High-saturation and high-luminosity effect pigments, methods for producing them, and their use.

Abstract

To provide a high-chroma pigment having high gloss and high hiding power, which has high mechanical stability and high chemical stability and is simultaneously producible with low material input in a simple manner.SOLUTION: There is provided an 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 comprising or consisting of tin oxide, tin hydroxide and / or tin oxide hydrate; b) a layer 2 comprising at least one of metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion is at least one metal ion selected from the group of metals consisting of Ti, Fe, Sn, Mn, Zr, Ag, Zn, Cu, and Ce; and c) a layer 3 comprising at least one of metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion is at least one metal ion selected from Ti or the like.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a microplate-shaped nonmetallic substrate and a coating applied thereto, wherein the coating comprises an absorbent effect pigment including at least one spacer layer, as well as a process for producing the same and its use. [Background technology]

[0002] Multilayer pigments based on a microplate-shaped nonmetallic substrate and comprising at least one layer arrangement consisting of alternating high, low, and high refractive index layers are known from, for example, 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. For example, as described in EP 1 375 601 A1, EP 1 281 732 A1, EP 0 753 545 A2, and US 2004 / 0003758 A1, multilayer pigments can change their appearance depending on the viewing angle, depending on the optical thickness of the low refractive index layer. A common factor in all of the applications listed above is that their layer arrangement includes a low refractive index layer composed of a low refractive index metal oxide, such as silicon oxide.

[0003] Compared to single-layer effect pigments having only one identical first layer, and assuming the same substrate and particle size, multilayer pigments are characterized by higher gloss and, in some cases, higher saturation.

[0004] EP 1 029 900 A1 discloses (A) a mixture of TiO2 and Fe2O3 in a ratio of 10:1 to 1:3, and optionally a high refractive index imitation titanium plate coating consisting of one or more metal oxides in an amount of ≤20 wt% based on layer (A), (B) a colorless coating having a refractive index n ≤ 1.8, and optionally a pigment coated with an outer protective layer. This application does not provide any guidance regarding spacer layers within or between layers (A) and (B).

[0005] EP 1 230 308 A1 discloses a high refractive index coating comprising (A) a colorless coating having a refractive index n ≤ 1.8, (B) a mixture of TiO2 and Fe2O3 in a ratio of 1:0.1 to 1:5, and optionally a high refractive index coating consisting of ≤ 20 wt% of one or more metal oxides based on layer (B), and optionally (C) a pigment comprising at least two layer arrangements of outer protective layers. EP 1 230 308 A1 does not provide any guidance regarding spacer layers within or between layers (A) and (B).

[0006] EP 1 230 310 A1 discloses a pigment comprising a layered arrangement consisting of (A) a mixture of TiO2 and Fe2O3 in a ratio of 1:0.1 to 1:5, and optionally, a high refractive index coating consisting of one or more metal oxides in an amount of ≤20 wt% based on layer (A), (B) a colorless coating having a refractive index n ≤ 1.8, (C) a colorless coating having a refractive index n > 1.8, (D) an absorbent coating having a refractive index n > 1.8, and optionally, (E) an outer protective layer. EP 1 230 310 A1 does not describe spacer layers within or between the above layers.

[0007] WO 2014 / 094993 A1 discloses interference pigments based on a multilayer coated microplate-shaped substrate having a layer arrangement on the surface of the substrate comprising: (A0) optionally a layer composed of TiO2; (A) optionally a coating of a mixture of TiO2 and Fe2O3 which may be doped with one or more further oxides; (B) a layer composed of SnO2; (C) a high refractive index coating which absorbs in the visible wavelength range; and optionally (D) an outer protective layer. In layers (A) and / or (C), the mixing ratio of TiO2 to Fe2O3 is preferably 10:1 to 1:3. To increase the color intensity of layers (A) and / or (C), one or more oxides, such as Al2O3, Ce2O3, B2O3, ZrO2, and SnO2, may also be added to the TiO2 / Fe2O3 mixture. WO 2014 / 094993 A1 does not disclose spacer layers within or between the above layers.

[0008] CN 101289580 A describes the production of a gold pigment with strong interference colors that has the appearance of 24K gold. In this case, a mica substrate is suspended in water, and a solution of TiCl4 is added for the first coating layer, a solution of FeCl3 and TiCl4 for the second coating layer, a solution of SnO2 for the third coating layer, and a solution of TiCl4 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 does not include any guidelines regarding spacer layers in the coating.

[0009] EP 1 422 268 A2 discloses a multilayer pigment having two or more metal oxide layers, wherein at least one of the metals (ions) in the metal oxide layers is selected from the group consisting of cerium, tin, titanium, iron, zinc, and zirconium. The object of this application is a pigment having high saturation and high brightness, and having the minimum number of minimum-sized pores within its coating. According to EP 1 422 268 A2, a low pore volume ensures a coating with high visual quality.

[0010] US 2015 / 0344677 A1 relates to an effect pigment based on a coated substrate in the shape of a microplate. The coating comprises first and second layers of high refractive index, and a third component intended to be partially or 100% diffused into one or both of the high refractive index layers. The third component may be SiO2 or another metal oxide. The object of this application is to provide a D of 15 μm or less. 50 The objective is to obtain a coating with SiO2 without aggregation in the case of an effective pigment having [specific properties]. [Overview of the project] [Problems that the invention aims to solve]

[0011] The objective of the present invention was to provide a highly saturated pigment that has high gloss and high opacity, high mechanical stability and high chemical stability, and can be produced using a simple method with minimal material input. [Means for solving the problem]

[0012] The objective is to provide an absorbent pigment comprising a microplate-shaped nonmetallic substrate and a coating applied to the substrate, wherein the coating is a) Optionally, layer 1 containing or consisting of tin oxide, tin hydroxide, and / or tin oxide hydrate, b) Layer 2 comprising at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, c) comprising layer 3 containing at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, This is achieved by providing an absorbent pigment in which at least one of layers 2 and 3 contains at least two different metal ions, and layers 2 and 3 are blocked by a spacer layer. [Brief explanation of the drawing]

[0013] [Figure 1]This is a scanning electron microscope image of a cross-section of the effect pigment of the present invention at a magnification of 50,000x (based on Polaroid 545). [Figure 2] This is a scanning electron microscope image of a cross-section of the effect pigment of the present invention at a magnification of 50,000x (based on Polaroid 545). [Figure 3] This is a scanning electron microscope image of a cross-section of the effect pigment of the present invention at a magnification of 20,000x (based on Polaroid 545). [Figure 4] This is a detailed scanning electron microscope image of a cross-section from Figure 2, showing a baseline drawn on the interface between a microplate-shaped nonmetallic substrate and a coating, and lines positioned perpendicular to the baseline. The "×" marks the intersections at the interface. [Figure 5] This is a scanning electron microscope image of a cross-section of SYMIC C261 (manufactured by ECKART GmbH), a titanium dioxide-coated pearlescent pigment, at a magnification of 20,000x (based on Polaroid 545). [Figure 6] This is a schematic diagram of the spacer layer. [Figure 7] This is a schematic diagram of the spacer layer's position. [Figure 8] This is a concentration profile (line scan) using a cross-section of Example 12 before calcination, obtained with a scanning electron microscope equipped with an energy-dispersive trace analyzer (EDX). [Figure 9] This is a concentration profile (line scan) obtained using a cross-section of Example 12 after calcination, as measured by a scanning electron microscope equipped with an energy-dispersive trace analyzer (EDX). [Modes for carrying out the invention]

[0014] According to the present invention, "separated" means that layers 2 and 3 are spaced apart or kept apart from each other by a spacer layer.

[0015] What is meant by the general expression "metal oxides, metal hydroxides, and / or metal oxide hydrates" is, according to the present invention, "metal oxides and / or metal hydroxides and / or metal oxide hydrates." This also applies when the metal or metal ion is specified as, for example, titanium (ion), iron (ion), tin (ion), zirconium (ion), etc.

[0016] According to the present invention, the expression "metal ion" or "iron ion" means not a single metal ion or iron ion, but multiple metal ions or iron ions.

[0017] In one preferred embodiment, an optional layer 1 is directly adjacent to a microplate-shaped nonmetallic substrate, layer 2 immediately follows layer 1, and layer 3 follows layer 2, with layers 2 and 3 separated by a spacer layer.

[0018] In a further embodiment, layer 2 is directly adjacent to a microplate-shaped nonmetallic substrate, and layer 3 follows layer 2, with layers 2 and 3 separated by a spacer layer.

[0019] Preferred applications of absorbent pigments are shown in dependent claims 2 to 9.

[0020] The objective is, in addition, a process for producing the absorbent pigment of the present invention, wherein the process is (i) optionally, a non-calcined layer containing or consisting of tin oxide, tin hydroxide, and / or tin oxide hydrate is applied to a microplate-shaped non-metallic substrate; (ii) Three non-calcined layers A, B, and C are sequentially applied, each consisting of or containing at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, wherein layers A, B, and C are directly stacked on top of each other, and the at least one metal oxide, metal hydroxide, and / or metal oxide hydrate applied in layer B is different in respect to metal ions from the metal ions (may be multiple) of the metal oxides, metal hydroxides, and / or metal oxide hydrates in layers A and C. This is achieved by providing a process that includes (iii) calcining the product obtained in step (ii) at a temperature in the range of 600°C to 1000°C to obtain an absorbent effect pigment containing at least one spacer layer.

[0021] Alternatively, the objective is a process for producing the absorbent pigment of the present invention, wherein the process is (i) Two non-calcined layers B and C, each consisting of or containing at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, are sequentially applied to a calcined single-layer or multi-layer coated non-metallic substrate, wherein layers B and C are directly stacked on top of each other, and the at least one metal oxide, metal hydroxide, and / or metal oxide hydrate applied in layer B is different in respect to metal ions from the metal ions (may be multiple) of the metal oxide, metal hydroxide, and / or metal oxide hydrate in layers directly adjacent to layer B in the direction of layer C and the substrate. This is achieved by providing a process that includes (ii) calcining the product obtained in step (i) at a temperature in the range of 600°C to 1000°C to obtain an absorbent effect pigment containing at least one spacer layer.

[0022] The present invention further provides the use of the absorbent effect pigments of the present invention in cosmetic formulations, plastics, films, textiles, ceramic materials, glass, paints, printing inks, writing inks, varnishes, and powder coatings, and / or in functional applications for, for example, laser marking, IR reflection, and photocatalytic action.

[0023] In addition, the object on which the present invention is based is achieved by providing an article comprising at least one absorbent pigment of the present invention.

[0024] The microplate-shaped nonmetallic substrate to be coated may be selected from the group consisting of natural mica microplates, synthetic mica microplates, biotite microplates, glass microplates, iron oxide microplates, SiO2 microplates, Al2O3 microplates, kaolin microplates, talc microplates, and bismuth oxychloride microplates. According to the present invention, the absorbent effect pigment may be based on a mixture of the microplate-shaped nonmetallic substrates specified above. The above-mentioned microplate-shaped nonmetallic substrates may consist of at least one high and / or low refractive index metal oxide, metal hydroxide, and / or metal oxide hydrate, or may encompass one or more layers containing them. Therefore, for example, the substrate used may be a single-layer or multi-layer coated pearlescent pigment or interference pigment. In one preferred embodiment, the substrate used according to the present invention is an uncoated microplate-shaped nonmetallic substrate.

[0025] The microplate-shaped nonmetallic substrate is preferably selected from the group consisting of natural mica microplates, synthetic mica microplates, glass microplates, SiO2 microplates, Al2O3 microplates, and mixtures thereof. The microplate-shaped nonmetallic substrate is more preferably selected from the group consisting of natural mica microplates, synthetic mica microplates, glass microplates, and mixtures thereof. Very particularly preferred microplate-shaped nonmetallic substrates are synthetic mica microplates and / or glass microplates and mixtures thereof. Glass microplates are especially preferred as microplate-shaped nonmetallic substrates.

[0026] Glass microplates that can be used as substrates may, in terms of 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. Preferably, the glass microplates have the composition according to the teachings of EP 1 980 594 B1, in particular the main claims, and more preferably the teachings of EP 1 829 833 B1 or EP 2 042 474 B1, in particular the main claims of each respective document. Glass microplates that can be used as substrates are preferably produced by the process described in EP 289 240 B1.

[0027] In a further embodiment, glass microplates can be colored in a controlled manner during their production by adding at least one inorganic colorant. Suitable colorants are those that do not decompose at the individual melting temperatures of the glass composition. The proportion of the colorant is, here, based on the total weight of the glass composition in each case, preferably in the range of 0.1% to 50% by weight in total, more preferably in the range of 1% to 35% by weight in total, and most preferably in the range of 5% to 25% by weight in total. Suitable colorants are, in particular, elemental noble metals such as Au, Pd, or Pt, cations or complex anions of the elements Cu, Cr, Mn, Fe, Ti, and / or Co, and mixtures of the colorants listed above.

[0028] In a further embodiment, the refractive index of the glass microplate that can be used as a substrate is in the range of 1.45 to 1.80, preferably in the range of 1.50 to 1.70.

[0029] In a further embodiment, a microplate-shaped substrate, particularly a glass microplate, may be coated with a layer containing or composed of silicon dioxide, silicon hydroxide, or silicon dioxide hydrate. For example, when using a glass microplate, the above-described coating can protect the glass surface from chemical changes such as expansion, leaching of glass components, or dissolution in aggressive acid coating solutions.

[0030] Synthetic mica microsheets that can be used as a substrate may have a composition according to the main claims of CN 102718229 A or US 2014 / 0251184 A1. In addition, this can be produced according to the details on pages 3 to 4 of EP 0 723 997 A1.

[0031] The synthetic mica microplates that can be used as a substrate are preferably those of the formula KMg3AlSi3O, which, according to X-ray fluorescence analysis (XRF), preferably have the components specified in Table 1 as metal oxides within the ranges listed therein. 10 F2, KMg 2·1 / 2 (Si4O 10 )F2, or NaMg 2·1 / 2 (Si4O 10 )Fluorine fluorphlogopite of F2, in particular, formula KMg3AlSi3O 10 This is F2 fluorinated phlogopite.

[0032] [Table 1]

[0033] The average thickness of the micro-plate-shaped nonmetallic substrate to be coated is preferably in the range of 50 nm to 5000 nm, more preferably in the range of 60 nm to 3000 nm, and most preferably in the range of 70 nm to 2000 nm. Unless otherwise specified, the average thickness in this invention is understood to mean the arithmetic mean.

[0034] In one embodiment, the average thickness of the glass microplate as the microplate-shaped nonmetallic substrate to be coated is in the range of 750 nm to 1500 nm, preferably in the range of 850 nm to 1400 nm, and more preferably in the range of 900 nm to 1300 nm. The thinner the microplate-shaped substrate, the smaller the overall thickness of the absorbent effect pigment of the present invention. Therefore, glass microplates with an average thickness in the range of 50 nm to 700 nm, more preferably in the range of 101 nm to 600 nm, more preferably in the range of 160 nm to 500 nm, and most preferably in the range of 200 nm to 400 nm are also preferred as microplate-shaped nonmetallic substrates. In a further embodiment, the average thickness of the natural or synthetic mica microplate as the microplate-shaped nonmetallic substrate to be coated is preferably in the range of 80 nm to 1300 nm, more preferably in the range of 90 nm to 1000 nm, more preferably in the range of 99 nm to 800 nm, and most preferably in the range of 200 nm to 600 nm.

[0035] When microplate-shaped nonmetallic substrates are coated with a high refractive index metal oxide to an average thickness of less than 50 nm, they are easily broken, even during introduction into the respective application medium, resulting in extremely fragile pigments that lead to a significant decrease in gloss. Beyond an average substrate thickness of 5000 nm, the pigment can become too thick overall. This is accompanied by less favorable specific opacity (meaning a smaller coverage area per unit weight of the absorbent effect pigment of the present invention). Furthermore, such thick pigments exhibit a lower degree of orientation parallel to the substrate in the application medium. This less favorable orientation, in turn, leads to a decrease in gloss. Excessively thick effect pigments can also be disadvantageous in terms of tactile properties during application.

[0036] In one embodiment, the relative standard deviation of the thickness distribution of a microplate-shaped nonmetallic substrate is 15% to 100%, preferably 17% to 70%, more preferably 19% to 61%, and most preferably 21% to 41%. The relative standard deviation in [%] is the quotient of the calculated standard deviation and the average thickness.

[0037] The average thickness of the non-metallic substrate in the form of microplates is determined using the cured lacquer film, in which case, according to the details in the following Section IIk "Determination of the average thickness of the non-metallic substrate in the form of microplates, the average layer thicknesses of layers 2 and 3, the average layer thickness of the entire coating, the average height h of the spacer layer a , as well as the average height h of the cavity H of the determination", the absorbent effect pigments of the present invention are aligned essentially parallel to the plane of the substrate. For this purpose, the cross-section of the cured lacquer film is examined under a scanning electron microscope (SEM), and in this case, the thickness of the non-metallic substrate in the form of microplates is determined for at least 100 effect pigments and statistically averaged. In the present invention, the term "average" always means the arithmetic mean unless otherwise indicated.

[0038] Scanning electron microscope photographs were obtained using the cross-section of the absorbent effect pigments of the present invention with a Supra35 scanning electron microscope (manufactured by Zeiss).

[0039] The absorbent effect pigments of the present invention optionally include or consist of layer 1 containing tin oxide, tin hydroxide, and / or tin oxide hydrate. Layer 1 may optionally exist, at least in part, as a mixed layer with a layer directly adjacent to layer 1, for example, layer 2.

[0040] Layers 2 and 3 of the absorbent effect pigments of the present invention after calcination are preferably each a high refractive index layer, and the refractive index thereof is preferably n > 1.8, more preferably n ≥ 1.9, and most preferably n ≥ 2.1. In the present invention, the selection of 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 preferably each have an average refractive index of n > 1.8.

[0041] The at least one metal oxide, metal hydroxide, and / or metal oxide hydrate of layers 2 and 3 preferably contains 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; more preferably selected from the group of metals consisting of Ti, Fe, Sn, Mn, Zr, Ag, Zn, Cu, and Ce; even more preferably selected from the group of metals consisting of Ti, Fe, Sn, Ag, Zr, and Ce; more preferably selected from the group of metals consisting of Fe, Sn, Ag, Zr, and Ce; and most preferably selected from the group of metals consisting of Zr, Fe, and Sn. According to the present invention, the selection of at least two different metal ions is made such that the resulting effect pigment of the present invention is absorbent. In the context of the present invention, "absorbent effect pigment" means,

[0042]

number

[0043] The concealment index D is defined as q This is understood to mean that the opacity is ≥0.41, preferably ≥0.45, more preferably ≥0.50, and most preferably ≥0.55. The opacity index is determined here using a lacquer application on the black / white opacity chart (Byko-Chart 2853, Byk-Gardner) of a nitrocellulose lacquer (Erco 2615e bronze mixing lacquer colorless; manufactured by Maeder Plastiklack AG) mixed with 6 wt% of the specific effect pigment of the present invention, according to the details in Section IIc, “Comparison of Opacity.” *25 黒色 and L *25 白色 Here, the lightness values ​​are preferably measured using a BYK-mac multi-angle colorimeter manufactured by Byk-Gardner at a measurement angle of 25° on the black and white backgrounds of a black / white opacity chart.

[0044] The proportion of uncolored metal ions selected from the group of metals consisting of Ti, Sn, Zr, Ca, Sr, Ba, and Zn, determined by XRF in each case, calculated as elemental metals in each case, and based on the total weight of the absorbent effect pigment of the present invention in each case, is preferably ≤40 wt% in total, more preferably in the range of 0.1 wt% to 35 wt%, and more preferably in the range of 1 wt% to 24 wt%, and the proportion of colored metal ions selected from the group of metals consisting of Fe, Ti, Sn, Mn, Ni, Sb, Ag, Cu, Ce, Cr, and Co, is preferably ≥4 wt% in total, and more preferably in the range of 5 wt% to 80 wt%, and most preferably in the range of 20 wt% to 72 wt%. The weight ratio of uncolored metal ions to colored metal ions in the absorbent effect pigment of the present invention is preferably <20, more preferably <10, more preferably <1, and most preferably <0.8.

[0045] The colored metal ions from the group of metallic Ti and Sn are particularly related to Ti in oxidation state +3 or +2 and Sn in oxidation state +2.

[0046] Preferably, at least two different metal ions are homogeneously distributed in layers 2 and / or 3, or form a gradient therein. In exceptional cases, at least two different metal ions may be heterogeneously distributed in layers 2 and / or 3.

[0047] What is meant by "at least two different metal ions" is, according to the present invention, the presence of at least two metal ions of different elements, 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. Various metal ions may be present in layers 2 and / or 3 of the absorbent effect pigment of the present invention as mixtures of metal oxides and / or metal hydroxides and / or metal oxide hydrates, and / or otherwise as mixed oxides and / or mixed hydroxides and / or mixed oxide hydrates. Layers 2 and / or 3 may contain or consist of these mixtures 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.

[0048] Preferably, according to the present invention, when metal ions Ti and Fe are used, the iron ion-containing components in each layer are present in layer 2 and / or layer 3 of the calcined absorbent pigment of the present invention in the form of iron titanate, preferably in the form of imitation titanite and / or imitation rutile.

[0049] In one embodiment, one of the two layers 2 and 3 contains only one metal ion, preferably Fe, Ti, Sn, and Zr, more preferably selected from the group of metals consisting of Fe, Ti, and Sn. Correspondingly, the other layer of each of the two layers 3 and 2 contains at least two different metal ions, preferably Ti, Sn, Zr, and Fe, more preferably selected from the group of metals consisting of Ti, Sn, and Fe.

[0050] In a preferred embodiment, both layer 2 and layer 3 are composed of at least two metal ions selected from the group consisting of Ti, Sn, Zr, and Fe, more preferably Ti, Sn, and Fe, or contain at least one metal oxide, metal hydroxide, and / or metal oxide hydrate containing them.

[0051] In a further embodiment, layers 2 and 3, which are separated by the spacer layer, are substantially identical with respect to their respective compositions.

[0052] If the absorbent effect pigment of the present invention contains at least one colorable metal ion selected from the group of metals consisting of Fe, Ti, Sn, Mn, Cu, Cr, Co, Ag, and Ce, the proportion determined by XRF in each case and calculated as elemental metal in each case is preferably ≥4% by weight in total, more preferably in the range of 6% to 85% by weight in total, more preferably in the range of 8% to 79% by weight in total, and most preferably in the range of 10% to 76% by weight in total, based on the total weight of the absorbent effect pigment in each case.

[0053] In a preferred embodiment, at least one of layers 2 and 3 contains 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, determined in each case by XRF, and calculated in each case as an elemental metal, and the proportion of coloring metal ions selected from the group of metals consisting of Fe, Ti, Sn, Mn, Cu, Cr, Co, Ag, and Ce is preferably >4% by weight in total, based on the total weight of the absorbent effect pigment of the present invention.

[0054] In one particularly preferred embodiment, at least one of layers 2 and 3 comprises 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 include or are metal Ti and Fe, where the weight ratio of Ti to Fe, determined by XRF in each case and calculated as elemental metal in each case, is <15, preferably <10, more preferably <5, most preferably <1, and the percentage of Fe, determined by XRF and calculated as elemental metal, is preferably >4% by weight, based on the total weight of the absorbent effect pigments of the present invention.

[0055] In a particularly preferred embodiment, at least one of layers 2 and 3 comprises 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 include or are metal Fe and Sn, and the weight ratio of Fe to Sn, determined in each case by XRF and calculated in each case as an elemental metal, is preferably in the range of 1 to 80, more preferably in the range of 2 to 60, more preferably in the range of 3 to 50, and most preferably in the range of 4 to 40, and the proportion of Sn, determined by XRF and calculated as an elemental metal, is preferably selected in each case from the range of 1% to 25% by weight, more preferably in the range of 2% to 19% by weight, and more preferably in the range of 4% to 15% by weight, based on the total weight of the absorbent effect pigments of the present invention.

[0056] In a particularly preferred embodiment, at least one of layers 2 and 3 comprises 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 include or are metal Fe and Zr, and the weight ratio of Fe to Zr, determined in each case by XRF and calculated in each case as an elemental metal, is selected in each case from a range of 1 to 75, preferably 2 to 65, more preferably 4 to 48, and most preferably 8 to 36, based on the total weight of the absorbent effect pigments of the present invention.

[0057] The content of metal oxides, metal hydroxides, and / or metal oxide hydrates in the absorbent pigment of the present invention can be determined as each metal oxide by X-ray fluorescence analysis (XRF) and calculated as each elemental metal. For this purpose, the absorbent pigment is incorporated into a lithium tetraborate glass tablet, fixed in a solid sample measuring cup, and analyzed from there. The measuring instrument used was the Thermo Scientific Advantix ARL system.

[0058] The average thickness of layer 1 is preferably less than 10 nm, more preferably less than 5 nm, and most preferably less than 3 nm, in which case layer 1 completely or incompletely encloses a microplate-shaped nonmetallic substrate or optionally an existing coating.

[0059] The average layer thickness of layers 2 and 3 of the absorbent pigment of the present invention is preferably in the range of 30 nm to 350 nm, more preferably in the range of 35 nm to 310 nm, even more preferably in the range of 90 nm to 340 nm, more preferably in the range of 40 nm to 280 nm, and most preferably in the range of 50 nm to 210 nm.

[0060] In one preferred embodiment, the average thicknesses of layers 2 and 3 are substantially identical. "Substantially identical average thicknesses" means, according to the present invention, that the quotient of the average thickness of layer 2 and the average thickness of layer 3 is preferably in the range of 0.5 to 1.8, more preferably in the range of 0.7 to 1.6, more preferably in the range of 0.8 to 1.4, and most preferably in the range of 0.9 to 1.2.

[0061] In a further embodiment, when the compositions of layers 2 and 3 are materially different, their respective optical thicknesses are substantially the same, in which case the optical thicknesses of layers 2 and 3 may or may not conform to the known lambda / 4 rule. The optical thickness is defined as the product of the refractive index and the average thickness of each layer.

[0062] The average layer thickness of the entire coating of the absorbent pigment of the present invention is preferably ≤800 nm. The average layer thickness of the entire coating is preferably in the range of 45 nm to 650 nm, more preferably in the range of 65 nm to 530 nm, and most preferably in the range of 80 nm to 380 nm. "Entire coating" is understood to mean the entire coating starting from the substrate surface and extending perpendicularly in one direction from there.

[0063] In one embodiment, the relative standard deviation of the thickness distribution of layers 2 and 3 is 2% to 74%, preferably 3% to 63%, more preferably 4% to 57%, and most preferably 5% to 49%, and the relative standard deviation of the thickness distribution of the entire coating is 0.3% to 31%, preferably 1% to 27%, more preferably 1.2% to 24%, and most preferably 1.9% to 22%. The relative standard deviation in [%] is the quotient of the calculated standard deviation and the average thickness.

[0064] The spacer layer between layers 2 and 3 is preferably positioned essentially parallel to the surface of the microplate-shaped nonmetallic substrate. "Essentially parallel" in the context of this invention means that, in a scanning electron microscope image of the cross section, the regression line drawn through the spacer layer has a slope preferably close to zero with respect to the regression line drawn on the surface of the microplate-shaped nonmetallic substrate.

[0065] The position of the spacer layer within the overall coating can vary. For example, if the average thickness of layers 2 and 3 is virtually the same, and an optional layer 1 is preferably very thin, more preferably only a few atoms thick, the spacer layer is preferably located approximately in the center of the overall coating with respect to the optional layer 1, and even more so to the overall coating composed of layers 2 and 3. The spacer layer is preferably located between 1 / 6 and 6 / 6 of the overall coating with respect to the overall coating. Here, 1 / 6 refers to the proportion on the side of the microplate-shaped nonmetallic substrate, and 6 / 6 refers to the proportion of the overall coating on the opposite side of the microplate-shaped nonmetallic substrate (Figure 7).

[0066] The spacer layer formed between layers 2 and 3 preferably has a connecting portion, also called a spacer, that connects adjacent layers on both sides of the spacer layer on the one hand, and leaves them spaced apart on the other. As can be seen from the scanning electron microscope images of the cross section, this connecting portion or spacer may be positioned, for example, in the form of a bar or column, at an angle of about 90°, for example, 80° to 100°, with respect to the surface of the microplate-shaped nonmetallic substrate. However, it may represent any other angle between 5° and 175°. Preferably, the longitudinal axis of the spacer, in particular a bar, preferably a spacer, preferably a bar, is positioned at an angle in the range of 15° to 150°, more preferably 35° to 135°, with respect to the surface of the microplate-shaped nonmetallic substrate in each case. When determining the angle, the substrate surface forms a first arm. One of the outer sides of the bar in each case forms a second arm. The formed angle is determined starting from the apex of the angle between the two arms, and it is assumed that, when viewing the scanning electron microscope image of the cross section from above, 0° is placed to the left and 180° is placed to the right on the substrate surface.

[0067] The connectors or spacers may take on various geometric shapes and are preferably uniformly distributed across the entire spacer layer. For example, the connectors or spacers may take the form of a mesh, grid, ladder, sponge, or honeycomb. It is also possible to identify several structural elements similar to those in known photonic crystals or inverse photonic crystals from, for example, EP 2 371 908 A2, EP 1 546 063 A1, or EP 1 121 334 A1.

[0068] The connector or spacer comprises at least one metal oxide, metal hydroxide, and / or metal oxide hydrate. In a preferred embodiment, the connector or spacer comprises the same material composition as the layers on both sides of the spacer layer. Alternatively, a gradient may be formed within the connector or spacer between various metal oxides, metal hydroxides, and / or metal oxide hydrates.

[0069] In one preferred embodiment, the connector or spacer comprises a metal oxide, metal hydroxide, and / or metal oxide hydrate, wherein the metal ions in the metal oxide, metal hydroxide, and / or metal oxide hydrate comprise or are comprised of at least two metal ions selected from the group 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; more preferably from the group consisting of Ti, Fe, Sn, Zr, Ag, and Ce; and most preferably from the group consisting of Ti, Fe, and Sn.

[0070] The inventors hypothesize that the connectors or spacers may also contribute to the mechanical stabilization of the adjacent layers, and therefore of the absorbent effect pigment of the present invention. Perhaps, the number of connectors or spacers, the various angles and geometric shapes that the connectors or spacers may bring within the spacer layer, and their preferred uniform distribution across the entire spacer layer contribute to the formation of a mechanically very stable effect pigment. Adhesion between the entire coating and the microplate-shaped nonmetallic substrate is very good with the absorbent effect pigment of the present invention. The absorbent effect pigment of the present invention withstands extreme shear conditions, such as those occurring in the so-called Waring Blender test, without any detectable damage. The procedure for the Waring Blender test is described in Section IIf, “Waring Blender Test,” below.

[0071] In addition to its surprisingly good mechanical stability, the absorbent pigment of the present invention has excellent chemical stability, as described in detail in Section IIg "Determination of Chemical Stability" below.

[0072] The spacer layer of the absorbent pigment of the present invention preferably has an average height h in the range of 5 nm to 120 nm, more preferably 9 nm to 95 nm, even more preferably 16 nm to 76 nm, even more preferably 21 nm to 69 nm, more preferably 22 nm to 62 nm, and most preferably 26 nm to 56 nm. aIt has (Figure 6).

[0073] Average height h of the spacer layer a To determine the average layer thickness of layers 2 and 3, as well as the average layer thickness of the entire coating, the upper and lower substrate surfaces are established as baselines using a cross-sectional scanning electron microscope image. In the cross-sectional scanning electron microscope image, the upper and lower substrate surfaces represent, in each case, the longitudinal side of the microplate-shaped nonmetallic substrate. The baselines are drawn along the surface of the microplate-shaped nonmetallic substrate on the cross-sectional scanning electron microscope image. The cross-sectional scanning electron microscope images were analyzed using AxioVision 4.6.3. Image Processing Software (Zeiss). A sufficient number of parallel lines are drawn at 90° angles from these two baselines and at 50 nm intervals to create a grid on the effect pigment shown in the cross-sectional scanning electron microscope image (Figure 4). The magnification of the cross-sectional scanning electron microscope image is preferably at least 50,000x, based on a Polaroid 545 (4 inches × 5 inches). Starting from the baseline of each microplate-shaped nonmetallic substrate, manually analyze the intersections between parallel lines positioned perpendicular to each baseline in the direction of each outer layer 3 or each outermost layer, and the respective interfaces between any selected layer 1 and layer 2, layer 2 and the spacer layer, the spacer layer and layer 3, and layer 3 and the environment or possible further applied layers. In this case, one of the lines drawn at 50 nm intervals may be directly above a connection point or spacer. In this case, only the respective intersections at the interface between layer 3 and the environment or possible further applied layers are recorded.

[0074] From these measurements, by creating a difference, the layer thickness of layers 2 and 3, the overall layer thickness of the coating, the layer thickness of any additional layers present, and the height h of the spacer layer can be determined. aThe following is obtained. The thickness of layer 2 is calculated from the difference between the intersection measured at the interface between layer 2 and the spacer layer and the intersection measured at the interface between any selected layer 1 and layer 2 or the interface between the baseline and layer 2, provided that the microplate-shaped nonmetallic substrate has not been previously coated with any further layers. The thickness of layer 3 is calculated from the difference between the intersection measured between layer 3 and the environment or any further applied layer and the intersection measured between the spacer layer and layer 3. The total thickness of the coating is calculated from the difference between the intersection of layer 3 and the environment or any further applied layer and the environment and the respective baselines. Spacer layer height h a This is calculated from the difference between the intersection measured between the spacer layer and layer 3 and the intersection measured between layer 2 and the spacer layer. The thickness of any further applied layers can be determined similarly and taken into account when creating a difference.

[0075] Average layer thickness and average height h a To determine the values ​​shown above, the layer thickness and height h thus determined a The individual values ​​are used to form the respective arithmetic mean. To ensure statistical significance, the above measurements are performed on at least 100 parallel lines positioned perpendicular to the baseline.

[0076] height h ma refers to the center point of the spacer layer. It is the thickness of the optionally selected layer 1 and layer 2, as well as the height h of the spacer layer. a It is calculated as the sum of half of the values. The relative height h of the center point of the spacer layer. Rma is, h ma This arises from the ratio of the total layer thickness of the coating. The standard deviation of the relative height is σh. Rma The standard deviation of relative height σh is preferably in the range of 0.2% to 18%, more preferably in the range of 0.3% to 15%, more preferably in the range of 0.4% to 11%, and most preferably in the range of 0.5% to 8%. Rma This means that the spacer layer is positioned to a certain extent at a predetermined location parallel to the surface of the microplate-shaped nonmetallic substrate throughout the entire coating.

[0077] If the absorbent pigment of the present invention has at least one further spacer layer, its height h ma and the relative height h of the center point of at least one further spacer layer Rma This is confirmed by the above method using scanning electron microscope images of the cross section. The standard deviation of the relative height is σh. Rma The values ​​shown above also apply to additional spacer layers.

[0078] Those skilled in the art know that a pearlescent pigment coated with titanium dioxide has, for example, vacancies that are statistically distributed throughout the coating (Figure 5). This pearlescent pigment does not have a spacer layer. In contrast, the spacer layer and cavities within the spacer layer in the absorbent effect pigment of the present invention are not statistically distributed throughout the coating, but are arranged parallel to the surface of the microplate-shaped nonmetallic substrate throughout the coating. The distance from the substrate surface to the center point of the statistically distributed vacancies was also determined by scanning electron microscopy of the cross section using the method described above. For this purpose, a sufficient number of parallel lines were drawn at 90° angles to the upper and lower baselines corresponding to the two surfaces of the microplate-shaped substrate, at 50 nm intervals, to create a grid on the pearlescent pigment without a spacer layer as shown in the scanning electron microscopy of the cross section. If one of the parallel lines was over one or more vacancies, its height(s), the center point(s) of the vacancy(s), and the distance from the substrate surface to the center point(s) of the vacancy(s) were determined. The standard deviation can also be determined using the statistical distribution of void center points. In pearlescent pigments from the current art, i.e., pearlescent pigments without a spacer layer, the standard deviation of the distances of the statistically distributed void center points from the substrate surface is >20%. The standard deviation of the distances of the statistically distributed void center points from the substrate surface is therefore clearly different in its value from the standard deviation of the relative height of the spacer layer center points in the absorbent effect pigment of the present invention. Thus, the standard deviation of the distance from the substrate surface to the void center points in pearlescent pigments without a spacer layer can be compared to the standard deviation of the relative height of the spacer layer center points in the absorbent effect pigment of the present invention.

[0079] In addition, the network density in percentage is determined using the lines drawn at 50 nm intervals on the scanning electron microscope image, which are defined as the number of connections or spacers per micrometer and the number of connections or spacers per line.

[0080] If the absorbent pigment of the present invention has more than one spacer layer within the entire coating, the method described immediately above is applied accordingly to measure each individual layer and the spacer layer.

[0081] In one embodiment, the relative standard deviation of the height distribution of the spacer layer is 4% to 75%, preferably 7% to 69%, more preferably 9% to 63%, and most preferably 13% to 60%. The relative standard deviation of the height distribution in percentages is the quotient of the calculated standard deviation and the mean height.

[0082] In one preferred embodiment, the absorbent pigment of the present invention has a number of connectors or spacers within at least one spacer layer ranging from 0 to 11 per micrometer, more preferably from 0 to 9, more preferably from 1 to 7, and most preferably from 1 to 3.

[0083] In a preferred embodiment, the absorbent effect pigment of the present invention has a network density defined as the number of connections or spacers per line, defined as a percentage, within at least one spacer layer, in the range of <85%, preferably 1% to 75%, more preferably 1% to 63%, and most preferably 1% to 49%. Above a network density of 85%, in the context of the present invention, a high proportion of connections or spacers results in a substantially continuous coating and can no longer be called a spacer layer.

[0084] In a more preferred embodiment, the absorbent effect pigment of the present invention includes at least one spacer layer arranged essentially parallel to the surface of a microplate-shaped nonmetallic substrate, wherein the at least one spacer layer has an average height h in the range of 19 nm to 83 nm, more preferably 27 nm to 66 nm, and most preferably 33 nm to 57 nm. a It holds.

[0085] In one particularly preferred embodiment, the absorbent pigment of the present invention has an average height h in the range of 16 nm to 79 nm, preferably in the range of 21 nm to 66 nm, and most preferably in the range of 23 nm to 57 nm. a The device has at least one spacer layer, in which the number of connections or spacers per micrometer within the at least one spacer layer is selected from the range of 0 to 8, preferably 0 to 6, more preferably 1 to 5, and most preferably 1 to 4.

[0086] In addition to the aforementioned connectors or spacers, the spacer layer includes a cavity. This cavity is spatially separated by layers 2 and 3, as well as the connectors or spacers.

[0087] Energy-dispersive X-ray trace analysis (EDX analysis) of this cavity does not yield any conclusion as to whether the material is solid or liquid; therefore, the inventors infer, based on currently available analytical methods, that the cavity within the spacer layer contains gas, possibly air. In contrast, the connection or spacer contains at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, as detailed above.

[0088] The cavity within the spacer layer of the absorbent pigment of the present invention has an average height h in the range of 2 nm to 119 nm, preferably 6 nm to 105 nm, more preferably 11 nm to 85 nm, and most preferably 18 nm to 53 nm. H This can be shown. Height h H This is understood to mean the maximum difference between the bottom and top cavity boundaries. a Therefore, in the scanning electron microscope image of the cross section, parallel lines are drawn at a 90° angle to the surface of the microplate-shaped nonmetallic substrate at 50 nm intervals, as determined by the method described above. The difference between the two intersections of these lines with the upper and lower cavity boundaries is the height h H In this case as well, the above measurements are performed on at least 100 lines to ensure statistical significance. Therefore, the average height ha is the average height h H This is the maximum value. Therefore, some cavities may exist above and below the spacer layer.

[0089] Average height h of the spacer layer a and the average height h of the cavity H This is determined using a cured lacquer film, and in this case, Section IIk "Average thickness of microplate-shaped nonmetallic substrate, average layer thickness of layers 2 and 3, average layer thickness of the entire coating, average height h of the spacer layer" a , as well as the average height h of the cavity H In accordance with the details shown in "Decision of," the absorbent effect pigment of the present invention is aligned essentially parallel to the surface with respect to the substrate. For this purpose, h a As described above, the cross-section of the cured lacquer film is inspected under a scanning electron microscope (SEM). Apart from this cross-section, the absorbent effect pigment of the present invention can be cut by 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 to a point by an ion optical element and guided line by line on the effect pigment surface to be treated. Upon collision with the effect pigment surface, the ions radiate most of their energy, destroying the coating at this point, which results in line-by-line material removal. Furthermore, using the scanning electron microscope images recorded by the above method, the average height h a This allows for the determination of the average layer thickness of layers 2 and 3, as well as the average layer thickness of the entire coating. Furthermore, the average thickness of a microplate-shaped nonmetallic substrate can be determined using scanning electron microscope images of the effect pigment cut by the FIB method.

[0090] In a further embodiment, the absorbent effect pigment of the present invention includes a spacer layer distributed throughout the effect pigment, with a cavity area percentage in the range of 51% to 99%, preferably 63% to 96%, more preferably 76% to 95%, most preferably 84% to 94%, and a connection or spacer area percentage in the range of 1% to 49%, preferably 4% to 37%, more preferably 5% to 24%, most preferably 6% to 16%, as measured using a scanning electron microscope image of the cross section, within the spacer layer distributed throughout the effect pigment.

[0091] It is even more preferable that the total volume occupied by the connectors and spacers in the spacer layer is smaller than the total volume occupied by the cavity. Preferably, the total volume occupied by the connectors or spacers in the spacer layer is less than 50 volume%, more preferably less than 30 volume%, more preferably less than 20 volume%, and most preferably less than 10 volume% of the total volume occupied by the cavity.

[0092] In the absorbent pigments of the present invention, cavities within the spacer layer are clearly desirable, in contrast to the voids taught by EP 1 422 268 A2. EP 1 422 268 A2 requires a coating with low porosity and a minimum number of voids to obtain pigments with high saturation and high brightness. Pigments according to EP 1 422 268 A2 do not have a spacer layer. In the present invention, cavities that are not randomly distributed throughout the coating and are essentially parallel to the surface of the microplate-shaped nonmetallic substrate within the spacer layer do not have any detrimental effect on the optical properties of the absorbent pigments of the present invention. In contrast, the absorbent pigments of the present invention, compared to pigments with a single-layer coating, of course assuming the same microplate-shaped nonmetallic substrate, the same particle size, and the same first coating, are characterized by higher gloss and higher saturation. At the same time, different interference colors and / or different absorption colors can be obtained depending on the coating thickness and type of coating.

[0093] This higher gloss and higher saturation can be explained by the fact that the difference in refractive index between the spacer layer and the adjacent layer is maximized, which, according to Fresnel's law, results in maximum light reflection at these interfaces in each case. In the cavity, the basis used in this case is the refractive index of air, which is about 1. Light rays striking the spacer layer are partially reflected at its interface, and the intensity of each reflection according to Fresnel's law depends on the difference in refractive index from the spacer layer to the adjacent layer. Since such partial reflections occur at each individual interface, the total reflection also increases with the number of interfaces. Thus, in the absorbent effect pigment of the present invention, light rays are partially reflected multiple times, and this effect results in even stronger gloss and considerably stronger intensity of interference colors compared to conventional single-layer coated pigments. If the cavities are statistically distributed throughout the coating, i.e., not essentially parallel to the microplate-shaped nonmetallic substrate, the optical path lengths will vary throughout the coating. As a result, the interference conditions will not be sufficiently met, and therefore, neither amplification nor vanishing will be present.

[0094] The gloss of the absorbent pigment of the present invention is determined using a Byk-Gardner Micro-Tri-Gloss gloss meter with a white / black opacity card, according to the details shown in Section IId, “Gloss Measurement” below. The saturation of the absorbent pigment of the present invention is also determined using a BYK-mac multi-angle colorimeter (Byk-Gardner) with a white / black opacity card, according to the details shown in Section IIb, “Angle-Based Color Measurement” below. Further optical effects such as sparkle and granularity are determined according to the details shown in Section IIe, “Effect Measurement” below.

[0095] In one embodiment, the absorbent effect pigment of the present invention includes, in addition to the above layers 1, 2, and 3, further layers of high and / or low refractive index which may be located below any selected layer 1 or layer 2 and / or above layer 3 when observed from a microplate-shaped nonmetallic substrate. These further layers may contain metal oxides, metal hydroxides, or metal oxide hydrates, wherein the metal ions of the metal oxides, metal hydroxides, or metal oxide hydrates contain 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 more preferably selected from the group of metals consisting of Ti, Fe, and Sn. Furthermore, these additional layers may include translucent 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 respective alloys, and / or mixtures thereof. According to the present invention, the additional layers are selected such that the proportion of coloring metal ions selected from the group consisting of metals consisting of Fe, Ti, Sn, Mn, Cu, Cr, Co, Ag, and Ce, determined in each case by XRF analysis and calculated in each case as elemental metals, is preferably in the range of 5% to 82% in total, more preferably in the range of 7% to 72% in total, and most preferably in the range of 10% to 68% in total, based on the total weight of the absorbent effect pigments in each case. Furthermore, the proportion of at least one translucent metal determined by XRF is preferably ≥1% by weight in total, more preferably in the range of 2% to 20% by weight in total, and most preferably in the range of 3% to 12% by weight in total, based on the total weight of the absorbent effect pigment in each case. If the absorbent effect pigment of the present invention contains at least one coloring metal ion and at least one translucent metal, their proportion is preferably ≥5% by weight in total, based on the total weight of the absorbent effect pigment, regardless of whether they are in a microplate-shaped nonmetallic substrate or in a coating.

[0096] In one embodiment, each layer of the absorbent effect pigment of the present invention may be provided with a dopant, in which case the dopant may contain a metal oxide, a metal hydroxide, and / or a metal oxide hydrate, and the metal ion of the metal oxide, metal hydroxide, and / or metal oxide hydrate contains or is 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 the dopant is preferably ≤1% by weight in total, more preferably ≤0.5% by weight in total, and most preferably ≤0.2% by weight in total, based on the total weight of the absorbent effect pigment in each case.

[0097] In a further embodiment, the entire coating of the absorbent pigment of the present invention may include, in addition to the spacer layer, at least one further spacer layer between layers 2 and 3, also essentially parallel to the surface of a microplate-shaped nonmetallic substrate. Preferably, the absorbent pigment of the present invention has four or fewer spacer layers in the entire coating, as this degrades its optical quality. According to the present invention, even when the absorbent pigment of the present invention contains more than one spacer layer, with respect to the entire coating, spacer layers are absent in either 1 / 6 or 6 / 6 of the entire coating.

[0098] The absorbent pigment of the present invention has an arbitrary median particle size D 50 The D of the absorbent pigment of the present invention may have 50 The value is preferably in the range of 3 μm to 350 μm. Preferably, the absorbent pigment D of the present invention 50 The value is in the range of 4 μm to 211 μm, more preferably in the range of 6 μm to 147 μm, more preferably in the range of 7 μm to 99 μm, and most preferably in the range of 8 μm to 56 μm. Most preferably, the absorbent effect pigment of the present invention is in the range of 3 μm to 15 μm, or 10 μm to 35 μm, or 25 μm to 45 μm, or 30 μm to 65 μm, or 40 μm to 140 μm, or 135 μm to 250 μm.50 The present invention has D of the absorbent effect pigment. 10 The value preferably includes a range of 1 μm to 120 μm. More preferably, the D of the absorbent pigment of the present invention. 10 The values ​​are within the range of 1 μm to 5 μm, or 5 μm to 25 μm, or 10 μm to 30 μm, or 20 μm to 45 μm, or 25 μm to 65 μm, or 75 to 110 μm. D of the absorbent effect pigment of the present invention 90 The value preferably includes a range of 6 μm to 500 μm. More preferably, the D of the absorbent effect pigment of the present invention. 90 The values ​​are within the range of 8 μm to 250 μm, or 10 μm to 150 μm, or 40 μm to 70 μm, or 68 μm to 110 μm, or 120 μm to 180 μm, or 400 μm to 490 μm.

[0099] The cumulative frequency distribution of the volume-averaged size distribution function obtained by laser diffraction is D 10 , D 50 , and D 90 This indicates that 10%, 50%, and 90% of the analyzed effect pigments have a volume-average diameter less than or equal to the value indicated in each case. In this context, the size distribution curve of the absorbent effect pigment of the present invention is determined using a Malvern Mastersizer 2000 instrument according to the manufacturer's instructions. The scattered light signal is evaluated by Fraunhofer theory, which also includes the diffraction and absorption properties of the particles.

[0100] In one preferred embodiment, the absorbent pigment of the present invention has a range of 0.7 to 2.0, preferably 0.7 to 1.5, more preferably 0.8 to 1.3, more preferably 0.8 to 1.2, and most preferably 0.85 to 1.1.

[0101]

number

[0102] It has a span ΔD defined as follows. The advantages of the narrow size division with respect to the color purity and / or gloss of the resulting effect pigment 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, and EP 2 367 889 A1.

[0103] The absorbent pigment of the present invention can be produced as follows: At a temperature in the range of -50°C to 100°C, a micro-plate-shaped non-metallic substrate is suspended in water. -Optionally, by adding a water-soluble tin salt along with the simultaneous addition of an inorganic alkali, a non-calcined layer containing or consisting of tin oxide, tin hydroxide, and / or tin oxide hydrate may be applied. -In each case, three non-calcined layers A, B, and C are sequentially provided in the form of metal oxides, metal hydroxides, and / or metal oxide hydrates by sequentially adding three water-soluble metal salts along with the simultaneous addition of an inorganic alkali, wherein the second water-soluble metal salt (for generating layer B) differs from the other two water-soluble metal salts for generating layers A and C with respect to metal ions, - Separate the coated substrate from the coating solution(s), optionally wash the coated substrate and / or optionally dry it. A substrate coated at a temperature in the range of -600°C to 1100°C, preferably in the range of 625°C to 930°C, more preferably in the range of 750°C to 890°C, is calcined to obtain the absorbent pigment of the present invention, which includes at least one spacer layer.

[0104] In one preferred embodiment, the absorbent pigment of the present invention is produced by the process described above.

[0105] The application, preferably deposition, of each metal oxide, metal hydroxide, and / or metal oxide hydrate is preferably carried out at a constant pH within the range of pH 1.4 to 10.0, depending on the metal salt.

[0106] In addition to the preferably deposited metal oxides, metal hydroxides, and / or metal oxide hydrates, which are applied in at least three sequential steps, further layers may, of course, be placed below or above the layer array [any choice of layer 1 / layer 2 / spacer layer / layer 3] by applying additional metal oxides, metal hydroxides, and / or metal oxide hydrates before and / or after.

[0107] During the calcination process, metal ions present in layer B unexpectedly diffuse into layer A and / or layer C, forming 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. The diffusion of metal ions from layer B to layer A and / or layer C during the calcination process forms layers 2 and 3 of the present invention, as well as the spacer layer between them, in which at least one of the two layers 2 and 3 contains at least two different metal ions. Thus, from the originally three sequentially deposited layers A, B, and C, layers 2 and 3, as well as the spacer layer between them, are obtained during the calcination process, in which at least one of the two layers 2 and 3 contains at least two different metal ions.

[0108] It is hypothesized that the differing mobilities of metal oxides, metal hydroxides, and / or metal oxide hydrates relative to each other during the calcination process are one of the factors responsible for the formation of the spacer layer. In this context, it is hypothesized that the mobility of metal ions present in layer B competes with the mobility of metal ions present in layers A and / or C, causing metal ions to diffuse from layer B to at least one of the adjacent layers A and / or C, and metal ions to diffuse from at least one of layers A and / or C to layer B. Currently, the inventors hypothesize that whether the mobility of metal ions present in layer B during calcination is higher than the mobility of metal ions present in layers A and / or C is one possible explanation for the formation of the spacer layer. Furthermore, it is hypothesized that a concentration gradient for metal ions promotes the formation of the spacer layer, i.e., more mobile metal ions can diffuse from layer B to one of the adjacent layers A and / or C rather than in the reverse direction. In summary, the formation of spacer layers has been found to be brought about during calcination by a complex interaction of various other factors, such as entropy and / or enthalpy effects, although this has not yet been fully elucidated. The above considerations also apply correspondingly to the formation of at least one additional spacer layer.

[0109] In one preferred embodiment, the first and third preferably deposited metal oxides, metal hydroxides, and / or metal oxide hydrates, which are applied in three sequence, contain at least one metal ion selected from the group of metals consisting of Fe, Ti, and Sn. After application, the first and third metal oxides, metal hydroxides, and / or metal oxide hydrates generate layers A and C, respectively. The second preferably deposited metal oxides, metal hydroxides, and / or metal oxide hydrates, which are applied in three sequence, generate layer B and contain 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 in the metal oxides, metal hydroxides, and / or metal oxide hydrates deposited to generate layers A and C. In layers A and C, the applied, preferably deposited metal oxides, metal hydroxides, and / or metal oxide hydrates may be identical or different with respect to the metal ion(s).

[0110] Alternatively, the absorbent pigment of the present invention can be produced as follows: A single-layer or multi-layer coated micro-plate-shaped non-metallic substrate, which has been calcined at a temperature in the range of -50°C to 100°C, is suspended in water. -In each case, two non-calcined layers B and C are sequentially applied in the form of metal oxides, metal hydroxides, and / or metal oxide hydrates by sequentially adding two water-soluble metal salts along with the simultaneous addition of an inorganic alkali, wherein the first water-soluble metal salt (for generating layer B) differs from the other water-soluble metal salts for generating layers directly adjacent to layer B in the direction of layer C and the substrate, with respect to metal ions. - Separate the coated substrate from the coating solution(s), optionally wash the coated substrate and / or optionally dry it. A substrate coated at a temperature in the range of -600°C to 1100°C, preferably in the range of 625°C to 930°C, more preferably in the range of 750°C to 890°C, is calcined to obtain the absorbent pigment of the present invention, which includes at least one spacer layer.

[0111] In this case as well, the application, preferably deposition, of each metal oxide, metal hydroxide, and / or metal oxide hydrate is preferably carried out at a constant pH within the range of pH 1.4 to 10.0, depending on the metal salt.

[0112] During the calcination process, it is presumed that metal ions present in layer B diffuse to at least layer C, forming a mixture of 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. Through the diffusion of metal ions from layer B to layer C, calcination forms layer 3 and the spacer layer of the present invention. Thus, from the originally two sequentially deposited layers B and C, layer 3 and the spacer layer are obtained during the calcination process, in which at least layer 3 contains at least two different metal ions. Layer 2 is already present in this case. Layer 2 refers to the outermost layer of a calcined single-layer or multi-layer coated microplate-shaped nonmetallic substrate used as the starting material.

[0113] Cross-sectional concentration profiles (line scans) obtained using a scanning electron microscope equipped with an energy-dispersive trace analyzer (EDX) show significant position-dependent changes in the chemical composition of the coating before and after calcination (Figures 8 and 9).

[0114] Figure 8 shows the concentration profiles of Example 12 after coating and drying, but before calcination. Using the concentration curves for Ti and Fe, the maximum values ​​for the Ti-containing layer and the Fe-containing layer, respectively, can be determined. In contrast, the oxygen concentration curve has a substantially uniform distribution without any recognizable minimum or maximum values.

[0115] Similarly, Figure 9 shows the concentration profile of Example 12 after coating and drying, but after calcination. It can be seen that the maximum Fe value present in Figure 9 is decreased and shifted. Fe ions are diffusing into the surrounding Ti-containing layer. In addition, it should be emphasized that there is a prominent minimum in the oxygen concentration curve, which clearly indicates the location of the spacer layer. At the same location, corresponding minimums are present in the Ti and Fe concentration curves.

[0116] In one particularly preferred embodiment, the layers B and C, or the two or three metal oxides, metal hydroxides, and / or metal oxide hydrates that are preferably deposited sequentially to form A, B, and C, do not contain any metal ions selected from the group of metals consisting of Si, Mg, and Al.

[0117] In the case of sequential application of two non-calcined layers B and C to a substrate that is already coated and optionally calcined, the layer to which layer B is applied contains, in this invention, a high refractive index metal oxide, metal hydroxide, and / or metal oxide hydrate. In the case of sequential application of three non-calcined layers A, B, and C to a substrate that is already coated and optionally calcined, the layer to which layer A is applied may contain, in this invention, a high or low refractive index metal oxide, metal hydroxide, and / or metal oxide hydrate.

[0118] The above findings will be explained in detail below with reference to various coatings. For example, when water-soluble titanium(IV) salt, water-soluble iron(III) salt, and again water-soluble titanium(IV) salt are successively applied to a suspension of optionally coated microplate-shaped nonmetallic substrates, the calcination, when observed in an SEM cross-section starting from the substrate, will optionally result in a layer 2 containing metal oxides, metal hydroxides, and / or metal oxide hydrates (in which case the metal ions of the metal oxides, metal hydroxides, and / or metal oxide hydrates include or are titanium ions and / or iron ions), a spacer layer, and a layer 3 containing metal oxides, metal hydroxides, and / or metal oxide hydrates (in which case the metal ions of the metal oxides, metal hydroxides, and / or metal oxide hydrates include or are titanium ions and / or iron ions). At least one of the layers containing metal oxides, metal hydroxides, and / or metal oxide hydrates (where the metal ions in the metal oxides, metal hydroxides, and / or metal oxide hydrates include or are titanium ions and / or iron ions) contains iron titanate, preferably tartanite and / or rutile. The above findings regarding coloring and non-coloring metal ions may also apply in this case regarding the amount used.

[0119] For example, if a water-soluble titanium(IV) salt is added to a suspension of optionally coated microplate-shaped nonmetallic substrates, and after deposition of titanium dioxide, titanium hydroxide, and / or titanium oxide hydrates, the substrate is calcined, and the product is resuspended after calcination, and water-soluble iron(III) salt and water-soluble tin(IV) salt are successively added, further calcination, when observed in an SEM cross-section starting from the substrate, yields optionally an already present coating, and a layer 2 containing metal oxides, metal hydroxides, and / or metal oxide hydrates (where the metal ions in the metal oxides, metal hydroxides, and / or metal oxide hydrates are titanium ions or are titanium ions), followed by a spacer layer, and a layer 3 containing metal oxides, metal hydroxides, and / or metal oxide hydrates (where the metal ions in the metal oxides, metal hydroxides, and / or metal oxide hydrates are iron ions and / or tin ions or are iron ions and / or tin ions).

[0120] If the absorbent pigment of the present invention includes a further layer containing metal oxides, metal hydroxides, and / or metal oxide hydrates in addition to preferably deposited metal oxides, metal hydroxides, and / or metal oxide hydrates, which are applied in order of at least two or three types, a further spacer layer may be formed within the further layer, provided that the above process steps for the preferably deposited metal oxides, metal hydroxides, and / or metal oxide hydrates, which are applied in order of at least two or three types, are followed.

[0121] In one embodiment, calcination is carried out under reducing conditions, preferably in the presence of a foaming gas (N2 / H2). Calcination under reducing conditions results in a lower brightness value L than calcination in air. * This may be related.

[0122] The absorbent pigment of the present invention may optionally be provided with at least one outer protective layer that further increases climatic stability and / or chemical stability and / or further decreases photoactivity. UV stability and condensation water stability were determined according to the details shown in sections IIj "UV Resistance" and IIi "Condensation Water Test" below.

[0123] The optionally present protective layer comprises metal oxides, metal hydroxides, and / or metal oxide hydrates, and the 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 metallic Si, Ce, Al, Zr, and mixtures thereof. In this context, the proportion of the optionally present protective layer is preferably in the range of 0.1% to 7.0% by weight, more preferably in the range of 0.2% to 5.2% by weight, and most preferably in the range of 0.3% to 3.1% by weight, based on the total weight of the absorbent effect pigments of the present invention in each case. In addition, the optionally present protective layer may be surface-modified, for example, with a silane. The silane does not have to have functional bonding groups, or it may have one or more functional bonding groups. A silane having at least one functional bonding group is also referred to below as an organically functional silane.

[0124] For example, one or more types of silanes may be applied to this outermost protective layer. The silane may be an alkylsilane having a branched or unbranched alkyl radical having 1 to 24 carbon atoms, preferably 6 to 18 carbon atoms.

[0125] In a more preferred embodiment, the silane that does not contain a functional bonding group is an alkylsilane. The alkylsilane is preferably of the formula R (4-z) Si(X) zThe formula is as follows: 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 is a halogen and / or alkoxy group. Alkylsilanes having an alkyl chain having at least 12 carbon atoms are preferred. R may be cyclically bonded to Si, in which case z is usually 2.

[0126] In a further embodiment, at least one organically functionalized silane can be used for surface modification, enabling chemical bonding to plastics or binders of lacquers or paints. These groups of the organically functionalized silane may also be referred to as coupling groups or functional bonding groups, and are preferably selected from the group consisting of hydroxyl, amino, acryloyl, methacryloyl, vinyl, epoxy, isocyanate, cyano, and mixtures thereof.

[0127] Organofunctional silanes with suitable functional groups, which are preferable for use as surface modifiers, are commercially available, for example, produced by Evonik and sold under the trade name "Dynasylan". Further products can be purchased from Momentive (Silquest silanes) or Wacker, for example, standard silanes and α-silanes from the GENIOSIL product line. These examples include 3-methacryloyloxypropyltrimethoxysilane (Dynasylan MEMO, Silquest A-174NT), vinyltri(me)ethoxysilane (Dynasylan VTMO and VTEO, Silquest A-151 and A-171), methyltri(me)ethoxysilane (Dynasylan MTMS and MTES), 3-mercaptopropyltrimethoxysilane (Dynasylan MTMO; Silquest A-189), 3-glycidooxypropyltrimethoxysilane (Dynasylan GLYMO, Silquest A-187), tris[3-(trimethoxysilyl)propyl]isocyanurate (Silquest Y-11597), bis[3-(triethoxysilyl)propyl]tetrasulfide (Silquest A-1289), and bis[3-(triethoxysilyl)propyl disulfide (Silquest A-1589), Beta-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane (Silquest A-186), Bis(triethoxysilyl)ethane (Silquest Y-9805), Gamma-Isocyanatopropyltrimethoxysilane (Silquest A-Link 35, GENIOSIL GF 40), Methacryloyloxymethyltri(me)ethoxysilane (GENIOSIL XL 33, XL 36), (Methacryloyloxymethyl)(me)ethyldimethoxysilane (GENIOSIL XL 32, XL 34), (Isocyanatomethyl)methyldimethoxysilane, (Isocyanatomethyl)trimethoxysilane, 3-(triethoxysilyl)propylsuccinic anhydride (GENIOSIL GF20) (methacryloyloxymethyl)methyldiethoxysilane, 2-acryloyloxyethylmethyldimethoxysilane, 2-methacryloyloxyethyltrimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltripropoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltriacetoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane (GENIOSIL XL 10), vinyltris(2-methoxyethoxy)silane (GENIOSIL GF 58), vinyltriacetoxysilane, or mixtures thereof. 3-Methacryloyloxypropyltrimethoxysilane (Dynasylan MEMO, Silquest A-174NT), vinyltri(me)ethoxysilane (Dynasylan VTMO and VTEO, Silquest A-151 and A-171), methyltri(me)ethoxysilane (Dynasylan MTMS and MTES), beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Silquest A-186), bis(triethoxysilyl)ethane (Silquest Y-9805), gamma-isocyanatopropyltrimethoxysilane (Silquest A-Link 35, GENIOSIL GF 40), methacryloyloxymethyltri(me)ethoxysilane (GENIOSIL XL 33, XL 36), (methacryloyloxymethyl)(me)ethyldimethoxysilane (GENIOSIL XL 32, XL 36) 34) 3-(triethoxysilyl)propyl succinic anhydride (GENIOSIL GF 20), vinyltrimethoxysilane (GENIOSIL XL 10), and / or vinyltris(2-methoxyethoxy)silane (GENIOSIL GFPreferably, 58) is used as an organic functional silane. Other organic functional silanes may also be applied to the particles or pigments of the present invention. In addition, aqueous pre-hydrolyzed products commercially available from Degussa, for example, may be used. These include aqueous aminosiloxanes (Dynasylan Hydrosil 1151), aqueous amino / alkyl functional siloxanes (Dynasylan Hydrosil 2627 or 2909), aqueous diamino functional siloxanes (Dynasylan Hydrosil 2776), aqueous epoxy functional siloxanes (Dynasylan Hydrosil 2926), amino / alkyl functional oligosiloxanes (Dynasylan 1146), vinyl / alkyl functional oligosiloxanes (Dynasylan 6598), oligomeric vinylsilanes (Dynasylan 6490), or oligomeric short-chain alkyl functional silanes (Dynasylan 9896). In a preferred embodiment, the organic functionalized silane mixture comprises at least one amino-functionalized silane in addition to at least one silane without functionalized groups. The amino functional group is a functional group that can engage in one or more chemical interactions with most groups present in the binder. These may include, for example, covalent bonding with isocyanate or carboxylate functional groups of the binder, or hydrogen bonding with OH or COOR functional groups, or other ionic interactions. Therefore, amino functional groups are very well suited for the purpose of chemically bonding pigments to various types of binders.

[0128] For this purpose, the following compounds are preferable: 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, triamino-functional 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-cyclohexylaminomethyltriethoxysilane (GENIOSIL XL 926), N-(phenylaminomethyl)trimethoxysilane (GENIOSIL XL 973), or mixtures thereof.

[0129] In a preferred embodiment, the optionally present protective layer has the composition disclosed in the main claims of WO 2006 / 021386 A1, WO 2012 / 130897 A1, or WO 2014 / 053454 A1, respectively.

[0130] In addition, the absorbent effect pigment of the present invention can be given surface modifications that facilitate the introduction of the effect pigment into various media, for example. When the absorbent effect pigment of the present invention is used, for example, in a powder coating, the effect pigment preferably has 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 pigment of the present invention may have an outermost coating according to claim 32 of WO 2006 / 136435 A2, which is preferably applied by a spray drying method according to claim 1 of WO 2006 / 136435 A2.

[0131] When the absorbent pigment of the present invention is used in cosmetic formulations, for example, its incorporation into O / W, W / O, or W / Si emulsion systems can be facilitated by, for example, hydrophobic surface coating with triethoxycaprylylsilane, thereby achieving longer-lasting emulsion stability.

[0132] The absorbent pigment of the present invention may also be used in mixtures with transparent and / or opaque inorganic or organic white, colored, or black pigments, and / or metallic pigments, and / or pearlescent pigments, and / or fillers, in each case for the desired application. The amount of absorbent pigment of the present invention used depends on the specific application and the optical effect to be achieved.

[0133] The absorbent pigments of the present invention can be used in cosmetic formulations, plastics, films, textiles, ceramic materials, glass, paints, printing inks, writing inks, lacquers, and powder coatings. In addition, the absorbent pigments of the present invention can also be used for functional applications, such as laser marking, greenhouse films, or agricultural films.

[0134] In cosmetic formulations, such as body powders, face powders, pressed or loose powders, powder creams, eye makeup, such as eyeshadows, mascaras, eyeliners, liquid eyeliners, eyebrow pencils, lip balms, lipsticks, lip glosses, lip liners, hair styling compositions, such as hair sprays, hair mousses, hair gels, hair waxes, hair mascaras, permanent or semi-permanent hair dyes, temporary hair dyes, and skincare compositions, such as lotions, gels, emulsions, and nail polish compositions, the absorbent pigments of the present invention can be mixed with raw materials, auxiliaries, and active ingredients suitable for the specific application. The total concentration of the absorbent pigments of the present invention in a cosmetic formulation may range from 0.001% by weight in rinse-off products to 40.0% by weight in leave-on products, based on the total weight of the formulation in each case.

[0135] In a further embodiment, the absorbent effect pigment of the present invention may be in the form of compressed particles. The compressed particle form is understood to mean pellets, preferably in the form of cylinders and / or beads. Here, the cylinders preferably have a diameter in the range of 0.2 cm to 4.2 cm, more preferably in the range of 0.5 cm to 2.3 cm, most preferably in the range of 0.7 cm to 1.7 cm, and a length preferably in the range of 0.2 cm to 7.1 cm, more preferably in the range of 0.6 cm to 5.3 cm, most preferably in the range of 0.8 cm to 3.7 cm. The beads preferably have a radius of ≤1 cm, more preferably in the range of 0.2 cm to 0.7 cm, most preferably in the range of 0.3 cm to 0.5 cm.

[0136] In a further embodiment, the present invention relates to an absorbent effect pigment comprising a microplate-shaped nonmetallic substrate, preferably a synthetic mica microplate or a glass microplate, and a coating applied thereto, wherein the coating is a) Optionally, layer 1 containing or consisting of tin oxide, tin hydroxide, and / or tin oxide hydrate, b) Layer 2 comprises at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, wherein the metal ion comprises or is selected from the group of metals consisting of Ti, Sn, and Fe. c) Layer 3 comprises at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, wherein the metal ion comprises or is selected from the group of metals consisting of Ti, Sn, Ce, and Fe. In this case, at least one of layers 2 and 3 contains at least two different metal ions from the group listed above, and in each case the proportion of coloring metal ions determined by XRF and calculated as elemental metals in each case is in the range of 7.5% to 75% by weight based on the total weight of the effect pigment, and layers 2 and 3 have an average height h in the range of 10 nm to 66 nm. a , relative height h Rma This relates to absorbent pigments that are blocked by a spacer layer having a standard deviation in the range of 0.2% to 11% and a network density in the range of 1% to 79%.

[0137] In a further embodiment, the present invention relates to an absorbent effect pigment comprising a microplate-shaped nonmetallic substrate, preferably a synthetic mica microplate or a glass microplate, and a coating applied thereto, wherein the coating is a) Optionally, layer 1 containing or consisting of tin oxide, tin hydroxide, and / or tin oxide hydrate, b) 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 uncolored metal ion selected from the group consisting of metals Fe, Ti, Sn, and Zr. c) Layer 3 comprises at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, wherein the metal ion comprises or is at least one uncolored metal ion selected from the group consisting of metals Fe, Ti, Sn, and Zr. Furthermore, at least one of layers 2 and 3 contains at least two different metal ions from the group enumerated above, and layers 2 and 3 are separated by a spacer layer, wherein the effect pigment is an absorbent effect pigment having a span ΔD in the range of 0.8 to 1.9.

[0138] In one preferred embodiment, the present invention relates to an absorbent effect pigment comprising a microplate-shaped nonmetallic substrate, preferably a synthetic mica microplate or a glass microplate, and a coating applied thereto, wherein the coating is a) Optionally, layer 1 containing or consisting of tin oxide, tin hydroxide, and / or tin oxide hydrate, b) Layer 2 comprising at least one metal ion selected from the group of metals consisting of Ti, Fe, Sn, and Zr, or at least one metal oxide, metal hydroxide, and / or metal oxide hydrate containing them, c) A layer 3 comprising at least one metal ion selected from the group of metals consisting of Ti, Fe, Sn, and Zr, or at least one metal oxide, metal hydroxide, and / or metal oxide hydrate containing them, Furthermore, the present invention relates to an absorbent effect pigment having chemical resistance at dE <3, preferably <2, where at least one of layers 2 and 3 contains at least two different metal ions from the group listed above, wherein the proportion of the coloring metal ions determined by XRF in each case and calculated as elemental metals in each case is in the range of 4.0% to 79% by weight, preferably 5.0% to 72% by weight, based on the total weight of the effect pigment in each case, wherein layers 2 and 3 are separated by a spacer layer, and the effect pigment is an absorbent effect pigment having chemical resistance at dE <3, preferably <2.

[0139] In one particularly preferred embodiment, the present invention provides an absorbent effect pigment comprising a microplate-shaped nonmetallic substrate, preferably a synthetic mica microplate or a glass microplate, and a coating applied thereto, wherein the coating is a) Optionally, layer 1 containing or consisting of tin oxide, tin hydroxide, and / or tin oxide hydrate, b) Layer 2 comprising at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, wherein the metal ions include or are at least two metal ions selected from the group of metals consisting of Fe and Sn. c) Layer 3 comprises at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, wherein the metal ions comprise at least two metal ions selected from the group consisting of Fe and Sn, or are such. Furthermore, layers 2 and 3 are separated by a spacer layer, in which case the coating includes further layers of high and / or low refractive index, and the effect pigment runs essentially parallel to the surface of the microplate-shaped nonmetallic substrate, with an average height h in the range of 11 nm to 76 nm, preferably 19 nm to 54 nm. a The present invention relates to an absorbent effect pigment comprising at least one further spacer layer having [a specific characteristic].

[0140] In a further embodiment, the present invention relates to an absorbent effect pigment comprising a microplate-shaped nonmetallic substrate, preferably a synthetic mica microplate or a glass microplate, and a coating applied thereto, wherein the coating is a) Optionally, layer 1 containing or consisting of tin oxide, tin hydroxide, and / or tin oxide hydrate, b) Layer 2 comprises at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, wherein the metal ion comprises or is selected from the group of metals consisting of Zr, Sn, and Fe. c) Layer 3 comprises at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, wherein the metal ion comprises or is selected from the group of metals consisting of Zr, Sn, Ce, and Fe. In this case, at least one of layers 2 and 3 contains at least two different metal ions from the group listed above, the quotient of the average thickness of layer 2 and the average thickness of layer 3 is preferably in the range of 0.5 to 1.8, and the relative height h Rma This relates to absorbent pigments whose standard deviation is within the range of 0.2% to 11%.

[0141] In a further embodiment, the absorbent pigment of the present invention has a hue angle h in the CIE LCh color space in the ranges of 0°~60° and 120°~360°, more preferably 0°~45° and 135°~360°, more preferably 0°~35° and 140°~360°, and most preferably 0°~30° and 145°~360°. * 15 It has a chroma C within the above-mentioned hue angle range. Preferably, * 15 The h-angle is >15, more preferably >20, and most preferably >30. * 15 and saturation C * 15 This is determined here using a lacquer application on a black / white opacity chart (Byko-Chart 2853, Byk-Gardner) of nitrocellulose lacquer (Erco 2615e bronze mixing lacquer colorless; manufactured by Maeder Plastiklack AG) mixed with 6 wt% of the specific effect pigment of the present invention, in accordance with the details in Section IIb, “Measurement of Color by Angle”.

[0142] The CIE LCh color space is the CIELab color space, in which the rectangular coordinate a * , b * Instead, cylindrical coordinate C * (Saturation, relative saturation, distance from the L axis) and h * (Hue angle, the angle of hue on the CIELab color circle) is reported.

[0143] In a further embodiment, the present invention relates to an absorbent effect pigment comprising a microplate-shaped nonmetallic substrate, preferably a synthetic mica microplate or a glass microplate, and a coating applied thereto, wherein the coating has at least one spacer layer that is essentially parallel to the surface of the microplate-shaped nonmetallic substrate, and the effect pigment can be obtained by i) optionally applying a non-calcined tin oxide, tin hydroxide, and / or tin oxide hydrate layer to the microplate-shaped nonmetallic substrate; ii) applying three non-calcined metal oxides, metal hydroxides, and / or metal oxide hydrates, wherein the second of these three non-calcined metal oxides, metal hydroxides, and / or metal oxide hydrates is materially different from the others and has properties that allow it to diffuse into at least one of the other non-calcined metal oxides, metal hydroxides, and / or metal oxide hydrates; and iii) optionally calcining the product obtained in step ii) under reducing conditions at a temperature in the range of 400°C to 980°C.

[0144] In one particularly preferred embodiment, the present invention relates to an absorbent effect pigment comprising a microplate-shaped nonmetallic substrate, preferably a synthetic mica microplate or a glass microplate, and a coating applied thereto, wherein the coating is essentially parallel to the surface of the microplate-shaped nonmetallic substrate and has an average height h in the range of 14 nm to 51 nm. a The present invention relates to an absorbent effect pigment having at least one spacer layer having a certain property, and the effect pigment can be obtained by i) optionally applying a non-metallic substrate in the shape of a microplate using a water-soluble tin(IV) salt to form a non-calcined tin oxide, tin hydroxide, and / or tin oxide hydrate layer; ii) sequentially applying a first layer A using a water-soluble iron(III) salt, a second layer B using a water-soluble tin(IV) salt and / or titanium(IV) salt, and 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.

[0145] In one preferred embodiment, the coating of the absorbent effect pigment of the present invention comprises, in each case, at least one high refractive index layer composed of or containing titanium dioxide, titanium hydroxide, and / or titanium dioxide hydrate, and at least two non-adjacent high refractive index layers composed of or containing 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 the range of 0.01 to 0.9, and more preferably in the range of 0.1 to 0.8.

[0146] In a more preferred embodiment, the coating of the absorbent effect pigment of the present invention comprises, in each case, at least one high refractive index layer composed of or containing tin oxide, tin hydroxide, and / or tin oxide hydrate, and at least two high refractive index layers composed of or containing 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 the range of 0.01 to 0.9, and more preferably in the range of 0.1 to 0.8. In this embodiment, it is particularly preferred that the at least one high refractive index layer of iron oxide, iron hydroxide, and / or iron oxide hydrate be applied first, followed by at least one high refractive index layer of tin oxide, tin hydroxide, and / or tin oxide hydrate, and further high refractive index layers of iron oxide, iron hydroxide, and / or iron oxide hydrate be applied directly to the microplate-shaped substrate or directly to the respective top layer near the substrate. In addition, before applying at least one high refractive index layer of iron oxide, iron hydroxide, or iron oxide hydrate, a layer or preceding coating containing metal oxides, metal hydroxides, or metal oxide hydrates (where the metal ions include, or are, metal ions selected from the group of metals consisting of Sn and Si) can be deposited directly onto a microplate-shaped nonmetallic substrate or directly onto the uppermost layer close to the substrate, in which case the layer thickness may be several nanometers, preferably less than 10 nm, more preferably less than 5 nm, and most preferably less than 3 nm, and the layer does not need to completely surround the substrate. Tin oxide, tin hydroxide, and / or tin oxide hydrate may be present in a mixed layer containing at least a portion of iron oxide, iron hydroxide, and / or iron oxide hydrate.

[0147] In a further preferred embodiment, the coating of the absorbent effect pigment of the present invention comprises, in each case, a high refractive index layer of iron oxide, iron hydroxide, and / or iron oxide hydrate before drying and / or calcination, 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 each case, based on the absorbent effect pigment, in a range of 1% to 25% by weight, preferably 2% to 20% by weight, more preferably 3% to 16% by weight, and most preferably 4% to 13% by weight. Alternatively, the at least one high refractive index layer of iron oxide, iron hydroxide, and / or iron oxide hydrate may be doped with Mg or Ce. After calcination, the iron oxide present in the coating may be present in the form of hematite and / or goethite.

[0148] In a further embodiment, the present invention relates to an absorbent effect pigment comprising a microplate-shaped nonmetallic substrate, preferably a synthetic mica microplate or a glass microplate, and a coating applied to the substrate, wherein the coating has at least one spacer layer essentially parallel to the surface of the microplate-shaped nonmetallic substrate, and the effect pigment is calcined under reducing conditions or has a translucent metal layer as the outermost layer, preferably optionally present in the entire coating, directly beneath a protective layer.

[0149] In one embodiment, the coating of the absorbent pigment of the present invention comprises a corresponding metal suboxide, metal fluoride, metal nitride, metal oxynitride, metal oxyhalide, and / or metal sulfide instead of at least one metal oxide, metal hydroxide, and / or metal oxide hydrate.

[0150] In one embodiment, the coating of the absorbent pigment of the present invention comprises at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, in addition to at least one metal suboxide, metal fluoride, metal nitride, metal oxynitride, metal oxyhalide, and / or metal sulfide.

[0151] The present invention will be described below with reference to several examples, but these examples are not intended to limit the present invention. All percentage values ​​in the examples and comparative examples should be understood as weight percentages.

[0152] I. Production of absorbent pigments of the present invention Example 1 According to the MALVERN Mastersizer MS 2000, particle size distribution: D 10 =10μm, D 50 =22μm, D 90 200 g of synthetic mica microplates (fluorinated phlogopite microplates) with a thickness of 40 μm were suspended in 1300 mL of desalted water and heated to 85°C while turbulent stirring. The pH of the suspension was reduced to pH 2.2. A layer of tin oxide was deposited on the surface of the glass microplates by adding 75 g of tin chloride solution with a concentration of c(Sn) = 12 g / L. Next, the pH of the suspension was reduced to pH 1.9, and then 570 mL of TiCl4 solution (200 g of TiO2 / L of desalted 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. Then, 1.42 g / cm³ was added. 3 50 mL of an aqueous iron chloride solution with a density of was administered. After administration was complete, the mixture was stirred for a further 10 minutes to adjust the pH to 1.9, and 630 mL of TiCl4 solution (200 g TiO2 / L desalted water) was added to the suspension. Subsequently, 1.42 g / cm³ was added. 3 A further dose of 40 mL of an aqueous iron chloride solution having a density of was added after 10 minutes. Fifteen minutes after the addition was complete, the suspension was filtered off and the filter cake was washed. The filter cake was dried and baked at 850°C for 60 minutes. A highly saturated, high-gloss golden interference effect pigment with a yellow absorption color and very good opacity was obtained.

[0153] Example 2 The filtered cake from Example 1 was dried and baked at 820°C for 60 minutes under a hydrogen atmosphere. A highly saturated, high-gloss green / gold interference effect pigment with black absorption color and good opacity was obtained.

[0154] Example 3 According to the MALVERN Mastersizer MS 2000, particle size distribution: D 10 =10μm, D 50 =22μm, D 90 200 g of synthetic mica microplates (fluorinated fluorphlogopite microplates) with a thickness of 40 μm were suspended in 1300 mL of desalted water and heated to 85°C while turbulent stirring. The pH of the suspension was reduced to pH 2.2. A layer of tin oxide was deposited on the surface of the synthetic mica microplates by adding 100 g of tin chloride solution with a concentration of c(Sn) = 12 g / L. The pH of the suspension was reduced to pH 1.9, and then 400 mL of TiCl4 solution (TiO2 200 g / L of desalted 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. Then, 1.42 g / cm³ was added. 3 30 mL of an aqueous iron chloride solution with a density of was administered. After the addition was complete, the mixture was stirred for a further 10 minutes, and an additional 405 mL of TiCl4 solution (200 g of TiO2 / L of desalted water) was added to the suspension. Then, after 10 minutes, a further dose of 1.42 g / cm³ was administered. 3 40 mL of an aqueous iron chloride solution having a density of was added. Fifteen 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. A highly saturated, glossy blue interference effect pigment with a gray absorption color was obtained.

[0155] Example 4 According to the MALVERN Mastersizer MS 2000, particle size distribution: D 10 =34μm, D 50 = 57 μm, D 90200 g of glass microplates having a size of 96 μm were suspended in 1300 mL of DM water (DM = demineralized water), and heated to 85 °C while stirring turbulently. 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 microplates. Then, the pH was lowered to pH 2.0 with dilute HCl, and then 148 mL of a TiCl4 solution (200 g of TiO2 / L of demineralized water) was added to the suspension. After the addition was completed, the mixture was stirred for an additional 10 minutes, and then the pH was adjusted to pH 2.6. Then, 8 mL of an iron chloride aqueous solution having a density of 1.25 g / cm 3 was added. After the addition was completed, the mixture was stirred for an additional 10 minutes, and by adding 75 mL of a tin chloride solution with a concentration c(Sn) = 12 g / L, an additional thin layer of tin oxide was deposited on the pigment surface. Then, 180 mL of a TiCl4 solution (200 g of TiO2 / L of demineralized water) was added to the suspension. Then, 20 mL of an iron chloride aqueous solution having a density of 1.25 g / cm 3 was added 10 minutes later. 15 minutes after the addition, the suspension was filtered off, and the filter cake was washed. The filter cake was dried and calcined at 750 °C for 60 minutes under reducing conditions. A golden interference effect pigment with extremely high chroma and high gloss, having a gray absorption color, was obtained.

[0156] Example 5 According to the MALVERN Mastersizer MS 2000, the particle size distribution: D 10 = 10 μm, D 50 = 22 μm, D 90 = 40 μm. 200 g of synthetic mica microplates (fluorophlogopite microplates) were suspended in 1300 mL of demineralized water, and heated to 85 °C while stirring turbulently. The pH of the suspension was lowered to pH 2.6. Then, 40 mL of an iron chloride aqueous solution having a density of 1.42 g / cm 3 was added. Then, the mixture was stirred for 10 minutes, and at pH 1.9, 560 mL of a TiCl4 solution (200 g of TiO2 / L of demineralized water) was added to the suspension. After adjusting the pH to the initial value, then, 1.42 g / cm 340 mL of an iron chloride aqueous solution having a density of 1.42 g / cm³ was added to the suspension. Again, the pH was adjusted to pH 1.9, and 600 mL of a TiCl₄ solution (200 g of TiO₂ / L of demineralized water) was administered to the suspension. 15 mL of an iron chloride aqueous solution having a density of 1.42 g / cm³ was further added, and then the mixture was stirred for an additional 120 minutes and filtered. The washed filter cake was dried and calcined at 800 °C for 45 minutes. A golden interference effect pigment with extremely high chroma, high gloss, a yellow absorption color, and very good hiding power was obtained. 3 15 mL of an iron chloride aqueous solution having a density of 1.42 g / cm³ was further added, and then the mixture was stirred for an additional 120 minutes and filtered. The washed filter cake was dried and calcined at 800 °C for 45 minutes. A golden interference effect pigment with extremely high chroma, high gloss, a yellow absorption color, and very good hiding power was obtained.

[0157] Example 6 According to the MALVERN Mastersizer MS 2000, the particle size distribution: D 10 = 10 μm, D 50 = 22 μm, D 90 200 g of synthetic mica platelets (fluorophlogopite platelets) having D = 40 μm were suspended in 1300 mL of demineralized water and heated to 85 °C with turbulent stirring. The pH of the suspension was adjusted to pH 2.6. By adding 500 g of an iron chloride aqueous solution having a density of 1.42 g / cm³, an iron oxide layer was deposited on the surface of the synthetic mica platelets. After the addition was completed, the mixture was stirred for an additional 120 minutes, and then the pH was adjusted to pH 2.2. Then, 1000 g of a tin chloride solution with a concentration c(Sn) = 12 g / L was administered. When the administration was complete, the mixture was stirred for an additional 120 minutes, and then an additional layer of iron oxide was deposited on the surface of the synthetic mica platelets by adding 710 g of an iron chloride aqueous solution having a density of 1.42 g / cm³. 60 minutes after the addition was completed, the suspension was filtered off, and the filter cake was washed. The filter cake was dried if appropriate and calcined at 800 °C for 60 minutes under reducing conditions. A red interference effect pigment with extremely high chroma, high gloss, a red absorption color, and very good hiding power was obtained. 3 200 g of synthetic mica platelets (fluorophlogopite platelets) having D = 40 μm were suspended in 1300 mL of demineralized water and heated to 85 °C with turbulent stirring. The pH of the suspension was adjusted to pH 2.6. By adding 500 g of an iron chloride aqueous solution having a density of 1.42 g / cm³, an iron oxide layer was deposited on the surface of the synthetic mica platelets. After the addition was completed, the mixture was stirred for an additional 120 minutes, and then the pH was adjusted to pH 2.2. Then, 1000 g of a tin chloride solution with a concentration c(Sn) = 12 g / L was administered. When the administration was complete, the mixture was stirred for an additional 120 minutes, and then an additional layer of iron oxide was deposited on the surface of the synthetic mica platelets by adding 710 g of an iron chloride aqueous solution having a density of 1.42 g / cm³. 60 minutes after the addition was completed, the suspension was filtered off, and the filter cake was washed. The filter cake was dried if appropriate and calcined at 800 °C for 60 minutes under reducing conditions. A red interference effect pigment with extremely high chroma, high gloss, a red absorption color, and very good hiding power was obtained. 3 200 g of synthetic mica platelets (fluorophlogopite platelets) having D = 40 μm were suspended in 1300 mL of demineralized water and heated to 85 °C with turbulent stirring. The pH of the suspension was adjusted to pH 2.6. By adding 500 g of an iron chloride aqueous solution having a density of 1.42 g / cm³, an iron oxide layer was deposited on the surface of the synthetic mica platelets. After the addition was completed, the mixture was stirred for an additional 120 minutes, and then the pH was adjusted to pH 2.2. Then, 1000 g of a tin chloride solution with a concentration c(Sn) = 12 g / L was administered. When the administration was complete, the mixture was stirred for an additional 120 minutes, and then an additional layer of iron oxide was deposited on the surface of the synthetic mica platelets by adding 710 g of an iron chloride aqueous solution having a density of 1.42 g / cm³. 60 minutes after the addition was completed, the suspension was filtered off, and the filter cake was washed. The filter cake was dried if appropriate and calcined at 800 °C for 60 minutes under reducing conditions. A red interference effect pigment with extremely high chroma, high gloss, a red absorption color, and very good hiding power was obtained.

[0158] Example 7 According to the MALVERN Mastersizer MS 2000, the particle size distribution: D 10 = 10 μm, D 50=22μm, D 90 200 g of synthetic mica microplates (fluorinated phlogopite microplates) with a thickness of 40 μm were suspended in 1300 mL of desalinated water and heated to 85°C while turbulent stirring. The pH of the suspension was adjusted to pH 2.2. A layer of tin oxide was deposited on the surface of the synthetic mica microplates by adding 100 g of tin chloride solution with a concentration of c(Sn) = 12 g / L. Subsequently, the pH of the suspension was lowered to pH 1.9, and then 400 mL of TiCl4 solution (TiO2 200 g / L of desalinated 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 2.2. Next, 150 mL of 20 wt% zirconium chloride aqueous solution was added. After the weighing and addition was complete, the mixture was stirred for a further 40 minutes, and then 300 mL of TiCl4 (TiO2 200 g / L of desalinated water) was 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. A highly saturated, high-gloss blue interference effect pigment with a gray absorption color was obtained.

[0159] Example 8 15 g of pigment from Example 6 was suspended in 450 mL of demineralized water. Then, 30 mL of a silver salt solution consisting of 350 g of AgNO and 50 mL of a 28 wt% ammonia solution were added to 1 L of demineralized water, and the suspension was added simultaneously. The mixture was stirred at room temperature for 5 minutes. Next, 9 mL of a 35 wt% formaldehyde solution was added, and the mixture was stirred for a further 1 hour. The suspension was then filtered, and the pigment cake was dried under reduced pressure at 120°C. A dark blue interference effect pigment with a black absorption color and a silver content of 11.1% was obtained.

[0160] Example 9 100 g of the effect pigment obtained from Example 1 was suspended in 850 mL of demineralized water and heated to 85°C with turbulent stirring. The pH was lowered to pH 4.2 with dilute hydrochloric acid. Next, a solution of 0.93 g of Ce(NO3)3×6H2O dissolved in 40 mL of demineralized water was weighed and added. Simultaneously, the pH was maintained constant by adding 10% NaOH solution dropwise. After the solution had been completely added, the mixture was stirred for a further 1 hour, and then the pH was adjusted to pH 10 with dilute sodium hydroxide solution. Subsequently, 5.7 g of Dynasylan 1146 diluted with 24.3 g of demineralized water was added to the suspension, and the suspension was stirred for a further 180 minutes, filtered, and the filtered cake was washed with demineralized water. The filtered cake was dried under reduced pressure at 95°C.

[0161] Example 10 According to the MALVERN Mastersizer MS 2000, particle size distribution: D 10 =10μm, D 50 =22μm, D 90 200 g of synthetic mica microplates (fluorinated fluorphlogopite microplates) with a thickness of 40 μm were suspended in 1300 mL of desalted water and heated to 85°C while turbulent stirring. The pH of the suspension was adjusted to pH 2.6. 1.42 g / cm³ 3 A layer of iron oxide was deposited on the surface of a synthetic mica microplate by adding 570 g of an aqueous iron chloride solution having a density of 1.42 g / cm³. The pH of the suspension was then lowered to 1.9, and 250 mL of TiCl₄ solution (200 g TiO₂ / L desalted water) was added to the suspension. The mixture was then stirred for a further 120 minutes, and then 1.42 g / cm³ was added. 3 By adding 600 g of an aqueous iron chloride solution having a density of , a further layer of iron oxide was deposited on the surface of the synthetic mica microplate. 60 minutes after the addition was complete, the suspension was filtered off and the filter cake was washed. The filter cake was dried if necessary and baked at 400°C for 60 minutes. A highly saturated, high-gloss red interference effect pigment with red absorption color and very good opacity was obtained.

[0162] Example 11 100 g of the effect pigment obtained from Example 6 was suspended in 850 mL of demineralized water and heated to 85°C with turbulent stirring. The pH was lowered to pH 4.2 with dilute hydrochloric acid. Next, a solution of 0.93 g of Ce(NO3)3×6H2O dissolved in 40 mL of demineralized water was added. Simultaneously, the pH was maintained constant by dropwise addition of 10% NaOH solution. After the solution had been completely added, the mixture was stirred for a further 1 hour, and then the pH was adjusted to pH 10 with dilute sodium hydroxide solution. Subsequently, 5.7 g of Dynasylan 1146 diluted with 24.3 g of demineralized water was added to the suspension, and the suspension was stirred for a further 180 minutes, filtered, and the filtered cake was washed with demineralized water. The filtered cake was dried under reduced pressure at 95°C.

[0163] Example 12 According to the MALVERN Mastersizer MS 2000, particle size distribution: D 10 =10μm, D 50 =20μm, D 90 300 g of glass microplates with a thickness of 40 μm were suspended in 1500 mL of desalted water and heated to 85°C with turbulent stirring. The pH of the suspension was reduced to pH 2.2. A layer of tin oxide was deposited on the surface of the glass microplates by adding 70 mL of a tin chloride solution with a concentration of c(Sn) = 12 g / L. Subsequently, the pH was reduced to pH 2.0 with dilute HCl, and then 250 mL of TiCl4 solution (TiO2 200 g / L desalted 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. Then, 1.25 g / cm³ was added. 3 100 mL of an aqueous iron chloride solution having a density of was added. Then, 300 mL of a TiCl4 solution (200 g of TiO2 / L of desalted water) was added to the suspension. Fifteen minutes after the completion of the addition, the suspension was filtered off and the filter cake was washed. The filter cake was dried and baked at 760°C for 60 minutes. An extremely saturated, high-gloss gold effect pigment was obtained.

[0164] Comparative Example 1 According to the MALVERN Mastersizer MS 2000, particle size distribution: D 10 =25μm, D50 = 55 μm, D 90 200 g of synthetic mica microplates (fluorinated fluorphlogopite microplates) with a thickness of 100 μm and a span ΔD of 1.36 was suspended in 1300 mL of DM water (DM = desalted water) and heated to 85°C while stirring. The pH of the suspension was lowered to pH 2.2. A layer of "SnO2" was deposited on the surface of the synthetic mica microplates by adding 100 g of a tin chloride solution with a concentration of c(Sn) = 12 g / L. Subsequently, the pH was lowered to pH 1.9 with dilute HCl, and then 500 mL of TiCl4 solution (TiO2 200 g / L desalted water) was weighed and 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. Then, 1.42 g / cm³ was added. 3 60 mL of an aqueous iron chloride solution having a density of was weighed and added. Fifteen 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 700°C for 60 minutes under reducing conditions. A glossy gold pigment with a dark absorption color was obtained.

[0165] Comparative Example 2 Merck's Iriodin 504 Red is a red pigment based on natural mica microplates and coated with iron oxide.

[0166] Comparative Example 3 Merck's Iriodin 4504 Lava Red is a red pigment based on SiO2 microplates and coated with iron oxide.

[0167] II. Characterization of Pigments from Absorbent Pigments and Comparative Examples IIa Measurement of particle size The size distribution curves of the absorbent pigments of the present invention and the pigments from comparative examples were determined using a Malvern Mastersizer 2000 instrument according to the manufacturer's instructions. For this purpose, approximately 0.1 g of each pigment was added as an aqueous solution to the sample preparation cell of the measuring instrument using a Pasteur pipette, under constant stirring, without the addition of dispersion aids, and repeatedly analyzed. The median was calculated using the individual measurement results. Scattered light signals were evaluated by the Fraunhofer method.

[0168] In the context of the present invention, the median particle size D 50 This is the cumulative frequency distribution of the volume-averaged size distribution function as obtained by laser diffraction. 50 This is understood to mean D 50 This indicates that 50% of the pigment has a diameter of the reported value, e.g., 20 μm or less. Correspondingly, D 10 and D 90 These indicate that 10% and 90% of the pigment have a diameter less than or equal to their respective measured values.

[0169]

number

[0170] The span ΔD, as defined, indicates the width of the particle size distribution. With respect to the appearance of the absorbent effect pigment of the present invention, a small value of ΔD, i.e., a narrow span, is preferred.

[0171] [Table 2]

[0172] IIb Measurement of color by angle To measure the color and lightness values, the effect pigments of the present invention and the pigments from the comparative examples were added by stirring into conventional nitrocellulose lacquer (Erco 2615e bronze mixing lacquer colorless; manufactured by Maeder Plastiklack AG) at a pigment addition level of 6% by weight, based on the total weight of the wet lacquer. This was done by adding each pigment first, and then dispersing it in the lacquer using a brush. The finished lacquer was applied to a black / white opacity chart (Byko-Chart 2853, manufactured by Byk-Gardner) with a wet film thickness of 40 μm or 76 μm (Example 4) using a spiral applicator on an applicator drawdown apparatus (RK Print Coat Instr. Ltd. Citenco K 101 drawdown apparatus), and then dried at room temperature. The selection of the spiral applicator was determined in each case by the D of the pigment or substrate being applied. 50 The process is carried out according to Table A. Using a BYK-mac multi-angle colorimeter (manufactured by Byk-Gardner), color values ​​were determined on a black background of the opacity chart at a constant incidence angle of 45° (as specified by the manufacturer) and at various observation angles relative to the reflection angle. The characterization of color intensity was performed using the saturation value C. * 15 This was achieved using [a specific method / tool], and was measured at a measurement angle 15° away from the reflection angle on a black background of a black / white opacity chart.

[0173] A highly reflective sample (ideally a mirror) reflects virtually all incident light at the so-called reflection angle. The closer the lacquered material is measured to the reflection angle, the stronger the interference colors become.

[0174] [Table 3]

[0175] [Table 4]

[0176] [Table 5]

[0177] Table 3 shows the color values ​​of the gold interference effect pigments. From this, it is clear that the color intensity of the effect pigments of the present invention is considerably higher than that of the single-layer pearlescent pigment from Comparative Example 1. The exception is Example 4, which contains a fairly thick glass substrate. The color values ​​for the red interference effect pigments listed in Table 4 for the examples of the present invention are also considerably higher than those of Comparative Example 2.

[0178] IIc Comparison of concealment levels

[0179]

number

[0180] The concealment index D is defined as q To determine the lightness value L of the lacquer application from IIb, * 25° was recorded using a BYK-mac multi-angle colorimeter (Byk-Gardner) at a measurement angle of 25° on the black and white backgrounds of a black / white opacity chart. At a constant incidence angle of 45°, the measurement position of 25° is related to the difference from the reflection angle. The observation angle is measured away from the specular reflection on the illuminated surface. The effect pigment of the present invention has good opacity. Its opacity index D q The opacity index D of the microplate-shaped absorbent effect pigments of the present invention from Examples 1 to 10. q As can be inferred from Table 5, in each case, the value is considerably higher than 0.41.

[0181] IId gloss measurement Gloss is a measure of directional reflectivity. To determine gloss, coatings from IIb on a white background of a black / white opacity chart were analyzed using a Byk-Gardner Micro-Tri-Gloss gloss meter at a measurement angle of 60° based on the vertical. The gloss values ​​of the absorbent effect pigments of the present invention and pigments from comparative examples are listed in Table 5. Some of the microplate-shaped absorbent effect pigments of the present invention from Examples 1-10 show significantly higher gloss values ​​than the pigments with single-layer coatings from Comparative Examples 2 and 3. The gloss measurements from Table 5 confirm the extremely high reflectivity of the pigments of the present invention compared to the prior art.

[0182] Measurement of the IIe effect To objectively describe the optical effects of the absorbent pigments of the present invention, the effects were measured using a BYK-mac spectrophotometer (manufactured by Byk-Gardner) with lacquer samples from IIb onwards (see Byk-Gardner Catalogue "Qualitaetskontrolle fuer Lacke und Kunststoffe" [Quality control for Lacquers and Adhesives], 2011 / 2012, pp. 97 / 98). The corresponding measured values ​​for sparkle intensity S_i, sparkle area S_a, and granularity G are summarized in Table 5.

[0183] [Table 6]

[0184] The effect values ​​S_i, S_a, and G of the microplate-shaped absorbent effect pigments of the present invention from Examples 1-10 and 12 are higher than those in Comparative Examples 2 and 3. The achievable optical effect of the microplate-shaped absorbent effect pigments of the present invention is considerably more pronounced than in the case of conventional effect pigments with single-layer coatings from Comparative Examples 2 and 3.

[0185] IIf Waring Blender In industry, many lacquers are processed in circulating systems. In this case, the lacquer components are subjected to high shear forces. The Waring Blender test is useful for simulating these conditions and evaluating cyclic circuit stability / shear stability. Specifically, in this test, pigments whose coating is not sufficiently anchored to the support material show a significant deviation in chrominance compared to the untreated application. Therefore, the Waring Blender test can be considered a measure of the inter-adhesion of pigment coatings with respect to shear forces. For this purpose, pigments from the absorbent effect pigment of the present invention or from comparative examples were weighed according to the following formulation and converted into a paste stepwise in an 880 mL beaker using conventional acrylic lacquer. The viscosity was then adjusted to 17 seconds in a DIN 4 mm cup using 1:1 butyl acetate / xylene. A total of 600 g of lacquer was produced, of which 400 g was introduced into a jacketed water-cooled 1 kg container and stirred under a Dispermat (manufactured by Waring Blenders) using a special attachment. The stirring time was 8 minutes at 13,500 rpm, after which 200 g of lacquer was removed and the remainder was stirred for a further 12 minutes. Formulation: 6% pigment 8% Butyl Acetate 85 86% colorless acrylic lacquer 1:1 30% dilute butyl acetate 85 / xylene Using a spray machine and a Sata LP-90 spray gun, 200g each of untreated and treated lacquer were applied to the test sheets according to the following settings. Settings: Hands: 1, 3, 4 Pressure: 4 bar Procedure: The number of spray applications was selected to ensure a dry lacquer layer thickness of 15-20 μm. Conventionally, an effect pigment is considered shear-stable if, after the Waring Blender test, the difference in gloss and color measured near the reflection angle is relatively small in the applied sample. ΔC compared to the untreated sample. *The 15° value should ideally be less than 2. Table 6 shows the color change ΔC of the samples subjected to the Waring Blender test compared to the untreated samples in Examples 5 and 10 of the present invention. * It exhibits a gloss change of Δ60° and a gloss of 15°.

[0186] [Table 7]

[0187] The absorbent pigments of the present invention from Examples 5 and 10 meet the test criteria. The color difference is negligibly small. Even under a microscope, virtually no changes such as peeling of the coating or other surface defects could be detected. The absorbent pigments of the present invention have been found to be extremely shear-stable despite their spacer layer.

[0188] Determination of the chemical stability of IIg The chemical stability of the absorbent effect pigments of the present invention and the pigments from comparative examples was determined with respect to the application of lacquer to plastic panels. 6 g of each pigment was stirred into a mixture of 90 g of conventional colorless acrylic lacquer and 10 g of butyl 85 acetate. The viscosity was then adjusted to 17 seconds in a DIN 4 mm cup using a 1:1 mixture of butyl 85 acetate and xylene. In each case, 100 g of this lacquer was applied to the panel using a spray machine in an opaque manner, similar to the IIf method. After coating, the panel was baked at 80°C for 30 minutes. After 24 hours, the panel was immersed in a 10% sodium hydroxide solution up to half its height. After a 7-day contact time, the panel was rinsed with demineralized water and then visually evaluated for damage and / or fading after a 2-hour drying time. In addition, fading was analyzed using BYK-mac (Byk-Gardner). The color change was characterized using the ΔE value of the exposed sample relative to the corresponding unexposed sample at a measurement angle of 15°. The results are shown in Table 7 below.

[0189] [Table 8]

[0190] Pigments having ΔE(15°)<3 can be considered stable to chemicals. The absorbent effect pigments of the present invention from Example 10 are below the limit value, while the pigments from Comparative Example 3 clearly exceed the limit value.

[0191] IIh X-ray fluorescence analysis (XRF) The content of metal oxides, metal hydroxides, and / or metal oxide hydrates in the absorbent pigments of the present invention and pigments from comparative examples was determined by X-ray fluorescence analysis (XRF). For this purpose, each pigment was incorporated into a lithium tetraborate glass tablet, fixed in a solid sample measuring cup, and analyzed from there. The measuring instrument used was the Thermo Scientific Advantix ARL system. The measured values ​​are shown in Table 8. The values ​​for various content are reported here as TiO2 for titanium, Fe2O3 for iron, and SnO2 for tin.

[0192] [Table 9]

[0193] IIi Condensate Test To determine condensate stability, absorbent pigments from the present invention and pigments from comparative examples were incorporated into an aqueous lacquer system, and test samples were produced by spray coating onto aluminum sheets. The base coat was overcoated with a conventional one-component clear coat and then baked. These samples were tested according to DIN 50 017 (Water Condensation - Constant Pressure). Adhesion strength was tested immediately after the end of the test, compared to an unexposed sample, by a grid test according to DIN EN ISO 2409. In this context, Cc0 means no change, and Cc5 means a very significant change. Expansion characteristics were visually evaluated immediately after exposure to condensate according to DIN 53230. In this context, an index of 0 means no change, and an index of 5 means a very significant change. Finally, DOI(d Distinctness o f i The (image) was determined using a Wave-scan II made by Byk-Gardner.

[0194]

Table 10

[0195] The pigments from Comparative Example 2 had significant swelling properties and poor intermediate layer adhesion. The DOI could no longer be measured due to the advanced microstructure after condensed water exposure. In contrast, the absorbent effect pigments of the present invention from Examples 9 and 11 were found to be stable and showed virtually no change before and after the test.

[0196] IIj UV stability To determine the photochemical UV activity of the TiO2 pigment, the UV stability of the absorbent effect pigments of the present invention and the pigments from the comparative examples was determined according to the rapid UV test described in EP 0 870 730 A1. For this purpose, 1.0 g of the corresponding pigment was dispersed in 9.0 g of a double bond-rich melamine-containing lacquer. An applicator drawdown was prepared on white cardboard and dried at room temperature. The applicator drawdown was divided and one of each of the two sections was stored in the dark as an unexposed comparative sample. Then, the samples were irradiated with UV-containing light (UVA-340 lamp, radiation intensity 1.0 W / m 2 / nm) for 150 minutes in a Q-Panel QUV system. Immediately after the end of the test, the color values of the exposed samples were determined for each reference sample using a Minolta CM-508i colorimeter. Hunter L * a * b * The obtained ΔE calculated according to the formula * values are shown in Table 9.

[0197] In this test, the Ti(III) species formed under UV light causes the TiO2 layer of each pigment to be essentially gray / blue. The condition for this is that electron pores leave the surrounding TiO2 and cannot immediately recombine with the remaining electrons, for example, through reaction with the olefinic double bonds of the binder. The melamine-containing lacquer layer significantly slows the diffusion of water (vapor) and oxygen to the pigment surface, so the reoxidation of titanium(III) species occurs at a significantly delayed rate, and thus graying can be measured, and ΔE * The value can then be used as a measure of the UV stability of the pigment. Therefore, the ΔE of the exposed sample relative to the unexposed reference sample is calculated. * A higher number indicates lower UV stability of the tested pigment.

[0198] [Table 11]

[0199] The comparative example shows a considerably large color change (ΔE) after the corresponding exposure. * ) had.

[0200] IIk: Average thickness of micro-plate shaped non-metallic substrate, average layer thickness of layers 2 and 3, average layer thickness of the entire coating, average height h of the spacer layer a , as well as the average height h of the cavity H decision For this purpose, the absorbent pigment of the present invention was incorporated at a concentration of 10% into Autoclear Plus HS, a two-component clear coat manufactured by Sikkens GmbH, using a sleeve brush, and applied to a film using a spiral applicator (wet film thickness of 26 μm), and then dried. After a drying period of 24 hours, a cross-section of the applicator drawdown was obtained. The cross-section was analyzed by SEM, and at least 100 individual pigments were analyzed to ensure statistical significance in determining the average thickness of the microplate-shaped nonmetallic substrate. The average layer thickness of layers 2 and 3, the average thickness of the entire coating, and the average height h of the spacer layer were also analyzed. a, as well as the average height h of the cavity H To determine the baseline, the upper and lower substrate surfaces, i.e., the longitudinal sides of the microplate-shaped nonmetallic substrates recognizable in the SEM cross-section in each case, were used as baselines. In this case, the baseline was drawn by connecting two intersections of the microplate-shaped nonmetallic substrate - layer 1 of any choice or the microplate-shaped nonmetallic substrate - layer 2 with a straight line along the surface of the microplate-shaped substrate, from the left and right edges of the cross-sectional scanning electron microscope image to the other. The scanning electron microscope images of the cross-sections were analyzed using AxioVision 4.6.3. Image Processing Software (Zeiss).

[0201] A sufficient number of parallel lines were drawn at 90° angles from these two baselines and at 50 nm intervals to create a grid on the full-scan electron microscope image of the cross-section of the effect pigment (Figure 4). The magnification of the scanning electron microscope image of the cross-section was preferably at least 50,000x based on Polaroid 545. Starting from the upper and lower baselines of each microplate-shaped nonmetallic substrate, the distances between these lines and the respective interfaces of the interfaces of an optional layer 1 to layer 2, layer 2 to the spacer layer, the spacer layer to layer 3, and layer 3 to the environment were manually measured in the direction of layer 3 in each case. In this case, one of the 50 nm marked lines was sometimes just above a connection point or spacer. In this case, only the respective intersections of line 3 to the environment were recorded. From these measurements, the layer thicknesses of layers 2 and 3, the overall coating thickness, and the height h of the spacer layer were determined by taking the difference. a I obtained it.

[0202] Average cavity height h H To determine the average layer thickness and average height h, the intersections of these parallel lines and the upper and lower cavity boundaries within the spacer layer were used. H , and average height h a To determine the values ​​shown above, the layer thickness and height h thus determined a , and height h HThe individual values ​​were used to obtain their respective arithmetic mean. The above measurements were performed on a line of at least 100 to ensure statistical significance. In all cases, the term "mean" refers to the arithmetic mean.

[0203] Cross-sections of pigments from comparative examples that lack a spacer layer but may have statistically distributed voids within the coating were also examined using scanning electron microscope images of the cross-sections in the same manner as described above. In this case, if one of the parallel lines occurred over one or more voids, the height of the void(s), the void(s) center(s), and the distance from the substrate surface to the void(s) center(s) were determined.

[0204] In addition to cross-sections, the absorbent effect pigment of the present invention can be cut by 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 to a point by an ion optical element and guided line by line on the surface of the effect pigment to be treated. Upon collision with the effect pigment surface, the ions radiate most of their energy, destroying the coating at this point, which results in line-by-line material removal. Furthermore, using the subsequently recorded scanning electron microscope images, the average height h can be determined by the above method. a This allows for the determination of the average layer thickness of layers 2 and 3, as well as the average layer thickness of the entire coating. Furthermore, the average thickness of a microplate-shaped nonmetallic substrate can be determined using scanning electron microscope images of the effect pigment cut by the FIB method.

[0205] Therefore, the advantages of the absorbent pigment of the present invention are evident from its overall properties. The absorbent pigment of the present invention possesses high permeability, excellent mechanical and chemical stability, and high gloss and color intensity. Judging as a whole, none of the comparative pigments possess all of the above properties to a sufficient degree.

[0206] [Table 12]

[0207] Table 8 shows the average height h of the spacer layer of the tested pigments. a This demonstrates that, in contrast to the pigments from Comparative Examples 1-3, all absorbent pigments of the present invention have a spacer layer.

[0208] The pigments from Comparative Examples 1 and 2 do not have a spacer layer, but they have statistically distributed pores within the coating. In Table 11, in Comparative Examples 1 and 2, σh Rma The value in the [%] column represents the standard deviation of the void center points from the substrate surface. However, the pigment from Comparative Example 2 contains only a small number of statistically distributed voids, so the network density S D The ratio is 65.0%. The standard deviation of the void center points from the substrate surface is 24.7%, which demonstrates that the voids are statistically distributed throughout the coating. This situation differs from the absorbent pigments of the present invention from Examples 1, 3, 5-7 and 10. In this case, the relative height h of the center point of the spacer layer Rma The standard deviation is <14% in each case, which indicates that each spacer layer is in a specified position within the coating. Thus, the standard deviation of the distance from the substrate surface to the void center point of the pigment from Comparative Examples 1 and 2 can be compared with the standard deviation of the relative height of the center point of the spacer layer of the absorbent effect pigment of the present invention.

[0209] IIl Scanning electron microscope image Scanning electron microscope images were obtained using a Supra35 scanning electron microscope (Zeiss) on a cross-section of the absorbent pigment of the present invention. Energy-dispersive X-ray trace analysis (EDX analysis) was performed using an EDAX Sapphire instrument (EDAX).

[0210] III Application examples Example Use 1: Body lotion

[0211] [Table 13]

[0212] The effect pigments from Example 1 can be used in the range of 0.1% to 2.5% by weight based on the total weight of the body lotion formulation. The supplementation up to 100% by weight of the formulation can be carried out with water. Keltrol CG-T was dispersed in Phase A and heated to 75°C. Phase B was heated separately to 75°C. Then, Phase B was gradually added to Phase A. With stirring, the emulsion was cooled to room temperature and Phase C was added individually.

[0213] Application Example 2: Eye shadow cream

[0214] [Table 14]

[0215] The effect pigments from Example 3 can be used in the range of 5% to 30.0% by weight based on the total weight of the eye shadow formulation. The supplementation up to 100% by weight of the formulation can be carried out with isododecane. Phase A was mixed and heated to 85°C, then Phase B was added to Phase A with stirring. After dispensing into a suitable container, the mixture was cooled to room temperature.

[0216] Application Example 3: Shower gel

[0217] [Table 15]

[0218] The effect pigments from Example 5 can be used in the range of 0.01% to 1.0% by weight based on the total weight of the shower gel formulation. The supplementation up to 100% by weight of the formulation can be carried out with water. Phase A was stirred, then Phase B was added and stirred until a uniform appearance was achieved. Phase C was weighed separately, mixed briefly, and added to Phase AB. Then, the mixture was stirred again and Phase D was added individually.

[0219] Application Example 4: Eye shadow compact

[0220] [Table 16]

[0221] The effect pigments from Example 8 can be used in a range of 5.0% to 40.0% by weight based on the total weight of the eyeshadow formulation. Replenishing up to 100% by weight of the formulation can be done with talc. Phase A was mixed in a high-speed mixer at 2500 rpm for 30 seconds. Then, Phase B was added and the mixture was mixed in the same mixer at 3000 rpm for 60 seconds. Finally, the powder mixture was pressed into shape using an eyeshadow press at 100 bar for 30 seconds.

[0222] Example Use 5: Mascara

[0223] [Table 17]

[0224] The effective pigment from Example 8 can be used in a range of 1.0% to 10.0% by weight based on the total weight of the mascara formulation. Replenishing up to 100% by weight of the formulation can be done with water from Phase A. Phase A was stirred under high shear. Phase B was weighed separately. Phases A and B were heated separately to 85°C, and then Phase B was added to Phase A. Phases A and B were then cooled to 45°C, and while cooling, Phase C was gradually added under stirring.

[0225] Example Use 6: Hair Gel

[0226] [Table 18]

[0227] The effect pigment from Example 6 can be used in an amount ranging from 0.01% to 2.0% by weight based on the total weight of the hair gel formulation. Replenishing up to 100% by weight of the formulation can be done with water. Laponite XLG was stirred with water until Phase A became clear. Then, while stirring, the effect pigment from Example 6 was added to Phase B. Then, the remaining components of Phase B were gradually added.

[0228] Example Use 7: Body Powder

[0229] [Table 19]

[0230] The effective pigments from Example 5 can be used in a range of 0.2% to 5.0% by weight based on the total weight of the body powder formulation. Replenishing up to 100% by weight of the formulation can be done with Synafil S 1050. Phase A was mixed, and then the powder was dispensed into appropriate containers.

[0231] Example Use 8: Lip Gloss

[0232] [Table 20]

[0233] The effect pigment from Example 6 can be used in an amount ranging from 0.10% to 8.00% by weight based on the total weight of the lip gloss formulation. Replenishing up to 100% by weight of the formulation can be done using Versagel ME 750. Phase A was heated to 85°C, then the effect pigment from Example 6 was added to Phase B, stirred until uniform consistency was achieved, and then dispensed into lip gloss containers.

[0234] Example Use 9: Lipstick

[0235] [Table 21]

[0236] The effective pigments from Example 10 can be used in a range of 0.5% to 20.0% by weight based on the total weight of the lipstick formulation. Replenishment up to 100% by weight of the formulation can be done with Eutanol G. Phase A was heated to 85°C, then Phase B was added to Phase A and mixed. This mixture was then dispensed into lipstick molds at a temperature of 75°C.

[0237] Example Use 10: Liquid Eyeliner

[0238] [Table 22]

[0239] The effective pigment from Example 2 can be used in an amount ranging from 0.5% to 8.0% by weight based on the total weight of the eyeliner formulation. Replenishing up to 100% by weight of the formulation can be done with water. Optigel WX-PC was dispersed in water for phase A and stirred for 10 minutes. Phases A and B were heated separately to 80°C. Then, phase B was gradually added to phase A under stirring. After cooling to 45°C, the components of phase C were gradually added and the mixture was dispensed into appropriate packages.

[0240] Example Use 11: Mousse

[0241] [Table 23]

[0242] The effect pigments from Example 4 can be used in amounts ranging from 0.1% to 8.0% by weight based on the total weight of the mousse formulation. Replenishing up to 100% by weight of the formulation can be done using a Dow Corning 9041 elastomer. Phase A was mixed and heated until all was melted. Phase B was weighed separately and mixed in a high-speed mixer at 2400 rpm for 60 seconds. Half of the molten Phase A was added to Phase B and the mixture was again mixed in the mixer at 2400 rpm for 30 seconds. The remaining Phase B was then added to Phase A and the mixture was again mixed in a high-speed mixer at 2400 rpm for 30 seconds. Finally, Phase C was added to Phases A and B and the mixture was again mixed in a high-speed mixer at 2400 rpm for 30 seconds.

[0243] Example Use 12: Nail Polish

[0244] [Table 24]

[0245] The effective pigments from Example 6 can be used in a range of 0.1% to 8.0% by weight based on the total weight of the nail polish formulation. Replenishing up to 100% by weight of the formulation can be done with International Lacquers Nailpolish. Phase A and Phase B were mixed and then dispensed into appropriate containers.

[0246] Example of use 13: Nail polish with a soft-touch effect

[0247] [Table 25]

[0248] The effective pigments from Example 10 can be used in a range of 0.1% to 8.0% by weight based on the total weight of the nail polish formulation. Replenishing up to 100% by weight of the formulation can be done with International Lacquers Nailpolish. Phase A was mixed and added to Phase B, and then the nail polish was dispensed into appropriate containers.

[0249] Example Use 14: Water-based nail polish The effective pigments from Examples 1-8 and Example 10 can be used in the aqueous nail polish according to Example 1 of WO 2007 / 115675 A2. In this case, the pigment addition level is 0.1% to 10.0% by weight based on the total weight of the formulation.

[0250] Example Use 15: Liquid Eyeshadow

[0251] [Table 26]

[0252] The effective pigments from Example 3 can be used in an amount ranging from 0.10% to 20.00% by weight based on the total weight of the eyeshadow formulation. Replenishing up to 100% by weight of the formulation can be done with water. Phase A was stirred, then the components of Phase B were individually added to Phase A and stirred until the consistency was uniform. Subsequently, the components of Phase C were individually added to Phases A and B, and the mixture was stirred until the consistency was uniform.

Claims

1. An absorbent pigment comprising a microplate-shaped nonmetallic substrate and a coating applied to the substrate, wherein the coating is a) Optionally, layer 1 containing or consisting of tin oxide, tin hydroxide, and / or tin oxide hydrate, b) Layer 2 comprises at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, wherein the metal ion is at least one metal ion selected from the group consisting of metals Ti, Fe, Sn, Mn, Zr, Ag, Zn, Cu, and Ce. c) A layer 3 comprising at least one metal oxide, metal hydroxide, and / or metal oxide hydrate, wherein the metal ion is at least one metal ion selected from the group consisting of metals Ti, Fe, Sn, Mn, Zr, Ag, Zn, Cu, and Ce, At least one of layers 2 and 3 contains at least two different metal ions, and at least one of the at least two different metal ions contained is a colorable metal ion selected from the group of metals consisting of Fe, Ti in oxidation state +3 or +2, Sn in oxidation state +2, Mn, Ag, Cu, and Ce, and the microplate-shaped nonmetal substrate is an uncoated natural mica microplate, synthetic mica microplate, biotite, glass microplate, SiO ２ Microplatelet, Al ２ O ３ The layers are selected from the group consisting of microplates, kaolin microplates, talc microplates, bismuth oxychloride microplates, and mixtures thereof, and each of layers 1, 2, and 3 may be given a dopant, and when layers 2 and / or 3 are given a dopant, the dopant may contain a metal oxide, a metal hydroxide, and / or a metal oxide hydrate, and the metal ion of the metal oxide, metal hydroxide, and / or metal oxide hydrate is at least one metal ion selected from the group consisting of metals Ca, Mg, Al, Ce, Zr, or Sn, and the proportion of the dopant is ≤1% by weight in total, based on the total weight of the absorbent effect pigment in each case, and layers 2 and 3 are separated by a spacer layer formed between layers 2 and 3, and at least one spacer layer contains a cavity including a connection and gas, has a network density of <85%, and the D of the effect pigment ５０ The value is within the range of 3 μm to 350 μm, and the concealment index D is defined by the following formula. ｑ Absorbent pigments whose ≥ 0.

41. [Math 1] (where L ＊２５ 黒色 and L ＊２５ 白色 are the lightness values measured at a measurement angle of 25° on the black and white backgrounds of a black / white hiding power chart of nitrocellulose lacquer in which 6% by weight of an effect pigment is mixed)

2. The absorbent effect pigment according to claim 1, wherein the effect pigment comprises a further layer of high and / or low refractive index, and optionally, at least one further spacer layer.

3. The absorbent pigment according to claim 1 or 2, wherein, in each case, the proportion of uncolored metal ions selected from the group of metals consisting of Ti, Sn, Zr, and Zn, determined by XRF, calculated as elemental metals in each case, and based on the total weight of the absorbent pigment of the present invention, is ≤40% by weight in total, and the proportion of colored metal ions selected from the group of metals consisting of Fe, Ti in oxidation state +3 or +2, Sn in oxidation state +2, Mn, Ag, Cu, and Ce, is ≥4% by weight in total.

4. The absorbent pigment according to claim 3, wherein the weight ratio of uncolored metal ions to colored metal ions in the absorbent pigment of the present invention, as determined by XRF and calculated as elemental metals, is <20.

5. The absorbent effect pigment according to any one of claims 1 to 4, wherein at least one spacer layer is arranged essentially parallel to the surface of a microplate-shaped nonmetallic substrate.

6. At least one spacer layer has an average height h in the range of 5 nm to 120 nm. ａ An absorbent pigment according to any one of claims 1 to 5, having the following characteristics.

7. The absorbent effect pigment according to any one of claims 1 to 6, wherein at least one spacer layer has a network density in the range of 1% to 75%.

8. The absorbent effect pigment according to any one of claims 1 to 7, wherein at least one spacer layer has a network density in the range of 1% to 63%.

9. A process for producing an absorbent pigment according to any one of claims 1 to 8, wherein the process comprises: (i) optionally, a non-calcined layer comprising or consisting of tin oxide, tin hydroxide, and / or tin oxide hydrate is applied to an uncoated microplate-shaped non-metallic substrate; (ii) Three non-calcined layers A, B, and C are sequentially applied, each consisting of one type of metal oxide, metal hydroxide, and / or metal oxide hydrate, with layers A, B, and C directly stacked on top of each other, and the one type of metal oxide, metal hydroxide, and / or metal oxide hydrate applied in layer B is different from the metal ions (multiple) of the metal oxides, metal hydroxides, and / or metal oxide hydrates in layers A and C with respect to metal ions, A process comprising (iii) calcining the product obtained in step (ii) at a temperature in the range of 400°C to 1000°C for 30 minutes or more, thereby diffusing the metal ions present in layer B to layer A and / or layer C, at least partially, to form at least one spacer layer in the calcined effect pigment, thereby obtaining an absorbent effect pigment containing at least one spacer layer, wherein a water-soluble iron(III) salt is used to form the non-calcined layer in step (ii) in which the metal ions are Fe.

10. The process according to claim 9, wherein the two or three metal oxides, metal hydroxides, and / or metal oxide hydrates applied sequentially to form layers B and C, or layers A, B, and C, do not contain any metal ions selected from the group of metals consisting of Si, Mg, and Al.

11. Use of an absorbent pigment according to any one of claims 1 to 8 in cosmetic formulations, plastics, films, textiles, ceramic materials, glass, paints, printing inks, writing inks, varnishes, powder coatings, and / or in functional applications.

12. An article comprising at least one absorbent pigment according to any one of claims 1 to 8.

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