><li>Distance nozzle substrate: 27 cm</li></ul>

&lt;?page 12?&gt;Example A2: flexography

Preparation of ink:

The multi-layer pigment of Example 4 is pre-wetted with Prewetting Byk 348 (0.6%) and incorporated in a concentration of 22.9% in the binder.

Binder: Koustom Kote 9000 / USA waterbased,

The paste is diluted with water to a viscosity of 40 sec with 4 mm-Erichsen cup at 25 ° C achieved.

The pigments are of an anilox ceramic cylinder (24 cc / m²) Printed on a coating plate cliché on matt-black art paper. The pigments of the invention show a very strong color and glitter.

Example A3: screen printing

The pigment concentration can be varied widely depending on the desired effect here.

Suitable binders are both aqueous and solvent-based systems are suitable. For the light-exposed areas of the addition of a UV-protection, such. As benzotriazoles or HALS is recommended to increase the durability of the coating.

The screen mesh is selected according to grain size of the pigment used. . Thus, for example, a mesh size of 61-64 has the pigment Basket fraction of 5-40 microns proven (threads / cm - thread diameter). Substrates comes a wide range of areas in question - the main materials are fabrics, foils, cardboard and paper or wallpaper.

Example of use:

<ul list-style="bullet"><li>15% of pigment from Example 1</li><li>"Binder": Pröll Aqua Jet FGL M 093: 85%</li><li>screen mesh 61-64</li><li>If necessary, Dilution with water</li><li>Laboratory test: 50-150 g color</li><li>Substrate: Luxo Satin 250 g / m² (Prod. "Papyrus").</li></ul>

&lt;?page 13?&gt;QUOTES INCLUDED IN THE DESCRIPTION

This list of references cited by the applicant is generated automatically and is included solely to inform the reader. The list is not part of the German patent or utility model application. The DPMA assumes no responsibility for errors or omissions.

Cited patent literature

<ul list-style="bullet"><li>WO 98/53011 <b>[0005]</b></li><li>WO 99/20695 <b>[0005]</b></li><li>CN 101289580 A <b>[0005, 0006, 0084, 0088]</b></li><li>US 5433779 <b>[0034]</b></li><li>US 4038099 <b>[0034]</b></li><li>US 6626989 <b>[0034]</b></li><li>DE 2522572 C2 <b>[0034]</b></li><li>EP 0271767 B1 <b>[0034]</b></li><li>EP 0045851 <b>[0044]</b></li><li>EP 0106235 <b>[0044]</b></li><li>DE 2215191 <b>[0046]</b></li><li>DE 3151354 A <b>[0046]</b></li><li>DE 3235017 A <b>[0046]</b></li><li>DE 3334598 A <b>[0046]</b></li><li>EP 0090259 <b>[0046]</b></li><li>EP 0634459 <b>[0046]</b></li><li>WO 99/57204 <b>[0046, 0046]</b></li><li>WO 96/32446 <b>[0046]</b></li><li>US 5759255 <b>[0046]</b></li><li>US 5571851 <b>[0046]</b></li><li>WO 01/92425 <b>[0046]</b></li></ul>

Cited non-patent literature

<ul list-style="bullet"><li>JJ Ponjeé, Philips Technical Review, Vol. 44, No. 3, 81 ff., And PH Harding JC Berg, J. Adhesion Sci. Technol. Vol. 11 No. 4, pp 471-493<b>[0046]</b></li></ul>