pigment

Abstract

To provide a pigment exhibiting a dark grayish-black pearlescent effect or a metallic dark blue / green pearlescent effect with high gloss and high opacity. [Solution] The present invention relates to pigments based on particles coated with at least one layer consisting of a mixture of amorphous carbon (aC) and nanocrystalline graphite (nc-graphite), and to the use of these pigments in paints, plastics, industrial coatings, automotive coatings, printing inks and cosmetic formulations.

Description

Technical Field

[0001] The present invention relates to pigments based on particles coated with at least one layer consisting of a mixture of amorphous carbon and nanocrystalline graphite, and to the use of these pigments in paints, plastics, industrial coatings, automotive coatings, printing inks and cosmetic formulations.

Background Art

[0002] Currently, dark blue / green / grey to black is achieved using inorganic absorbent pigments such as Prussian blue (in the case of dark blue), chromium oxide (in the case of dark green), spinel or hematite type black iron oxide or cobalt oxide, copper-manganese-iron oxide, copper-chromium oxide and manganese-iron oxide. Furthermore, graphite or graphite-like pigments and carbon black pigments are commercially available and can also be applied in a physical blend / mixture to assist in creating a deep colour shade. Dark blue, dark green, grey to black effect pigments are commercially available and are generally produced by precipitating a dark coloured copper oxide or iron oxide such as Fe3O4, Co3O4 or FeTiO3 onto a small platelet substrate such as natural mica, synthetic mica, glass flakes or Al2O3 flakes. Commercially available black or dark grey pigments are produced by precipitation methods.

[0003] However, these dark grey blue / green to black effect / pearl pigments exhibit significant drawbacks and limit their use in some applications: · Prussian blue and chromium oxide and cobalt-containing pearl pigments cannot be used in cosmetic applications because they are known to be allergenic to heavy metals and cobalt ions; · Pearl pigments coated with black iron oxide will exhibit a magnetic effect and are not advantageous for coating applications; Ilmenite-containing pearl pigments frequently exhibit an inherently brownish absorption color, requiring further color adjustment in applications targeting neutral gray tones. Furthermore, ilmenite-containing pearl pigments are not permitted in cosmetic formulations. Carbon black or graphitan-containing pigments can be used instead of heavy metal oxide pigments to produce a black pearl effect.

[0004] Carbon black-containing pigments are known from the prior art, for example from DE-AS 11 65 182, DE 25 577 96 A1, and DE 41 25 134 A1, and are prepared by applying carbon from an aqueous solution using a surfactant or by the thermal decomposition of an organic compound. However, particles or effect pigments mixed with pure carbon black or graphiten exhibit an unattractive sheen. When mimicking a dark pearl effect with carbon black or graphiten, the interference pigment must be physically blended with carbon black or graphiten particles. However, these physical blends are prone to separation in certain applications (e.g., cosmetics), which can be prevented by adding dispersion and rheological additives. Non-metallic interference pigments based on flake-like non-metallic supports coated with layers containing crystalline carbon layers in the form of graphite and / or graphene are known from US Patent No. 2017 / 0321057 A1. These interference pigments have the disadvantage of being conductive pigments and lacking sufficiently high chemical and weather stability. In addition, prior art pigments exhibit insufficient opacity, little to no metallic color effect, and / or low colored metallic shine or gloss. Interference pigments themselves exhibit insufficient opacity. To improve opacity, absorbent pigments, such as carbon black, are added to compensate. In certain applications, particularly cosmetic formulations (solid powders, lipsticks, etc.), the blend of pigment and carbon black will separate under pressure / shear stress. As a result, the application of optical / cosmetic colors will appear dull, or rather, black / dirty. [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of the present invention is to provide a pigment that exhibits a dark grayish-black pearlescent effect or a metallic dark blue / green pearlescent effect with high gloss and high opacity, without exhibiting the drawbacks of prior art pigments. At the same time, the pigment must satisfy at least one of the following requirements: • Beautiful intermediate colors: dark gray / dark blue / dark green / dark metallic colors ~ blackish absorbent tones • No magnetic properties (due to carbon layer addition) • Does not separate / Does not require additives to prevent separation • Adjustable opacity of each pigment in varying shades • Low conductivity • The cosmetic formulation does not contain any ingredients considered to be of significant importance, such as Prussian blue, chromium oxide, or aluminum. • Increased liquidity. Surprisingly, we found that particles coated with at least one layer of a mixture of amorphous carbon (aC) and nanocrystalline graphite (nc-graphite) exhibited a dark metallic appearance, better fluidity, and simultaneously increased opacity and UV stability. The optical properties of these coated particles can be influenced by varying the thickness of this aC / nc-graphite layer. [Means for solving the problem]

[0006] The present invention relates to a pigment based on particles comprising a mixture of amorphous carbon (aC) and nanocrystalline graphite (nc-graphite) containing at least one layer. The coated particles according to the present invention exhibit improved adaptations that result in a metallic appearance, (liquid) metallic effect, and increased opacity. The present invention further relates to the use of pigments according to the present invention as tracers and fillers in paints, coatings, preferably industrial coatings and automotive coatings, printing inks, security printing inks, plastics, ceramic materials, and glass, and particularly in cosmetic formulations and applications, as well as in automotive coatings. Furthermore, the pigments according to the present invention are suitable for both the preparation of pigment preparations and the preparation of dry preparations, such as granules, perlets, chips, pellets, sausages, briquettes, etc. These dry preparations are used particularly in printing inks and cosmetic formulations. The dark pigments according to the present invention exhibit a highly attractive dark metallic or (liquid) metallic or colored metallic appearance in their final applications, such as automotive coatings and cosmetic formulations. Since coatings with sufficient opacity are generally produced using black iron oxide pigments, the pigments according to the present invention can be used as an attractive alternative because these pigment particles are inherently nonmagnetic and have weaker (heavy)metallic properties. In addition, the pigments according to the present invention exhibit improved fluidity, which is highly beneficial for processing and addition. Furthermore, the pigments exhibit remarkable dispersibility and do not exhibit aggregation.

[0007] The conformal and homogeneous aC / nc-graphite layer preferably consists of a mixture of amorphous carbon and nanocrystalline graphite (nc-graphite) on the surface of the pigment, with the mass ratio of aC to nc-graphite preferably in the range of 60:40 to 80:20, particularly 50:50 to 95:5, and most preferably 80:20 to 90:10. In a preferred embodiment, the aC / nc-graphite layer contains a higher proportion of amorphous carbon compared to the nanocrystalline graphite in the aC / nc-graphite layer. In a further preferred embodiment, the aC / nc-graphite layer is precipitated as the final layer on the pigment. However, the aC / nc-graphite layer can also be an intermediate layer precipitated between two layers, preferably between two metal oxide layers. The number of aC / nc-graphite layers is not limited. The layer arrangement on the surface of the substrate may include aC / nc-graphite layers, i.e., 1, 2, 3, 4, 5 or more, but only one or two layers are preferred.

[0008] The aC / nc-graphite layer is preferably prepared by chemical vapor deposition (CVD). The aC / nc-graphite layer must be smooth and completely cover the particles with a homogeneous and conformal layer. Compared to the prior art, the aC / nc-graphite layer is not composed of single-crystal carbon domains deposited on the surface of the particles, but is a mixture of amorphous carbon and nanocrystalline graphite, and consists of a layer grown directly on the particles so as to yield a conformal and homogeneous layer without pinholes. The aC / nc-graphite layer arises from heterogeneous growth on the surface of the particles. The phase boundary between aC and nc-graphite increases the transition resistance at the aforementioned phase boundary, resulting in reduced conductivity. The higher amorphous phase leads to numerous boundaries that further reduce conductivity. In addition, aC is inherently low conductive. Consequently, the aC / nc-graphite layer of the present invention exhibits low conductive behavior.

[0009] In a preferred embodiment, each aC / nc-graphite layer has a thickness of 0.5 to 10 nm, particularly 1 to 5 nm, and especially preferably 0.5 to 3 nm. The amount of nanocrystalline graphite based on the above particles is very small, meaning that the pigment according to the present invention exhibits no or very little conductivity. All known particles, preferably having a particle size of 0.5 to 500 μm or a particle diameter of 1 to 150 μm, are suitable as substrates for the pigments according to the present invention. The shape of the particles is not important. The particles may be plate-like, needle-like, spherical, or irregular in shape. In preferred embodiments, the particles are plate-like or spherical. The size of the flake or plate-like particles is not critical in itself and can be adapted to suit each application. Flake particles preferably have a thickness of 0.05 to 1 μm, particularly 0.1 to 1 μm, and especially very preferably 200 to 500 nm. The sizes of the other two (lateral) dimensions are usually between 1 μm and 250 μm, preferably between 2 μm and 200 μm, and especially between 5 μm and 60 μm. Plate-like particles of different particle sizes can also be used. Mixtures of mica fractions of N mica (10 to 60 μm), F mica (5 to 20 μm), and M mica (<15 μm) are particularly preferred. Furthermore, N and S fractions (10 to 130 μm) and F and S fractions (5 to 130 μm) are preferred.

[0010] Suitable particles are preferably selected from the following group of substrates: natural mica, synthetic mica, talc, kaolin, Fe2O3 flakes, Fe3O4 flakes, Al2O3 flakes, BiOCl flakes, glass flakes, SiO2 flakes, TiO2 flakes, BN flakes, Si- / Al-oxynitride flakes, aluminum flakes, Si- / Ti-nitride flakes and graphite flakes, pearl essence, flakes without synthetic supports, glass beads, hollow glass beads, silicon pigments, substrate-based pigments, such as filler pigments and effect pigments. Suitable filler pigments and effect pigments are, for example, interference pigments, multilayer pigments, color flop pigments, goniochromatic pigments, metal effect pigments, one or more metal oxides, preferably SiO2 spheres coated with TiO2 and / or Fe2O3. The above particles can be coated with one or more layers, preferably one, two, or three layers, particularly an inorganic layer. The inorganic layer preferably contains absorbent and non-absorbent oxides or hydroxides or metals. When the above substrate is coated with one or more metal oxide layers and / or metal layers, the total thickness of all layers on the surface of the substrate is 50 to 1000 nm, preferably 100 to 800 nm, most preferably 100 to 500 nm, and this includes an aC / nc-graphite layer. Each aC / nc-graphite layer preferably has a thickness of 0.5 to 10 nm. Suitable particles are preferably selected from the following group of substrates: natural mica, synthetic mica, talc, kaolin, Fe2O3 flakes, Fe3O4 flakes, Al2O3 flakes, BiOCl flakes, glass flakes, SiO2 flakes, TiO2 flakes, coated or uncoated SiO2 spheres, interference pigments based on plate-like substrates, and multilayer pigments based on plate-like substrates.

[0011] It is also possible to use a mixture of different particles. Particularly preferred particle mixtures consist of the following: Natural mica flakes + SiO2 flakes Natural mica flakes + Al2O3 flakes Natural mica flakes + glass flakes Natural mica flakes + TiO2 flakes Natural mica flakes + oxynitride flakes Natural mica flakes + nitride flakes Natural mica flakes + pearl essence Natural mica flakes + graphite flakes SiO2 flakes + Al2O3 flakes Glass flakes + SiO2 flakes Natural mica flakes + SiO2 spheres Synthetic mica flakes + SiO2 spheres Al2O3 flakes + SiO2 spheres SiO2 flakes + SiO2 spheres Glass flakes + SiO2 spheres Natural mica flakes + glass spheres Synthetic mica flakes + glass spheres Al2O3 flakes + glass spheres SiO2 flakes + glass spheres Glass flakes + glass spheres Synthetic mica flakes + SiO2 flakes ]>Synthetic mica flakes + Al2O3 flakes Synthetic mica flakes + glass flakes Synthetic mica flakes + TiO2 flakes Synthetic mica flakes + Si-oxynitride flakes Synthetic mica flakes + Si- / Ti-nitride flakes Synthetic mica flakes + pearl essence Synthetic mica flakes + graphite flakes Synthetic mica flakes + natural mica flakes

[0012] The above particles or the above particle mixture are coated with one or more a-C / nc-graphite layers. The a-C / nc-graphite layer can be on the surface and / or in an intermediate layer in the layer arrangement. The particles are preferably coated with one a-C / nc-graphite layer on the surface. In a preferred embodiment, the particles are interference pigments or single-layer or multi-layer pigments based on a plate-like substrate. A preferred interference pigment is a plate-like substrate coated with one, two, three or more metal oxide layers. The aC / nc-graphite layer is deposited on the surface of the interference pigment. The above particles (= interference pigments) are preferably coated with at least one high refractive index layer, such as metal oxides, for example TiO2, ZrO2, SnO2, ZnO, Ce2O3, Fe2O3, Fe3O4, FeTiO5, Cr2O3, CoO, Co3O4, VO2, V2O3, NiO, as well as titanium dioxide (TiO2 partially reduced to oxidation state <4-2, for example lower oxides Ti3O5, Ti2O3, TiO), titanium oxynitride, FeO(OH), and a thin, translucent metal layer, for example, a layer containing Al, Fe, Cr, Ag, Au, Pt or Pd, or a combination thereof.

[0013] The TiO2 layer described above may be rutile-modified or anatase-modified. Generally, when this TiO2 is rutile-modified, the highest quality and luster, as well as the most stable pigment, are obtained. To obtain rutile modification, additives that can advance this TiO2 to rutile modification can be used. Convenient rutile directors are disclosed in US Patent Nos. 4,038,099, US Patent No. 5,433,779, and EP No. 0 271 767. A preferred rutile director is SnO2. Preferred particles are coated small plate-like substrates containing one or more layers of metal oxide, particularly selected from TiO2, Fe2O3, Fe3O4, SnO2, ZrO2, or Cr2O3, preferably only one metal oxide layer. Natural mica, synthetic mica, glass flakes, SiO2 flakes, and Al2O3 flakes coated with TiO2 or Fe2O3 or mixtures thereof are particularly preferred.

[0014] In this patent application, the term "high refractive index" means that the refractive index n is ≥ 1.8. In this patent application, the term "low refractive index" means that the refractive index n is < 1.8. The thickness of each high refractive index layer depends on the desired interference color. The thickness of each layer on the surface of the plate-like particles is preferably 20 to 400 nm, preferably 30 to 300 nm, and particularly 30 to 200 nm. The number of layers on the surface of the above-mentioned substrate is preferably 1 or 2, and more preferably 3, 4, 5, 6 or 7 layers. In particular, interference packages consisting of high-refractive-index and low-refractive-index layers on the surface of a small plate-like substrate result in pigments with increased gloss and increased interference color or color flop. Suitable colorless, low refractive index materials for coating are preferably metal oxides or corresponding oxide hydrates, such as SiO2, Al2O3, AlO(OH), B2O3, MgO*SiO2, CaO*SiO2, Al2O3*SiO2, B2O3*SiO2 compounds, such as MgF2, or mixtures of the above metal oxides. Preferred multilayer systems applied to the surface of a small plate-shaped substrate are TiO2-SiO2-TiO2 arrays or TiO2-MgO*SiO2-TiO2 arrays. The above-mentioned plate-like particles may also be coated with one or more layers of metals or metal alloys selected from, for example, chromium, nickel, silver, bismuth, copper, tin, and Hastelloy®, or with metal sulfides or sulfides selected from, for example, tungsten, molybdenum, cerium, lanthanum, or rare earth elements. The aC / nc-graphite layer can be deposited directly on the surface of the substrate, between one or more metal or metal oxide layers, or on the surface of each metal or metal oxide layer or on the surface of the particles. In a preferred embodiment, at least one aC / nc-graphite layer is applied to the surface of the particles, particularly on the surface of interference pigments and multilayer pigments.

[0015] Preferred pigments according to the present invention are listed below: Substrate + aC / nc-graphite layer Substrate + aC / nc-graphite layer + TiO2 Substrate + aC / nc - Graphite layer + Fe2O3 Substrate + aC / nc-graphite layer + Fe3O4 Substrate + aC / nc - Graphite layer + Cr2O3 Substrate + aC / nc - Graphite layer + SnO2 Substrate + aC / nc-graphite layer + SiO2 Substrate + aC / nc - Graphite layer + ZrO2 Substrate + aC / nc-graphite layer + ZnO Substrate + aC / nc - Graphite layer + Al Substrate + aC / nc - Graphite layer + Fe Substrate + aC / nc - Graphite layer + Cr Substrate + TiO2 + aC / nc-graphite layer Substrate + TiO2 / Fe2O3 + aC / nc-graphite layer Substrate + Fe2O3 + aC / nc-graphite layer Substrate + Fe3O4 + aC / nc-graphite layer Substrate + TiO2 + Fe2O3 + aC / nc-graphite layer Substrate + TiO2 + Fe3O4 + aC / nc-graphite layer Substrate + TiO2 + SiO2 + TiO2 + aC / nc-graphite layer Substrate + TiO2 + Al2O3 + TiO2 + aC / nc-graphite layer Substrate + TiO2 + MgO*SiO2 + TiO2 + aC / nc-Graphite layer Substrate + TiO2 + CaO*SiO2 + TiO2 + aC / nc-graphite layer Substrate + TiO2 + Al2O3*SiO2 + TiO2 + aC / nc-Graphite layer Substrate + TiO2 + B2O3*SiO2 + TiO2 + aC / nc-Graphite layer Substrate + Fe2O3 + SiO2 + TiO2 + aC / nc-graphite layer Substrate + Fe2O3 + Al2O3 + TiO2 + aC / nc-graphite layer Substrate + Fe2O3 + MgO*SiO2 + TiO2 + aC / nc-Graphite layer Substrate + Fe2O3 + CaO*SiO2 + TiO2 + aC / nc - Graphite layer Substrate + Fe2O3 + Al2O3*SiO2 + TiO2 + aC / nc-Graphite layer Substrate + Fe2O3 + B2O3*SiO2 + TiO2 + aC / nc-Graphite layer Substrate + TiO2 / Fe2O3 + SiO2 + TiO2 + aC / nc-graphite layer Substrate + TiO2 / Fe2O3 + Al2O3 + TiO2 + aC / nc-graphite layer Substrate + TiO2 / Fe2O3 + MgO*SiO2 + TiO2 + aC / nc-Graphite layer Substrate + TiO2 / Fe2O3 + CaO*SiO2 + TiO2 + aC / nc-Graphite layer Substrate + TiO2 / Fe2O3 + Al2O3*SiO2 + TiO2 + aC / nc-Graphite layer Substrate + TiO2 / Fe2O3 + B2O3*SiO2 + TiO2 + aC / nc-Graphite layer Substrate + TiO2 + SiO2 + TiO2 / Fe2O3 + aC / nc-graphite layer Substrate + TiO2 / Fe2O3 + SiO2 + TiO2 / Fe2O3 + aC / nc-graphite layer Substrate + TiO2 / Fe2O3 + MgO*SiO2 + TiO2 / Fe2O3 + aC / nc-Graphite layer Substrate + TiO2 + Al2O3 + TiO2 / Fe2O3 + aC / nc-graphite layer Substrate + TiO2 + MgO*SiO2 + TiO2 / Fe2O3 + aC / nc-Graphite layer Substrate + TiO2 + CaO*SiO2 + TiO2 / Fe2O3 + aC / nc-Graphite layer Substrate + TiO2 + Al2O3*SiO2 + TiO2 / Fe2O3 + aC / nc-Graphite layer Substrate + TiO2 + B2O3*SiO2 + TiO2 / Fe2O3 + aC / nc-Graphite layer Substrate + TiO2 + SiO2 + aC / nc-graphite layer Substrate + TiO2 + SiO2 / Al2O3 + aC / nc-Graphite layer Substrate + TiO2 + Al2O3 + aC / nc-graphite layer Substrate + SnO2 + aC / nc-graphite layer Substrate + SnO2 + TiO2 + aC / nc-graphite layer Substrate + SnO2 + Fe2O3 + aC / nc - Graphite layer Substrate + SiO2 + aC / nc-graphite layer Substrate + SiO2 + TiO2 + aC / nc-graphite layer Substrate + SiO2 + TiO2 / Fe2O3 + aC / nc-graphite layer Substrate + SiO2 + Fe2O3 + aC / nc - Graphite layer Substrate + SiO2 + TiO2 + Fe2O3 + aC / nc-graphite layer Substrate + SiO2 + TiO2 + Fe3O4 + aC / nc-graphite layer Substrate + SiO2 + TiO2 + SiO2 + TiO2 + aC / nc-graphite layer Substrate + SiO2 + Fe2O3 + SiO2 + TiO2 + aC / nc - Graphite layer Substrate + SiO2 + TiO2 / Fe2O3 + SiO2 + TiO2 + aC / nc-graphite layer Substrate + SiO2 + TiO2 + SiO2 + TiO2 / Fe2O3 + aC / nc-graphite layer Substrate + SiO2 + TiO2 + SiO2 + aC / nc-graphite layer Substrate + SiO2 + TiO2 + SiO2 / Al2O3 + aC / nc-Graphite layer Substrate + SiO2 + TiO2 + Al2O3 + aC / nc - Graphite layer Substrate + aC / nc-graphite layer + TiO2 + aC / nc-graphite layer Substrate + aC / nc-graphite layer + Fe2O3 + aC / nc-graphite layer Substrate + aC / nc-graphite layer + SiO2 + SnO2 + TiO2 + aC / nc-graphite layer Substrate + aC / nc-graphite layer + SiO2 + SnO2 + TiO2 + aC / nc-graphite layer + TiO2 Substrate + aC / nc-graphite layer + SiO2 + SnO2 + TiO2 + aC / nc-graphite layer + Fe2O3

[0016] In a particularly preferred embodiment, the preferred pigment described above is based on a plate-like substrate and is selected in particular from natural mica and synthetic mica. The TiO2 layer in the preferred embodiment described above may be rutile or anatase-modified. In the preferred embodiments described above, the synthetic substrate, such as synthetic mica, glass flakes, SiO2 flakes, or Al2O3 flakes, may or may not be doped. The dopant amount is preferably in the range of 0.005 to 5% by mass relative to the substrate. The use of one or more aC / nc-graphite layers makes it possible to vary or adjust the pigment's color, gloss, and opacity over a wide range. In a preferred embodiment, the pigment according to the present invention contains only one aC / nc-graphite layer, which is an outer layer applied to the surface of the particles. The particles can be a substrate such as mica, passivated aluminum flakes, or glass flakes, and their surface is coated with an aC / nc-graphite layer.

[0017] Pigments containing at least one carbon / graphite layer exhibit good opacity and a dark metallic appearance. The pigment according to the present invention preferably consists of 90 to 99% by mass of particles and 10 to 1% by mass of aC / nc-graphite layer relative to the total pigment. The coating of the above substrate with at least one metal oxide layer is preferably carried out by a wet chemical coating process, such as CVD or PVD. The metal oxide layer on the surface of the above-mentioned substrate is preferably applied by a wet chemical coating method developed for the preparation of pearlescent pigments. This type of method is used for, for example, US 3087828, US 3087829, US 3553001, DE 14 67 468, DE 19 59 988, DE 20 09 566, DE 22 14 545, DE 22 15 191, DE 22 44 298, DE 23 13 331, DE 25 22 572, DE 31 37 808, DE 31 37 809, DE 31 51 343, DE 31 51 354, DE 31 51 355, DE 32 11 602, DE 32 35 017, DE 196 18 This is described in Patent No. 568, EP 0 659 843, or in further patent documents and other publications known to those skilled in the art.

[0018] In a preferred embodiment, the conformal and homogeneous aC / nc-graphite layer is obtained by a fluidized bed assisted CVD (FBCVD) process operated at a temperature in the range of 200 to <500°C. The carbon source is selected from carbon-containing organic solvents, in particular solvents that decompose at temperatures below 500°C, such as ethanol, isopropanol, 2-methyl-3-buty-2-ol, or sugar compounds, such as powdered sugar, glucose, fructose, or other sugars known to those skilled in the art. The carbon precursor may be in liquid or solid form. A mixture of liquid carbon and a solid carbon precursor is also possible. It is also possible to use a mixture of different organic solvents, a mixture of different sugars, or a mixture of sugar and solvent as the carbon precursor. In a preferred embodiment, only one carbon source is used, i.e., a solvent or a solid sugar. The above particles are heated in a fluidized bed reactor to a desired temperature in the range of 200 to <500°C, preferably 200 to 480°C, and particularly 250 to 450°C. The heating and carbon decomposition reaction are carried out in an inert gas atmosphere, for example, under N2, argon, or helium. The inert fluidizing gas is preferably adjusted so that a minimum fluidization rate of 2 to 6 mm / second, preferably 2 to 4 mm / second, is maintained throughout the process. When the desired reaction temperature is reached, a carbon precursor such as an organic solvent or sugar compound is added to the fluidizing gas. After chemical vapor deposition, the reactor is cooled in an inert gas atmosphere to room temperature. Further post-treatment of the obtained pigment may include sieving depending on the desired application of the pigment. In particular, deposition of a thin layer of aC / nc-graphite of at least 4 nm on coated or uncoated particles enhances opacity by 3.5 to 4.4 times compared to particles without the aC / nc-graphite layer. Furthermore, the aC / nc-graphite layer also increases the UV stability of the pigment.

[0019] The present invention also relates to a method for preparing pigments according to the present invention. In this patent application, the terms “coating” or “layer” are used to mean the complete covering / envelopment of each surface of a coated or uncoated substrate or particle. Furthermore, to increase stability against light, water, and weather, it is often appropriate to post-coat or post-treat the pigments according to the present invention, depending on the application field. Suitable post-coating or post-treatment methods are, for example, those described in German Patent No. 22 15 191, DE-A 31 51 354, DE-A 32 35 017, or DE-A 33 34 598. This post-coating further increases chemical and photochemical stability or facilitates the handling of the pigment mixture, particularly its incorporation into various media. To improve wetting, dispersibility, and / or compatibility with the application medium, a functional coating containing Al2O3 or ZrO2 or a mixture thereof can be applied to the pigment surface. Furthermore, organic post-coating with silanes is possible, for example, as described in EP 0090259, EP 0 634 459, WO 99 / 57204, WO 96 / 32446, WO 99 / 57204, US 5,759,255, US 5,571,851, WO 01 / 92425, or JJ Ponjee, 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.

[0020] The pigments according to the present invention are preferably adapted to multiple color systems from the fields of paints, coatings, and printing inks. The binders, in particular, water-soluble products such as those sold by BASF, Marabu, Proell, Sericol, Hartmann, Gebr, Schmidt, Sicpa, Aarberg, Siegwerk, GSB-Wahl, Follmann, Ruco, or Coates Screen GmbH, are suitable for preparing printing inks for gravure printing, flexographic printing, offset printing, or offset overprint burnishing. The printing inks may be water-based or solvent-based. Needless to say, the pigments according to the present invention can be advantageously used for various applications, for example, as a blend with the following: - For example, metallic effect pigments based on iron flakes or aluminum flakes; - Pearlescent pigments based on synthetic mica flakes coated with metal oxides, natural mica flakes, glass flakes, Al2O3 flakes, Fe2O3 flakes, or SiO2 flakes; - Interference pigments based on synthetic mica flakes coated with metal oxides, natural mica flakes, glass flakes, Al2O3 flakes, Fe2O3 flakes, or SiO2 flakes; - Goniochromatic pigments; - Multilayer pigments based on synthetic mica flakes coated with metal oxides, natural mica flakes, glass flakes, Al2O3 flakes, Fe2O3 flakes, or SiO2 flakes (preferably containing 2, 3, 4, 5, or 7 layers); -Organic dyes; - Organic pigments; - Inorganic pigments, such as transparent and opaque white, colored and black pigments; -Flaked iron oxide; -Carbon black.

[0021] The pigments according to the present invention can be mixed in any ratio with commercially available pigments and / or further commercially available fillers. Commercially available fillers that can be listed include, for example, natural mica, synthetic mica, nylon powder, pure or filler-filled melamine resin, talc, glass, kaolin, aluminum, magnesium, calcium, zinc oxides or hydroxides, BiOCl, barium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, carbon, boron nitride, and physical or chemical combinations of these substances. There are no restrictions regarding the particle shape of the filler. Depending on the requirements, the particle shape may be, for example, flake-shaped, spherical, or needle-shaped. The pigments according to the present invention can, of course, be combined in formulations with any type of cosmetic raw materials and auxiliary agents. These include, in particular, oils, fats, waxes, film-forming agents, preservatives, and auxiliary agents that generally determine application properties, such as thickeners and rheological additives, e.g., bentonite, hectorite, silicon dioxide, calcium silicate, gelatin, high molecular weight carbohydrates and / or surfactants. The pigments according to the present invention are easy to process and handle. They can be incorporated into systems by simple stirring. The pigments according to the present invention exhibit increased powder fluidity, which is highly beneficial for processing.

[0022] The pigments according to the present invention can be used for coloring coating materials, printing inks, plastics, agricultural films, and button pastes; for coating seeds; and for coating food, pharmaceuticals, or cosmetic formulations. The concentration of the pigment in the system used for coloring is typically between 0.01% and 50% by mass, preferably between 0.1% and 5% by mass, relative to the total solids content of the system. This concentration usually depends on the individual application. Plastics containing the pigment according to the present invention in an amount of 0.1 to 50% by mass, particularly 0.5 to 7% by mass, often exhibit a specific dark metallic and glossy effect.

[0023] In the coating sector, particularly in automotive coatings and automotive repairs, the pigments according to the present invention are used in amounts of 0.5 to 10% by mass. For example, for use in automotive coatings, the pigments according to the present invention are mixed into a base coat formulation consisting of a mixture of resins (e.g., polyester, melamine, and polyurethane) in combination with an amine for pH adjustment, a cosolvent to improve film formation, and at least one thickener to adjust the rheology. To achieve a sprayable viscosity, an antifoaming agent, a wetting agent, and optionally further additives, fillers, pigments and / or matting agents and water are added. This base coat is applied to the desired substrate by spray coating. The resulting dry film thickness is 10 to 20 μm, preferably 12 to 18 μm. After pre-drying, a clear coat is applied over this base coat and a complete coating is baked on. In the above-described coating material, the pigment according to the present invention has the advantage that the desired metallic (liquid) color and gloss can be obtained by a single-layer coating (as a base coat in a one-coat system or a two-coat system). In a preferred embodiment, the pigment according to the present invention is used in the base coat.

[0024] There are no restrictions on the concentration of the pigment according to the present invention in cosmetic formulations. The concentration can be between 0.001% (rinse-off products, e.g., shower gel) and 60%, depending on the application. The pigment according to the present invention may further be combined with cosmetic active compounds. Suitable active compounds include, for example, insect repellents, such as TiO2, inorganic UV filters such as UV A / BC protective filters (e.g., OMC, B3, MBC), anti-aging active compounds, vitamins and their derivatives (e.g., vitamins A, C, E, etc.), sunscreens (e.g., DHA, erythritol), and further cosmetic active compounds such as bisabolol, LPO, ectoin, emblica, allantoin, bioflavonoids and their derivatives. Organic UV filters are typically used in an amount of 0.5 to 10% by mass, preferably 1 to 8% by mass, relative to the above formulation, while inorganic UV filters are used in an amount of 0.1 to 30% by mass. In addition, the above formulation may also contain further conventional skin protection or skincare active ingredients, such as aloe vera, avocado oil, coenzyme Q10, green tea extract, and active compound complexes. The present invention also relates to formulations, particularly cosmetic formulations, which, in addition to the pigments according to the present invention, contain at least one component selected from the group consisting of absorbents, astringents, antimicrobial substances, antioxidants, sweat inhibitors, defoaming agents, anti-dandruff compounds, antistatic agents, binders, biological additives, bleaching agents, chelating agents, deodorants, emollients, emulsifiers, emulsifying stabilizers, dyes, wetting agents, film-forming agents, fillers, fragrances, scents, insecticides, preservatives, corrosion inhibitors, cosmetic oils, solvents, water, oxidizing agents, plant components, buffering substances, reducing agents, surfactants, propellant gases, opacifiers, UV filters and UV absorbers, denaturants, aloe vera, avocado oil, coenzyme Q10, green tea extract, viscosity modifiers, perfumes, and vitamins.

[0025] The present invention thus also relates to the use of pigments according to the present invention in paints, coatings, automotive coatings, automotive finishes, industrial coatings, paints, powder coatings, printing inks, security printing inks, plastics, ceramic materials, and cosmetics. The pigments according to the present invention can further be used in glass, paper, toners for electrophotographic printing processes, seeds, greenhouse sheets and tarpaulins, thermally conductive, self-supporting, electrically insulating, and flexible sheets for insulating machinery or equipment, as absorbers in laser marking of paper and plastics, as absorbers in laser welding of plastics, in pigment pastes with water, organic solvents and / or aqueous solvents, in pigment preparations and dried preparations, for example in granules, for example in clear coats in the industrial and automotive sectors, in sunscreens, as fillers, particularly in automotive coatings and automotive repairs, and in cosmetic formulations. All percentage data in this application are mass percentages unless otherwise specified. The following examples are intended to illustrate the present invention in more detail, but are not intended to limit it. [Examples]

[0026] Example 1 Disperse 150 g of natural mica flakes with a particle size of 5-15 μm in 2000 ml of deionized water while stirring. Then, heat this suspension to 75°C while continuously stirring. Set the precipitation pH of the suspension to 1.8 by carefully adding 50% SnCl4 solution dropwise. Gradually add the remaining SnCl4 solution to this suspension. During this procedure, maintain a constant pH of 1.8 by adding 32% sodium hydroxide. After the addition of this solution is complete, stir the suspension for another 10 minutes. At a constant pH of 1.4, add 135 g of 25% TiCl4 solution until the color endpoint (bluish-silver) is reached, i.e., 12% by mass, TiO2. Thus, obtain a TiO2 layer thickness of 12 nm. Maintain a constant pH during the precipitation process by continuously adding 32% sodium hydroxide solution. After completion, the suspension is stirred for a further 10 minutes, filtered by suction, and washed with deionized water until no salt remains. The particulate matter is dried at 120°C for 24 hours. Following the drying process, a calcination process is carried out at 800°C for 45 minutes. The resulting pigment has a strong bluish-silver color to a pale silver color.

[0027] Example 2 Disperse 150 g of natural mica flakes with a particle size of 5-15 μm in 2000 ml of deionized water while stirring. Then, heat this suspension to 75°C while continuously stirring. Set the precipitation pH of the suspension to 1.8 by carefully adding 50% SnCl4 solution dropwise. Gradually add the remaining SnCl4 solution to this suspension. During this procedure, maintain a constant pH of 1.8 by adding 32% sodium hydroxide. After the addition of this solution is complete, stir the suspension for another 10 minutes. At a constant pH of 1.4, add 201 g of 25% TiCl4 solution until the color endpoint (bluish-silver) is reached, i.e., 18% by mass, TiO2. Thus, obtain a TiO2 layer thickness of 18 nm. Maintain a constant pH during the precipitation process by continuously adding 32% sodium hydroxide solution. After completion, the suspension is stirred for a further 10 minutes, filtered by suction, and washed with deionized water until no salt remains. The particulate matter is dried at 120°C for 24 hours. Following the drying process, a calcination process is carried out at 800°C for 45 minutes. The resulting pigment has a pale bluish-silver color to a strong silver color.

[0028] Example 3 Disperse 150 g of natural mica flakes with a particle size of 5-15 μm in 2000 ml of deionized water while stirring. Then, heat this suspension to 75°C while continuously stirring. Set the precipitation pH of the suspension to 1.8 by carefully adding 50% SnCl4 solution dropwise. Gradually add the remaining SnCl4 solution to this suspension. During this procedure, maintain a constant pH of 1.8 by adding 32% sodium hydroxide. After the addition of this solution is complete, stir the suspension for another 10 minutes. At a constant pH of 1.4, add 390 g of 25% TiCl4 solution until the color endpoint (bluish-silver) is reached, i.e., 35% by mass, TiO2. Thus, a TiO2 layer thickness of 35 nm is obtained. Maintain a constant pH during the precipitation process by continuously adding 32% sodium hydroxide solution. After completion, the suspension is stirred for a further 10 minutes, filtered by suction, and washed with deionized water until no salt remains. The particulate matter is dried at 120°C for 24 hours. Following the drying process, a calcination process is carried out at 800°C for 45 minutes. The resulting pigment has a strong silver color with faint bluish highlights.

[0029] Example 4 - Chemical vapor deposition 150 g of bluish-silver particles from Example 1 are heated to 490°C in a fluidized bed reactor (DI: 63 mm) under a constant inert gas atmosphere (N2). The volumetric flow rate is adjusted to reach a minimum fluidization rate of 2 mm / second, ensuring good mixing and heat and mass transfer properties. As soon as the reaction temperature is reached, the total amount of C precursor acetone is added to the fluidization volumetric flow rate. Due to the high reaction temperature, the C precursor decomposes so that the growth of the C layer on the bluish-silver pigment surface begins. This CVD process is carried out for 60 minutes to achieve a C layer thickness of 4 nm. After a cooling step under an inert gas atmosphere, the final pigment is removed from the reactor and sieved. This dark pigment exhibits a metallic effect with high gloss and high opacity. The deposited C layer consists of a mixture of aC and nc-graphite with a mass ratio of 90:10. This ratio is based on RAMAN Raman spectroscopy studies by Ferrari et al. and Mueller et. al[Mueller, JO; Su, Dang Sheng; Jentoft, Rolf E.; Kroehnert, Jutta; Jentoft, Friederike C.; 259-265.] and Trigueiro et al. [Trigueiro, Joao Paulo C.; Silva, Glaura G.; Lavall, Rodrigo L.; Furtado, Clascidia A.; Oliveira, Sergio; Ferlauto, Andre S.; Lacerda, Rodrigo G.; Ladeira, Luiz O.; thermogravimetric, TEM, and SEM The determination was made using thermogravimetric analysis in conjunction with the method described in [Journal of nanoscience and nanotechnology, 7, 2007, pp. 3477-3486.].

[0030] Example 5 - Chemical vapor deposition 150 g of bluish-silver particles according to Example 2 are heated to 490°C in a fluidized bed reactor (DI: 63 mm) under a constant inert gas atmosphere (N2). The volumetric flow rate is adjusted to reach a minimum fluidization rate of 2 mm / second, ensuring good mixing and heat and mass transfer properties. As soon as the reaction temperature is reached, the total amount of the C precursor 2-methyl-3-butyne-2-ol is added to the fluidization volumetric flow rate. Due to the high reaction temperature, the C precursor decomposes so that the growth of the C layer on the surface of the particles begins. This CVD process is carried out for 60 minutes to achieve a C layer thickness of 4 nm. After a cooling step under an inert gas atmosphere, the final pigment is removed from the reactor and sieved. This dark pigment exhibits a metallic effect with high gloss and high opacity. The deposited carbon layer consists of a mixture of aC and nc-graphite with a mass ratio of 90:10. This ratio was determined using a combination of RAMAN spectroscopy by Ferrari et al. and thermogravimetric analysis by Mueller et al.

[0031] Example 6 - Chemical vapor deposition 150 g of bluish-silver pigment particles according to Example 3 are heated to 490°C in a fluidized bed reactor (DI: 63 mm) under a constant inert gas atmosphere (N2). The volumetric flow rate is adjusted to reach a minimum fluidization rate of 2 mm / second, ensuring good mixing and heat and mass transfer properties. As soon as the reaction temperature is reached, the total amount of C precursor acetone is added to the fluidization volumetric flow rate. Due to the high reaction temperature, the C precursor decomposes so that the growth of the C layer on the surface of the particles begins. This CVD process is carried out for 60 minutes to achieve a C layer thickness of 4 nm. After a cooling step under an inert gas atmosphere, the final pigment is removed from the reactor and sieved. This dark pigment exhibits a deep metallic effect, high gloss, and high opacity. The deposited carbon layer consists of a mixture of aC and nc-graphite in a ratio of 90:10. This ratio was determined using a combination of RAMAN spectroscopy by Ferrari et al. and thermogravimetric analysis by Mueller et al.

[0032] Example 7 - aC / nc-graphite coating on commercially available blue interference pigments 1 kg of commercially available blue interference pigment Example 7a): Iriodin® 7225 Ultra Blue (Merck KGaA, natural mica coated with TiO2, particle size 10-60 μm) Example 7b): Timiron® Splendid Blue (a multilayer pigment based on natural mica coated with Merck KGaA, TiO2, and SiO2, particle size 10-60 μm) Example 7c): Pyrisma® Color Space Blue (Merck KGaA, natural mica coated with TiO2 and SiO2, particle size 5-35 μm) Example 7d): Xirona® Caribbean Blue (a multilayer pigment based on natural mica coated with Merck KGaA, TiO2, SiO2, and SnO2, particle size 10-60 μm) Example 7e): Lumina® Royal Exterior Blue (natural mica coated with BASF, TiO2, SiO2 and SnO2, d 10 = 10 μm, d 50 = 19 μm, d 90 (= 34 μm) Example 7f): Mirage Bright Blue (Eckart, borosilicate glass flakes coated with TiO2 and SiO2, particle size 10-70 μm) Example 7g): Thin Crystal Blue (Eckart, synthetic mica (fluorinated fluorphlogopite coated with TiO2 and SiO2, particle size 10-50 μm) Example 7h): XillaMay (synthetic mica coated with Kuncai, TiO2 and SnO2, SiO2 and Ce2O3, particle size 6-30 μm) The mixture is heated in a fluidized bed reactor (DI: 100 mm) to the desired reaction temperature of 480°C. The heating and carbon deposition reaction are carried out in an inert gas atmosphere (N2). The inert fluidizing gas is adjusted so that a minimum fluidization rate of 2 mm / second is maintained throughout the process. When the reaction temperature of 480°C is reached, carbon precursor acetone or 2-methyl-3-butyne-2-ol is added to the fluidizing gas. After a cooling step under an inert gas atmosphere (N2), the final pigment is removed from the reactor and sieved. The deposited C layer consists of a mixture of aC / nc-graphite: Example 7a): aC / nc-graphite ratio: 85:15, layer thickness: 1-2 nm Example 7b): aC / nc-graphite ratio: 85:15, layer thickness: 1~2nm Example 7c): aC / nc-graphite ratio: 95:5, layer thickness: 1-2nm Example 7d): aC / nc-graphite ratio: 90:10, layer thickness: 1-2 nm Example 7e): aC / nc-graphite ratio: 95:5, layer thickness: 1-2nm Example 7f): aC / nc-graphite ratio: 95:5, layer thickness: 1~2nm Example (7g): aC / nc-graphite ratio: 90:10, layer thickness: 1-2nm Example 7h): aC / nc-graphite ratio: 85:15, layer thickness: 1~2nm The coated pigments of Examples 7a) to 7h) exhibit a (dark) mastertone blue shade. At the same time, their opacity is significantly improved compared to the uncoated pigments. Furthermore, the aC / nc-graphite coated pigments appear more metallic compared to the natural (=uncoated) pigments. In the case of Example 7d), the aC / nc-graphite layer enhances the color migration effect, i.e., a very strong color migration from blue to purple to green (= a multicolor flop of at least three colors). This effect is very suitable for cosmetic applications, such as eyeshadow, lip gloss, lipstick, and nail polish, as the so-called holographic effect can be seen in the enhanced color migration.

[0033] Example 8 - Carbon / graphite coating on commercially available green interference pigments 1 kg of commercially available interference pigment, green Example 8a): Pyrisma® Color Space Turquoise (Merck KGaA; TiO2-coated mica, particle size 5-35 μm) Example 8b): Timiron® Splendid Green (a pigment based on natural mica coated with Merck KGaA, TiO2, and SiO2, particle size 10-60 μm) Example 8c): Xirona® Nordic Sunset (Merck KGaA, SiO2 flakes coated with SnO2 and TiO2, particle size: 5-50 μm) Example 8d): Mirage Dazzling Green (Eckart, borosilicate glass flakes coated with TiO2 and SnO2, particle size 150-200 μm) Example 8e): Adamas® AE-791K-OP Splendor Green (Al2O3 flakes coated with CQV, TiO2 and SnO2, d 10 = 5 μm, d 50 = 15~19 μm, d 90 (=30μm) The mixture is heated in a fluidized bed reactor (DI: 100 mm) to a desired reaction temperature of 450 °C. The heating and carbon deposition reaction are carried out in an inert gas atmosphere. The inert fluidizing gas is adjusted so that a minimum fluidization rate of 2 mm / second is maintained throughout the process. When the reaction temperature, e.g., 450 °C, is reached, the carbon precursor acetone or 2-methyl-3-butyne-2-ol is added to the fluidizing gas. After a cooling step under an inert gas atmosphere (e.g., N2), the final pigment is removed from the reactor and sieved. The deposited C layer consists of a mixture of aC / nc-graphite: Example 8a): aC / nc-graphite ratio: 85:15, layer thickness: 1-2 nm Example 8b): aC / nc-graphite ratio: 85:15, layer thickness: 1~2nm Example 8c): aC / nc-graphite ratio: 85:15, layer thickness: 1-2 nm Example 8d): aC / nc-graphite ratio: 95:5, layer thickness: 1-2nm Example 8e): aC / nc-graphite ratio: 85:15, layer thickness: 1-2 nm The pigments coated according to Examples 8a) to 8e) exhibit (dark) master tone green shades and significantly improved opacity. Furthermore, the aC / nc-graphite coated pigments appear more metallic than the natural (uncoated) pigments. In Example 8c), the aC / nc-graphite layer enhances the color migration effect, exhibiting a very strong color migration from silver-green to silver-red to green-gold. This effect can be utilized in cosmetic applications, such as eyeshadow, lip gloss, lipstick, and nail polish, particularly as the so-called holographic effect can be seen through the enhanced color migration.

[0034] Examples 9-15 - aC / nc-graphite coating on commercially available interference pigments Select 1 kg of commercially available interference pigment from the table below.

[0035] JPEG2026137679000001.jpg226170 JPEG2026137679000002.jpg118170

[0036] The mixture is heated in a fluidized bed reactor (DI: 100 mm) to the desired reaction temperature. The heating and carbon deposition reaction are carried out in an inert N2 gas atmosphere. The N2 inert gas fluidization is adjusted so that a minimum fluidization rate of 2 mm / second is maintained throughout the process. When the reaction temperature is reached, the carbon precursor is added to the fluidizing gas. After a cooling step under an inert gas atmosphere (N2), the final pigment is removed from the reactor and sieved. The C coatings of Examples 9b) and 9c) produce a liquid metal effect, particularly in cosmetic applications such as lipstick, lip gloss, and nail polish. These three C-coated pigments have a liquid metal index of 8.58 (Fop Index = 18.09, roughness = 2.11). To date, such an effect has only been achieved by using aluminum flakes, which cannot be used in lip gloss, lipstick, and eyeshadow due to regulatory restrictions.

[0037] Examples of Use Example of Use A1 - Coating The aC / nc-graphite coated pigment according to Example 4 is incorporated into the base coat MIPA WBC 000 (MIPA SE, Germany) by stirring. Depending on the desired hue, a certain concentration of pigment must be used. To achieve the full hue of the pigment in Example 4, 1% by mass of pigment is used in the formulation. If necessary, this coating can be diluted with deionized water for 1000s. -1The spray viscosity is adjusted to 70-75 mPa·s. The colored base coat is applied to a black white metal panel (Metopac T21G, purchased from Leneta) by spray coating. For application, an automatic spray application Oerter APL 4.6 with a DeVilbiss AGMD2616 spray gun is used (nozzle 1.4 mm, cap 767 c). The spray pressure is 4200 mbar, the material supply is approximately 110 ml / min, and the distance between the spray gun and the substrate is approximately 30 cm. The spray gun is moved at 0.45 m / sec, and three layers are applied with an intermediate flash-off time of 30 seconds between each layer. The resulting dry film thickness is 10-20 μm, preferably 11-15 μm. If the carbon content of the pigment is sufficiently high, it is possible to apply only one layer with a dry film thickness of 1-3 μm. After pre-drying the colored layer at room temperature with air circulation, a clear coat is applied over this base coat and the complete coating is baked.

[0038] Example of Use A2 - Coating The aC / nc-graphite coated pigment according to Example 5 is incorporated into the base coat MIPA WBC 000 (MIPA SE, Germany) by stirring. Depending on the desired hue, a certain concentration of pigment must be used. To achieve the full hue of the pigment in Example 4, 1% by mass of pigment is used for the formulation. If necessary, this coating can be diluted with deionized water for 1000s. -1The spray viscosity is adjusted to 70-75 mPa·s. The colored base coat is applied to a black white metal panel (Metopac T21G, purchased from Leneta) by spray coating. For application, an automatic spray application Oerter APL 4.6 with a DeVilbiss AGMD2616 spray gun is used (nozzle 1.4 mm, cap 767 c). The spray pressure is 4200 mbar, the material supply is approximately 110 ml / min, and the distance between the spray gun and the substrate is approximately 30 cm. The spray gun is moved at 0.45 m / sec, and three layers are applied with an intermediate flash-off time of 30 seconds between each layer. The resulting dry film thickness is 10-20 μm, preferably 11-15 μm. If the carbon content of the pigment is sufficiently high, it is possible to apply only one layer with a dry film thickness of 1-3 μm. After pre-drying the colored layer at room temperature with air circulation, a clear coat is applied over this base coat and the complete coating is baked.

[0039] Example of use A3 - Lipstick JPEG2026137679000003.jpg113170 JPEG2026137679000004.jpg129170

[0040] Example of use A4 - Lipstick JPEG2026137679000005.jpg108170 JPEG2026137679000006.jpg123170

[0041] Example of use A5 - Lipstick JPEG2026137679000007.jpg123170 JPEG2026137679000008.jpg108170

[0042] Example of use A6 - Lipstick JPEG2026137679000009.jpg134170 JPEG2026137679000010.jpg98170

[0043] Example of use A7 - Eyeshadow JPEG2026137679000011.jpg144170 JPEG2026137679000012.jpg93170

[0044] Example of use A8 - Lip balm JPEG2026137679000013.jpg211170

[0045] Example of use A9 - Lip balm JPEG2026137679000014.jpg206170

Claims

1. A particle-based pigment, characterized in that the particles are coated with at least one layer consisting of a mixture of amorphous carbon (aC) and nanocrystalline graphite (nc-graphite).

2. The pigment according to claim 1, characterized in that the aC / nc-graphite ratio is in the range of 60:40 to 80:

20.

3. The pigment according to claim 1 or 2, characterized in that the aC / nc-graphite layer has a thickness of 1 to 10 nm.

4. The pigment according to any one of claims 1 to 3, characterized in that the particles are selected from the group of substrates listed below: Natural mica, synthetic mica, talc, kaolin, Fe 2 O 3 Flakes, Fe 3 O 4 Flakes, Al 2 O 3 Flakes, BiOCl flakes, glass flakes, SiO 2 Flake, TiO 2 Flakes, BN flakes, aluminum flakes, Si-oxynitride flakes, Si- / Ti-nitride flakes, graphite flakes, pearl essence, synthetic supported-free flakes, glass beads, filler pigments, interference pigments, multilayer pigments, color flop pigments, goniochromatic pigments, metal effect pigments, silicon particles, or mixtures thereof.

5. The pigment according to any one of claims 1 to 4, characterized in that the substrate is spherical or plate-shaped.

6. The pigment according to any one of claims 1 to 5, characterized in that the substrate is coated with at least one metal oxide and / or metal.

7. The pigment according to any one of claims 1 to 6, characterized in that the particles are selected from the following group: Substrate + a-C / nc-graphite layer Substrate + a-C / nc-graphite layer + TiO 2 Substrate + a-C / nc-graphite layer + Fe 2 O 3 Substrate + a-C / nc-graphite layer + Fe 3 O 4 Substrate + a-C / nc-graphite layer + Cr 2 O 3 Substrate + a-C / nc-graphite layer + SiO 2 Substrate + a-C / nc-graphite layer + ZrO 2 Substrate + a-C / nc-graphite layer + SnO 2 Substrate + a-C / nc-graphite layer + ZnO Substrate + a-C / nc-graphite layer + Al Substrate + a-C / nc-graphite layer + Fe Substrate + a-C / nc-graphite layer + Cr Base material + TiO 2 +a-C / nc-graphite layer Base material + TiO 2 / Fe 2 O 3 +a-C / nc-graphite layer Base material + Fe 2 O 3 +a-C / nc-graphite layer Base material + Fe 3 O 4 +a-C / nc-graphite layer Base material + TiO 2 +Fe 2 O 3 +a-C / nc-graphite layer Base material + TiO 2 +Fe 3 O 4 +a-C / nc-graphite layer Base material + TiO 2 +SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + TiO 2 +Al 2 O 3 +TiO 2 +a-C / nc-graphite layer Base material + TiO 2 +MgO*SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + TiO 2 + CaO*SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + TiO 2 +Al 2 O 3 *SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + TiO 2 +B 2 O 3 *SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + Fe 2 O 3 +SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + Fe 2 O 3 +Al 2 O 3 +TiO 2 +a-C / nc-graphite layer Base material + Fe 2 O 3 +MgO*SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + Fe 2 O 3 + CaO*SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + Fe 2 O 3 +Al 2 O 3 *SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + Fe 2 O 3 +B 2 O 3 *SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + TiO 2 / Fe 2 O 3 +SiO 2 +TiO 2 +a-C / nc-graphite layer Substrate + TiO 2 / Fe 2 O 3 +Al 2 O 3 +TiO 2 +a-C / nc-graphite layer Substrate + TiO 2 / Fe 2 O 3 + MgO*SiO 2 + TiO 2 + a-C / nc-graphite layer Base material + TiO 2 / Fe 2 O 3 + CaO*SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + TiO 2 / Fe 2 O 3 +Al 2 O 3 *SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + TiO 2 / Fe 2 O 3 +B 2 O 3 *SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + TiO 2 +SiO 2 +TiO 2 / Fe 2 O 3 +a-C / nc-graphite layer Base material + TiO 2 / Fe 2 O 3 +SiO 2 +TiO 2 / Fe 2 O 3 +a-C / nc-graphite layer Base material + TiO 2 / Fe 2 O 3 +MgO*SiO 2 +TiO 2 / Fe 2 O 3 +a-C / nc-graphite layer Base material + TiO 2 +Al 2 O 3 +TiO 2 / Fe 2 O 3 +a-C / nc-graphite layer Base material + TiO 2 +MgO*SiO 2 +TiO 2 / Fe 2 O 3 +a-C / nc-graphite layer Base material + TiO 2 + CaO*SiO 2 +TiO 2 / Fe 2 O 3 +a-C / nc-graphite layer Base material + TiO 2 +Al 2 O 3 *SiO 2 +TiO 2 / Fe 2 O 3 +a-C / nc-graphite layer Base material + TiO 2 +B 2 O 3 *SiO 2 +TiO 2 / Fe 2 O 3 +a-C / nc-graphite layer Base material + TiO 2 +SiO 2 +a-C / nc-graphite layer Base material + TiO 2 +SiO 2 / Al 2 O 3 +a-C / nc-graphite layer Base material + TiO 2 +Al 2 O 3 +a-C / nc-graphite layer Base material + SnO 2 +a-C / nc-graphite layer Base material + SnO 2 +TiO 2 +a-C / nc-graphite layer Base material + SnO 2 +Fe 2 O 3 +a-C / nc-graphite layer Base material + SiO 2 +a-C / nc-graphite layer Base material + SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + SiO 2 +TiO 2 / Fe 2 O 3 +a-C / nc-graphite layer Base material + SiO 2 +Fe 2 O 3 +a-C / nc-graphite layer Base material + SiO 2 +TiO 2 +Fe 2 O 3 +a-C / nc-g graphite layer Base material + SiO 2 +TiO 2 +Fe 3 O 4 +a-C / nc-graphite layer Base material + SiO 2 +TiO 2 +SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + SiO 2 +Fe 2 O 3 +SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + SiO 2 +TiO 2 / Fe 2 O 3 +SiO 2 +TiO 2 +a-C / nc-graphite layer Base material + SiO 2 +TiO 2 +SiO 2 +TiO 2 / Fe 2 O 3 +a-C / nc-graphite layer Base material + SiO 2 +TiO 2 +SiO 2 +a-C / nc-graphite layer Base material + SiO 2 +TiO 2 +SiO 2 / Al 2 O 3 +a-C / nc-graphite layer Base material + SiO 2 +TiO 2 +Al 2 O 3 +a-C / nc-graphite layer Substrate + a-C / nc-graphite layer + TiO 2 +a-C / nc-graphite layer Substrate + a-C / nc-graphite layer + Fe 2 O 3 +a-C / nc-graphite layer Substrate + a-C / nc-graphite layer + SiO 2 +SnO 2 +TiO 2 +a-C / nc-graphite layer Substrate + aC / nc-graphite layer + SiO 2 +SnO 2 +TiO 2 +a-C / nc-graphite layer +TiO 2 Substrate + a-C / nc-graphite layer + SiO 2 +SnO 2 +TiO 2 +a-C / nc-graphite layer +Fe 2 O 3

8. The pigment according to any one of claims 1 to 7, characterized in that the pigment consists of 90 to 99% by mass of particles and 1 to 10% by mass of an aC / nc-graphite layer relative to the total pigment.

9. A method for preparing a pigment according to any one of claims 1 to 8, characterized in that particles are heated to a desired temperature in a fluidized bed reactor in an inert gas atmosphere, a carbon precursor is added to the fluidizing gas when a desired reaction temperature is reached, and the fluidized bed reaction is cooled to room temperature in an inert gas atmosphere after chemical deposition.

10. The method according to claim 9, characterized in that the carbon precursor is selected from the group consisting of sugars and organic solvents.

11. The method according to claim 10 or 11, characterized in that the precursor is ethanol, isopropanol, acetone, 2-methyl-3-butynicol, powdered sugar, fructose, glycose, or dextrose.

12. The method according to any one of claims 10 to 12, characterized in that the reaction temperature is 200 to <500°C.

13. The method according to any one of claims 10 to 13, characterized in that the fluidized bed reactor is a fluidized bed assisted CVD reactor (FBCVD).

14. Use of the pigment according to any one of claims 1 to 8 in paints, coatings, automotive coatings, automotive repair, industrial coatings, paints, powder coatings, printing inks, security printing inks, plastics, ceramic materials, cosmetics, glass, paper, paper coatings, toners for electrophotographic printing processes, seeds, greenhouse sheets and tarpaulins, thermally conductive, self-supporting, electrically insulating, flexible sheets for insulation of machinery or equipment, as an absorber in laser marking of paper and plastics, as an absorber in laser welding of plastics, in pigment pastes with water, organic solvents and / or aqueous solvents, in pigment preparations and dried preparations.

15. A formulation containing the pigment described in any one of claims 1 to 8 in an amount of 0.01 to 95% by mass relative to the entire formulation.

16. The formulation according to claim 15, further characterized by containing at least one component selected from the group consisting of absorbents, astringents, antimicrobial substances, antioxidants, sweat inhibitors, defoamers, anti-dandruff compounds, antistatic agents, binders, biological additives, bleaching agents, chelating agents, deodorants, skin emollients, emulsifiers, emulsifying stabilizers, dyes, wetting agents, film-forming agents, fillers, fragrances, scents, insecticides, preservatives, corrosion inhibitors, cosmetic oils, solvents, water, oxidizing agents, plant components, buffering substances, reducing agents, surfactants, propellant gases, opacifiers, UV filters and UV absorbers, denaturants, aloe vera, avocado oil, coenzyme Q10, green tea extract, viscosity modifiers, perfumes, and vitamins.

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