HIGH CHROMA AND HIGH BRILLIANCE EFFECT PIGMENTS, METHOD FOR THEIR MANUFACTURE AND USE THESE

Description

[0001] The present invention relates to absorbing effect pigments comprising a non-metallic platelet-shaped substrate and a coating applied thereon, wherein the coating comprises at least one spacer layer, a process for the preparation and the use thereof.

[0002] Multilayer pigments which, based on a non-metallic platelet-shaped substrate, comprise at least one layer sequence of alternating high-, low-, high-refractive-index layers are known, for example, from EP 1 572 812 A1, EP 1 213 330 A1, EP 1 025 168 B2, EP 1 621 585 A2, EP 0 948 572 A1, EP 0 950 693 A1, EP 1 306 412 A1, EP 1 587 881 A2, EP 2 632 988 A1 or EP 1 474 486 A2. Depending on the optical layer thickness of the low-refractive-index layer, the multilayer pigments can change their optical appearance depending on the viewing angle, as described, for example, in EP 1 375 601 A1, EP 1 281 732 A1, EP 0 753 545 A2, and US 2004 / 0003758 A1. All of the above-mentioned applications have in common that a low-refractive-index layer made of a low-refractive-index metal oxide, such as silicon oxide, is present in the layer sequence.

[0003] Multi-layer pigments are characterized by a higher gloss and, if necessary, a higher chroma compared to single-layer effect pigments with only a single identical first layer; the same substrate and the same particle size are of course assumed.

[0004] EP 1 029 900 A1 discloses pigments coated with (A) a high-index pseudobrookite coating consisting of a mixture of TiO 2 and Fe 2 O 3 in a ratio of 10:1 to 1:3 and optionally one or more metal oxides in amounts of ≤ 20 wt.% based on layer (A), (B) a colorless coating with a refractive index n ≤ 1.8, and optionally an outer protective layer. The application contains no reference to a spacer layer within or between layers (A) and (B).

[0005] EP 1 230 308 A1 discloses pigments comprising at least two layer sequences of (A) a colorless coating with a refractive index n ≤ 1.8, (B) a high-index coating of pseudobrookite consisting of a mixture of TiO 2 and Fe 2 O 3 in a ratio of 1:0.1 to 1:5 and optionally one or more metal oxides in amounts of ≤ 20 wt.% based on layer (B), and optionally (C) an outer protective layer. EP 1 230 308 A1 contains no indication of a spacer layer within or between layers (A) and (B).

[0006] EP 1 230 310 A1 discloses pigments comprising a layer sequence of (A) a high-index coating consisting of a mixture of TiO 2 and Fe 2 O 3 in a ratio of 1:0.1 to 1:5 and optionally one or more metal oxides in amounts of ≤ 20 wt.% based on layer (A), (B) a colorless coating with a refractive index n ≤ 1.8, (C) a colorless coating with a refractive index n > 1.8, (D) an absorbing coating with a refractive index n > 1.8 and optionally (E) an outer protective layer. A spacer layer within or between the aforementioned layers is not described in EP 1 230 310 A1.

[0007] WO 2014 / 094993 A1 discloses interference pigments based on multiply coated platelet-shaped substrates having on the surface of the substrate a layer sequence comprising (A0) optionally a layer of TiO 2 , (A) a coating consisting of a mixture of TiO 2 and Fe 2 O 3 , which may optionally be doped with one or more further oxides, (B) a layer of SnO 2 , (C) a highly refractive coating absorbing in the visible wavelength range, and optionally (D) an outer protective layer. In layer (A) and / or (C), the mixing ratio of TiO 2 to Fe 2 O 3 is preferably 10:1 to 1:3. To increase the color strength of layer (A) and / or layer (C), one or more oxides, such as Al 2 O 3 , Ce 2 O 3 , B 2 O 3 , ZrO 2 , SnO 2 , can be added to the TiO 2 / Fe 2 O 3 mixture. WO 2014 / 094993 A1 does not disclose any spacer layer within or between the layers described above.

[0008] CN 101289580 A describes the production of golden pigments with strong interference color, whereby the pigments are intended to create the impression of 24K gold. A mica substrate is suspended in water and a solution of TiCl 4 is added for the first coating layer, a solution of FeCl 3 and TiCl 4 for the second coating layer, a solution of SnO 2 for the third coating layer, and a solution of TiCl 4 for the fourth coating layer. After filtration and washing, the pigment is dried at 120°C to 200°C and calcined at 820°C. CN 101289580 A contains no reference to a spacer layer in the coating.

[0009] EP 1 422 268 A2 discloses a pigment with a multilayer structure, wherein this pigment comprises two or more metal oxide layers, wherein the at least one metal (ion) of the metal oxide layer is selected from the group consisting of cerium, tin, titanium, iron, zinc, and zirconium. The aim of this application is to produce highly chromatic and highly brilliant pigments that have as few and as small as possible pores in their coating. According to EP 1 422 268 A2, a low pore volume is intended to ensure a high-quality optical coating.

[0010] US 8,585,818 B1 discloses a pearlescent effect pigment with a multilayer structure based on pearlite flakes, in which a layer sequence of SnO 2 / TiO 2 / Fe 2 O 3 is applied. The layer thickness of the first SnO 2 layer is < 10 nm and thus no layer structure is achieved in which a spacer layer is formed.

[0011] WO 2003 / 006558 A2 discloses a pearlescent pigment with a multilayer structure in which the low-refractive-index layer is SiO 2 or Al 2 O 3.

[0012] US 2015 / 0344677 A1 relates to effect pigments based on coated platelet-shaped substrates. The coating comprises a first and a second high-index layer and a third component, which is intended to diffuse partially or fully into one or both of the high-index layers. The third component can be SiO 2 or another metal oxide. The aim of this application is to obtain SiO 2 coverage without agglomeration in effect pigments with a D 50 value of 15 µm or less.

[0013] The object of the present invention was to provide a highly chromatic pigment with high gloss and high opacity, which has high mechanical stability and high chemical stability and at the same time can be produced in a simple manner with low material usage.

[0014] This object is achieved by providing an absorbing effect pigment according to claim 1

[0015] According to the invention, "interrupted" means that layers 2 and 3 are spaced from each other or kept at a distance by a spacer layer.

[0016] The general term "metal oxide, metal hydroxide, and / or metal oxide hydrate" refers, for the purposes of the invention, to "metal oxide and / or metal hydroxide and / or metal oxide hydrate." This also applies if the metal or metal ion is specified, for example, as titanium (ion), iron (ion), tin (ion), zirconium (ion), etc.

[0017] According to the invention, the expression "a metal ion" or "an iron ion" does not mean a single metal ion or iron ion, but rather a plurality of metal ions or iron ions.

[0018] According to a preferred embodiment, the optional layer 1 lies directly on the non-metallic platelet-shaped substrate, the layer 2 follows directly on the layer 1 and the layer 3 follows on the layer 2, wherein the layers 2 and 3 are interrupted by a spacer layer.

[0019] According to a further embodiment, layer 2 lies directly on the non-metallic platelet-shaped substrate and layer 3 follows layer 2, wherein layers 2 and 3 are interrupted by a spacer layer.

[0020] Preferred developments of the absorbing effect pigment are specified in the dependent claims 2 to 8.

[0021] Furthermore, the object is achieved by providing a process for producing the absorbing effect pigment according to the invention, the process comprising the following steps: (i) Optionally applying a non-calcined layer comprising or consisting of tin oxide, tin hydroxide and / or tin oxide hydrate to the non-metallic platelet-shaped substrate, (ii) sequentially applying three non-calcined layers A, B and C each comprising or containing at least one metal oxide, metal hydroxide and / or metal oxide hydrate, wherein layers A, B and C are arranged directly on top of one another and wherein the at least one metal oxide, metal hydroxide and / or metal oxide hydrate applied in layer B is different in terms of the metal ion from the metal ion(s) of the metal oxides, metal hydroxides and / or metal oxide hydrates of layer A and layer C, wherein the three sequentially applied metal oxides, metal hydroxides and / or metal oxide hydrates for producing layers A, B and C do not comprise a metal ion selected from the group of metals consisting of Si, Mg and Al,(iii) calcining the product obtained in step (ii) at a temperature in the range from 600°C to 1000°C to obtain the absorbing effect pigment comprising at least one spacer layer.

[0022] Alternatively, the object is achieved by providing a process for producing the absorbing effect pigment according to the invention, the process comprising the following steps: (i) Sequential application of two non-calcined layers B and C each comprising or containing at least one metal oxide, metal hydroxide and / or metal oxide hydrate onto a calcined single- or multiply-coated non-metallic substrate, wherein the layers B and C are arranged directly on top of one another and wherein the at least one metal oxide, metal hydroxide and / or metal oxide hydrate applied in layer B is different in terms of the metal ion from the metal ion(s) of the metal oxide, metal hydroxide and / or metal oxide hydrate of layer C and the layer which directly adjoins layer B in the direction of the substrate, wherein the two sequentially applied metal oxides, metal hydroxides and / or metal oxide hydrates for producing layers B and C do not comprise a metal ion selected from the group of metals consisting of Si, Mg and Al,(ii) calcining the product obtained in step (i) at a temperature in the range from 600°C to 1000°C to obtain the absorbing effect pigment comprising at least one spacer layer.

[0023] The invention further relates to the use of the absorbing effect pigment according to the invention in cosmetic formulations, plastics, films, textiles, ceramic materials, glasses, paints, printing inks, inks, varnishes, powder coatings and / or in functional applications, such as for laser marking, IR reflection, photocatalysis.

[0024] The object underlying the invention is further achieved by providing an article, wherein the article comprises at least one absorbing effect pigment according to the invention.

[0025] The non-metallic platelet-shaped substrates to be coated can be selected from the group consisting of natural mica platelets, synthetic mica platelets, iron mica platelets, glass platelets, iron oxide platelets, SiO 2 platelets, Al 2 O 3 platelets, kaolin platelets, talc platelets, and bismuth oxychloride platelets. According to the invention, the absorbing effect pigments can also be based on mixtures of the above-mentioned non-metallic platelet-shaped substrates. The aforementioned non-metallic platelet-shaped substrates can also have one or more layers made of or with at least one high- and / or low-refractive-index metal oxide, metal hydroxide, and / or metal oxide hydrate. Thus, single- or multiply-coated pearlescent pigments or interference pigments can also be used as substrates.According to a preferred embodiment, the substrates to be used according to the invention are uncoated, non-metallic platelet-shaped substrates.

[0026] The non-metallic platelet-shaped substrates are preferably selected from the group consisting of natural mica platelets, synthetic mica platelets, glass platelets, SiO 2 platelets, Al 2 O 3 platelets, and mixtures thereof. The non-metallic platelet-shaped substrates are particularly preferably selected from the group consisting of natural mica platelets, synthetic mica platelets, glass platelets, and mixtures thereof. Synthetic mica platelets and / or glass platelets, and mixtures thereof, are very particularly preferred as non-metallic platelet-shaped substrates. Glass platelets are particularly preferred as non-metallic platelet-shaped substrates.

[0027] The glass flakes usable as substrates can, with regard to their composition, consist of silicate glass, such as soda-lime glass, lead crystal glass, E-glass, A-glass, C-glass, ECR glass, Duran glass, window glass, laboratory glass, aluminosilicate glass, or borosilicate glass. The glass flakes preferably have a composition according to the teaching, in particular according to the main claim, of EP 1 980 594 B1, particularly preferably according to the teaching, in particular according to the respective main claim, of EP 1 829 833 B1 or EP 2 042 474 B1. The glass flakes usable as substrates are preferably produced by the process described in EP 289 240 B1.

[0028] In a further embodiment, the glass flakes can be deliberately colored by adding at least one inorganic colorant during their production. Suitable colorants are those that do not decompose at the respective melting temperature of the glass composition. The proportion of colorant is preferably in a total range of 0.1 wt.% to 50 wt.%, particularly preferably in a total range of 1 wt.% to 35 wt.%, and most preferably in a total range of 5 wt.% to 25 wt.%, in each case based on the total weight of the glass composition. Suitable colorants are, in particular, elemental noble metals such as Au, Pd or Pt, the cations or complex anions of the elements Cu, Cr, Mn, Fe, Ti and / or Co, and mixtures of the above-listed colorants.

[0029] In a further embodiment, the refractive index of the glass flakes usable as substrate is in a range from 1.45 to 1.80, preferably in a range from 1.50 to 1.70.

[0030] In a further embodiment, the platelet-shaped substrates, in particular glass platelets, can be coated with a layer comprising or consisting of silicon oxide, silicon hydroxide, or silicon oxide hydrate. For example, when using glass platelets, the aforementioned coating can protect the glass surface from chemical changes, such as swelling, leaching of glass components, or dissolution in aggressive acidic coating solutions.

[0031] The synthetic mica flakes usable as substrates can have a composition according to the main claim of CN 102718229 A or according to the main claim of US 2014 / 0251184 A1. They can also be produced according to the information in EP 0 723 997 A1, pages 3 to 4.

[0032] The synthetic mica platelets that can be used as substrates are preferably fluorphlogopite of the formula KMg 3 AlSi 3 Q 10 F 2 , KMg 2 ½(Si 4 O 10 )F 2 or NaMg 2 ½(Si 4 O 10 )F 2 , in particular fluorphlogopite of the formula KMg 3 AlSi 3 O 10 F 2 , which according to X-ray fluorescence analysis (XRF) preferably comprises the components listed in Table 1 as the respective metal oxide in the ranges listed there.

[0033] Table 1: Preferred compositions of synthetic mica flakes according to RFA Composition of synthetic mica flakes, data in wt.%, based on the total weight of the synthetic mica flakes SiO2 38 to 46 Al2O3 10 to 14 K2O 9 to 13 Fe 2 O 3 0.01 to 0.25 MgO 26 to 34 MnO 0 to 0.05 Na2O 0 to 13

[0034] The average thickness of the non-metallic platelet-shaped substrates to be coated is preferably in a range from 50 nm to 5000 nm, particularly preferably in a range from 60 nm to 3000 nm and very particularly preferably in a range from 70 nm to 2000 nm. According to the invention, the average thickness is understood to mean the arithmetic mean, unless otherwise stated.

[0035] In one embodiment, the average thickness for glass flakes as the non-metallic flake-shaped substrate to be coated is in a range from 750 nm to 1500 nm, preferably in a range from 850 nm to 1400 nm and particularly preferably in a range from 900 nm to 1300 nm.

[0036] Thinner platelet-shaped substrates lead to a smaller overall thickness of the absorbing effect pigments according to the invention. Thus, glass platelets whose average thickness is in a range from 50 nm to 700 nm, more preferably in a range from 101 nm to 600 nm, particularly preferably in a range from 160 nm to 500 nm, and most preferably in a range from 200 nm to 400 nm, are also preferred as non-metallic platelet-shaped substrates.

[0037] In a further embodiment, the average thickness of the natural or synthetic mica platelets as the non-metallic platelet-shaped substrate to be coated is preferably in a range from 80 nm to 1300 nm, more preferably in a range from 90 nm to 1000 nm, particularly preferably in a range from 99 nm to 800 nm and most preferably in a range from 200 nm to 600 nm.

[0038] If non-metallic platelet-shaped substrates with an average thickness of less than 50 nm are coated with, for example, highly refractive metal oxides, extremely fragile pigments are obtained which can break even when incorporated into the respective application medium, which in turn causes a significant reduction in gloss.

[0039] Above an average substrate thickness of 5000 nm, the pigments can become too thick overall. This is accompanied by poorer specific hiding power, i.e., the covered area per unit weight of the absorbing effect pigment according to the invention is smaller. Furthermore, such thick pigments are less likely to orient themselves plane-parallel to the substrate in the application medium. Poorer orientation, in turn, results in reduced gloss.

[0040] Effect pigments that are too thick can also be disadvantageous in terms of feel.

[0041] In one embodiment, the relative standard deviation of the thickness distribution of the non-metallic platelet-shaped substrates is 15% to 100%, preferably 17% to 70%, particularly preferably 19% to 61%, and most particularly preferably 21% to 41%. The relative standard deviation in [%] is the quotient of the calculated standard deviation and the mean thickness.

[0042] The average thickness of the non-metallic platelet-shaped substrate is determined using a cured coating film in which the absorbing effect pigments according to the invention are aligned essentially plane-parallel to the substrate, according to the information below in Section IIk "Determination of the average thickness of the non-metallic platelet-shaped substrates, the average layer thickness of layers 2 and 3, the average layer thickness of the entire coating, the average height ha of the spacer layer, and the average height h H of the cavities." For this purpose, a cross-section of the cured coating film is examined under a scanning electron microscope (SEM), with the thickness of the non-metallic platelet-shaped substrate of at least 100 effect pigments being determined and statistically averaged. According to the invention, the term "average" always refers to the arithmetic mean, unless otherwise stated.

[0043] The scanning electron micrographs were obtained from cross-sections of the absorbing effect pigments according to the invention using the scanning electron microscope Supra 35 (Zeiss).

[0044] The absorbent effect pigments according to the invention optionally comprise a layer 1 comprising or consisting of tin oxide, tin hydroxide, and / or tin oxide hydrate. Layer 1 can optionally be present at least partially as a mixed layer with a layer directly adjacent to layer 1, for example layer 2.

[0045] According to the invention, layers 2 and 3 of the absorbing effect pigments according to the invention each comprise, after calcination, a high-index layer whose refractive index is n > 1.8, preferably n ≥ 1.9, and very particularly preferably n ≥ 2.1. The selection of the at least two different metal ions in layers 2 and 3 is carried out such that the metal oxide(s), metal hydroxide(s), and / or metal oxide hydrate(s) formed therefrom in layers 2 and / or 3 each has or have an average refractive index of n > 1.8.

[0046] According to the invention, the at least one metal oxide, metal hydroxide and / or metal oxide hydrate of layers 2 or 3 comprises at least two different metal ions selected from the group of metals consisting of Ti, Fe, Sn, Mn, Zr, Ca, Sr, Ba, Ni, Sb, Ag, Zn, Cu, Ce, Cr and Co, preferably selected from the group of metals consisting of Ti, Fe, Sn, Mn, Zr, Ag, Zn, Cu and Ce, further preferably selected from the group of metals consisting of Ti, Fe, Sn, Ag, Zr and Ce, particularly preferably selected from the group of metals consisting of Fe, Sn, Ag, Zr and Ce, and very particularly preferably selected from the group of metals consisting of Zr, Fe and Sn. According to the invention, the at least two different metal ions are selected such that the resulting effect pigments according to the invention are absorbent. In the context of this invention, "absorbing effect pigments" means that their coverage quotient D q , defined as D q = L schwarz * 25 L weiß * 25 , is ≥ 0.41, preferably ≥ 0.45, particularly preferably ≥ 0.50, and most preferably ≥ 0.55. The coverage ratio is determined based on paint applications on black-and-white coverage charts (Byko Chart 2853, Byk-Gardner) of a nitrocellulose paint (Erco Bronze Mischlack 2615e colorless; Maeder Plastiklack AG) mixed with 6 wt. % of the respective effect pigment according to the invention, in accordance with the following information in Section IIc "Coverage Comparison". L *25< Black and L *25< White are the brightness values ​​measured at a measurement angle of 25° on a black or white background of the black-and-white coverage charts, respectively, preferably using the BYK-mac multi-angle colorimeter from Byk-Gardner.

[0047] According to the invention, the proportion of non-coloring metal ions selected from the group of metals consisting of Ti, Sn, Zr, Ca, Sr, Ba and Zn is < 40 wt.% in total, preferably the proportion of non-coloring metal ions is in a range from 0.1 wt.% to 35 wt.% in total and particularly preferably in a range from 1 wt.% to 24 wt.% in total, and the proportion of coloring metal ions selected from the group of metals consisting of Fe, Ti, Sn, Mn, Ni, Sb, Ag, Cu, Ce, Cr and Co is > 4 wt.% in total, preferably the proportion of coloring metal ions is in a range from 5 wt.% to 80 wt.% in total and particularly preferably in a range from 20 wt.% to 72 wt.% in total, in each case determined by means of XRF, in each case calculated as elemental metal and in each case based on the total weight of the absorbent effect pigment according to the invention.The total ratio of non-coloring metal ions in the absorbing effect pigment according to the invention is preferably < 20, more preferably < 10, particularly preferably < 1 and very preferably < 0.8.

[0048] Coloring metal ions from the group of metals Ti and Sn particularly concern Ti in the oxidation state +3 or +2 and Sn in the oxidation state +2.

[0049] The at least two different metal ions are preferably either homogeneously distributed in layers 2 and / or 3 or form a gradient therein. In exceptional cases, the at least two different metal ions may also be inhomogeneously distributed in layers 2 and / or 3.

[0050] According to the invention, "at least two different metal ions" means that at least two metal ions of different elements are present, for example, titanium and iron ions, or titanium and tin ions, or titanium and zirconium ions, or iron and tin ions, or iron and zirconium ions, etc. The different metal ions can be present in a mixture of metal oxides and / or metal hydroxides and / or metal oxide hydrates and / or also in mixed oxides and / or mixed hydroxides and / or mixed oxide hydrates in layer 2 and / or layer 3 of the absorbent effect pigment according to the invention. Layer 2 and / or layer 3 can comprise or consist of this mixture of metal oxides and / or metal hydroxides and / or metal oxide hydrates and / or mixed oxides and / or mixed hydroxides and / or mixed oxide hydrates.

[0051] Preferably, according to the invention, when using the metal ions Ti and Fe in layer 2 and / or in layer 3 in the calcined absorbing effect pigment according to the invention, the portion of the respective layer containing iron ions is present as iron titanate, preferably as pseudobrookite and / or pseudorutile.

[0052] In one embodiment, one of the two layers 2 or 3 comprises only one type of metal ion, preferably selected from the group of metals consisting of Fe, Ti, Sn and Zr, particularly preferably consisting of Fe, Ti and Sn. Accordingly, the other of the two layers 3 or 2 has at least two different metal ions, preferably selected from the group of metals consisting of Ti, Sn, Zr and Fe, more preferably consisting of Ti, Sn and Fe.

[0053] In a preferred embodiment, both layer 2 and layer 3 comprise at least one metal oxide, metal hydroxide and / or metal oxide hydrate made of or with at least two metal ions selected from the group of metals consisting of Ti, Sn, Zr and Fe, more preferably consisting of Ti, Sn and Fe.

[0054] In a further embodiment, the layers 2 and 3 interrupted by the spacer layer are almost identical with respect to their respective composition.

[0055] If the absorbing effect pigments according to the invention comprise at least one coloring metal ion selected from the group of metals consisting of Fe, Ti, Sn, Mn, Cu, Cr, Co, Ag and Ce, their proportion, in each case determined by means of XRF and in each case calculated as elemental metal, is preferably ≥ 4 wt.% in total, more preferably in a range from 6 wt.% to 85 wt.% in total, particularly preferably in a range from 8 wt.% to 79 wt.% in total and very particularly preferably in a range from 10 wt.% to 76 wt.% in total, in each case based on the total weight of the absorbing effect pigment.

[0056] In a preferred embodiment, at least one of the layers 2 or 3 comprises at least two different metal ions selected from the group of metals consisting of Ti, Fe, Sn, Mn, Zr, Ca, Sr, Ba, Ni, Sb, Ag, Zn, Cu, Ce, Cr and Co, wherein at least one of these two metal ions is selected from the group of metals consisting of Ti, Sn, Zr and Zn and wherein the proportion of coloring metal ions selected from the group of metals consisting of Fe, Ti, Sn, Mn, Cu, Cr, Co, Ag and Ce, in each case determined by means of XRF and in each case calculated as elemental metal, is in total > 4 wt.%, based on the total weight of the absorbing effect pigment according to the invention.

[0057] In a particularly preferred embodiment, at least one of the layers 2 or 3 comprises metal oxides, metal hydroxides and / or metal oxide hydrates, wherein the metal ions of the metal oxides, metal hydroxides and / or metal oxide hydrates comprise or are the metals Ti and Fe, wherein the weight ratio of Ti to Fe, in each case determined by means of XRF and in each case calculated as elemental metal, is < 15, preferably < 10, particularly preferably < 5 and very particularly preferably < 1 and wherein the proportion of Fe, determined by means of XRF and calculated as elemental metal, is preferably > 4 wt.%, based on the total weight of the absorbent effect pigment according to the invention.

[0058] In a further particularly preferred embodiment, at least one of the layers 2 or 3 comprises metal oxides, metal hydroxides and / or metal oxide hydrates, wherein the metal ions of the metal oxides, metal hydroxides and / or metal oxide hydrates comprise or are the metals Fe and Sn, wherein the weight ratio of Fe to Sn, in each case determined by means of XRF and in each case calculated as elemental metal, is preferably from a range of 1 to 80, more preferably from a range of 2 to 60, particularly preferably from a range of 3 to 50 and very particularly preferably from a range of 4 to 40, and wherein the proportion of Sn, determined by means of XRF and calculated as elemental metal, is preferably selected from a range of 1 wt.% to 25 wt.%, more preferably from a range of 2 wt.% to 19 wt.% and particularly preferably from a range of 4 wt.% to 15 wt.%, in each case based on the total weight of the absorbent effect pigment according to the invention.

[0059] In a further particularly preferred embodiment, at least one of the layers 2 or 3 comprises metal oxides, metal hydroxides and / or metal oxide hydrates, wherein the metal ions of the metal oxides, metal hydroxides and / or metal oxide hydrates comprise or are the metals Fe and Zr, wherein the weight ratio of Fe to Zr, in each case determined by means of XRF and in each case calculated as elemental metal, is selected from a range of 1 to 75, preferably from a range of 2 to 65, particularly preferably from a range of 4 to 48 and very particularly preferably from a range of 8 to 36, in each case based on the total weight of the absorbing effect pigment according to the invention.

[0060] The metal oxide, metal hydroxide, and / or metal oxide hydrate contents of the inventive absorbent effect pigments are determined as the respective metal oxide by X-ray fluorescence analysis (XRF) and can be calculated as the respective elemental metal. For this purpose, the absorbent effect pigment is incorporated into a lithium tetraborate glass tablet, fixed in solid sample measuring cups, and measured from there. The Advantix ARL device from Thermo Scientific was used as the measuring device.

[0061] According to the invention, the average layer thickness of layer 1 is less than 10 nm, preferably less than 5 nm and particularly preferably less than 3 nm, wherein layer 1 completely or not completely envelops the non-metallic platelet-shaped substrate or an optionally present coating.

[0062] The average layer thickness of layers 2 and 3 of the absorbing effect pigments according to the invention is in each case preferably in a range from 30 nm to 350 nm, more preferably in each case in a range from 35 nm to 310 nm, more preferably in each case in a range from 90 nm to 340 nm, particularly preferably in each case in a range from 40 nm to 280 nm and very particularly preferably in each case in a range from 50 nm to 210 nm.

[0063] In a preferred embodiment, the average layer thickness of layers 2 and 3 is almost the same.

[0064] According to the invention, "almost equal average layer thicknesses" means that the quotient of the average layer thickness of layer 2 and the average layer thickness of layer 3 is preferably in a range from 0.5 to 1.8, more preferably in a range from 0.7 to 1.6, particularly preferably in a range from 0.8 to 1.4 and most preferably in a range from 0.9 to 1.2.

[0065] In a further embodiment, if layers 2 and 3 have different material compositions, their respective optical layer thicknesses are approximately the same, whereby the optical layer thicknesses of layers 2 and 3 may or may not follow the well-known lambda / 4 rule. The optical layer thickness is defined as the product of the refractive index and the average layer thickness of the respective layer.

[0066] The average layer thickness of the entire coating of the absorbing effect pigments according to the invention is preferably ≤ 800 nm. The average layer thickness of the entire coating is preferably in a range from 45 nm to 650 nm, particularly preferably in a range from 65 nm to 530 nm and very particularly preferably in a range from 80 nm to 380 nm.

[0067] The term “entire coating” refers to the complete coating that extends from the substrate surface perpendicularly to it in one direction.

[0068] In one embodiment, the relative standard deviation of the layer thickness distribution of layers 2 and 3 is 2% to 74%, preferably 3% to 63%, particularly preferably 4% to 57%, and very particularly preferably 5% to 49%, and the relative standard deviation of the layer thickness distribution of the entire coating is 0.3% to 31%, preferably 1% to 27%, particularly preferably 1.2% to 24%, and very particularly preferably 1.9% to 22%. The relative standard deviation in [%] is the quotient of the calculated standard deviation and the mean thickness.

[0069] The spacing layer between layers 2 and 3 is preferably arranged substantially parallel to the surface of the non-metallic platelet-shaped substrate. Within the context of this invention, "substantially parallel" means that, in a scanning electron micrograph, a regression line drawn through a spacing layer has a gradient of preferably close to zero with respect to a regression line drawn on the surface of the non-metallic platelet-shaped substrate.

[0070] The position of the spacer layer within the entire coating can vary. For example, if the average layer thicknesses of layers 2 and 3 are almost identical, the spacer layer, with respect to the entire coating, preferably comprising optional layer 1 and layers 2 and 3, is located approximately in the middle of the entire coating, since optional layer 1 is preferably extremely thin, particularly preferably only a few atomic layers thick. The spacer layer is preferably arranged, with respect to the entire coating, between the first sixth and the sixth sixth of the entire coating. The first sixth refers to the portion of the entire coating facing the non-metallic platelet-shaped substrate, and the sixth sixth refers to the portion of the entire coating facing away from the non-metallic platelet-shaped substrate ( Figure 7 ).

[0071] The spacer layer formed between layers 2 and 3 preferably has connections, which can also be referred to as spacers, which, on the one hand, connect the layers adjacent on either side of the spacer layer to one another and, on the other hand, keep them spaced apart. As can be seen from cross-section images taken under scanning electron microscopy, these connections or spacers, e.g., in the form of webs or columns, can be arranged at an angle of approximately 90°, for example, from 80° to 100°, to the surface of the non-metallic platelet-shaped substrate. However, they can also assume any other angle between 5° and 175°.The spacers, in particular webs, preferably the longitudinal axes of the spacers, preferably webs, are preferably arranged at an angle from a range of 15° to 150° and particularly preferably at an angle from a range of 35° to 135°, to the surface of the non-metallic platelet-shaped substrate. When determining the angle, the substrate plane forms the first leg. One of the outer sides of the web under consideration forms the second leg. Starting from the angle vertex of the two legs, the included angle is determined, whereby in the plan view of the cross-section images taken using a scanning electron microscope, 0° is assumed to be on the left and 180° to the right in the substrate plane.

[0072] The connections or spacers can take on various geometric shapes and are preferably evenly distributed throughout the entire spacing layer. For example, the connections or spacers can be net-like, lattice-like, ladder-like, sponge-like, or honeycomb-like. In some cases, structural elements similar to those in a photonic or inverse photonic crystal, such as those known from EP 2 371 908 A2, EP 1 546 063 A1, or EP 1 121 334 A1, can also be identified.

[0073] The compounds or spacers comprise at least one metal oxide, metal hydroxide, and / or metal oxide hydrate. In a preferred embodiment, the compounds or spacers comprise an identical material composition to the layers located on either side of the spacer layer. Alternatively, a gradient between different metal oxides, metal hydroxides, and / or metal oxide hydrates can also be formed within the compounds or spacers.

[0074] In a preferred embodiment, the compounds or spacers comprise a metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ions of the metal oxides, metal hydroxides and / or metal oxide hydrates comprise or are at least two metal ions selected from the group of metals consisting of Ti, Fe, Sn, Mn, Zr, Ca, Sr, Ba, Ni, Ag, Zn, Cu, Ce, Cr and Co, more preferably from the group consisting of Ti, Fe, Sn, Mn, Zr, Ag, Zn, Cu and Ce, particularly preferably from the group consisting of Ti, Fe, Sn, Zr, Ag and Ce, and most particularly preferably from the group consisting of Ti, Fe and Sn.

[0075] The inventors assume that the connections or spacers can also mechanically stabilize the adjacent layers and thus the absorbent effect pigment according to the invention. Presumably, due to the number of connections or spacers, the various angles and geometric shapes that the connections or spacers can assume within the spacer layer, and their preferably uniform distribution within the spacer layer, a mechanically very stable effect pigment is formed. The adhesion between the entire coating and the non-metallic platelet-shaped substrate is very good with the absorbent effect pigments according to the invention. Even extreme shear conditions, such as those encountered in the so-called Waring Blender Test, are withstood without detectable damage.The procedure for conducting the Waring Blender Test is described below in Section IIf "Waring Blender Test".

[0076] In addition to their surprisingly good mechanical stability, the absorbing effect pigments according to the invention have excellent chemical resistance, as explained below in Section IIg "Determination of Chemical Resistance".

[0077] The spacer layer of the absorbing effect pigments according to the invention preferably has an average height ha from a range of 5 nm to 120 nm, more preferably from a range of 9 nm to 95 nm, more preferably from a range of 16 nm to 76 nm, more preferably from a range of 21 nm to 69 nm, particularly preferably from a range of 22 nm to 62 nm and very particularly preferably from a range of 26 nm to 56 nm ( Figure 6 ).

[0078] To determine the average height ha of the spacer layer, the average layer thickness of layers 2 and 3, and the average layer thickness of the entire coating, the upper and lower substrate surfaces are used as baselines based on scanning electron micrographs. In the scanning electron micrograph, the upper and lower substrate surfaces refer to the longer sides of the non-metallic platelet-shaped substrate. The baseline is placed along the surface of the non-metallic platelet-shaped substrate in the scanning electron micrograph. The scanning electron micrographs were examined using the AxioVision 4.6.3 image processing software (Zeiss).At a 90° angle to these two base lines, a sufficient number of parallel lines are drawn at a distance of 50 nm to form a grid over the effect pigment shown in the scanning electron micrograph (. Figure 4). The magnification of the scanning electron micrograph of the cross-section is preferably at least 50,000 times, based on Polaroid 545 (4" x 5"). Starting from the respective base line of the non-metallic platelet-shaped substrate, the intersection points between the parallel lines arranged perpendicular to the respective base line and the respective interfaces of the optional layer 1 to layer 2, of layer 2 to the spacer layer, of the spacer layer to layer 3 and of layer 3 to the surroundings or to any further layer applied are manually measured in the direction of the respective outermost layer 3 or the respective outermost layer. It may happen that one of the lines drawn at a distance of 50 nm ends up directly above a connection point or a spacer. In this case, only the respective intersection point of the line at the interface between layer 3 and the surroundings or to any further layer applied is recorded.

[0079] From these measured values, the layer thicknesses of layers 2 and 3, the layer thickness of the entire coating, the layer thickness of any additional optional layers and the height ha of the spacer layer are determined by taking the difference. The layer thickness of layer 2 results from the difference between the respective measured intersection points at the respective interfaces between layer 2 and the spacer layer and either the optional layer 1 and layer 2 or the base line to layer 2, provided that the non-metallic platelet-shaped substrate is not pre-coated with further layers. The layer thickness of layer 3 results from the difference between the respective measured intersection points of layer 3 and the surroundings or of any further applied layer and the spacer layer to layer 3. The layer thickness of the entire coating results from the difference between the respective intersection points of layer 3 and the surroundings orof any additionally applied layer to the surroundings and the respective baseline. The height ha of the distance layer results from the difference between the respective measured intersection points of the distance layer to layer 3 and layer 2 to the distance layer. The layer thicknesses of any additionally applied layers must be determined analogously and taken into account when calculating the difference.

[0080] The respective arithmetic mean values ​​are calculated from the individual values ​​of the layer thicknesses and heights ha determined in this way to determine the values ​​of the average layer thicknesses and heights ha specified above. For meaningful statistics, the measurements described above are performed on at least 100 of the parallel lines arranged perpendicular to the baseline.

[0081] The height h ma designates the center of the spacer layer. It results from the sum of the layer thickness of the optional layer 1, layer 2 and half the height ha of the spacer layer. The relative height h Rma of the center of the spacer layer is formed from the ratio of h ma and the layer thickness of the entire coating. The standard deviation of the relative height σh Rma is preferably in a range from 0.2% to 18%, more preferably in a range from 0.3% to 15%, particularly preferably in a range from 0.4% to 11% and most preferably in a range from 0.5% to 8%. The standard deviation of the relative height σh Rma is a measure of whether the spacer layer is arranged in a defined position parallel to the surface of the non-metallic platelet-shaped substrate within the entire coating.

[0082] If the absorbent effect pigments according to the invention have at least one additional spacer layer, their height h ma and the relative height of the center of the at least one additional spacer layer h Rma are also determined using the method described above based on cross-section images taken using a scanning electron microscope. The values ​​given above for the standard deviation of the relative height σh Rma apply accordingly to additional spacer layers.

[0083] It is known to the person skilled in the art that, for example, pearlescent pigments coated with titanium dioxide have pores in the coating that are statistically distributed over the entire coating ( Figure 5These pearlescent pigments do not have a spacer layer. The spacer layer and the cavities located within the spacer layer of the absorbing effect pigments according to the invention, however, are not distributed randomly over the entire coating, but are arranged parallel to the surface of the non-metallic platelet-shaped substrate within the entire coating.

[0084] The distances of the centers of the statistically distributed pores from the substrate surface were also determined using scanning electron micrographs using the method described above. For this purpose, sufficient parallel lines were drawn at a 90° angle to the upper and lower baseline, which correspond to the two surfaces of the platelet-shaped substrate, at 50 nm intervals, to create a grid over the pearlescent pigment shown in the scanning electron micrograph without a spacer layer. If one of the parallel lines lay over one or more pores, its height(s), its pore center(s), and the distance of the pore center(s) from the substrate surface were determined. A standard deviation can also be determined from the statistical distribution of the pore centers.

[0085] The standard deviation of the distances between the centers of the randomly distributed pores and the substrate surface in state-of-the-art pearlescent pigments, i.e., pearlescent pigments without a spacer layer, is > 20%. The standard deviation of the distances between the centers of the randomly distributed pores and the substrate surface thus differs significantly from the standard deviation of the relative height of the center of the spacer layer of the absorbing effect pigments according to the invention.

[0086] Thus, the standard deviation of the distances of the pore centers to the substrate surface of pearlescent pigments without a spacing layer can be compared with the standard deviation of the relative height of the center of the spacing layer of absorbing effect pigments according to the invention.

[0087] Furthermore, with the help of the lines described above, which are drawn at a distance of 50 nm in a scanning electron microscope image, the number of connections or spacers per micrometer as well as the web density, defined as the number of connections or spacers per number of lines in percent, are determined.

[0088] If the absorbing effect pigments according to the invention have more than one spacer layer within the entire coating, the method just described for measuring the individual layers and the spacer layers is transferred accordingly.

[0089] In one embodiment, the relative standard deviation of the height distribution of the spacing layer is 4% to 75%, preferably 7% to 69%, particularly preferably 9% to 63%, and most particularly preferably 13% to 60%. The relative standard deviation in [%] of the height distribution is the quotient of the calculated standard deviation and the mean height.

[0090] In a preferred embodiment, the absorbing effect pigments according to the invention have within the at least one spacer layer a number of compounds or spacers per micrometer from a range of 0 to 11, more preferably from a range of 0 to 9, particularly preferably from a range of 1 to 7 and most preferably from a range of 1 to 3.

[0091] In a preferred embodiment, the absorbing effect pigments according to the invention have within the at least one spacer layer a web density, defined as the number of connections or spacers per number of lines in percent, of < 85%, preferably from a range of 1% to 75%, particularly preferably from a range of 1% to 63% and most particularly preferably from a range of 1% to 49%.

[0092] Above a web density of 85%, the term "spacer layer" is no longer used in the context of this invention, since the high proportion of connections or spacers then leads to a largely continuous coating.

[0093] In a further preferred embodiment, the absorbing effect pigments according to the invention comprise at least one spacer layer arranged substantially parallel to the surface of the non-metallic platelet-shaped substrate, wherein the at least one spacer layer in each case has an average height ha from a range of 19 nm to 83 nm, particularly preferably from a range of 27 nm to 66 nm and very particularly preferably from a range of 33 nm to 57 nm.

[0094] In a particularly preferred embodiment, the absorbing effect pigments according to the invention have at least one spacer layer of average height ha from a range of 16 nm to 79 nm, preferably from a range of 21 nm to 66 nm and very particularly preferably from a range of 23 nm to 57 nm, wherein within the at least one spacer layer the number of connections or spacers per micrometer is selected from a range of 0 to 8, preferably from a range of 0 to 6, particularly preferably from a range of 1 to 5 and very particularly preferably from a range of 1 to 4.

[0095] In addition to the connections and spacers described above, the spacer layer includes cavities. These cavities are spatially delimited by layers 2 and 3 and the connections and spacers.

[0096] Energy-dispersive X-ray microanalysis (EDX analysis) of these cavities does not allow any conclusions to be drawn about solid or liquid matter, so the inventors, based on the analytical methods currently available, assume that the cavities within the spacer layer contain a gas, presumably air. The compounds or spacers, however, comprise at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, as described above.

[0097] The cavities within the spacer layer of the absorbing effect pigments according to the invention can have an average height h H from a range of 2 nm to 119 nm, preferably from a range of 6 nm to 105 nm, more preferably from a range of 11 nm to 85 nm and most preferably from a range of 18 nm to 53 nm. The height h H is understood to be the greatest distance between the lowest and uppermost cavity boundaries. It is determined according to the method described above for the height ha by drawing parallel lines 50 nm apart at a 90° angle to the surface of the non-metallic platelet-shaped substrate in cross-section images taken under a scanning electron microscope. The difference between the two points of intersection of these lines with the upper and lower cavity boundaries represents the height h H. Here, too, the measurements described above are carried out on at least 100 lines to ensure meaningful statistics.

[0098] Therefore, the mean height ha represents a maximum value for the mean height h H. Accordingly, several cavities can be present one above the other within the spacing layer.

[0099] The average height of the spacer layer ha and the average height of the cavities h H are determined using a cured coating film in which the absorbing effect pigments according to the invention are aligned essentially plane-parallel to the substrate, in accordance with the explanations in Section IIk "Determination of the average thickness of the non-metallic platelet-shaped substrates, the average layer thickness of layers 2 and 3, the average layer thickness of the entire coating, the average height ha of the spacer layer and the average height h H of the cavities". For this purpose, a cross-section of the cured coating film is examined under a scanning electron microscope (SEM), as described above for ha. As an alternative to these cross-sections, the absorbing effect pigments according to the invention can be sectioned using the FIB method (FIB = focused ion beam). For this purpose, a fine beam of highly accelerated ions (e.g.Gallium, xenon, neon or helium) is focused onto a point using ion optics and guided line by line over the effect pigment surface to be treated. When the ions hit the effect pigment surface, they release a large part of their energy and destroy the coating at this point, leading to line-by-line material removal. The scanning electron microscope images then taken can also be used to determine the average height ha, the average layer thickness of layers 2 and 3 and the average layer thickness of the entire coating using the method described above. The average thickness of the non-metallic platelet-shaped substrate can also be determined using scanning electron microscope images of the effect pigments cut through using the FIB method.

[0100] In a further embodiment, the absorbing effect pigments according to the invention within the spacer layer, distributed over the entire effect pigment and measured by means of scanning electron microscopic cross-section images, comprise an area proportion of voids from a range of 51% to 99%, preferably from a range of 63% to 96%, particularly preferably from a range of 76% to 95% and very particularly preferably from a range of 84% to 94% and an area proportion of connections or spacers from a range of 1% to 49%, preferably from a range of 4% to 37%, particularly preferably from a range of 5% to 24% and very particularly preferably from a range of 6% to 16%.

[0101] Furthermore, it is preferred that in the spacing position the total volume occupied by the connections or spacers is smaller than the total volume occupied by the cavities.

[0102] Preferably, in the spacer layer, the total volume occupied by the connections or spacers is less than 50 vol.%, more preferably less than 30 vol.%, particularly preferably less than 20 vol.% and most preferably less than 10 vol.% of the total volume occupied by the cavities.

[0103] In the absorbent effect pigments according to the invention, the cavities located within the spacer layer are expressly desired, in contrast to the pores of the teaching according to EP 1 422 268 A2. According to EP 1 422 268 A2, a coating with low porosity and the smallest possible pores is required to obtain pigments with high chroma and high brilliance. The pigments according to EP 1 422 268 A2 do not have a spacer layer. According to the invention, the cavities, which are not randomly distributed throughout the coating but are located essentially parallel to the surface of the non-metallic platelet-shaped substrate within the spacer layer, do not have a negative influence on the optical properties of the absorbent effect pigments according to the invention.On the contrary, the absorbing effect pigments according to the invention are characterized by higher gloss and higher chroma compared to single-layer coated pigments, assuming, of course, the same non-metallic platelet-shaped substrate, the same particle size, and an identical first coating. Depending on the coating thickness and the type of coating, different interference colors and / or different absorption colors can be obtained.

[0104] The higher gloss and the higher chroma can be explained by the maximum difference in refractive index between the spacer layer and the adjacent layers, which, according to Fresnel's law, leads to maximum light reflection at these interfaces. For the cavities, the refractive index of air is assumed to be approximately 1. A light beam incident at the spacer layer is partially reflected at their interfaces, with the respective intensity of the reflection depending, according to Fresnel's law, on the difference in refractive index between the adjacent layers and the spacer layer. Since such partial reflection occurs at each individual interface, the total reflection also increases with the number of interfaces.With the absorbing effect pigments according to the invention, a light beam is thus partially reflected multiple times, resulting in significantly stronger gloss and greater intensity of the interference color compared to conventional, single-coated pigments. If the voids are randomly distributed throughout the coating, i.e., not essentially parallel to the non-metallic platelet-shaped substrate, the optical path length varies throughout the coating. This results in the interference conditions not being sufficiently met, and thus no amplification or cancellation occurs.

[0105] The gloss of the inventive absorbent effect pigments is determined using black-and-white opacity charts with a Micro-Tri-Gloss gloss meter from Byk-Gardner, as described below in Section IId, "Gloss Measurements." The chroma of the inventive absorbent effect pigments is also determined using black-and-white opacity charts with the BYK-mac multi-angle colorimeter (Byk-Gardner), as described below in Section IIb, "Angle-Dependent Color Measurements." Other optical effects, such as glitter and graininess, are determined as described below in Section IIe, "Effect Measurements."

[0106] In one embodiment, the absorbing effect pigments according to the invention comprise, in addition to the above-described layers 1, 2 and 3, further high- and / or low-refractive-index layers which, viewed from the non-metallic platelet-shaped substrate, can be arranged either below the optional layer 1 or layer 2 and / or above layer 3. These further layers can comprise metal oxides, metal hydroxides, metal oxide hydrates, wherein the metal ions of the metal oxides, metal hydroxides, metal oxide hydrates comprise or are at least one metal ion selected from the group of metals consisting of Ti, Fe, Sn, Mn, Zr, Ca, Sr, Ba, Ni, Ag, Zn, Cu, Ce, Cr and Co, preferably selected from the group of metals consisting of Ti, Fe, Sn, Zr, Ag, Zn, Cu, Ce, Cr and particularly preferably selected from the group of metals consisting of Ti, Fe and Sn.In addition, these further layers can comprise semi-transparent metals selected from the group consisting of Ag, Al, Cr, Ni, Au, Pt, Pd, Cu, Zn and Ti, preferably selected from the group consisting of Ag, Au and Cu, their alloys and / or mixtures thereof. According to the invention, the further layers are selected such that the proportion of coloring metal ions selected from the group of metals consisting of Fe, Ti, Sn, Mn, Cu, Cr, Co, Ag and Ce, in each case determined by XRF and in each case calculated as elemental metal, is preferably > 4 wt.% in total, further preferably in a range from 5 wt.% to 82 wt.% in total, particularly preferably in a range from 7 wt.% to 72 wt.% in total, and most particularly preferably in a range from 10 wt.% to 68 wt.% in total, in each case based on the total weight of the absorbing effect pigment.Furthermore, the proportion of at least one semitransparent metal, determined by XRF, is preferably ≥ 1 wt. %, particularly preferably in a range from 2 wt. % to 20 wt. %, and very particularly preferably in a range from 3 wt. % to 12 wt. %, in each case based on the total weight of the absorbent effect pigment. If the absorbent effect pigments according to the invention, regardless of whether in the non-metallic platelet-shaped substrate or in the coating, comprise at least one coloring metal ion and at least one semitransparent metal, their proportion is preferably ≥ 5 wt. %, based on the total weight of the absorbent effect pigment.

[0107] In one embodiment, each of the layers of the absorbent effect pigments according to the invention can be doped, wherein the dopant can comprise metal oxides, metal hydroxides, and / or metal oxide hydrates, and the metal ions of the metal oxides, metal hydroxides, and / or metal oxide hydrates comprise or are at least one metal ion selected from the group of metals consisting of Ca, Mg, Al, Ce, Zr, or Sn, preferably Al, Zr, or Sn. The proportion of dopant is preferably ≤ 1 wt.% in total, more preferably ≤ 0.5 wt.% in total, and most preferably ≤ 0.2 wt.% in total, in each case based on the total weight of the absorbent effect pigments.

[0108] According to the invention, there is no spacer layer in the entire coating, neither in the first sixth nor in the sixth sixth of the entire coating.

[0109] The absorbent effect pigments according to the invention can have any desired average particle size D 50 . The D 50 values ​​of the absorbent effect pigments according to the invention are preferably in a range from 3 µm to 350 µm. The D 50 values ​​of the absorbent effect pigments according to the invention are preferably in a range from 4 µm to 211 µm, more preferably in a range from 6 µm to 147 µm, particularly preferably in a range from 7 µm to 99 µm, and most preferably in a range from 8 µm to 56 µm. Most preferably, the absorbing effect pigments according to the invention have a D 50 value from a range of 3 µm to 15 µm or from a range of 10 µm to 35 µm or from a range of 25 µm to 45 µm or from a range of 30 µm to 65 µm or from a range of 40 µm to 140 µm or from a range of 135 µm to 250 µm.

[0110] The D 10 values ​​of the absorbing effect pigments according to the invention preferably cover a range from 1 µm to 120 µm. The D 10 values ​​of the absorbing effect pigments according to the invention are particularly preferably in a range from 1 µm to 5 µm or in a range from 5 µm to 25 µm or in a range from 10 µm to 30 µm or in a range from 20 µm to 45 µm or in a range from 25 µm to 65 µm or in a range from 75 to 110 µm. The D 90 values ​​of the absorbing effect pigments according to the invention preferably cover a range from 6 µm to 500 µm. The D 90 values ​​of the absorbing effect pigments according to the invention are particularly preferably in a range from 8 µm to 250 µm or in a range from 10 µm to 150 µm or in a range from 40 µm to 70 µm or in a range from 68 µm to 110 µm or in a range from 120 µm to 180 µm or in a range from 400 to 490 µm.

[0111] The D 10 , D 50 , or D 90 values ​​of the cumulative frequency distribution of the volume-averaged size distribution function, as obtained by laser diffraction methods, indicate that 10%, 50%, or 90% of the measured effect pigments have a volume-averaged diameter equal to or smaller than the respective specified value. The size distribution curve of the absorbing effect pigments according to the invention is determined using the Mastersizer 2000 device from Malvern according to the manufacturer's instructions. The evaluation of the scattered light signals is carried out according to the Fraunhofer theory, which also includes the refraction and absorption behavior of the particles.

[0112] In a preferred embodiment, the absorbing effect pigments according to the invention have a span ΔD, defined as Δ D = D 90 − D 10 D 50 , from a range of 0.7 to 2.0, preferably from a range of 0.7 to 1.5, more preferably from a range of 0.8 to 1.3, particularly preferably from a range of 0.8 to 1.2 and very particularly preferably from a range of 0.85 to 1.1. The advantages of a narrow size classification with regard to color purity and / or gloss of the resulting effect pigments are described, for example, in EP 2 217 664 A1, EP 2 346 950 A1, EP 2 356 181 A1, EP 2 346 949 A1, EP 2 367 889 A1.

[0113] The absorbing effect pigments according to the invention can be prepared as follows: Suspending the non-metallic platelet-shaped substrates in water at a temperature in a range from 50°C to 100°C, optionally applying a non-calcined layer which comprises or consists of tin oxide, tin hydroxide and / or tin oxide hydrate by adding a water-soluble tin salt with simultaneous addition of a mineral alkali, sequentially applying three non-calcined layers A, B and C in the form of metal oxides, metal hydroxides and / or metal oxide hydrates by sequentially adding three water-soluble metal salts, in each case with simultaneous addition of mineral alkali, wherein the second water-soluble metal salt - for producing layer B - is different in terms of the metal ion from the two other water-soluble metal salts for producing layer A or C.Layer C is, separating the coated substrates from the coating solution(s), optionally washing and / or optionally drying the coated substrates, calcining the coated substrates at temperatures from a range of 600°C to 1100°C, preferably from a range of 625°C to 930°C and particularly preferably from a range of 750°C to 890°C to obtain the absorbent effect pigments according to the invention comprising at least one spacer layer.

[0114] In a preferred embodiment, the absorbing effect pigments according to the invention are prepared by the above process.

[0115] The application, preferably deposition, of the respective metal oxides, metal hydroxides and / or metal oxide hydrates is preferably carried out at a constant pH value in a range from pH 1.4 to 10.0 depending on the metal salt.

[0116] In addition to the at least three sequentially applied, preferably deposited, metal oxides, metal hydroxides and / or metal oxide hydrates, further metal oxides, metal hydroxides and / or metal oxide hydrates can of course be applied beforehand and / or subsequently, so that further layers can be arranged below or above the layer sequence [optional layer 1 / layer 2 / spacer layer / layer 3].

[0117] During calcination, surprisingly, the metal ions present in layer B presumably diffuse into layer A and / or layer C to form mixed metal oxides and / or mixed metal hydroxides and / or metal oxide hydrates and / or mixtures of metal oxides and / or metal hydroxides and / or metal oxide hydrates in layer A and / or layer C. Due to the diffusion of the metal ions from layer B into layer A and / or layer C, layers 2 and 3 according to the invention and the spacer layer therebetween are formed during calcination, with at least one of the two layers 2 and 3 comprising at least two different metal ions. From the originally three successively deposited layers A, B and C, layers 2 and 3 and the spacer layer therebetween are thus formed during calcination, with at least one of the two layers 2 and 3 comprising at least two different metal ions.

[0118] It is assumed that, among other things, the different mobility of the metal oxides, metal hydroxides, and / or metal oxide hydrates relative to one another during calcination is responsible for the formation of the spacer layer. The mobility of the metal ions contained in layer B competes with the mobility of the metal ions contained in layers A and / or C, provided that the metal ions diffuse from layer B into at least one of the adjacent layers A and / or C, and the metal ions from at least one of layers A and / or C diffuse into layer B. The inventors currently believe that, if the mobility of the metal ions contained in layer B during calcination is higher than the mobility of the metal ions contained in layers A and / or C, this is one possible explanation for the formation of the spacer layer.Furthermore, it is assumed that a concentration gradient with respect to the metal ions favors the formation of a spacer layer, i.e., when more mobile metal ions can diffuse from layer B into one of the adjacent layers A and / or C than vice versa. In summary, it has been determined that the formation of a spacer layer is caused by a complex interplay of various other factors, such as entropic and / or enthalpic effects, during calcination, which, however, have not yet been conclusively clarified. The above considerations naturally apply accordingly to the formation of at least one further spacer layer.

[0119] In a preferred embodiment, the first and third of the three sequentially applied, preferably deposited, metal oxides, metal hydroxides and / or metal oxide hydrates comprise at least one metal ion selected from the group of metals consisting of Fe, Ti, and Sn. The first and third metal oxides, metal hydroxides and / or metal oxide hydrates produce layer A and layer C respectively after application. The second of the three sequentially applied, preferably deposited, metal oxides, metal hydroxides and / or metal oxide hydrates produces layer B and comprises at least one metal ion selected from the group of metals consisting of Fe, Sn, Zr and Ce, which is different from the metal ions of the metal oxides, metal hydroxides and / or metal oxide hydrates deposited to produce layer A and layer C.In layer A and layer C, the applied, preferably deposited, metal oxides, metal hydroxides and / or metal oxide hydrates may be the same or different from one another with respect to the metal ion(s).

[0120] Alternatively, the absorbing effect pigments according to the invention can be prepared as follows: Suspending the calcined, singly or multiply coated non-metallic platelet-shaped substrates in water at a temperature ranging from 50°C to 100°C, sequentially applying two non-calcined layers B and C in the form of metal oxides, metal hydroxides, and / or metal oxide hydrates by sequentially adding two water-soluble metal salts, each with simultaneous addition of mineral lye, wherein the first water-soluble metal salt - for producing layer B - is different in terms of the metal ion from the other water-soluble metal salt for producing layer C and the layer which, in the direction of the substrate, is immediately adjacent to layer B, separating the coated substrates from the coating solution(s), optionally washing and / or optionally drying the coated substrates, calcining the coated substrates at temperatures ranging from 600°C to 1100°C,preferably from a range of 625°C to 930°C and particularly preferably from a range of 750°C to 890°C to obtain the absorbing effect pigments according to the invention comprising at least one spacer layer. ,

[0121] The application, preferably deposition, of the respective metal oxides, metal hydroxides and / or metal oxide hydrates is also preferably carried out at a constant pH value in a range from pH 1.4 to 10.0 depending on the metal salt.

[0122] It is assumed that during calcination, the metal ions present in layer B diffuse at least into layer C to form mixed metal oxides and / or mixed metal hydroxides and / or metal oxide hydrates and / or mixtures of metal oxides and / or metal hydroxides and / or metal oxide hydrates in layer C. Due to the diffusion of the metal ions from layer B into layer C, layer 3 according to the invention and the spacer layer are formed during calcination. From the originally two successively deposited layers B and C, layer 3 and the spacer layer are thus formed during calcination, with at least layer 3 comprising at least two different metal ions. Layer 2 is already present here. Layer 2 refers to the outermost layer of the calcined, singly or multiply coated non-metallic platelet-shaped substrate used as the starting material.

[0123] The concentration profile (line scan) based on cross-sections in the scanning electron microscope with an energy dispersive micro-area analyzer (EDX) shows a significant location-dependent change in the chemical composition of the coating before and after calcination (Figures 8 and 9).

[0124] In Figure 8 A concentration profile of Example 12 is shown after coating and drying, but before calcination. The concentration curves of Ti and Fe clearly show the maxima of the Ti- and Fe-containing layers. The oxygen concentration curve, on the other hand, is largely homogeneously distributed, with no discernible minima or maxima.

[0125] In Figure 9 A concentration profile of Example 12 is also shown after coating and drying, but after calcination. It can be seen that the Figure 9The existing Fe maximum is reduced and shifted. The Fe ions have diffused into the surrounding Ti-containing layers. Also noteworthy is a pronounced minimum in the oxygen concentration curve, which clearly indicates the position of the spacing layer. Corresponding minima in the Ti and Fe concentration curves are located at the same position.

[0126] According to the invention, the two or three sequentially applied, preferably deposited, metal oxides, metal hydroxides and / or metal oxide hydrates for producing the layers B and C or A, B and C, do not comprise any metal ion(s) selected from the group of metals consisting of Si, Mg and A'.

[0127] In the sequential application of two non-calcined layers B and C to an already coated and optionally calcined substrate, the layer to which layer B is applied comprises, according to the invention, a high-refractive-index metal oxide, metal hydroxide and / or metal oxide hydrate.

[0128] In the sequential application of three non-calcined layers A, B and C to an already coated and optionally calcined substrate, the layer to which layer A is applied may, according to the invention, comprise a high-refractive index or a low-refractive index metal oxide, metal hydroxide and / or metal oxide hydrate.

[0129] The above statements are explained in more detail below using various coatings as examples.

[0130] If, for example, a water-soluble titanium(IV) salt, a water-soluble iron(III) salt and again a water-soluble titanium(IV) salt are applied one after the other to a suspension of an optionally coated, non-metallic platelet-shaped substrate, the result during calcination, viewed in the SEM cross-section starting from the substrate, following the optionally already present coating, is a layer 2 comprising a metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ions of the metal oxide, metal hydroxide and / or metal oxide hydrate comprise or are titanium ions and / or iron ions, a spacer layer and a layer 3 comprising a metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ions of the metal oxide, metal hydroxide and / or metal oxide hydrate comprise or are titanium ions and / or iron ions.At least one of the layers comprising a metal oxide, metal hydroxide, and / or metal oxide hydrate, wherein the metal ions of the metal oxide, metal hydroxide, and / or metal oxide hydrate comprise or are titanium ions and / or iron ions, contains an iron titanate, preferably pseudobrookite and / or pseudorutile. With regard to the amounts used, the above statements regarding coloring and non-coloring metal ions also apply here.

[0131] If, for example, a water-soluble titanium(IV) salt is added to a suspension of the optionally coated, non-metallic platelet-shaped substrate, calcined after deposition of titanium dioxide, titanium hydroxide and / or titanium oxide hydrate, this product is resuspended after calcination and a water-soluble iron(III) salt and a water-soluble tin(IV) salt are added one after the other, the renewed calcination produces, as viewed in the SEM cross section starting from the substrate, a spacer layer and a layer 3 comprising a metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion of the metal oxide, metal hydroxide and / or metal oxide hydrate comprises or is titanium ions, following the optionally already present coating and the layer 2 comprising a metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion of the metal oxide, metal hydroxide and / or metal oxide hydrate comprises or is iron ions and / or tin ions.

[0132] If the absorbing effect pigments according to the invention have, in addition to the at least two or three sequentially applied, preferably deposited, metal oxides, metal hydroxides and / or metal oxide hydrates, further layers comprising metal oxides, metal hydroxides and / or metal oxide hydrates, further spacer layers can also form within the further layers, provided that the process steps described above for the at least two or three sequentially applied, preferably deposited, metal oxides, metal hydroxides and / or metal oxide hydrates are observed.

[0133] In one embodiment, calcination takes place under reducing conditions, preferably in the presence of forming gas (N 2 / H 2 ). Calcination under reducing conditions may result in lower brightness values ​​L* than is the case with calcination in air.

[0134] The absorbent effect pigments according to the invention can optionally be provided with at least one outer protective layer, which further increases weather resistance and / or chemical stability and / or further reduces photoactivity. UV resistance and condensation resistance were determined as described below in Sections IIIj "UV Resistance" and IIIi "Condensation Test," respectively.

[0135] The optionally present protective layer comprises metal oxides, metal hydroxides, and / or metal oxide hydrates whose metal ions are selected from the group of metals consisting of Si, Ce, Cr, Al, Zr, Zn, and mixtures thereof, preferably from the group of metals Si, Ce, Al, Zr, and mixtures thereof. The proportion of the optionally present protective layer is preferably in a range from 0.1 wt.% to 7.0 wt.%, particularly preferably in a range from 0.2 wt.% to 5.2 wt.%, and most preferably in a range from 0.3 wt.% to 3.1 wt.%, in each case based on the total weight of the absorbent effect pigment according to the invention.

[0136] The optionally present protective layer can further be surface-modified, for example, with silanes. The silanes can have no functional bonding group or one or more functional bonding groups. Silanes with at least one functional bonding group are also referred to below as organofunctional silanes.

[0137] For example, one or more silanes can be applied to this outer protective layer. The silanes can be alkylsilanes with branched or unbranched alkyl radicals containing 1 to 24 carbon atoms, preferably 6 to 18 carbon atoms.

[0138] In a further preferred embodiment, the silane without a functional bonding group is an alkylsilane. The alkylsilane preferably has the formula R(4-z)Si(X)z. Here, z is an integer from 1 to 3, R is a substituted or unsubstituted, unbranched or branched alkyl chain having 10 to 22 carbon atoms, and X represents a halogen and / or alkoxy group. Alkylsilanes with alkyl chains having at least 12 carbon atoms are preferred. R can also be cyclically bonded to Si, in which case z is usually 2.

[0139] In a further embodiment, at least one organofunctional silane that enables chemical bonding to a plastic, a binder of a varnish or paint, etc., can also be used for surface modification. These groups of the organofunctional silane can also be referred to as coupling groups or functional bonding groups and are preferably selected from the group consisting of hydroxy, amino, acrylic, methacrylic, vinyl, epoxy, isocyanate, cyano, and mixtures thereof.

[0140] The organofunctional silanes that are preferably used as surface modifiers and contain suitable functional groups are commercially available and are manufactured, for example, by Evonik and sold under the trade name "Dynasylan." Other products can be obtained from Momentive (Silquest silanes) or Wacker, for example, standard and α-silanes from the GENIOSIL product group.

[0141] Examples include 3-methacryloxypropyltrimethoxysilane (Dynasylan MEMO, Silquest A-174NT), vinyltri(m)ethoxysilane (Dynasylan VTMO or VTEO, Silquest A-151 or A-171),

[0142] Methyltri(m)ethoxy¬silan (Dynasylan MTMS bzw. MTES), 3-Mercaptopropyltrimethoxysilan (Dynasylan MTMO; Silquest A-189), 3-Glycidoxypropyltrimethoxysilan (Dynasylan GLYMO, Silquest A-187), Tris[3-(trimethoxysilyl)¬propyl]isocyanurat (Silquest Y-11597), Bis[3-(triethoxysilyl)propyl)]tetrasulfid (Silquest A-1289), Bis[3-(triethoxysilyl)propyldisulfid (Silquest A-1589), beta-(3,4-Epoxycyclohexyl)ethyltrimethoxysilan (Silquest A-186), Bis(triethoxysilyl)ethan (Silquest Y-9805), gamma-Isocyanatopropyltrimethoxysilan (Silquest A-Link 35, GENIOSIL GF40), Methacryloxymethyltri(m)ethoxysilan (GENIOSIL XL 33, XL 36), (Methacryloxymethyl)(m)ethyldimethoxysilan (GENIOSIL XL 32, XL 34), (Isocyanatomethyl)¬methyldimethoxysilan, (Isocyanatomethyl)trimethoxysilan, 3-(Triethoxysilyl)propylbernsteinsäure¬anhydrid (GENIOSIL GF 20), (Methacryloxymethyl)methyldiethoxysilan, 2-Acryloxyethylmethyl¬dimethoxysilan, 2-Methacryloxyethyltri¬methoxysilan, 3-Acryloxypropylmethyl¬dimethoxysilan,2-Acryloxyethyltrimethoxysilan, 2-Methacryloxyethyl¬triethoxysilan, 3-Acryloxypropyltrimethoxysilan, 3-Acryloxypropyltripropoxy¬silan, 3-Methacryloxypropyltriethoxysilan, 3-Methacryloxypropyl¬triacetoxysilan, 3- Methacryloxypropylmethyldimethoxysilan, Vinyltrichlor¬silan, Vinyltrimethoxysilan (GENIOSIL XL 10), Vinyltris(2-methoxyethoxy)silan (GENIOSIL GF 58), Vinyltriacetoxysilan oder Mischungen davon.,

[0143] Preferred organofunctional silanes are 3-methacryloxypropyltrimethoxysilane (Dynasylan MEMO, Silquest A-174NT), vinyltri(m)ethoxysilane (Dynasylan VTMO or VTEO, Silquest A-151 or A-171), methyltri(m)ethoxysilane (Dynasylan MTMS or MTES), beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Silquest A-186), bis(triethoxysilyl)ethane (Silquest Y-9805), gamma-isocyanatopropyltrimethoxysilane (Silquest A-Link 35, GENIOSIL GF40), methacryloxymethyltri(m)ethoxysilane (GENIOSIL XL 33, XL 36), (methacryloxymethyl)(m)ethyldimethoxysilane (GENIOSIL XL 32, XL 34), 3-(triethoxysilyl)propylsuccinic anhydride (GENIOSIL GF 20), vinyltrimethoxysilane (GENIOSIL XL 10), and / or vinyltris(2-methoxyethoxy)silane (GENIOSIL GF 58) are used. However, it is also possible to apply other organofunctional silanes to the particles or pigments according to the invention.

[0144] Furthermore, aqueous prehydrolysates, for example, commercially available from Degussa, can be used. These include, among others, aqueous aminosiloxane (Dynasylan Hydrosil 1151), aqueous amino- / alkyl-functional siloxane (Dynasylan Hydrosil 2627 or 2909), aqueous diamino-functional siloxane (Dynasylan Hydrosil 2776), aqueous epoxy-functional siloxane (Dynasylan Hydrosil 2926), amino- / alkyl-functional oligosiloxane (Dynasylan 1146), vinyl- / alkyl-functional oligosiloxane (Dynasylan 6598), oligomeric vinylsilane (Dynasylan 6490), or oligomeric short-chain alkyl-functional silane (Dynasylan 9896).

[0145] In a preferred embodiment, the organofunctional silane mixture contains at least one silane without a functional bonding group and at least one amino-functional silane. The amino function is a functional group that can enter into one or more chemical interactions with most groups present in binders. This can include a covalent bond, such as with isocyanate or carboxylate functions of the binder, or hydrogen bonds such as with OH or COOR functions, or even ionic interactions. An amino function is therefore very well suited for the purpose of chemically bonding the pigment to various binders.

[0146] The following compounds are preferably used for this purpose: 3-aminopropyltrimethoxysilane (Dynasylan AMMO; Silquest A-1110), 3-aminopropyltriethoxysilane (Dynasylan AMEO), [3-(2-aminoethyl)-aminopropyl]trimethoxysilane (Dynasylan DAMO, Silquest A-1120), [3-(2-aminoethyl)-aminopropyl]triethoxysilane, triaminofunctional trimethoxysilane (Silquest A-1130), bis-(gamma-trimethoxysilylpropyl)amine (Silquest A-1170), N-ethyl-gamma-aminoisobutyltrimethoxysilane (Silquest A-Link 15), N-phenyl-gamma-aminopropyltrimethoxysilane (Silquest Y-9669), 4-amino-3,3-dimethylbutyltrimethoxysilane (Silquest A-1637), ((Cyclohexylamino)methyl)(diethoxy)methylsilane (GENIOSIL XL 924), N-cyclohexyl-aminomethyltriethoxysilane (GENIOSIL XL 926), N-phenylaminomethyl-trimethoxysilane (GENIOSIL XL 973) or mixtures thereof.

[0147] In a preferred embodiment, the optionally present protective layer has the composition disclosed in the respective main claims of WO 2006 / 021386 A1, WO 2012 / 130897 A1 or WO 2014 / 053454 A1.

[0148] Furthermore, the absorbent effect pigments according to the invention can be provided with a surface modification, which, for example, facilitates the incorporation of the effect pigments into different media. When using the absorbent effect pigments according to the invention, for example, in powder coatings, the effect pigments preferably have one of the surface modifications disclosed in the main claims of EP 2 698 403 A1 or EP 2 576 702 A1. Alternatively, the absorbent effect pigments according to the invention can have an outermost coating according to WO 2006 / 136435 A2, claim 32, which is preferably applied by the spray-drying process according to WO 2006 / 136435 A2, claim 1.

[0149] When using the absorbing effect pigments according to the invention in cosmetic formulations, for example, their incorporation into O / W, W / O or W / Si emulsion systems can be facilitated by a hydrophobic surface coating, e.g. with triethoxy caprylylsilane, and a longer emulsion stability can be achieved.

[0150] The absorbent effect pigments according to the invention can also be used in mixtures with transparent and / or opaque (in)organic white, colored, or black pigments and / or metallic effect pigments and / or pearlescent pigments and / or fillers in the respective desired application. The amount of the absorbent effect pigments according to the invention used depends on the respective application and the optical effect to be achieved.

[0151] The absorbent effect pigments of the invention can be used in cosmetic formulations, plastics, films, textiles, ceramic materials, glasses, paints, printing inks, inks, lacquers, and powder coatings. Furthermore, the absorbent effect pigments of the invention can also be used for functional applications, such as laser marking, greenhouse films, or agricultural films.

[0152] In cosmetic formulations such as body powder, face powder, pressed or loose powder, powder cream, eye makeup such as eye shadow, mascara, eyeliner, liquid eyeliner, eyebrow pencil, lip balm, lipstick, lip gloss, lip liner, hair styling compositions such as hairspray, hair mousse, hair gel, hair wax, hair mascara, permanent or semi-permanent hair dyes, temporary hair dyes, skin care compositions such as lotions, gels, emulsions, and nail polish compositions, the absorbing effect pigments according to the invention can be combined with raw materials, auxiliaries, and active ingredients suitable for the respective application. The total concentration of absorbing effect pigments according to the invention in the cosmetic formulation can be between 0.001 wt. % for rinse-off products and 40.0 wt. % for leave-on products, in each case based on the total weight of the formulation.

[0153] In a further embodiment, the absorbent effect pigments according to the invention can be in compact particle form. Compact particle form is understood to mean pellets in the form of preferably cylinders and / or spheres. The cylinders preferably have a diameter from a range of 0.2 cm to 4.2 cm, more preferably from a range of 0.5 cm to 2.3 cm and most preferably from a range of 0.7 cm to 1.7 cm and preferably a length from a range of 0.2 cm to 7.1 cm, more preferably from a range of 0.6 cm to 5.3 cm and most preferably from a range of 0.8 cm to 3.7 cm. The spheres preferably have a radius of ≤ 1 cm, more preferably from a range of 0.2 cm to 0.7 cm and most preferably from a range of 0.3 cm to 0.5 cm.

[0154] In a further embodiment, the present invention relates to an absorbing effect pigment comprising a non-metallic platelet-shaped substrate, preferably a synthetic mica platelet or a glass platelet, and a coating applied thereto, wherein the coating a) optionally a layer 1 comprising or consisting of tin oxide, tin hydroxide and / or tin oxide hydrate, b) a layer 2 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion comprises or is at least one metal ion selected from the group of metals consisting of Ti, Sn and Fe, c) a layer 3 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion comprises or is at least one metal ion selected from the group of metals consisting of Ti, Sn, Ce and Fe wherein at least one of the layers 2 or 3 comprises at least two different metal ions from the groups listed above, wherein the proportion of coloring metal ions, in each case determined via RFA and in each case calculated as elemental metal, is in a range from 7.5 wt.% to 75 wt.%, based on the total weight of the effect pigment, the layers 2 and 3 are separated by a spacer layer of average height h a from a range of 10 nm to 66 nm, the standard deviation of the relative height h Rma in a range of 0.2% to 11%, and the web density is in a range of 1% to 79%.

[0155] In a further embodiment, the present invention relates to an absorbing effect pigment comprising a non-metallic platelet-shaped substrate, preferably a synthetic mica platelet or a glass platelet, and a coating applied thereto, wherein the coating a) optionally a layer 1 comprising or consisting of tin oxide, tin hydroxide and / or tin oxide hydrate, b) a layer 2 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion comprises or is at least one non-staining metal ion selected from the group of metals consisting of Fe, Ti, Sn and Zr, c) a layer 3 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion comprises or is at least one non-staining metal ion selected from the group of metals consisting of Fe, Ti, Sn and Zr and at least one of the layers 2 or 3 comprises at least two different metal ions selected from the groups listed above, the layers 2 and 3 are interrupted by a spacer layer, and wherein the effect pigments have a span ΔD from a range of 0.8 to 1.9.

[0156] In a preferred embodiment, the present invention relates to an absorbing effect pigment comprising a non-metallic platelet-shaped substrate, preferably a synthetic mica platelet or a glass platelet, and a coating applied thereto, wherein the coating a) optionally a layer 1 comprising or consisting of tin oxide, tin hydroxide and / or tin oxide hydrate, b) a layer 2 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate from or with at least one metal ion selected from the group of metals consisting of Ti, Fe, Sn and Zr, c) a layer 3 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate from or with at least one metal ion selected from the group of metals consisting of Ti, Fe, Sn and Zr and at least one of the layers 2 or 3 comprises at least two different metal ions from the groups listed above, wherein the proportion of coloring metal ions, in each case determined via RFA and in each case calculated as elemental metal, is in a total range of 4.0 wt.% to 79 wt.%, preferably in a range of 5.0 wt.% to 72 wt.%, in each case based on the total weight of the effect pigment, the layers 2 and 3 are interrupted by a spacer layer and the effect pigment has a chemical resistance with a dE of <3, preferably <2.

[0157] In a further embodiment, the present invention relates to an absorbing effect pigment comprising a non-metallic platelet-shaped substrate, preferably a synthetic mica platelet or a glass platelet, and a coating applied thereto, wherein the coating a) optionally a layer 1 comprising or consisting of tin oxide, tin hydroxide and / or tin oxide hydrate, b) a layer 2 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion comprises or is at least one metal ion selected from the group of metals consisting of Zr, Sn and Fe, c) a layer 3 comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion comprises or is at least one metal ion selected from the group of metals consisting of Zr, Sn, Ce and Fe wherein at least one of the layers 2 or 3 comprises at least two different metal ions from the groups listed above, the quotient of the average layer thickness of the layer 2 and the average layer thickness of the layer 3 is preferably in a range from 0.5 to 1.8 and the standard deviation of the relative height h Rma in a range of 0.2% to 11%.

[0158] In a further embodiment, the absorbing effect pigments according to the invention have a hue angle h* 15 in the CIE LCh color space from a range of 0° to 60° and 120° to 360°, more preferably from a range of 0° to 45° and 135° to 360°, particularly preferably from a range of 0° to 35° and 140° to 360°, and very particularly preferably from a range of 0° to 30° and 145° to 360°. The chroma C* 15 in the aforementioned hue angle ranges is preferably > 15, particularly preferably > 20, and very particularly preferably > 30.

[0159] The hue angle h* 15 and the chroma C* 15 are determined using paint applications on black-and-white opacity charts (Byko Chart 2853, Byk-Gardner) of a nitrocellulose paint (Erco Bronze Mischlack 2615e colorless; Maeder Plastiklack AG) mixed with 6 wt.% of the respective effect pigment according to the invention, in accordance with the following information in Section IIb "Angle-dependent color measurements."

[0160] The CIE-LCh color space is the CIELab color space, where the cylindrical coordinates C* (chroma, relative color saturation, distance from the L-axis) and h* (hue angle, angle of the hue in the CIELab color circle) are specified instead of the Cartesian coordinates a*, b*.

[0161] In a further embodiment, the present invention relates to an absorbent effect pigment comprising a non-metallic platelet-shaped substrate, preferably a synthetic mica platelet or a glass platelet, and a coating applied thereon, wherein the coating has at least one spacer layer lying substantially parallel to the surface of the non-metallic platelet-shaped substrate and the effect pigment is obtainable by i) optionally applying a non-calcined tin oxide, tin hydroxide and / or tin oxide hydrate layer to the non-metallic platelet-shaped substrate, ii) applying three non-calcined metal oxides, metal hydroxides and / or metal oxide hydrates, wherein the second of these non-calcined metal oxides, metal hydroxides and / or metal oxide hydrates is materially different from the others and is such that it is incorporated into at least one of the other non-calcined metal oxides,metal hydroxides and / or metal oxide hydrates and iii) calcining the product obtained in step ii), optionally under reducing conditions, at a temperature in the range from 400°C to 980°C.,

[0162] In a particularly preferred embodiment, the present invention relates to an absorbent effect pigment comprising a non-metallic platelet-shaped substrate, preferably a synthetic mica platelet or a glass platelet, and a coating applied thereto, wherein the coating has at least one spacer layer lying substantially parallel to the surface of the non-metallic platelet-shaped substrate and having an average height ha from a range of 14 nm to 51 nm, and the effect pigment is obtainable by i) optionally applying a non-calcined tin oxide, tin hydroxide and / or tin oxide hydrate layer using a water-soluble tin(IV) salt to the non-metallic platelet-shaped substrate, ii) sequentially applying a first layer A using a water-soluble iron(III) salt, a second layer B using a water-soluble tin(IV) and / or titanium(IV) salt,a third layer C using a water-soluble iron(III) salt and iii) calcining the product obtained in step ii) at a temperature in the range of 400°C to 910°C.

[0163] In a preferred embodiment, the coating of the absorbing effect pigments according to the invention comprises, in each case before drying and / or calcination, at least one high-refractive-index layer made of or with titanium oxide, titanium hydroxide and / or titanium oxide hydrate and at least two non-adjacent, high-refractive-index layers made of or with iron oxide, iron hydroxide and / or iron oxide hydrate, wherein the weight ratio of titanium to iron in the effect pigment is <1, preferably in a range from 0.01 to 0.9 and particularly preferably in a range from 0.1 to 0.8.

[0164] In a further preferred embodiment, the coating of the absorbing effect pigments according to the invention comprises, in each case before drying and / or calcination, at least one high-refractive-index layer made of or with tin oxide, tin hydroxide and / or tin oxide hydrate and at least two high-refractive-index layers made of or with iron oxide, iron hydroxide and / or iron oxide hydrate, wherein the weight ratio of tin to iron in the effect pigment is <1, preferably in a range from 0.01 to 0.9 and particularly preferably in a range from 0.1 to 0.8.In this embodiment, it is particularly preferred that firstly at least one high-refractive-index layer of iron oxide, iron hydroxide and / or iron oxide hydrate and subsequently at least one high-refractive-index layer of tin oxide, tin hydroxide and / or tin oxide hydrate and a further high-refractive-index layer of iron oxide, iron hydroxide and / or iron oxide hydrate are applied directly to the platelet-shaped substrate or directly to the respective uppermost layer close to the substrate.Furthermore, it is also possible, before applying the at least one high-index layer of iron oxide, iron hydroxide, or iron oxide hydrate, to deposit a layer or pre-coating with metal oxides, metal hydroxides, or metal oxide hydrates, wherein the metal ion comprises or is a metal ion selected from the group of metals consisting of Sn and Si, directly on the non-metallic platelet-shaped substrate or directly on the respective uppermost layer close to the substrate, wherein the layer thickness can be a few nanometers, preferably less than 10 nm, more preferably less than 5 nm, and most preferably less than 3 nm, and this does not have to completely enclose the substrate. The tin oxide, tin hydroxide, and / or tin oxide hydrate can be present at least partially in a mixed layer with the iron oxide, iron hydroxide, and / or iron oxide hydrate.

[0165] In a further preferred embodiment, the coating of the absorbent effect pigments according to the invention comprises, in each case before drying and / or calcination, at least one high-refractive-index layer of iron oxide, iron hydroxide and / or iron oxide hydrate, wherein at least one further layer of tin oxide, tin hydroxide and / or tin oxide hydrate is applied to this at least one layer in a proportion from a range of 1 wt.% to 25 wt.%, preferably from a range of 2 wt.% to 20 wt.%, particularly preferably from a range of 3 wt.% to 16 wt.% and very particularly preferably from a range of 4 wt.% to 13 wt.%, in each case based on the absorbent effect pigment. Alternatively, the at least one high-refractive-index layer of iron oxide, iron hydroxide and / or iron oxide hydrate can be doped with Mg or Ce. After calcination, iron oxide present in the coating can be in the form of hematite and / or goethite.

[0166] In a further embodiment, the present invention relates to an absorbing effect pigment comprising a non-metallic platelet-shaped substrate, preferably a synthetic mica platelet or a glass platelet, and a coating applied to the substrate, wherein the coating has at least one spacer layer lying substantially parallel to the surface of the non-metallic platelet-shaped substrate and the effect pigment has been calcined under reducing conditions or has a semi-transparent metal layer in the entire coating, preferably as the outermost layer directly beneath an optionally present protective layer.

[0167] In one embodiment, the coating of the absorbing effect pigments according to the invention comprises, instead of the at least one metal oxide, metal hydroxide and / or metal oxide hydrate, the corresponding metal suboxides, metal fluorides, metal nitrides, metal oxynitrides, metal oxyhalides and / or metal sulfides.

[0168] In one embodiment, the coating of the absorbing effect pigments according to the invention comprises, in addition to the at least one metal oxide, metal hydroxide and / or metal oxide hydrate, at least one metal suboxide, metal fluoride, metal nitride, metal oxynitride, metal oxyhalide and / or metal sulfide.

[0169] The invention is further illustrated below by some examples; however, these examples do not limit the invention. All percentages in the examples and comparative examples are to be understood as weight percent. I Production of the absorbing effect pigments according to the invention Example 1

[0170] 200 g of synthetic mica flakes (fluorphlogopite flakes) with a particle size distribution according to the MALVERN Mastersizer MS 2000: D 10 = 10 µm, D 50 = 22 µm, D 90 = 40 µm were suspended in 1300 ml of deionized water and heated to 85°C with turbulent stirring. The pH of the suspension was lowered to pH 2.2. By adding 75 g of a tin chloride solution with a concentration c(Sn)=12 g / l, a layer of tin oxide was deposited on the surface of the glass flakes.

[0171] The pH of the suspension was then lowered to pH 1.9, and then a solution of 570 ml of TiCl 4 (200 g TIO 2 / l deionized water) was metered into the suspension. After the addition was complete, the mixture was stirred for a further 10 minutes, and then the pH was adjusted to pH 2.6. Subsequently, 50 ml of an aqueous ferric chloride solution with a density of 1.42 g / cm 3 was metered in. After the addition was complete, the mixture was stirred for a further 10 minutes, the pH was adjusted to pH 1.9, and 630 ml of a solution of TiCl 4 (200 g TIO 2 / l deionized water) was metered into the suspension. Subsequently, after 10 minutes, a further addition of 40 ml of an aqueous ferric chloride solution with a density of 1.42 g / cm 3 was metered in. 15 minutes after the addition was complete, the suspension was filtered off, and the filter cake was washed. The filter cake was dried and calcined at 850°C for 60 min.Extremely chromatic, high-gloss gold interfering effect pigments with a yellow absorption color and very good opacity were obtained. Example 2

[0172] The filter cake from Example 1 was dried and calcined at 820°C for 60 minutes under a hydrogen atmosphere. Highly chromatic, high-gloss green-gold interfering effect pigments with a black absorption color and good hiding power were obtained. Example 3

[0173] 200 g of synthetic mica flakes (fluorphlogopite flakes) with a particle size distribution according to the MALVERN Mastersizer MS 2000: D 10 = 10 µm, D 50 = 22 µm, D 90 = 40 µm were suspended in 1300 ml of deionized water and heated to 85°C with turbulent stirring. The pH of the suspension was lowered to pH 2.2. By adding 100 g of a tin chloride solution with a concentration of c(Sn)=12 g / l, a layer of tin oxide was deposited on the surface of the synthetic mica flakes.

[0174] The pH of the suspension was lowered to pH 1.9, and then a solution of 400 ml of TiCl 4 (200 g TiO 2 / l deionized water) was metered into the suspension. After the addition was complete, the mixture was stirred for a further 10 minutes, and then the pH was adjusted to pH 2.6. Subsequently, 30 ml of an aqueous ferric chloride solution with a density of 1.42 g / cm 3 was added. After the addition was complete, the mixture was stirred for a further 10 minutes, and then 405 ml of another solution of TiCl 4 (200 g TiO 2 / l deionized water) was metered into the suspension. Subsequently, after 10 minutes, a further 40 ml of an aqueous ferric chloride solution with a density of 1.42 g / cm 3 was added. 15 minutes after the addition was complete, the suspension was filtered off, and the filter cake was washed. The filter cake was dried and calcined at 650°C for 30 minutes under reducing conditions. Highly chromatic, lustrous blue-interfering effect pigments with a gray absorption color were obtained. Example 4

[0175] 200 g of glass slides with a particle size distribution according to the MALVERN Mastersizer MS 2000: D 10 = 34 µm, D 50 = 57 µm, D 90 = 96 µm, were suspended in 1300 ml of deionized water (DE = fully demineralized) and heated to 85°C with turbulent stirring. The pH of the suspension was lowered to pH 2.2. By adding 75 g of a tin chloride solution with a concentration of c(Sn)=12 g / l, a layer of tin oxide was deposited on the surface of the glass slides.

[0176] The pH was then reduced to 2.0 with dilute HCl, and then a solution of 148 ml of TiCl 4 (200 g TiO 2 / l deionized water) was metered into the suspension. After the addition was complete, the mixture was stirred for a further 10 minutes, and then the pH was adjusted to 2.6. 8 ml of an aqueous ferric chloride solution with a density of 1.25 g / cm 3 was then added. After the addition was complete, the mixture was stirred for a further 10 minutes, and another thin layer of tin oxide was deposited on the pigment surface by adding 75 ml of tin chloride solution with a concentration c(Sn)=12 g / l. 180 ml of a solution of TiCl 4 (200 g TiO 2 / l deionized water) was metered into the suspension. After this, after 10 minutes, 20 ml of an aqueous ferric chloride solution with a density of 1.25 g / cm 3 was then added. 15 minutes after the addition, the suspension was filtered and the filter cake was washed.The filter cake was dried and calcined at 750°C for 60 minutes under reducing conditions. Extremely chromatic, high-gloss gold-interfering effect pigments with a gray absorption color were obtained. Example 5

[0177] 200 g of synthetic mica flakes (fluorphlogopite flakes) with a particle size distribution according to the MALVERN Mastersizer MS 2000: D 10 = 10 µm, D 50 = 22 µm, D 90 = 40 µm were suspended in 1300 ml of deionized water and heated to 85°C with turbulent stirring. The pH of the suspension was lowered to pH 2.6.

[0178] Subsequently, 40 ml of an aqueous ferric chloride solution with a density of 1.42 g / cm 3 was added. Stirring was continued for 10 minutes, and at pH 1.9, 560 ml of a solution of TiCl 4 (200 g TIO 2 / l deionized water) was added to the suspension.

[0179] After adjusting the pH to the initial value, 40 ml of an aqueous ferric chloride solution with a density of 1.42 g / cm³ was added to the suspension. The pH was adjusted again to 1.9, and 600 ml of a TiCl² solution (200 g TiO² / l deionized water) was added to the suspension. A further 15 ml of an aqueous ferric chloride solution with a density of 1.42 g / cm³ was added, followed by stirring for 120 minutes and filtering. The washed filter cake was dried and calcined at 800°C for 45 minutes. Extremely chromatic, high-gloss gold-interfering effect pigments with a yellow absorption color and very good hiding power were obtained. Example 6

[0180] 200 g of synthetic mica flakes (fluorphlogopite flakes) with a particle size distribution according to the MALVERN Mastersizer MS 2000: D 10 = 10 µm, D 50 = 22 µm, D 90 = 40 µm were suspended in 1300 ml of deionized water and heated to 85 °C with turbulent stirring. The pH of the suspension was adjusted to 2.6. By adding 500 g of an aqueous ferric chloride solution with a density of 1.42 g / cm 3 , a layer of iron oxide was deposited on the surface of the synthetic mica flakes.

[0181] After the addition was complete, the mixture was stirred for a further 120 minutes and then the pH was adjusted to 2.2. 1000 g of a tin chloride solution with a concentration c(Sn)=12 g / l were then added. After the addition was complete, the mixture was stirred for a further 120 minutes and then 710 g of an aqueous ferric chloride solution with a density of 1.42 g / cm3 was added to deposit another layer of iron oxide on the surface of the synthetic mica flakes. 60 minutes after the addition was complete, the suspension was filtered off and the filter cake washed. The filter cake was dried if necessary and calcined at 800°C for 60 minutes under reducing conditions. Extremely chromatic, high-gloss red-interfering effect pigments with a red absorption color and very good hiding power were obtained. Example 7

[0182] 200 g of synthetic mica flakes (fluorphlogopite flakes) with a particle size distribution according to the MALVERN Mastersizer MS 2000: D 10 = 10 µm, D 50 = 22 µm, D 90 = 40 µm were suspended in 1300 ml of deionized water and heated to 85°C with turbulent stirring. The pH of the suspension was adjusted to 2.2. By adding 100 g of a tin chloride solution with a concentration of c(Sn)=12 g / l, a layer of tin oxide was deposited on the surface of the synthetic mica flakes. The pH of the suspension was subsequently lowered to 1.9, and a solution of 400 ml of TiCl 4 (200 g TiO 2 / l deionized water) was metered into the suspension. After the addition was complete, the mixture was stirred for a further 10 minutes, and then the pH was adjusted to 2.2. Subsequently, 150 ml of a 20 wt% aqueous zirconium chloride solution was added. After the addition, the mixture was stirred for 40 minutes, and 300 ml of TiCl 4 (200 g TIO 2 / l deionized water) were added to the suspension.After the addition was complete, the suspension was filtered off and the filter cake was washed. The filter cake was dried and calcined at 800°C for 60 minutes under reducing conditions. Highly chromatic, highly lustrous blue-interfering effect pigments with a gray absorption color were obtained. Example 8

[0183] 15 g of pigment from Example 6 were suspended in 450 ml of deionized water. 30 ml of silver salt solution consisting of 50 g of AgNO3 and 50 ml of 28 wt% ammonia solution were then added to the suspension with deionized water to make up to 1 l. The mixture was then added simultaneously to the suspension and stirred at room temperature for 5 minutes. 9 ml of a 35 wt% formaldehyde solution were then added and stirred for 1 hour. The suspension was then filtered off, and the pigment cake was dried at 120°C under vacuum.

[0184] Dark blue interfering effect pigments with black absorption color and a silver content of 11.1% were obtained. Example 9

[0185] 100 g of the effect pigment obtained from Example 1 were suspended in 850 ml of deionized water and heated to 85°C with turbulent stirring. The pH was lowered to pH 4.2 with dilute hydrochloric acid. A solution of 0.93 g of Ce(NO 3 ) 3 x 6 H 2 O dissolved in 40 ml of deionized water was then metered in. At the same time, the pH was kept constant by dropwise addition of a 10% NaOH solution. After the solution had been completely added, the mixture was stirred for a further hour and then the pH was adjusted to pH 10 with dilute sodium hydroxide solution. 5.7 g of Dynasylan 1146 diluted with 24.3 g of deionized water were then added to the suspension, stirring was continued for 180 minutes, the suspension was filtered off and the filter cake was washed with deionized water. The filter cake was dried at 95°C under vacuum. Example 10

[0186] 200 g of synthetic mica flakes (fluorphlogopite flakes) with a particle size distribution according to the MALVERN Mastersizer MS 2000: D 10 = 10 µm, D 50 = 22 µm, D 90 = 40 µm were suspended in 1300 ml of deionized water and heated to 85°C with turbulent stirring. The pH of the suspension was adjusted to 2.6. By adding 570 g of an aqueous ferric chloride solution with a density of 1.42 g / cm 3 , a layer of iron oxide was deposited on the surface of the synthetic mica flakes.

[0187] The pH of the suspension was then lowered to pH 1.9 and then a solution of 250 ml TiCl 4 (200 g TIO 2 / l deionized water) was added to the suspension.

[0188] Stirring was then continued for another 120 minutes, followed by the addition of 600 g of an aqueous ferric chloride solution with a density of 1.42 g / cm³, depositing another layer of iron oxide on the surface of the synthetic mica flakes. 60 minutes after the addition was complete, the suspension was filtered off and the filter cake washed. The filter cake was dried if necessary and calcined at 400°C for 60 minutes. Extremely chromatic, high-gloss red-interfering effect pigments with a red absorption color and very good hiding power were obtained. Example 11

[0189] 100 g of the effect pigment obtained from Example 6 were suspended in 850 ml of deionized water and heated to 85°C with turbulent stirring. The pH was lowered to pH 4.2 with dilute hydrochloric acid. A solution of 0.93 g of Ce(NO 3 ) 3 x 6 H 2 O dissolved in 40 ml of deionized water was then metered in. At the same time, the pH was kept constant by dropwise addition of a 10% NaOH solution. After the solution had been completely added, the mixture was stirred for a further hour and then the pH was adjusted to pH 10 with dilute sodium hydroxide solution. 5.7 g of Dynasylan 1146 diluted with 24.3 g of deionized water were then added to the suspension, stirring was continued for 180 minutes, the suspension was filtered off and the filter cake was washed with deionized water. The filter cake was dried at 95°C under vacuum. Example 12

[0190] 300 g of glass slides with a particle size distribution according to the MALVERN Mastersizer MS 2000: D 10 = 10 µm, D 50 = 20 µm, D 90 = 40 µm were suspended in 1500 ml of deionized water and heated to 85°C with turbulent stirring. The pH of the suspension was lowered to pH 2.2. By adding 70 ml of a tin chloride solution with a concentration of c(Sn)=12 g / l, a layer of tin oxide was deposited on the surface of the glass slides. The pH was then lowered to pH 2.0 with dilute HCl, and a solution of 250 ml of TiCl 4 (200 g TiO 2 / l deionized water) was added to the suspension. After the addition was complete, the mixture was stirred for a further 10 minutes, and then the pH was adjusted to pH 2.6. Subsequently, 100 ml of an aqueous ferric chloride solution with a density of 1.25 g / cm 3 was added. Subsequently, 300 ml of a solution of TiCl 4 (200 g TIO 2 / l deionized water) was added to the suspension.Fifteen minutes after the addition, the suspension was filtered off and the filter cake washed. The filter cake was dried and calcined at 760°C for 60 minutes. Extremely chromatic, high-gloss, gold-colored effect pigments were obtained. Comparison example 1

[0191] 200 g of synthetic mica flakes (fluorphlogopite flakes) with a particle size distribution according to the MALVERN Mastersizer MS 2000: D 10 = 25 µm, D 50 = 55 µm, D 90 = 100 µm, span ΔD = 1.36) were suspended in 1300 ml of deionized water (DE = fully demineralized) and heated to 85°C with stirring. The pH of the suspension was lowered to pH 2.2. By adding 100 g of a tin chloride solution with a concentration c(Sn)=12 g / l, a layer of "SnO 2 " was deposited on the surface of the synthetic mica flakes.

[0192] The pH was then lowered to 1.9 with diluted HCl, and a solution of 500 ml of TiCl 4 (200 g TiO 2 / l deionized water) was added to the suspension. After the addition, the mixture was stirred for 10 minutes, and then the pH was adjusted to 2.6. 60 ml of an aqueous ferric chloride solution with a density of 1.42 g / cm 3 was then added. Fifteen minutes after the addition, the suspension was filtered off, and the filter cake was washed. The filter cake was dried and calcined at 700°C for 60 minutes under reducing conditions. Bright, golden pigments with a dark absorption color were obtained. Comparison example 2

[0193] Red effect pigment based on natural mica flakes, coated with iron oxide, Iriodin 504 Red, Merck. Comparison example 3

[0194] Red effect pigment based on SiO2 platelets, coated with iron oxide, Iriodin 4504 Lava Red, Merck. II Characterization of the absorbing effect pigments and pigments of the comparative examples IIa Particle size measurement

[0195] The size distribution curve of the absorbing effect pigments according to the invention and the pigments of the comparative examples was determined using a Mastersizer 2000 instrument from Malvern, according to the manufacturer's instructions. For this purpose, approximately 0.1 g of the respective pigment was added as an aqueous suspension, without the addition of dispersing agents, to the sample preparation cell of the measuring instrument using a Pasteur pipette while continuously stirring, and measured several times. Averages were calculated from the individual measurement results. The scattered light signals were evaluated using the Fraunhofer method.

[0196] For the purposes of this invention, the mean particle size D 50 is understood to mean the D 50 value of the cumulative frequency distribution of the volume-averaged size distribution function, as obtained by laser diffraction methods. The D 50 value indicates that 50% of the pigments have a diameter equal to or smaller than the specified value, for example, 20 µm. Accordingly, the D 10 or D 50 value indicates that 10% or 90% of the pigments have a diameter equal to or smaller than the respective measured value.

[0197] The span ΔD, defined as Δ D = D 90 − D 10 D 50 , indicates the breadth of the particle size distribution. With regard to the optical appearance of the absorbent effect pigments according to the invention, a small value of ΔD, ie, a narrow span, is preferred. Table 2: Particle sizes Example / Comparison example D10 [µm] D50 [µm] D90 [µm] Span Example 1 10,8 22,5 40,6 1,326 Example 2 11,0 22,8 40,8 1,307 Example 3 12,4 23,7 42,1 1,254 Example 4 28,1 53,0 92,7 1,219 Example 5 11,9 22,9 40,9 1,271 Example 6 12,5 23,0 40,4 1,217 Example 7 11,9 22,4 39,9 1,247 Example 8 13,7 24,3 41,3 1,138 Example 9 11,1 22,6 40,8 1,314 Example 10 8,8 20,1 37,6 1,429 Example 12 9,7 21,3 41,3 1,482 Comparison example 1 12,0 22,9 40,8 1,260 Comparison example 2 10,8 21,9 41,5 1,402 Comparison example 3 9,7 19,3 35,5 1,337 IIb Angle-dependent color measurements

[0198] To measure the color and brightness values, the effect pigments according to the invention and the pigments from the comparative examples were stirred into a conventional nitrocellulose lacquer (Erco Bronze Mischlack 2615e colorless; Maeder Plastiklack AG) at a pigmentation level of 6 wt. %, based on the total weight of the wet lacquer. The respective pigments were initially introduced and then dispersed into the lacquer with a brush. The finished lacquer was applied to black-and-white opacity charts (Byko-Chart 2853, Byk-Gardner) using a doctor blade applicator (RK Print Coat Instr. Ltd. Citenco applicator model K 101) with a spiral doctor blade in a wet film thickness of 40 µm or 76 µm (Example 4) and subsequently dried at room temperature. The selection of the spiral doctor blade is made according to Table A depending on the D 50 value of the pigments or substrates to be applied.

[0199] Using the BYK-mac multi-angle colorimeter (Byk-Gardner), the color values ​​on the black background of the coverage chart were determined at various observation angles relative to the specular angle at a constant angle of incidence of 45° (according to the manufacturer's specifications). The chroma value C* 15 was used to characterize the color intensity, which was measured on the black background of the black-and-white coverage chart at a measurement angle 15° away from the specular angle.

[0200] Highly reflective samples (ideally mirrors) reflect almost all of the incoming light at the so-called gloss angle. The closer the paint application is measured to the gloss angle, the stronger the interference color appears. Table A: Wet film thickness depending on the D 50 value of the pigments or substrates to be applied D 50 value Spiral doctor blade <40 µm 40 µm 40 µm - 85 µm 76 µm > 85 µm 100 µm Table 3: Color and brightness values ​​of gold-colored effect pigments Example / NC varnish 6% 40µm BykMac Comparison example L 110° s 1< a*15° s b*15° s C* 15° s Example 1 91,7 -7,1 46,1 46,6 Example 2 84,3 -6,6 35,1 35,7 Example 4 77,4 -10,6 23,3 25,6 Example 5 90,8 -10,9 38,6 40,1 Example 9 92,4 -4,0 48,3 48,5 Example 12 73,74 -3,50 32,84 33,02 Comparison example 1 83,9 1,0 25,3 25,3 Table 4: Color and brightness values ​​of red effect pigments Example / NC varnish 6% 40µm BykMac Comparison example L 15° s 1< a*15° s b*15° s C* 15° s Example 6 57,8 42,3 26,8 50,0 Example 7 72,9 16,6 -29,6 34,0 Example 10 64,2 40,2 27,6 48,8 Comparison example 2 74,5 38,6 11,4 40,2 1< Measured on the black background of the black and white cover map.

[0201] Table 3 shows the color values ​​for gold-interfering effect pigments. It can be seen that the color intensity of the effect pigments according to the invention is significantly higher than that of the single-layer pearlescent pigment from Comparative Example 1. An exception is Example 4, which uses a significantly thicker glass substrate.

[0202] The color values ​​for red-interfering effect pigments, which are listed in Table 4, are also significantly higher in the examples according to the invention than those of Comparative Example 2. ILC coverage comparison

[0203] To determine the coverage ratio D q , defined as D q = L schwarz * 25 L weiß * 25 The brightness values ​​L*25° of the paint applications from IIb were recorded using the BYK-mac multi-angle colorimeter (Byk-Gardner) at a measurement angle of 25° on both a black and a white background of the black-and-white opacity chart. The 25° measurement geometry refers to the difference from the gloss angle at a constant angle of incidence of 45°. The viewing angle is measured away from the specular reflection in the illumination plane.

[0204] The effect pigments according to the invention exhibit good hiding power. Their hiding power Dq is preferably ≥ 0.41. The hiding power Dq of the platelet-shaped, absorbent effect pigments according to the invention from Examples 1 to 10 is, as can be seen from Table 5, significantly above 0.41 in each case. Ild gloss measurements

[0205] Gloss is a measure of specular reflection. To determine gloss, the coating applications from IIb were measured on the white background of the black-and-white opacity chart using a Micro-Tri-Gloss gloss meter from Byk-Gardner at a measurement angle of 60° relative to the vertical. The gloss values ​​of the inventive absorbing effect pigments and the pigments of the comparative examples are listed in Table 5.

[0206] The platelet-shaped absorbing effect pigments according to the invention from Examples 1 to 10 show, in some cases, significantly higher gloss values ​​than the single-layer coated pigments from Comparative Examples 2 and 3.

[0207] The gloss measurements in Table 5 confirm the very high reflectivity of the pigments according to the invention compared to the state of the art. Ile effect measurements

[0208] To objectively describe the optical effect of the absorbing effect pigments according to the invention, effect measurements were carried out using the BYK-mac spectrophotometer (Byk-Gardner) on the coating applications from IIb (see Byk-Gardner, catalog "Quality Control for Coatings and Plastics" 2011 / 2012, pp. 97 / 98). The corresponding measured values ​​for glitter intensity S_i, glitter area S_a, and grain size G are summarized in Table 5. Table 5: Effect measurements, coverage ratio and gloss values Example / Comparison example S_i 15° (s) 1< S_a 15° (s) 1< G (s) 1< D q 25° Gloss 60° (w) 2< Example 1 15,44 33,99 9,99 0,607 85,8 Example 2 12,75 33,59 8,59 0,618 70,5 Example 3 6,14 24,72 4,66 0,495 42,3 Example 4 53,95 33,66 13,85 0,522 81,5 Example 5 10,15 32,00 8,15 0,692 49,9 Example 6 6,16 30,01 4,37 0,558 52,6 Example 7 5,62 24,12 5,60 0,440 40,3 Example 8 7,84 33,93 4,04 0,505 48,8 Example 9 14,58 33,75 9,98 0,630 90,8 Example 10 6,35 27,85 4,68 0,505 53,9 Example 12 51,65 34,71 13,17 0,4760 69,1 Comparison example 2 4,70 19,38 4,15 0,661 41,8 Comparison example 3 4,28 18,57 3,45 0,719 32,3 1< Measured on the black background of the black-and-white coverage map. 2< Measured on the white background of the black-and-white coverage map.

[0209] The effect values ​​S_i, S_a and G of the platelet-shaped absorbing effect pigments according to the invention from Examples 1 to 10 and 12 are higher than the values ​​of Comparative Examples 2 and 3. The achievable optical effects of the platelet-shaped absorbing effect pigments according to the invention are significantly more pronounced than with conventional single-layer coated effect pigments from Comparative Examples 2 and 3. IIf Waring Blender

[0210] In industry, many coatings are processed in closed-loop systems. The coating components are exposed to high shear forces. The Waring Blender Test simulates these conditions and is used to evaluate closed-loop and shear stability. Pigments whose coatings are not sufficiently anchored to the substrate exhibit significant deviations in chroma values ​​in this test compared to untreated applications. The Waring Blender Test can therefore be understood as a measure of the interlayer adhesion of the pigment coating to shear forces.

[0211] For this purpose, the absorbent effect pigments according to the invention or the pigments of the comparative examples were weighed according to the following procedure and gradually mixed into a paste with a conventional acrylic lacquer in an 880 ml beaker. The viscosity was then adjusted to 17°C in a DIN 4 mm beaker using a 1:1 butyl acetate / xylene ratio. A total of 600 g of lacquer was produced, of which 400 g was poured into a double-walled 1 kg container with water cooling and stirred under a Dispermat (Waring Blender) with a special attachment. The stirring time was 8 minutes at 13,500 rpm, then 200 g of lacquer was removed, and the remainder was stirred for another 12 minutes. Approach: 6% pigment 8% Butyl acetate 85 86% acrylic lacquer, colorless 30% dilution Butyl acetate 85 / Xylene 1:1

[0212] 200 g each of the untreated and treated paint were applied to a test panel using a spray gun and the SATA LP-90 spray gun according to the following settings. Attitude: Needle: 1.3.4 Pressure: 4 bar Gears: The number of spray coats was chosen so that a dry paint layer thickness of 15-20 µm was achieved.

[0213] By convention, effect pigments are considered shear-stable if, according to the Waring Blender Test, the gloss and color difference, measured close to the gloss angle, are relatively small. The ΔC* 15° value compared to the untreated sample should ideally be less than 2.

[0214] Table 6 shows the color change ΔC* 15° and the gloss change ΔGloss 60° of the sample subjected to the Waring Blender Test compared to the untreated sample using examples 5 and 10 according to the invention. Table 6: Gloss and color difference in the Waring Blender Test ΔC*(15°) ΔGloss (60°) Example 5 0,9 -1,3 Example 10 1,3 -0,8

[0215] The inventive absorbent effect pigments from Examples 5 and 10 meet the test criteria. The color difference is negligible. Even under the microscope, hardly any changes such as flaking of the coating or other resulting surface defects could be detected.

[0216] The absorbing effect pigments according to the invention are extremely shear-stable despite their spaced position. Ilg Determination of chemical resistance

[0217] The chemical resistance of the inventive absorbent effect pigments and the pigments of the comparative examples was determined by applying coatings to plastic panels. 6 g of the respective pigment were stirred into a mixture of 90 g of a conventional colorless acrylic varnish and 10 g of Butyl Acetate 85. The viscosity was then adjusted to 17 in a DIN 4 mm cup using a 1:1 mixture of Butyl Acetate 85 and xylene.

[0218] 100 g of this coating was applied to each panel using a spray gun, similar to step 1If. After coating, the panels were baked for 30 minutes at 80°C. 24 hours later, the panels were half-immersed in 10% sodium hydroxide solution. After a contact time of 7 days, the panels were rinsed with deionized water and, after a drying time of 2 hours, visually inspected for damage and / or discoloration. Furthermore, discoloration was measured using a BYK-mac (Byk-Gardner). To characterize the color change, the ΔE value of the exposed sample was compared to the corresponding unexposed sample at a measurement angle of 15°. The results are shown in Table 7 below. Table 7: Color change ΔE Example / Comparison example ΔE(15°) Example 10 2,40 Comparison example 3 13,31

[0219] Pigments with a ΔE(15°) <3 can be considered chemically stable. The inventive absorbent effect pigments from Example 10 are below this limit, while the pigments from Comparative Example 3 significantly exceed it. Ilh X-ray fluorescence analysis (XRF)

[0220] The metal oxide, metal hydroxide, and / or metal oxide hydrate contents of the inventive absorbent effect pigments and the pigments of the comparative examples were determined by X-ray fluorescence analysis (XRF). For this purpose, the respective pigments were incorporated into a lithium tetraborate glass tablet, fixed in solid sample measuring cups, and measured from there. The Advantix ARL from Thermo Scientific was used as the measuring device. The measured values ​​are shown in Table 8. The various contents were given as TiO 2 for titanium, as Fe 2 O 3 for iron, and as SnO 2 for tin. Table 8: mean height ha of the distance layer and RFA values Example / Comparison example REM medium Height ha [nm] XRF (as oxide) Ti[%] Fe[%] Sn[%] Example 1 30 57,7 6,9 0,78 Example 2 28 57,7 6,9 0,78 Example 3 20 47,2 5,8 0,55 Example 4 25 28,6 3,1 0,98 Example 5 38 54,9 10,6 / Example 6 55 / 65,8 4,3 Example 7 51 48,2 0,04 3,1 Example 8 / / / / Example 10 20 9,1 51,1 / Example 12 20 23,9 4,6 1,26 Comparison example 1 No distance / / / Comparison example 2 No distance / / / Comparison example 3 No distance / / / Ili condensation test

[0221] To determine condensation resistance, the absorbent effect pigments according to the invention or the pigments from the comparative examples were incorporated into a water-based coating system, and the test applications were prepared by spray coating on aluminum sheets. The basecoat was overcoated with a commercially available one-component clearcoat and then baked. These applications were tested according to DIN 50 017 (condensation-constant climates). Adhesion strength was tested using a cross-cut test according to DIN EN ISO 2409 immediately after the test, in comparison to the unexposed sample. Gt 0 represents no change, and Gt 5 represents a very significant change.

[0222] The swelling behavior was visually assessed immediately after exposure to condensation water in accordance with DIN 53230. The index number 0 means no change and the index number 5 means very strong change.

[0223] Finally, the DOI (distinctness of image) was determined using a Wave-scan II (Byk-Gardner). Table 9: Condensation results sample Gloss 20° before SW test Gloss 20° according to SW test Loss of shine DOI Cross-cut immediately Swelling visually Example 9 90,3 89,7 <1 % 78,2 0 0 Example 11 92,8 90,6 2,4 % 80,1 1 0 Comparison example 2 91,2 21,7 76 % nb 5 4

[0224] The pigment from Comparative Example 2 exhibited severe swelling and poor interlayer adhesion. Due to the high fine structure, the DOI was no longer measurable after exposure to condensation.

[0225] The inventive absorbent effect pigments from Examples 9 and 11, however, proved to be stable and showed almost no changes before and after the test. Ilj UV resistance

[0226] The UV resistance of the absorbing effect pigments according to the invention and of the pigments of the comparative examples was determined based on the rapid UV test described in EP 0 870 730 A1 for determining the photochemical UV activity of TiO 2 pigments. For this purpose, 1.0 g of the corresponding pigment was dispersed in 9.0 g of a melamine-containing lacquer rich in double bonds. Doctor blade prints were made on white cardboard and dried at room temperature. The doctor blade prints were divided, and one of each of the two sections was stored in the dark as an unexposed comparison sample. The samples were then irradiated for 150 minutes in a Q-Panel QUV device with UV-containing light (UVA-340 lamp, irradiance 1.0 W / m 2 / nm). Immediately after the end of the test, color values ​​of the exposed samples relative to the respective reference sample were determined using a Minolta CM-508i colorimeter.The resulting ΔE* values, calculated according to the Hunter-L*a*b* formula, are shown in Table 9.

[0227] In this test, a gray-blue discoloration of the TiO2 layer of the respective pigment is essentially observed due to Ti(III) species formed under UV light. This requires that the electron hole has spatially left the TiO2 and cannot immediately recombine with the remaining electron - e.g., through reaction with olefinic double bonds in the binder. Since a melamine-containing coating layer significantly slows the diffusion of water (vapor) and oxygen to the pigment surface, reoxidation of the titanium(III) species is significantly delayed, so that the graying can be measured and the ΔE* value can be used as a measure of the pigment's UV stability. A larger ΔE* value for the exposed sample relative to the unexposed reference sample therefore means lower UV stability of the tested pigment. Table 10: UV test results Example comparison example ΔE* Example 5 3,23 Example 10 2,96 Comparison example 1 7,28

[0228] The comparison example showed a significantly stronger color change (ΔE*) after corresponding exposure.

[0229] Ilk Determination of the average thickness of the non-metallic platelet-shaped substrates, the average layer thickness of layers 2 and 3, the average layer thickness of the entire coating, the average height ha of the spacer layer and the average height h H of the cavities

[0230] For this purpose, the inventive absorbent effect pigments were incorporated at 10% into a 2K Autoclear Plus HS clearcoat from Sikkens GmbH using a sleeve brush, applied to a film using a spiral doctor blade (26 µm wet film thickness), and dried. After a drying time of 24 hours, cross-sections were taken from these doctor blade prints. The cross-sections were measured using an SEM. To determine the average thickness of the non-metallic platelet-shaped substrates, at least 100 individual pigments were measured to obtain meaningful statistics.

[0231] To determine the average layer thickness of layers 2 and 3, the average thickness of the entire coating, the average height ha of the spacer layer and the average height h H of the cavities, the upper and lower substrate surfaces, i.e. the longer side of the non-metallic platelet-shaped substrate visible in the SEM cross-section, were used as the baseline. The baseline was placed in the scanning electron micrograph along the surface of the platelet-shaped substrate in the cross-section by connecting the two intersection points of the non-metallic platelet-shaped substrate - optional layer 1 and the non-metallic platelet-shaped substrate - layer 2 from the left and right edges of the scanning electron micrograph with a straight line. The scanning electron micrographs were examined using the image processing software AxioVision 4.6.3 (Zeiss).

[0232] At a 90° angle to these two base lines, so many parallel lines were drawn at a distance of 50 nm that a grid was placed over the entire scanning electron micrograph of the effect pigment ( Figure 4). The magnification of the scanning electron micrograph was preferably at least 50,000 times, based on Polaroid 545. Starting from the respective upper and lower base line of the non-metallic platelet-shaped substrate in the direction of layer 3, the distances between the intersection points of these lines at the respective interfaces of the optional layer 1 to layer 2, layer 2 to the spacer layer, spacer layer to layer 3 and layer 3 to the environment were measured manually. It happened that one of the lines drawn at a distance of 50 nm lay directly above a connection point or a spacer. In this case, only the respective intersection point of the line at the interface between layer 3 and the environment was recorded. From these measured values, the layer thicknesses of layers 2 and 3, the thickness of the entire coating and the height ha of the spacer layer were determined by subtraction.

[0233] To determine the mean height h H of the cavities, the intersection points of these parallel lines with the upper and lower cavity boundaries within the distance layer were used. The individual values ​​of the layer thickness, height h H , and height h H determined in this way were used to calculate the respective arithmetic mean values ​​to determine the above-mentioned values ​​for the mean layer thickness, mean height h H , and mean height h H , respectively. To ensure meaningful statistics, the measurements described above were performed on at least 100 lines.

[0234] The term "mean" refers in all cases to the arithmetic mean.

[0235] Cross-sections of the pigments of the comparative examples, which do not have a spacer layer but possibly have randomly distributed pores within the coating, were also examined using the method described above using scanning electron micrographs. If one of the parallel lines lay over one or more pores, the height of the pore(s), their pore center(s), and the distance of the pore center(s) from the substrate surface were determined.

[0236] As an alternative to cross-sections, the absorbing effect pigments according to the invention can be sectioned using the FIB method (FIB = focused ion beam). For this purpose, a fine beam of highly accelerated ions (e.g. gallium, xenon, neon or helium) is focused on a point using ion optics and guided line by line over the effect pigment surface to be treated. Upon impact with the effect pigment surface, the ions release a large part of their energy and destroy the coating at this point, which leads to line-by-line material removal. The scanning electron microscope images then taken can also be used to determine the average height ha, the average layer thickness of layers 2 and 3 and the average layer thickness of the entire coating using the method described above.The average thickness of the non-metallic platelet-shaped substrate can also be determined using scanning electron micrographs of the effect pigments cut by the FIB method.

[0237] The advantages of the absorbent effect pigments according to the invention therefore arise from the sum of various properties. The absorbent effect pigments according to the invention exhibit high transparency, very good mechanical and chemical stability, as well as high gloss and color strength. None of the comparison pigments satisfactorily exhibits all of these properties when viewed as a whole. Table 11: Characterization of the coating Example / Comparison example ds2 [nm] dS3 [nm] dS2 / dS3 hma [nm] h Rma σh Rma [%] n S SD [%] UH [%] Example 1 85 91 0,94 100,4 0,49 3,8 1,1 5,4 94,6 Example 3 66 65 1,02 76,3 0,50 5,1 4,6 16,4 83,6 Example 5 83 105 0,79 94,7 0,52 4,9 3,2 15,9 84,1 Example 6 70 99 0,71 87,6 0,44 6,5 2,2 11,0 89,0 Example 7 55 57 0,96 62,0 0,49 13,5 3,6 18,1 81,9 Example 10 118 82 1,43 128,3 0,58 4,5 6,2 30,9 69,1 Example 12 100 118 0,85 110 0,46 4,9 2,2 11,1 88,9 Comparison example 1 No distance 21,3 18 90,0 10,0 Comparison example 2 No distance 24,7 13 65,0 35,0 d S2 [nm] = average layer thickness of layer 2 dss [nm] = average layer thickness of layer 3 n S = average number of ridges per µm AH [%] = area fraction of void SD = ridge number density [%] h ma = center of the spacer layer (sum of the layer thickness of the optional layer 1, layer 2 and half the height ha ) h Rma = relative height of the spacer layer σh Rma [%] = standard deviation of the relative height of the spacer layer

[0238] Table 8 shows the average height ha of the spacer layer of the measured pigments. In contrast to the pigments of Comparative Examples 1 to 3, all of the absorbent effect pigments according to the invention have a spacer layer.

[0239] The pigments from Comparative Examples 1 and 2 do not exhibit a spaced pore location, but rather randomly distributed pores within the coating. In Table 11, the value in column σh Rma [%] for Comparative Examples 1 and 2 refers to the standard deviation of the pore centers from the substrate surface.

[0240] However, since the pigment from Comparative Example 2 contains only a few randomly distributed pores, the number of pores density SD is 65.0%. The standard deviation of the pore centers from the substrate surface is 24.7%, which proves that the pores are randomly distributed throughout the coating. The situation is different for the inventive absorbent effect pigments from Examples 1, 3, 5 to 7, and 10. Here, the standard deviation of the relative height of the center of the spacer layer h Rma is < 14% in each case, which shows that their respective spacer layer lies in a defined position within the coating. The standard deviation of the distances of the pore centers from the substrate surface of the pigment from Comparative Examples 1 and 2 can thus be compared with the standard deviation of the relative height of the center of the spacer layer of the inventive absorbent effect pigments. III Scanning electron micrographs

[0241] The scanning electron micrographs were obtained from cross-sections of the absorbing effect pigments according to the invention using a Supra 35 scanning electron microscope (Zeiss). Energy-dispersive X-ray microanalysis (EDX analysis) was performed using an EDAX Sapphire instrument (EDAX). III Application examples Application example 1: Body lotion

[0242] INCI Name Product name % by weight Manufacturer / Supplier Phase A 85,80 Effect pigment from example 1 0,20 Aqua Water Glycerin Glycerin 85% 2,00 H. Erhard Wagner Xanthan Gum Keltrol CG-T 0,60 CP Kelco Phase B Isopropyl Palmitate Isopropyl palmitate 3,00 H. Erhard Wagner Glyceryl Stearate Aldo MS K FG 2,00 Lonza Cocos Nuifera Oil Ewanol KR 2,00 H. Erhard Wagner Cetearyl Alcohol Tego Alkanol 1618 2,00 Evonik Dimethicone Element 14 PDMS 1,00 Momentive Sodium polyacrylate Cosmedia SP 0,50 BASF Phase C Phenoxyethanol, Ethylhexylglycerin Euxyl PE 9010 0,80 Schülke & Meyr Fragrance Vitamin Bomb 0,10 Bell Europe

[0243] The effect pigment from Example 1 can be used in a range of 0.1 to 2.5 wt.%, based on the total weight of the body lotion formulation. The blend can be adjusted to 100 wt.% of the formulation with water.

[0244] Keltrol CG-T was dispersed in Phase A and heated to 75°C. Phase B was heated separately to 75°C. Phase B was then slowly added to Phase A. The emulsion was cooled to room temperature while stirring, and Phase C was added individually. Application example 2: Cream eye shadow

[0245] INCI Name Product name % by weight Manufacturer / Supplier Phase A Microcrystalline Wax TeCero Wax 1030 K 4,50 Drum wax Copernicia Cerifera Cera Carnauba wax LT 124 4,50 Drum wax Isohexadecanes Isohexadecanes 21,00 Ineos Cyclopentasiloxane, Dimethicone / Vinyltrimethylsiloxysilicate Crosspolymer Belsil RG 100 Silicone Elastomer Resin Gel 8,00 Brave Trimethylsiloxyphenyl Dimethicone Belsil PDM 20 6,00 Brave Dimethicone Belsil DM 100 14,00 Brave Capric Triqlvceride Miglyol 812 7,00 Sasol Cyclomethicone (and) Quaternium-90 Bentonite (and) Propylene Carbonate Tixogel VSP-1438 5,00 BYK Phase B Effect pigment from example 3 30,00

[0246] The effect pigment from Example 3 can be used in a range of 5 to 30.0 wt.%, based on the total weight of the eyeshadow formulation. The balance to 100 wt.% of the formulation can be achieved with isohexadecane.

[0247] Phase A was mixed and heated to 85 °C, then Phase B was added to Phase A while stirring. After filling into a suitable container, the mixture was cooled to room temperature. Application example 3: Shower gel

[0248] INCI Name Product name % by weight Manufacturer / Supplier Phase A Effect pigment from example 5 0,10 Aqua Water 58,50 Acrylates Copolymer Carbopol Aqua SF-1 5,50 Lubrizol Phase B Sodium hydroxide NaOH (10 wt%) 1,50 Phase C Sodium Laureth Sulfate Zetesol NL-2 U 22,00 Shimmer & Black Cocamidopropyl Betaine Amphoteric surfactant B5 6,00 Shimmer & Black PEG-7 Glyceryl Cocoate Emanon HE 2,00 Kao Corp. Disodium Laureth Sulfosuccinate Sectacin 103 Special 2,00 Zschimmer & Schwarz Phase D Phenoxyethanol (and) Piroctone Olamine Nipaguard PO 5 0,60 Clariant Fragrance Water Lily OA 0,20 Bell Flavors and Fragrances Sodium Chloride Sodium Chloride 1,60 VWR

[0249] The effect pigment from Example 5 can be used in a range of 0.01 to 1.0 wt.%, based on the total weight of the shower gel formulation. The amount can be adjusted to 100 wt.% of the formulation with water.

[0250] Phase A was stirred, then Phase B was added and stirred until a homogeneous appearance was achieved. Phase C was weighed separately, mixed briefly, and added to Phase AB. The mixture was then stirred again and Phase D was added individually. Application example 4: Pressed eye shadow

[0251] INCI Name Product name % by weight Manufacturer / Supplier Phase A Talc Talc Powder 36,00 VWR Bentonite Optigel CK-PC 5,00 BYK Synthetic Fluorphlogopite Synafil S 1050 13,00 ECKART Aluminum Starch Octenylsuccinate Agenaflo OS 9051 10,00 Agrana Magnesium Stearate Magnesium Stearate 6,00 VWR Effect pigment from example 8 20,00 Phase B Cyclomethicone Xiameter PMX-0345 5,00 Dow Corning Octyldodecyl Stearoyl Stearate Ceraphyl 847 5,00 Ashland

[0252] The effect pigment from Example 8 can be used in a range of 5.0 to 40.0 wt.%, based on the total weight of the eyeshadow formulation. Talc can be added to adjust the amount to 100 wt.% of the formulation.

[0253] Phase A was mixed for 30 seconds at 2500 rpm in a high-speed blender. Phase B was then added, and the mixture was mixed for 60 seconds at 3000 rpm in the same blender. Finally, the powder mixture was pressed into shape using an eyeshadow press at 100 bar for 30 seconds. Application example 5: Mascara

[0254] INCI Name Product name % by weight Manufacturer / Supplier Phase A Aqua Water 73,00 Bentonite (and) Xanthan Gum Optigel WX-PC 2,00 BYK Phase B Cetyl Alcohol (and) Glyceryl Stearate (and) PEG-75 Stearate (and) Ceteth-20 (and) Steareth-20 Emulium Delta 5,00 Gattefosse C10-18 Triglycerides Lipocire A Pellets 2,00 Gattefosse Ozokerite Kahlwax 1899 2,00 Bald Glyceryl Behenate Compritol 888 CG Pastilles 2,00 Gattefosse Butylene Glycol Cocoate Cocoate BG 4,00 Gattefosse Phase C Effect pigment from example 8 5,00 Phenoxyethanol (and) Piroctone Olamine Nipaguard PO5 0,50 Clariant Glycine Soja (Soybean) Oil, Dicaprylyl Ether, Magnolia Grandiflora Bark Extract, Lauryl Alcohol Follicusan DP 3,00 CLR Berlin Water, Hydrolyzed Corn Starch, Beta Vulgaris (Beet) Root Extract DayMoist CLR 1,00 CLR Berlin Linoleic Acid (and) Linolenic Acid Vitamin F forte 0,50 CLR Berlin

[0255] The effect pigment from Example 8 can be used in a range of 1.0 to 10.0 wt.%, based on the total weight of the mascara formulation. The water from Phase A can be used to balance the formulation to 100 wt.%.

[0256] Phase A was stirred under high shear. Phase B was weighed separately. Phase A and Phase B were heated separately to 85°C, after which Phase B was added to Phase A. Phase AB was then cooled to 45°C, and Phase C was gradually added while stirring during cooling. Application example 6: Hair gel

[0257] INCI Name Product name % by weight Manufacturer / Supplier Phase A Sodium Magnesium Silicate (nano) Laponite XLG 2,00 BYK Aqua Water 94,80 Phase B Effect pigment from example 6 0,10 Citric Acid (and) Water Citric Acid (10%) 0,30 Glycerin, Water, Avena Strigosa Seed Extract, Lecithin, Potassium Sorbate, Citric Acid Aquarich 1,50 Rahn AG Fragrance Lychee & Grape 0,10 Bell Europe Methylisothiazolinone (and) Phenethyl Alcohol (and) PPG-2-Methyl Ether Optiphen MIT Plus 1,20 Ashland

[0258] The effect pigment from Example 6 can be used in a range of 0.01 to 2.0 wt.%, based on the total weight of the hair gel formulation. The amount can be adjusted to 100 wt.% of the formulation with water.

[0259] The Laponite XLG was stirred with water until Phase A became clear. The effect pigment from Example 6 was then added to Phase B while stirring. The remaining ingredients of Phase B were then added gradually. Application example 7: Body powder

[0260] INCI Name Product name % by weight Manufacturer / Supplier Phase A Synthetic Fluorphlogopite Synafil S 1050 40,00 Eckart Polypropylene Synafil W 1234 8,00 Eckart Bentonite Optigel CK-PC 10,00 BYK Talc Talc Powder 18,00 VWR Magnesium Stearate Magnesium Stearate 4,00 Applichem Effect pigment from example 5 20,00

[0261] The effect pigment from Example 5 can be used in a range of 0.2 to 5.0 wt.%, based on the total weight of the body powder formulation. The amount can be adjusted to 100 wt.% of the formulation using Synafil S 1050.

[0262] Phase A was mixed and then the powder was filled into a suitable container. Application example 8: Lip gloss

[0263] INCI Name Product name % by weight Manufacturer / Supplier Phase A Hydrogenated Polyisobutene (and) Ethylene / Propylene / Styrene Copolymer (and) Butylene / Ethylene / Styrene Copolymer Versagel ME 750 75,30 Penreco Simmondsia Chinensis (Jojoba) Seed Oil Jojoba Oil - Natural 2,00 BioChemica Caprylyl Trimethicone Silcare Silicone 31M50 7,00 Clariant Stearyl Dimethicone Silcare Silicone 41M65 3,20 Clariant Hydrogenated Polydecene Dekanex 2004 FG 4,00 IMCD Isopropyl Myristate Isopropyl Myristate 4,50 VWR Phase B Effect pigment from example 6 4,00

[0264] The effect pigment from Example 6 can be used in a range of 0.10 to 8.00 wt.%, based on the total weight of the lip gloss formulation. The blend can be adjusted to 100 wt.% of the formulation using Versagel ME 750.

[0265] Phase A was heated to 85°C, then the pigment from Example 6 was added to Phase B, stirred until a uniform consistency was achieved and then filled into a lip gloss container. Application example 9: Lipstick

[0266] INCI Name Product name % by weight Manufacturer / Supplier Phase A Octyldodecanol Eutanol G 42,5 BASF Candelilla Cera Kahlwax 2039 6,00 Bald Copernicia Cerifera (Carnauba) Wax Kahlwax 2442 6,00 Bald Bis-Diglyceryl Polyacyladipate-2 Softisan 649 10,00 Sasol Polyisobutenes Rewopal PIB 1000 10,00 Evonik Hydrogenated Polydecene Silkflo 364 NF 5,00 Ineos C10-18 Triglycerides Lipocire A Pellets 5,00 Gattefosse Acacia Decurrens / Jojoba / Sunflower Seed Wax / Polyglyceryl-3 Esters Hydracire S 5,00 Gattefosse Tocopheryl Acetate dl-alpha-tocopheryl 0,50 IMCD Phase B Effect pigment from example 10 10,00

[0267] The effect pigment from Example 10 can be used in a range of 0.5 to 20.0 wt.%, based on the total weight of the lipstick formulation. Eutanol G can be used to balance the formulation to 100 wt.%.

[0268] Phase A was heated to 85°C, then Phase B was added to Phase A and mixed. This mixture was then filled into a lipstick mold at a temperature of 75°C. Application example 10: Liquid eyeliner

[0269] INCI Name Product name % by weight Manufacturer / Supplier Phase A Aqua Water 56,90 Bentonite (and) Xanthan Gum Optigel WX-PC 1,40 Phase B Lecithin Emulmetik 100 0,10 Lucas Meyer Copernicia Cerifera Cera Kahlwax 2442 1,00 Kahl StearicAcid Stearic Acid 3,50 Lipo Chemicals Hydrogenated Polyisobutene Panalane L14 E 5,00 Ineos Polysorbate 60 Mulsifan CPS 60 1,50 Zschimmer & Schwarz Phase C Effektpigment aus Beispiel 2 4,00 Polyurethane-35 Baycusan C 1004 18,00 Bayer Cosmetics Aqua and CI 77499 and Methylpropanediol and Ammonium Acrylates Copolymer and Simethicone and Caprylyl Glycol and Phenylpropanol Sodium Acrylates Copolymer WorléeBase AQ 77499 / 1 8,00 Worlee Phenoxyethanol, Ethylhexylglycerin Euxyl PE 9010 0,60 Schülke & Mayr

[0270] The effect pigment from Example 2 can be used in a range of 0.5 to 8.0 wt.%, based on the total weight of the eyeliner formulation. The amount can be adjusted to 100 wt.% of the formulation with water.

[0271] Optigel WX-PC was dispersed in Phase A water and stirred for 10 minutes. Phase A and Phase B were heated separately to 80°C. Phase B was then slowly added to Phase A with stirring. After cooling to 45°C, the ingredients of Phase C were gradually added and filled into a suitable container. Application example 11: Mousse

[0272] INCI Name Produktname Gew.-% Hersteller / Lieferant Phase A Cyclopentasiloxane Xiameter PMX-0245 Cyclosiloxane 8,60 Dow Corning Hydrogenated Polyisobutene MC 30 4,00 Sophim Dimethicone (and) Dimethicone Crosspolymer Dow Corning 9041 Silicone Elastomer Blend 37,14 Dow Corning Squalane Squalane 5,74 Impag Isononyl Isononanoate Dermol 99 10,16 Akzo International Hydrogenated Jojoba Oil Jojoba Butter LM 2,15 Desert Whale Hydrogenated Jojaba Oi Jojoba Butter HM 1,00 Desert Whale C30-45 Alkyl Methicone (and) C30-45 Olefin Dow Corning AMS-C30 Cosmetic Wax 1,15 Dow Corning Stearyl Dimethicone Dow Corning 2503 Cosmetic Wax 0,47 Dow Corning Cyclopentasiloxane (and) Polypropylsilsesquioxane Dow Corning 670 Fluid 5,00 Dow Corning Phase B Dimethicone / Vinyl Dimethicone Crosspolymer Dow Corning 9506 Powder 16,02 Dow Corning Silica Dimethyl Silylate Covasilic 15 0,17 LCW Talc Talc Powder 5,00 Sigma-Aldrich Effect pigment from example 4 3,00 Phase D Phenoxyethanol, Ethylhexylglycerin Euxyl PE 9010 0,40 Schülke & Mayr

[0273] The effect pigment from Example 4 can be used in a range of 0.1 to 8.0 wt.%, based on the total weight of the mousse formulation. The amount can be adjusted to 100 wt.% of the formulation using Dow Corning 9041 Elastomer.

[0274] Phase A was mixed and heated until completely melted. Phase B was weighed separately and mixed in a high-speed mixer for 60 seconds at 2400 rpm. Half of the molten phase A was added to phase B and mixed again in the mixer at 2400 rpm for 30 seconds. The remaining portion of phase B was then added to phase A and mixed again at 2400 rpm for 30 seconds. Finally, phase C was added to phase AB and mixed again at 2400 rpm for 30 seconds in the high-speed mixer. Application example 12: Nail polish

[0275] INCI Name Product name % by weight Manufacturer / Supplier Phase A Effect pigment from example 6 4,00 Phase B Butyl Acetate (and) Ethyl Acetate (and) Nitrocellulose (and) Isopropyl Alcohol International Lacquers Nail Polish Base 15244 96,00 International Lacquers

[0276] The effect pigment from Example 6 can be used in a range of 0.1 to 8.0 wt.%, based on the total weight of the nail polish formulation. The amount can be adjusted to 100 wt.% of the formulation using International Lacquers Nailpolish.

[0277] Phase A and Phase B were mixed and then filled into an appropriate container. Application example 13: Nail polish with "soft touch" effect

[0278] INCI Name Product name % by weight Manufacturer / Supplier Phase A Effect pigment from example 10 4,00 Polypropylene Synafil W 1234 5,00 Eckart Phase B Butyl Acetate (and) Ethyl Acetate (and) Nitrocellulose (and) Isopropyl Alcohol International Lacquers Nail Polish Base 15244 91,00 International Lacquers

[0279] The effect pigment from Example 10 can be used in a range of 0.1 to 8.0 wt.%, based on the total weight of the nail polish formulation. The balance to 100 wt.% of the formulation can be achieved with International Lacquers Nailpolish.

[0280] Phase A was mixed, added to Phase B and then the nail polish was filled into an appropriate container. Application example 14: water-based nail polish

[0281] The effect pigments from Examples 1 to 8 and from Example 10 can be used in an aqueous nail varnish according to WO 2007 / 115675 A2 Example 1. The pigmentation level is 0.1 to 10.0 wt. %, based on the total weight of the formulation. Application example 15: Liquid eye shadow

[0282] INCI Name Product name % by weight Manufacturer / Supplier Phase A Water Aqua 73,80 Glycerin Glycerin 3,00 H. Erhard Wagner Phase B PEG-800 Polyglycol 35000 S 0,60 Clariant Ammonium Acryloyldimethyltaurate / VP Copolymer Aristoflex AVC 0,80 Clariant Acrylates Copolymer Worlee Micromer CEK 20 / 50 5,00 Worlee Phase C Effect pigment from example 3 10,00 Divinyldimethicone / Dimethicone Copolymer C12-C13 Pareth-3, C12-C13 Pareth-23 Dow Corning HMW 2220 Non-Ionic Emulsion 6,00 Dow Corning Phenoxyethanol, Ethylhexylglycerin Euxyl PE9010 0,80 Schülke & Mayr

[0283] The effect pigment from Example 3 can be used in a range of 0.10 to 20.00 wt.%, based on the total weight of the eyeshadow formulation. The blend can be adjusted to 100 wt.% of the formulation with water.

[0284] Phase A was stirred, then the ingredients of Phase B were added individually to Phase A and stirred until a uniform consistency was achieved. The ingredients of Phase C were then added individually to Phase AB and stirred until a uniform consistency was achieved. Figure 1 : Scanning electron micrograph of an effect pigment according to the invention at 50,000x magnification (relative to Polaroid 545). Figure 2 : Scanning electron micrograph of an effect pigment according to the invention at 50,000x magnification (relative to Polaroid 545). Figure 3: Scanning electron micrograph of a cross-section of an effect pigment according to the invention at 20,000x magnification (relative to Polaroid 545). Figure 4 : Section of the scanning electron microscopic cross-section from Figure 2 with a baseline drawn at the interface between the non-metallic platelet-shaped substrate and the coating, and lines arranged perpendicular to the baseline. The intersection points at the interfaces are marked with "x." Figure 5 : Scanning electron micrograph of the titanium dioxide coated pearlescent pigment SYMIC C261 (ECKART GmbH) at 20,000x magnification (relative to Polaroid 545). Figure 6 : Schematic representation of the distance position. Figure 7 : Schematic representation of the position of the spacer layer. Figure 8 : Concentration profile (line scan) based on a cross-section in a scanning electron microscope with an energy dispersive micro-area analyzer (EDX) of Example 12 before calcination Figure 9 : Concentration profile (line scan) of a cross-section in a scanning electron microscope with an energy dispersive micro-area analyzer (EDX) of Example 12 after calcination.

Claims

1. Absorbent effect pigment comprising a nonmetallic substrate in platelet form and a coating applied to the substrate, wherein the coating includes a) optionally a layer 1, having an average layer thickness of less than 10 nm, comprising or consisting of tin oxide, tin hydroxide and / or tin oxide hydrate, b) a highly refractive layer 2 having a refractive index n > 1.8, comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, c) a highly refractive layer 3 having a refractive index n > 1.8, comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, at least one of layers 2 and 3 comprises at least two different metal ions and layers 2 and 3 are interrupted by a spacer layer, wherein the at least two different metal ions of layers 2 and 3 are selected from the group of metals consisting of Ti, Fe, Sn, Mn, Zr, Ca, Sr, Ba, Ni, Sb, Ag, Zn, Cu, Ce, Cr and Co, and wherein the proportion of non-colouring metal ions selected from the group of metals consisting of Ti, Sn, Zr, Ca, Sr, Ba and Zn totals ≤ 40% by weight, and the proportion of colouring metal ions selected from the group of metals consisting of Fe, Ti, Sn, Mn, Ni, Sb, Ag, Cu, Ce, Cr and Co totals ≥ 4% by weight, determined by means of XRF in each case, in each case calculated as elemental metal and based in each case on the total weight of the absorbent effect pigment according to the invention.

2. Absorbent effect pigment according to Claim 1, wherein the non-metallic substrate in platelet form is selected from the group consisting of natural mica platelets, synthetic mica platelets, mica iron, glass platelets, SiOz platelets, Al2O3 platelets, kaolin platelets, talc platelets, bismuth oxychloride platelets and mixtures thereof, and the non-metallic substrate in platelet form has optionally been coated with at least one metal oxide, metal hydroxide and / or metal oxide hydrate.

3. Absorbent effect pigment according to either of the preceding claims, wherein the effect pigment comprises further layers of high and / or low refractive index and optionally at least one further spacer layer.

4. Absorbent effect pigment according to any of the preceding claims, wherein the weight ratio, determined by XRF and calculated as elemental metal, of non-colouring metal ions to colouring metal ions in the absorbent effect pigment according to the invention is preferably < 20.

5. Absorbent effect pigment according to any of the preceding claims, wherein the at least one spacer layer is arranged essentially parallel to the surface of the non-metallic substrate in platelet form.

6. Absorbent effect pigment according to any of the preceding claims, wherein the at least one spacer layer has a mean height ha from a range of 5 nm to 120 nm.

7. Absorbent effect pigment according to any of the preceding claims, wherein the at least one spacer layer includes connections and cavities.

8. Absorbent effect pigment according to any of the preceding claims, wherein the at least one spacer layer has a network density of < 85%.

9. Process for producing the absorbent effect pigment according to any of Claims 1 to 8, wherein the process comprises the following steps: (i) optionally applying an uncalcined layer comprising or consisting of tin oxide, tin hydroxide and / or tin oxide hydrate to the nonmetallic substrate in platelet form, (ii) sequentially applying three uncalcined layers A, B and C each consisting of or comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, where layers A, B and C are arranged directly one on top of another and where the at least one metal oxide, metal hydroxide and / or metal oxide hydrate applied in the layer B, in relation to the metal ion, is different than the metal ion(s) of the metal oxides, metal hydroxides and / or metal oxide hydrates of layer A and layer C, wherein the three sequentially applied metal oxides, metal hydroxides and / or metal oxide hydrates for production of layers A, B and C do not comprise any metal ion selected from the group of the metals consisting of Si, Mg and Al, (iii) calcining the product obtained in step (ii) at a temperature from a range from 400°C to 1000°C to obtain the absorbent effect pigment comprising at least one spacer layer.

10. Process for producing the absorbent effect pigment according to any of Claims 1 to 8, wherein the process comprises the following steps: (i) sequentially applying two uncalcined layers B and C each consisting of or comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate to a calcined, singly or multiply coated nonmetallic substrate, where layers B and C are arranged directly one on top of another and where the at least one metal oxide, metal hydroxide and / or metal oxide hydrate applied in layer B, in relation to the metal ion, is different than the metal ion(s) of the metal oxide, metal hydroxide and / or metal oxide hydrate of layer C and of the layer which directly adjoins layer B in substrate direction, wherein the two sequentially applied metal oxides, metal hydroxides and / or metal oxide hydrates for production of layers B and C or do not comprise any metal ion selected from the group of the metals consisting of Si, Mg and Al, (ii) calcining the product obtained in step (i) at a temperature from a range from 400°C to 1000°C to obtain the absorbent effect pigment comprising at least one spacer layer.

11. Process according to either of Claims 9 and 10, wherein the metal ions present in layer B diffuse at least partly into layer A and / or layer C to form the at least one spacer layer in the calcined effect pigment.

12. Use of the absorbent effect pigment according to any of Claims 1 to 8 in cosmetic formulations, plastics, films, textiles, ceramic materials, glasses, paints, printing inks, writing inks, varnishes, powder coatings and / or in functional applications.

13. Article comprising at least one absorbent effect pigment according to any of Claims 1 to 8.