Effect Pigments Having High Transparency, High Chroma and High Brilliancy, Method for the Production and Use Thereof

Abstract

The invention relates to a transparent effect pigment which includes a non-metallic platelet-shaped substrate and a coating applied thereto, wherein the coating has a spacer layer. The invention further relates to a method for the production, as well as the use, of the transparent effect pigment.

Claims

1. A transparent effect pigment comprising a non-metallic platelet-shaped substrate and a coating applied to the substrate, wherein the coating comprises a) optionally a layer 1 which comprises or consists of at least one of tin oxide, tin hydroxide or tin oxide hydrate, b) a layer 2 comprising at least one of metal oxide, metal hydroxide or metal oxide hydrate, and c) a layer 3 comprising at least one of metal oxide, metal hydroxide or metal oxide hydrate, and wherein at least one of layers 2 or 3 comprises at least two different metal ions and layers 2 and 3 are interrupted by a spacer layer.

2. The transparent effect pigment according to claim 1, wherein the non-metallic platelet-shaped substrate is selected from the group consisting of natural mica platelets, synthetic mica platelets, glass platelets, SiO.sub.2 platelets, Al.sub.2O.sub.3 platelets, kaolin platelets, talc platelets, bismuth oxychloride platelets and mixtures thereof, and the non-metallic platelet-shaped substrate is optionally coated with at least one of metal oxide, metal hydroxide or metal oxide hydrate and calcined.

3. The transparent effect pigment according to claim 1, wherein the effect pigment comprises further high- and low-refractive-index layers as well as optionally at least one further spacer layer.

4. The transparent effect pigment according to claim 1, wherein the at least two different metal ions of layer 2 and/or layer 3 are selected from the group of metals consisting of Ti, Fe, Sn, Mn, Zr, Ca, Sr, Ba, Ni, Sb, Ag, Zn, Cu, Ce, Cr and Co.

5. The transparent effect pigment according to claim 1, wherein the at least two different metal ions of layer 2 and/or 3 are selected from the group of metals consisting of Ti, Fe, Sn and Zr.

6. The transparent effect pigment according to claim 1, wherein a proportion of non-coloring metal ions selected from the group of metals consisting of Ti, Sn, Zr, Ca, Sr, Ba and Zn is >13 wt.-% in total, and a proportion of coloring metal ions selected from the group of metals consisting of Fe, Ti, Sn, Mn, Ni, Sb, Ag, Cu, Ce, Cr and Co is ≦4 wt.-% in total in the effect pigment, in each case determined by means of XRF analysis, in each case calculated as elemental metal and in each case relative to the total weight of the transparent effect pigment according to the invention.

7. The transparent effect pigment according to claim 1, wherein the at least one spacer layer is arranged substantially parallel to the surface of the non-metallic platelet-shaped substrate.

8. The transparent effect pigment according to claim 1, wherein the spacer layer has connections and cavities.

9. The transparent effect pigment according to claim 1, wherein the spacer layer in each case has an average height h.sub.a from a range of from 5 nm to 120 nm.

10. A method for producing the transparent effect pigment according to claim 1, wherein the method comprises: (i) optionally applying a non-calcined layer, which comprises or consists of at least one of tin oxide, tin hydroxide or tin oxide hydrate, to the non-metallic platelet-shaped substrate, (ii) sequentially applying three non-calcined layers A, B and C, in each case made of or with at least one of metal oxide, metal hydroxide or metal oxide hydrate, wherein layers A, B and C are arranged directly on each other and wherein the at least one metal oxide, metal hydroxide and/or metal oxide hydrate applied in layer B, with respect to the metal ion, is different from the metal ion(s) of the metal oxides, metal hydroxides and/or metal oxide hydrates of layer A and layer C, (iii) calcining the product obtained in step (ii) at a temperature from a range of from 600° C. to 1000° C., obtaining the transparent effect pigment comprising at least one spacer layer.

11. A method for producing the transparent effect pigment according to claim 1, wherein the method comprises the following steps: (i) sequentially applying two non-calcined layers B and C, in each case made of or with at least one of metal oxide, metal hydroxide or metal oxide hydrate, to a calcined single- or multi-coated non-metallic substrate, wherein layers B and C are arranged directly on each other and wherein the at least one metal oxide, metal hydroxide and/or metal oxide hydrate applied in layer B, with respect to the metal ion, is different from the metal ion(s) of the metal oxide, metal hydroxide and/or metal oxide hydrate of layer C and the layer which directly adjoins layer B in the direction of the substrate, (ii) calcining the product obtained in step (i) at a temperature from a range of from 600° C. to 1000° C., obtaining the transparent effect pigment comprising at least one spacer layer.

12. The method according to claim 10, wherein the metal ions contained in layer B diffuse, at least partially, into layer A and/or layer C, forming the at least one spacer layer in the calcined effect pigment.

13. The method according to claim 10, wherein the two or three sequentially applied metal oxides, metal hydroxides and/or metal oxide hydrates for producing layers B and C or layers A, B and C do not comprise or are not a metal ion selected from the group of metals consisting of Si, Mg and Al.

14. A process for producing a pigmented cosmetic formulation, plastic, film, textile, ceramic material, glass, paint, printing ink, ink, varnish, powder coating, coating composition or a material for a functional application comprising introducing the transparent effect pigment of claim 1 into a cosmetic formulation, plastic, film, textile, ceramic material, glass, paint, printing ink, ink, varnish, powder coating, coating composition or a material for a functional application.

15. An item comprising at least one transparent effect pigment according to claim 1.

16. The method according to claim 11, wherein the metal ions contained in layer B diffuse, at least partially, into layer A and/or layer C, forming the at least one spacer layer in the calcined effect pigment.

17. The process according to claim 14, wherein the functional application is laser marking, IR reflection, or photocatalysis.

Description

EXAMPLE 1

[0182] 200 g of glass platelet with a particle-size distribution according to MALVERN Mastersizer MS 2000: D.sub.10=34 μm, D.sub.50=57 μm, D.sub.90=96 μm were suspended in 1300 ml of demineralized water and heated to 85° C. under turbulent stirring. The pH of the suspension was reduced to pH 2.2. By adding 75 g of a tin chloride solution with a concentration of c(Sn)=12 g/l a layer of tin oxide was deposited on the surface of the glass platelets.

[0183] The pH was then reduced to pH 2.0 with dilute HCl and a solution of 148 ml of TiCl.sub.4 (200 g of TiO.sub.2/l of demineralized water) was then dosed into the suspension. Completion of the addition was followed by 10 minutes of stirring, and the pH was then adjusted to pH 2.6. Then 8 ml of an aqueous iron chloride solution with a density of 1.25 g/cm.sup.3 was dosed in. Completion of the dosing was followed by another 10 minutes of stirring and by adding 75 ml of tin chloride solution with a concentration of c(Sn)=12 g/l, a further thin layer of tin oxide was deposited on the pigment surface. Then 180 ml of a solution of TiCl.sub.4 (200 g of TiO.sub.2/l of demineralized water) was dosed into the suspension, 15 minutes after completion of the addition the suspension was filtered off and the filter cake washed. The filter cake was dried and calcined at 900° C. for 60 minutes. Extremely chromatic, high-gloss, transparent effect pigments with golden interference color were obtained.

EXAMPLE 2

[0184] 200 g of synthetic mica platelets (fluorphlogopite platelets) with a particle-size distribution according to MALVERN Mastersizer MS 2000: D.sub.10=10 μm, D.sub.50=22 μm, D.sub.90=40 μm were suspended in 1300 ml of demineralized water and heated to 85° C. under turbulent stirring. The pH of the suspension was reduced to pH 2.2. By adding 100 g of a tin chloride solution with a concentration of c(Sn)=12 g/l a layer of tin oxide was deposited on the surface of the synthetic mica platelets. The pH of the suspension was reduced to pH 1.9 and a solution of 400 ml of TiCl.sub.4 (200 g of TiO.sub.2/l of demineralized water) was then dosed into the suspension. Completion of the addition was followed by 10 minutes of stirring, and the pH was than adjusted to pH 2.6. Then 30 ml of an aqueous iron chloride solution with a density of 1.42 g/cm.sup.3 was dosed in. Completion of the dosing was followed by 10 minutes of stirring, and 405 ml of a further solution of TiCl.sub.4 (200 g of TiO.sub.2/l of demineralized water) was dosed into the suspension. 15 minutes after completion of the addition the suspension was filtered off and the filter cake washed. The filter cake was dried and calcined at 850° C. for 60 minutes. Extremely chromatic, high-gloss, transparent effect pigments with blue interference color were obtained.

EXAMPLE 3

[0185] 200 g of synthetic mica platelets (fluorphlogopite platelets) with a particle-size distribution according to MALVERN Mastersizer MS 2000: D.sub.10=10 μm, D.sub.50=22 μm, D.sub.90=40 μm were suspended in 1300 ml of demineralized water and heated to 85° C. under turbulent stirring. The pH of the suspension was reduced to pH 2.2. By adding 100 g of a tin chloride solution with a concentration of c(Sn)=12 g/l a layer of tin oxide was deposited on the surface of the synthetic mica platelets. The pH of the suspension was reduced to pH 1.9 and a solution of 360 ml of TiCl.sub.4 (200 g of TiO.sub.2/l of demineralized water) was then dosed into the suspension. Completion of the addition was followed by 10 minutes of stirring, and the pH was than adjusted to pH 2.2. Then 1000 g of a tin chloride solution with a concentration of c(Sn)=12 g/l was dosed in. Completion of the dosing was followed by 10 minutes of stirring, and 400 ml of a further solution of TiCl.sub.4 (200 g of TiO.sub.2/l of demineralized water) was dosed into the suspension. 15 minutes after completion of the addition the suspension was filtered off and the filter cake washed. The filter cake was dried and calcined at 850° C. for 60 minutes. Extremely chromatic, high-gloss, transparent effect pigments with blue interference color were obtained.

EXAMPLE 4

[0186] 200 g of synthetic mica platelets (fluorphlogopite platelets) with a particle-size distribution according to MALVERN Mastersizer MS 2000: D.sub.10=10 μm, D.sub.50=22 μm, D.sub.90=40 μm were suspended in 1300 ml of demineralized water and heated to 85° C. under turbulent stirring. The pH of the suspension was reduced to pH 1.9 and a solution of 380 ml of TiCl.sub.4 (200 g of TiO.sub.2/l of demineralized water) was then dosed into the suspension. Completion of the addition was followed by 10 minutes of stirring, and the pH was then adjusted to pH 2.2. Then 150 ml of an aqueous zirconium tetrachloride solution (w(ZrCl.sub.2)=20%) was dosed in. Completion of the dosing was followed by 20 minutes of stirring, and 390 ml of a further solution of TiCl.sub.4 (200 g of TiO.sub.2/l of demineralized water) was dosed into the suspension. 15 minutes after completion of the addition the suspension was filtered off and the filter cake washed. The filter cake was dried and calcined at 850° C. for 60 minutes. Extremely chromatic, high-gloss, transparent effect pigments with blue interference color were obtained.

EXAMPLE 5

[0187] 200 g of glass platelets with a particle-size distribution according to MALVERN Mastersizer MS 2000: D.sub.10=10 μm, D.sub.50=20 μm, D.sub.90=40 μm were suspended in 1000 ml of demineralized water and heated to 85° C. under turbulent stirring. The pH of the suspension was reduced to pH 2.2. By addition 75 g of a tin chloride solution with a concentration of c(Sn)=12 g/l a layer of tin oxide was deposited on the surface of the glass platelets.

[0188] The pH was then reduced to pH 2.0 with dilute HCl and a solution of 100 ml of TiCl.sub.4 (200 g of TiO.sub.2/l of demineralized water) was then dosed into the suspension. Completion of the addition was followed by 60 minutes of stirring, and the pH was then adjusted to pH 2.2. Then 500 ml of a tin chloride solution with a concentration of c(Sn)=12 g/l was dosed in. Completion of the dosing was followed by 10 minutes of stirring, and 140 ml of a further solution of TiCl.sub.4 (200 g of TiO.sub.2/l of demineralized water) was dosed into the suspension. 60 minutes after completion of the addition the suspension was filtered off and the filter cake washed. The filter cake was dried and calcined at 800° C. for 60 minutes. Extremely chromatic, high-gloss, transparent effect pigments with blue interference color were obtained.

EXAMPLE 6

[0189] 100 g of the effect pigment obtained in Example 4 was suspended in 850 ml of demineralized water and heated to 85° C. under turbulent stirring. The pH was reduced to pH 4.2 with dilute hydrochloric acid. Then a solution of 0.93 g of Ce(NO.sub.3).sub.3×6 H.sub.2O dissolved in 40 ml of demineralized water was dosed in. Simultaneously, the pH was kept constant by adding a 10% NaOH solution dropwise. Complete addition of the solution was followed by one hour of stirring, and afterwards the pH was adjusted to pH 10 with dilute sodium hydroxide. Then 5.7 g of Dynasylan 1146 diluted with 24.3 g of demineralized water was added to the suspension, followed by 180 minutes of stirring, the suspension was filtered off and the filter cake subsequently washed with demineralized water. The filter cake was dried under vacuum at 95° C. Extremely chromatic, high-gloss, transparent effect pigments with blue interference color were obtained.

Comparison Example 1

[0190] Multilayer pigment with golden interference color based on natural mica platelets, coated with titanium dioxide, silicon dioxide, titanium dioxide, Timiron Splendid Gold, from Merck.

Comparison Example 2

[0191] Multilayer pigment with green interference color based on natural mica platelets, coated with titanium dioxide, silicon dioxide, titanium dioxide, Timiron Splendid Blue, from Merck.

Comparison Example 3

[0192] Effect pigment with blue interference color based on synthetic mica platelets, coated with titanium dioxide, SYMIC C261, from ECKART.

Comparison Example 4

[0193] Effect pigment with blue interference color based on natural mica platelets, coated with titanium dioxide, Pyrisima T40-23 SW Blue, from Merck.

Comparison Example 5

[0194] Multilayer pigment with blue interference color based on natural mica platelets, coated with titanium dioxide, silicon dioxide, titanium dioxide, Lumina Royal Blue, from BASF.

Comparison Example 6

[0195] Effect pigment with blue interference color based on natural mica platelets, coated with titanium dioxide, Iriodin 7225 Ultra Blue, from Merck.

II Characterization of the Transparent Effect Pigments According to the Invention as well as of the Pigments of the Comparison Examples

IIa Particle-Size Measurement

[0196] The size-distribution curve of the transparent effect pigments according to the invention as well as the pigments of the comparison examples was determined with Malvern's Mastersizer 2000 device according to the manufacturers instructions. For this, approximately 0.1 g of the respective pigment as aqueous suspension, without the addition of dispersion aids, was placed under constant stirring in the sample preparation cell of the measurement device by means of a Pasteur pipette and measured several times. The average values ware calculated from the individual measurement results. The evaluation of the scattered light signals was effected according to the Fraunhofer method.

[0197] By the “average particle size D.sub.50” is meant within the framework of this invention the D.sub.50 value of the cumulative frequency distribution of the volume-averaged size-distribution function, as obtained by laser diffraction methods. The D.sub.50 value indicates that 50% of the pigments have a volume-averaged diameter which is equal to or smaller than the indicated value, for example 20 μm. Correspondingly, the D.sub.10 or D.sub.90 value indicates that 10% or 90% respectively of the pigments have a volume-averaged diameter which is equal to or smaller than the respective measured value.

[0198] The span ΔD, defined as

[00004]$\Delta .Math..Math.D=\frac{D_{90}-D_{10}}{D_{50}},$

indicates the width of the particle-size distribution. With regard to the optical appearance of the transparent effect pigments according to the invention, a smaller value of ΔD, i.e. a narrow span, is preferred.

TABLE-US-00002 TABLE 2 Particle sizes Example/Comparison example D10 [μm] D50 [μm] D90 [μm] Span Example 1 28.1 53.0 92.7 1.219 Example 2 12.2 22.6 39.9 1.228 Example 3 12.5 23.0 40.4 1.217 Example 4 11.9 22.4 39.9 1.247 Example 5 9.3 21.0 43.0 1.608 Example 6 13.0 22.6 38.6 1.135 Comparison example 1 12.6 24.4 44.8 1.320 Comparison example 2 8.4 18.9 38.2 1.580 Comparison example 3 11.0 32.0 38.5 1.250 Comparison example 4 9.7 16.7 28.6 1.132 Comparison example 5 10.6 19.7 34.9 1.240

IIb Angle-Dependent Color Measurements

[0199] For measuring the color and lightness values, the effect pigments according to the invention, the pigments of the comparison examples and the non-metallic platelet-shaped substrates at a pigmentation level of 6 wt.-% (pigments) and 10 wt.-% (substrates) respectively, in each case relative to the total weight of the wet varnish, were stirred into a conventional nitrocellulose varnish (Erco bronze mixed varnish 2615e colorless; Maeder Plastiklack AG). The respective pigments or the respective non-metallic platelet-shaped substrates were taken and then dispersed in the varnish with a brush. The finished varnish was applied to a doctor-blade drawdown device (RK Print Coat Instr. Ltd. Citenco Printing Apparatus Model K 101) with a spiral blade in a wet-film thickness of 40 μm or 76 μm (Example 1) on black-white opacity charts (Byko-Chart 2853, Byk-Gardner) and then dried at room temperature. The selection of the spiral blade is made according to Table A depending on the D.sub.50 value of the pigments or substrates to be applied in each case. With the BYK-mac multi-angle colorimeter (Byk-Gardner) the color values ware determined on a black background of the opacity chart at a constant angle of incidence of 45° (in accordance with the manufacturer's instructions) at different angles of observation relative to the grazing angle. For characterizing the color intensity, the chroma value C*.sub.15 was used, which was measured on the black background of the black-white opacity chart as a measurement angle of 15° from the grazing angle.

[0200] Strongly reflecting samples (ideally mirrors) reflect almost all of the incident light at the so-called grazing angle. The closer the varnish application is measured to the grazing angle, the stronger the interference color appears.

TABLE-US-00003 TABLE A Wet-film thickness depending on the D.sub.50 value of the pigments or substrates to be applied D.sub.50 value Spiral blade <40 μm 40 μm 40 μm-85 μm 76 μm >85 μm 100 μm 

TABLE-US-00004 TABLE 3 Color values at an angle of observation of 15° relative to the grazing angle Example/Comparison example a* 15° (s).sup.1 b* 15° (s) C* 15° (s) Example 2 −9.10 −44.71 45.63 Example 3 3.84 −46.22 46.38 Example 5 6.49 −46.09 46.54 Comparison example 2 8.11 −49.70 50.36 Comparison example 3 3.30 −39.93 40.06 .sup.1Measured on a black background of the black-white opacity chart.

[0201] At the higher C*.sub.15 values of Table 3, measured on a black background of the black-white opacity chart, the transparent offset pigments according to rise invention with blue interference color from Examples 2, 3 and 5 are visibly clearly more color-intensive than the pigment covered only with a single titanium dioxide layer with blue interference color from comparison example 3. Their optical impression is approximately comparable to that of a multilayer pigment with blue interference color from comparison example 2.

IIc Opacity Comparison

[0202] For determining the opacity quotient D.sub.q, defined as

[00005]$D_q=\frac{L_{\mathrm{black}}^{*25}}{L_{\mathrm{white}}^{*25}},$

the lightness values L*25° of the varnish applications from IIb were recorded with the BYK-mac multi-angle colorimeter (Byk-Gardner) at a measurement aegis of 25° on the black and on the white background of the black-white opacity chart. At a constant angle of incidence of 45°, the measurement geometry 25° relates to the difference relative to the grazing angle. The angle of observation is measured from the secular reflection in the illumination plane.

[0203] The effect pigments according to the invention have a high transparency. Their opacity quotient D.sub.q is preferably ≦0.55. The opacity quotient D.sub.q of the transparent effect pigments according to the invention of Examples 1 to 5, as shown by Table 4, is in each case clearly below 0.5.

IId Gloss Measurements

[0204] The gloss is a measure of the directed reflection. For determining the gloss, the varnish applications from IIb were measured on the white background of the black-white opacity chart using a Byk-Gardner Micro-Tri-Gloss gloss meter at a measurement angle of 60° relative to the vertical. The gloss values of the transparent effect pigments according to the invention as well as of the pigments of the comparison examples are listed in Table 4.

[0205] The transparent effect pigments according to the invention from Examples 1 to 5 partly show clearly higher gloss values than the pigment coated with a single layer from comparison example 3. The gloss values of the transparent effect pigments according to the invention are sometimes even clearly higher than those of the multilayer pigments with the structure high-refractive-index/low-refractive-index/high-refractive-index from comparison examples 2, 4 and 5.

IIe Effect Measurements

[0206] In order to objectively describe the optical effect of the transparent effect pigments according to the invention, effect measurements ware carried out with the BYK-mac spectrophotometer (Byk-Gardner) on the basis of the varnish applications from IIb (cf. Byk-Gardner, Catalogue “Qualitätskontrolle für Lacke und Kunststoffe” [“Quality control for varnishes and plastics”] 2011/2012, pages 97/98). The corresponding measurement values for the glitter intensity S_i, the glitter area S_a and the granularity G are summarized in Table 4.

TABLE-US-00005 TABLE 4 Effect measurements, opacity quotient and gloss values Example/ Comparison S_i Gloss example 15° (s).sup.1 S_a 15 ° (s).sup.1 G (s).sup.1 D.sub.q 25° 60° (w).sup.2 Example 1 56.13 27.90 16.63 0.4070* 109.1 Example 2 7.03 26.22 5.75 0.4740 43.7 Example 3 5.44 22.25 4.62 0.4018 44.0 Example 4 8.06 28.05 7.12 0.4990 46.8 Example 5 18.65 34.94 6.24 0.3028 58.9 Comparison 6.70 29.53 5.14 0.3671 42.4 example 2 Comparison 4.69 20.65 4.14 0.3800 39.5 example 3 Comparison 4.70 21.22 3.13 0.3788 33.2 example 4 Comparison 4.52 21.80 3.58 0.3717 33.0 example 5 Nitrocellulose / / / 0.1130 92.1 varnish on black-white opacity chart .sup.1Measured on a black background of the black-white opacity chart. .sup.2Measured on a white background of the black-white opacity chart. *76 μm wet film thickness

[0207] The effect values S_i, S_a as well as G of the transparent effect pigments according to the invention from Examples 1 to 5 are either higher than or at least comparable to the values of comparison examples 2 to 5. Here too it can very easily be recognized that the achievable optical effects are clearly better than in the case of conventional pigments coated with a single layer from comparison examples 3 and 4. Even in comparison with the multilayer pigments from comparison examples 2, 4 and 5, the optical effects are at least equivalent, but usually better.

IIf Waring Blender Test

[0208] In the industry, many varnishes are processed in circulatory systems. Here the varnish components are exposed to high shear forces. The Waring Blender Test now simulates these conditions and serves to assess the ring-circuit or the shear stability. In this test, precisely pigments the coating of which is not sufficiently anchored to the carrier material show strong deviations of the chroma values compared with the untreated applications. The Waring Blender Test can thus be understood as a measure for the adhesion of the pigment coating vis-à-vis shear forces.

[0209] For this, the transparent effect pigments according to the invention or the pigments of the comparison examples were weighed in according to the following batch and mixed to a paste stepwise with a conventional acrylic varnish in an 880-ml beaker. The viscosity was then adjusted to 17″ in a DIN 4-mm beaker with butyl acetate/xylene 1:1. In total 600 g of varnish was produced, 400 g of which was poured into a double-walled 1-kg container with water cooling and stirred using a Dispermat (Waring Blender) with a special attachment. The stirring time was 8 minutes at 13,500 rpm then 200 g of varnish was removed and the remainder was stirred for another 12 minutes.

Batch: 6% pigment
 8% butyl acetate 85
 86% acrylic varnish, colorless
 30% dilution butyl acetate 85/xylene 1:1

[0210] In each case 200 g of the untreated and of the treated varnish were applied to a test plate with an automatic spraying system and the Sata LP-90 spray gun according to the following setting.

Setting: Needle: 1.3.4

 Pressure: 4 bar

[0211] Coats: The number of spray coats was selected such that there was a dry varnish layer thickness of 15-20 μm.

[0212] Conventionally, effect pigments are regarded as shear-stable when, in the application according to the Waring Blender Test, the gloss and also the color difference, measured close to the grazing angle, are relatively small. The ΔC* 15° value relative to the untreated sample should ideally be less than 2.

[0213] Table 5 shows the color change ΔC* 15° as well as the gloss change Δgloss 60° of the sample subjected to the Waring Blender Test relative to the untreated sample on the basis of Example 4 according to the invention.

TABLE-US-00006 TABLE 5 Gloss and color difference in the Waring Blender Test ΔC* 15° ΔGloss 60° Example 4 1.1 −1.0

[0214] The test plate of Example 4 according to the invention thus meets the test criteria. The color difference is negligibly small and scarcely perceptible to the naked eye. Even under a light microscope, changes such as flaking of the coating or other surface defects that had occurred could scarcely be detected. The transparent effect pigments according to the invention appear extremely shear-stable despite their spacer layer.

IIg Determination of the Chemical Resistance

[0215] The chemical resistance of the transparent effect pigments according to the invention and of the pigments of the comparison examples was determined on the basis of applications of varnish to plastic panels. 6 g of the respective pigment was stirred into a mixture of 90 g of a conventional colorless acrylic varnish and 10 g of butyl acetate 85. The viscosity was than adjusted to 17″ in a DIN 4-mm beaker with a mixture of butyl acetate 85 and xylene in the ratio of 1:1.

[0216] In each case 100 g of this varnish was applied with an automatic spray system analogously to IIf covering the panels. After the coating the panels were stoved at 80° C. for 30 minutes. 24 hours later the panels were immersed halfway in 10% sodium hydroxide. After a residence time of 7 days, the panels were washed with demineralized water and then after 2 hours' drying time visually assessed for damage and/or discolorations. Furthermore, discolorations were measured using the BYK-mac (Byk-Gardner). For characterizing the color change, the ΔE value of the loaded sample was used, against the corresponding unloaded sample, at a measurement angle of 15°. The results are reproduced in Table 6 below.

TABLE-US-00007 TABLE 6 Color change ΔE Example/Comparison example ΔE (15°) Example 3 0.3 Example 4 0.9 Comparison example 1 9.3 Comparison example 2 19.9 Comparison example 5 59.8

[0217] Pigments with an ΔE (15°) <3 can be regarded as chemically stable. The transparent effect pigments according to the invention from Examples 3 and 4 lie clearly below this, while the pigments of comparison examples 1, 2 and 5 clearly exceed the limit value.

IIh X-Ray Fluorescence (XRF) Analysis

[0218] The metal oxide, metal hydroxide and/or metal oxide hydrate contents of the transparent effect pigments according to the invention as well as of the pigments of the comparison examples were determined by means of X-ray fluorescence (XRF) analysis. For this, the respective pigments ware incorporated into a lithium tetraborate glass tablet, fixed in solid sample measuring beakers and measured therefrom. Thermo Scientific's Advantix ARL device was used as measuring device. The measured values are reproduced in Table 7. The values of the different contents were indicated as TiO.sub.2 for titanium, as Fe.sub.2O.sub.3 for iron, as ZrO.sub.2 for zirconium and as SnO.sub.2 for tin.

TABLE-US-00008 TABLE 7 Height h.sub.a of the spacer layer and XRF analysis values Example/ Comparison XRF analysis (as metal oxide) example h.sub.a [nm] from SEM Ti [%] Fe [%] Sn [%] Zr [%] Example 1 20 28.6 3.1 0.98 / Example 2 18 48.4 2.8 0.84 / Example 3 18 45.1 0.04 5.40 / Example 4 20 40.4 0.4 / 5.7 Example 5 13 22.0 / 1.60 / Comparison No spacer layer 52.8 0.6 / / example 1 Comparison No spacer layer 60.9 / / / example 2 Comparison No spacer layer 52.6 0.05 0.53 / example 3 Comparison No spacer layer 43.4 0.8 7.7 / example 4 Comparison No spacer layer 33.1 1.4 1.9 / example 5

IIi Condensation Water Test

[0219] For determining the condensation-water resistance, the transparent effect pigments according to the invention or the pigments of the comparison examples were incorporates into a water varnish system and the test applications were produced by spray painting on aluminum sheets. The base coat was painted over with a commercially available 1K clear varnish and then stoved. These applications were tested according to DIN EN ISO 6270-2 “Paints and varnishes—Determination of resistance to humidity—Part 2: Procedure for exposing test specimens in condensation-water atmospheres” (ISO 6270-2:2006). The adhesive strength was tested by means of the cross-cut test according to DIN EN ISO 2409 “Paints and varnishes—Cross-cut test” (ISO 2409:2013) immediately after the end of the last in comparison with the unloaded sample. Here Gt 0 means no change and Gt 5 means a very significant change.

[0220] The swelling behavior was visually assessed immediately after condensation-water loading according to DIN EN ISO 4628-1 “Paints and varnishes—Evaluation of degradation of coatings—Designation of quantity and size of defects, and of intensity of uniform changes in appearance—Part 1: General introduction and designation system” (ISO 4628-1:2003). Here the code number 0 means no change and 5 means a very significant change.

[0221] Finally the DOI (distinctness of image) was determined on the basis of a wave-scan II (Byk-Gardner).

TABLE-US-00009 TABLE 8 Condensation water results Example/ Gloss 20° Gloss 20° Comparison before CW after CW Loss of Cross-cut test Swelling example test test gloss DOI immediately visually Example 6 91.2 90.8 <1% 80.4 0 0 Comparison 90.3 62.1 31% 56.8 3 4 example 6

[0222] The pigment from comparison example 6 exhibited a strong swelling behavior and poor inter-layer adhesion. The transparent effect pigment according to the invention from Example 6 on the other hand appeared stable and exhibited almost no changes before and after the test.

IIj UV Resistance

[0223] The UV resistance of the transparent effect pigments according to the invention as well as of the pigments of the comparison examples was determined according to the UV rapid test described in EP 0 870 730 A1 for determining the photochemical UV activity of TiO.sub.2 pigments. For this, 1.0 g of the corresponding pigment was dispersed in 9.0 g of a melamine-containing varnish rich in double-bonds. Doctor-blade drawdowns were prepared on white card and dried at room temperature. The doctor-blade drawdowns were divided and in each case one of the two sections was stored in the dark as an unloaded reference sample. The samples were then irradiated for 150 minutes in a QUV device from Q-Panel with UV-containing light (UVA-340 lamp, irradiance 1.0 W/m.sup.2/nm). Immediately after the end of the test, color values of the loaded samples were determined with a CM-508i colorimeter from Minolta relative to the respective retention sample. The resulting ΔE* values, calculated according to the Hunter-L*a*b* formula, are shown in Table 9.

[0224] In this test, a substantially grey-blue discoloration of the TiO.sub.2 layer of the respective pigment is observed because of Ti(III) species formed under UV light. A precondition for this is that the electron hole has spatially left the TIO.sub.2 and—for instance by reaction with olefinic double bonds of the binder—cannot immediately recombine with the remaining electron again. As a melamine-containing varnish layer significantly slows down the diffusion of water (vapor) and oxygen at the pigment surface, the reoxidation of the titanium(III) species take place with a clear delay, with the result that the greying can be measured and the ΔE* value can be used as a measure of the UV stability of the pigments. A larger ΔE* numerical value of the loaded sample relative to the unloaded retention sample thus means a lower UV stability of the pigment examined.

TABLE-US-00010 TABLE 9 UV test results Example/Comparison example ΔE* Example 6 3.7 Comparison example 6 17.6 The pigment from comparison example 6 exhibited a clearly stronger color change (ΔE*) than Example 6 following corresponding exposure.
IIk Determination of the Average Thickness of the Non-Metallic Platelet-Shaped Substrates, the Average Layer Thickness of Layers 2 and 3, the Average Layer Thickness of the Entire Coating, the Average Height h.sub.a of the Spacer Layer as well as the Average Height h.sub.H of the Cavities

[0225] For this, the transparent effect pigments according to the invention were incorporated 10% in a 2K clear varnish, Autoclear Plus HS from Sikkens GmbH, with a brush, applied to a film using a spiral blade (26 μm wet film thickness) and dried. After 24 hours' drying time, polished cross-sections were prepared from these doctor-blade drawdowns. the polished cross-sections were measured using SEM, wherein for determining the average thickness of the non-metallic platelet-shaped substrates at least 100 individual pigments were measured in order to obtain meaningful statistics. For determining the average layer thickness of layers 2 and 3, the average thickness of the entire coating, the average height h.sub.a of the spacer layer as well as the average height h.sub.H of the cavities, the upper and lower substrate surface, i.e. in each case the longer side of the non-metallic platelet-shaped substrate recognizable in the SEM polished cross-section, was in each case used as base line. The base line was here placed in the scanning electron microscope polished cross-section photograph along the surface of the platelet-shaped substrate in the polished cross-section photograph, by connecting the two intersections, non-metallic platelet-shaped substrate—optional and non-metallic platelet-shaped substrate—layer 2, to each other by a straight line from the left- and right-hand edge of the scanning electron microscope polishes cross-section photograph. The scanning electron microscope polished cross-section photographs ware examined using AxioVision 4.6.3. image-processing software (Zeiss).

[0226] At an angle of 90° to these two base lines, so many parallel lines were drawn in 50 nm apart that a grid was placed over the complete scanning electron microscope polished cross-section photograph of the effect pigment (FIG. 4). The magnification of the scanning electron microscope polished cross-section photograph was preferably at least 50,000 times, relative to Polaroid 545. Starting from the respective upper and lower base line of the non-metallic platelet-shaped substrate, in each case in the direction of layer 3 the distances between the intersections of these lines at the respective boundary surfaces of optional layer 1 to layer 2, layer 2 to the spacer layer, spacer layer to layer 3 and layer 3 to the environment ware measured manually. It occurred here that a line drawn in at a distance of 50 nm lay directly over a connection or a spacer. In this case only the respective intersection of the line at the boundary surface of layer 3 to the environment was recorded. From these measured values, the layer thicknesses of layers 2 and 3, the thickness of the entire coating, as well as the height h.sub.a of the spacer layer were obtained by subtraction.

[0227] The intersections of these parallel lines with the upper and lower cavity boundary within the spacer layer were used for determining the average height h.sub.H of the cavities.

[0228] From the individual values determined in this way of the lever thicknesses, the height h.sub.a as well as the height h.sub.H, the respective arithmetic mean values were formed, in order to determine the above-indicated values of the average layer thicknesses, the average height h.sub.H or average height h.sub.a. For meaningful statistics, the above-described measurements were carried out on at least 100 lines. By the term “average” is meant in all cases the arithmetic mean value.

[0229] Polishes cross-sections of the pigments of the comparison examples, which have not a spacer layer, but optionally statistically distributed pores within the coating, were also examined according to the above-described method on the basis of scanning electron microscope polished cross-section photographs. Here, if one of the parallel lines has come to lie over one or more pores, the height of the pore(s), their pore center(s) and the distance from the pore center or pore centers to the substrate surface were determined.

[0230] Alternatively to polished cross-sections, the transparent effect pigments according to the invention can be cut by means of the FIB (focused ion beam) method. For this, a fine beam of highly accelerated ions (e.g. gallium, xenon, neon or helium) is focused at a point by means of an ion-optical system and guided line by line over the effect pigment surface to be processed. The ions emit most of their energy on impact with the effect pigment surface and destroy the coating at this point, which leads to material removal line by line. Also, based on the scanning electron microscope photographs then taken, the average height h.sub.a, the average layer thickness of layers 2 and 3 as well as the average layer thickness of the entire coating can be determined according to the method described above. Also, the average thickness of the non-metallic platelet-shaped substrate can be determined based on scanning electron microscope photographs of the effect pigments cut by the FIB method.

TABLE-US-00011 TABLE 10 Characterization of the coating Example/ Comparison d.sub.S2 d.sub.S3 h.sub.m h.sub.Rm S.sub.D A.sub.H example [nm] [nm] d.sub.S2/d.sub.S3 [nm] h.sub.Rm [%] n.sub.S [%] [%] Example 2 50 66 0.76 59.4 0.44 4.4 3.3 22.9 77.1 Example 3 53 61 0.87 62.0 0.49 6.4 6.3 31.0 69.0 Example 4 57 56 1.02 67.0 0.51 13.8 3.3 17.1 82.9 Example 5 56 51 1.10 62.6 0.52 6.4 13.3 66.5 33.5 Comparison No spacer layer 30.4 10 50.3 49.7 example 3 d.sub.S2 [nm] = average layer thickness of layer 2 d.sub.S3 [nm] = average layer thickness of layer 3 h.sub.m  = middle of the spacer layer (sum of the layer thickness of optional layer 1, layer 2 and half of height h.sub.a) h.sub.Rm  = relative height of the spacer layer h.sub.Rm  [%] = standard deviation of the relative height of the spacer layer n.sub.S = average number of bars per μm A.sub.H [%] = surface area of cavity S.sub.D = bar number density [%] indicates data missing or illegible when filed

[0231] Table 7 shows the average height h.sub.a of the spacer layer of the measured pigments. All the transparent effect pigments according to the invention, unlike the pigments of comparison examples 1 to 6, have a spacer layer.

[0232] The pigment from comparison example 3 has no spacer layer, but statistically distributed pores within the coating (FIG. 5). In Table 10, for comparison example 3, by the value in the column σh.sub.Rma[5]is meant the standard deviation of the pore centers relative to the substrate surface. As the pigment from comparison example 3 however only contains a few statistically distributed pones, the bar number density S.sub.D is 50.3%. The standard deviation of the pore centers relative to the substrate surface is 30.4%, proving that the pores are present statistically distributed within the entire coating. The case is different with the transparent effect pigment according to the invention from Example 5. Here too, at 66.5% the bar number density S.sub.D is very high, but the standard deviation of the relative height of the center of the spacer layer h.sub.Rma is 6.4%, which indicates that the spacer layer lies in a defined portion within the coating. The standard deviation of the distances from the pore centers to the substrate surface of the pigment from comparison example 3 can thus be contrasted with the standard deviation of the relative height of the center of the spacer layer of the transparent effect pigments according to the invention from Examples 2 to 5.

[0233] The spacer layer influences the optical properties of the transparent effect pigments according to the invention. In addition to high transparency, high gloss and high color intensity, the transparent effect pigments according to the invention have very good mechanical and chemical stability. None of the pigments from the comparison examples exhibits the named properties in the overall view in a satisfactory manner.

IIl Scanning Electron Microscope Photographs

[0234] The scanning electron microscope photographs ware obtained on the basis of polished cross-sections of the transparent effect pigments according to the invention, with the Supra 35 scanning electron microscope (Zeiss) (for example FIGS. 1-4). The energy-dispersive X-ray microanalysis (EDX analysis) was carried out with the EDAX Sapphire device from EDAX.

III Application-Specific Examples

Application-Specific Example 1: Body Lotion

[0235]

TABLE-US-00012 Manufacturer/ INCI Name Product name wt.-% Supplier Phase A 85.80 Effect pigment 0.20 from Example 1 Aqua Water Glycerin Glycerin 85% 2.00 H. Erhard Wagner Xanthan Gum Keltrol CG-T 0.60 CP Kelco Phase B Isopropyl Palmitate Isopropyl palmitate 3.00 H. Erhard Wagner Glyceryl Stearate Aldo MS K FG 2.00 Lonza Cocos Nuifera Oil Ewanol KR 2.00 H. Erhard Wagner Cetearyl Alcohol Tego Alkanol 1618 2.00 Evonik Dimethicone Element 14 PDMS 1.00 Momentive Sodium Polyacrylate Cosmedia SP 0.50 BASF Phase C Phenoxyethanol, Euxyl PE 9010 0.80 Schülke & Meyr Ethylhexylglycerin Fragrance Vitamin Bomb 0.10 Bell Europe

[0236] The effect pigment from Example 1 can be used in a range of from 0.1 to 2.5 wt.-%, relative to the total weight of the body lotion formulation. The formulation can be made up to 100 wt.-% with water. Keltrol CG-T was dispersed in phase A and heated to 75° C. Phase B was separately heated to 75° C. Phase B was then slowly added to phase A. Under stirring, the emulsion was cooled to room temperature and phase C added individually.

Application-Specific Example 2: Cream Eyeshadow

[0237]

TABLE-US-00013 Manufacturer/ INCI Name Product name wt.-% Supplier Phase A Microcrystalline Wax TeCero-Wax 1030 K 4.50 Tromm Wachs Copernicia Cerifera Cera Carnauba wax LT 4.50 Tromm Wachs 124 Isohexadecane Isohexadecane 21.00 Ineos Cyclopentasiloxane, Belsil RG 100 8.00 Wacker Dimethicone/Vinyltrimethylsiloxysilicate Silicone Elastomer Crosspolymer Resin Gel Trimethylsiloxyphenyl Dimethicone Belsil PDM 20 6.00 Wacker Dimethicone Belsil DM 100 14.00 Wacker Caprylic/Capric Triglyceride Miglyol 812 7.00 Sasol Cyclomethicone (and) Quaternium-90 Tixogel VSP-1438 5.00 BYK Bentonite (and) Propylene Carbonate Phase B Effect pigment from 30.00 Example 5

[0238] The effect pigment from Example 5 can be used in a range of from 5 to 30.0 wt.-%, relative to the total weight of the eyeshadow formulation. The formulation can be made up to 100 wt.-% with isohexadecane.

[0239] Phase A was mixed and heated to 85° C. phase B was then added to phase A under stirring. After being poured into a corresponding container the mixture is cooled to room temperature.

Application-Specific Example 3: Shower Gel

[0240]

TABLE-US-00014 INCI Name Product name wt.-% Manufacturer/Supplier Phase A Effect pigment from 0.10 Example 4 Aqua Water 58.50 Acrylates Copolymer Carbopol Aqua SF-1 5.50 Lubrizol Phase B Sodium Hydroxide NaOH (10 wt.-%) 1.50 Phase C Sodium Laureth Sulfate Zetesol NL-2 U 22.00 Zschimmer & Schwarz Cocamidopropyl Betaine Amphotensid B5 6.00 Zschimmer & Schwarz PEG-7 Glyceryl Cocoate Emanon HE 2.00 Kao Corp. Disodium Laureth Sulfosuccinate Sectacin 103 special 2.00 Zschimmmer & Schwarz Phase D Phenoxyethanol (and) Piroctone Nipaguard PO 5 0.60 Clariant Olamine Fragrance Water Lily OA 0.20 Bell Flavors and Fragrances Sodium Chloride Sodium Chloride 1.60 VWR

[0241] The effect pigment from Example 4 can be used in a range of from 0.01 to 1.0 wt.-%, relative to the total weight of the shower gel formulation. The formulation can be made up to 100 wt.-% with water. Phase A was stirred, then phase B was added and stirred until a homogeneous appearance was achieved. Phase C was weighed in separately, briefly mixed and added to phase AB. Stirring was then resumed and phase D added individually.

Application-Specific Example 4: Pressed Eyeshadow

[0242]

TABLE-US-00015 Manufacturer/ INCI Name Product name wt.-% Supplier Phase A Talc Talc Powder 36.00 VWR Bentonite Optigel CK-PC 5.00 BYK Synthetic Synafil S 1050 13.00 ECKART Fluorphlogopite Aluminum Starch Agenaflo OS 9051 10.00 Agrana Octenylsuccinate Magnesium Stearate Magnesium Stearate 6.00 VWR Effect pigment from 20.00 Example 3 Phase B Cyclomethicone Xiameter PMX-0345 5.00 Dow Corning Octyldodecyl Ceraphyl 847 5.00 Ashland Stearoyl Stearate

[0243] The effect pigment from Example 3 can be used in a range of 5.0 to 40.0 wt.-%, relative to the total weight of the eyeshadow formulation. The formulation can be made up to 100 wt.-% with talc.

[0244] Phase A was mixed at 2500 rpm in a high-speed mixer for 30 s. Phase B was then added and the mixture mixed at 3000 rpm in the same mixer for 60 s. Finally the powder mixture is pressed into shape by means of an eyeshadow press at 100 bar for 30 seconds.

Application-Specific Example 5: Mascara

[0245]

TABLE-US-00016 Manufacturer/ INCI Name Product name wt.-% Supplier Phase A Aqua Water 73.00 Bentonite (and) Xanthan Gum Optigel WX-PC 2.00 BYK Phase B Cetyl Alcohol (and) Glyceryl Stearate Emulium Delta 5.00 Gattefossé (and) PEG-75 Stearate (and) Ceteth-20 (and) Steareth-20 C10-18 Triglycerides Lipocire A Pellets 2.00 Gattefossé Ozocerite Kahlwax 1899 2.00 Kahl Glyceryl Behenate Compritol 888 CG 2.00 Gattefossé Pastilles Butylene Glycol Cocoate Cocoate BG 4.00 Gattefossé Phase C Effect pigment from 5.00 Example 1 Phenoxyethanol (and) Piroctone Olamine Nipaguard PO5 0.50 Clariant Glycine Soja (Soybean) Oil, Dicaprylyl Follicusan DP 3.00 CLR Berlin Ether, Magnolia Grandiflora Bark Extract, Lauryl Alcohol Water, Hydrolyzed Corn Starch, Beta DayMoist CLR 1.00 CLR Berlin Vulgaris (Beet) Root Extract Linoleic Acid (and) Linolenic Acid Vitamin F forte 0.50 CLR Berlin

[0246] The effect pigment from Example 1 can be used in a range of from 1.0 to 10.0 wt.-%, relative to the total weight of the mascara formulation. The formulation can be made up to 100 wt.-% with the water from phase A.

[0247] Phase A was stirred under high shear. Phase B was weighed in separately. Phase A and phase B were heated separately to 85° C., then phase B was added to phase A. Phase AB was then cooled to 45° C. and, during the cooling, phase C was added gradually under stirring.

Application-Specific Example 6: Hair Gel

[0248]

TABLE-US-00017 Manufacturer/ INCI Name Product name wt.-% Supplier Phase A Sodium Magnesium Silicate (nano) Laponite XLG 2.00 BYK Aqua Water 94.80 Phase B Effect pigment 0.10 from Example 1 Citric Acid (and) Water Citric Acid (10%) 0.30 Glycerin, Water, Avena Strigosa Seed Extract, Aquarich 1.50 Rahn AG Lecithin, Potassium Sorbate, Citric Acid Fragrance Lychee & Grape 0.10 Bell Europe Methylisothiazolinone (and) Phenethyl Alcohol Optiphen MIT 1.20 Ashland (and) PPG-2 Methyl Ether Plus

[0249] The effect pigment from Example 1 can be used in a range of from 0.01 to 2.0 wt.-%, relative to the total weight of the hair gel formulation. The formulation can be made up to 100 wt.-% with water.

[0250] The Laponite XLG was stirred with water until phase A became clear. The effect pigment from Example 1 was then added to phase B under stirring. The remaining ingredients were then gradually added to phase B.

Application-Specific Example 7: Body Powder

[0251]

TABLE-US-00018 Manufacturer/ INCI Name Product name wt.-% Supplier Phase A Synthetic Synafil S 1050 40.00 Eckart Fluorphlogopite Polypropylene Synafil W 1234 8.00 Eckart Bentonite Optigel CK-PC 10.00 BYK Talc Talc Powder 18.00 VWR Magnesium Stearate Magnesium Stearate 4.00 Applichem Effect pigment 20.00 from Example 1

[0252] The effect pigment from Example 1 can be used in a range of from 0.2 to 5.0 wt.-%, relative to the total weight of the body power formulation. The formulation can be made up to 100 wt.-% with Synafil S 1050.

[0253] Phase A was mixed and then the powder was poured into a suitable container.

Application-Specific Example 8: Lip Gloss

[0254]

TABLE-US-00019 Manufacturer/ INCI Name Product name wt.-% Supplier Phase A Hydrogenated Polyisobutene (and) Versagel ME 750 75.30 Penreco Ethylene/Propylene/Styrene Copolymer (and) Butylene/Ethylene/Styrene Copolymer Simmondsia Chinensis (Jojoba) Seed Oil Jojoba Oil - Natural 2.00 BioChemica Caprylyl Trimethicone Silcare Silicone 7.00 Clariant 31M50 Stearyl Dimethicone Silcare Silicone 3.20 Clariant 41M65 Hydrogenated Polydecene Dekanex 2004 FG 4.00 IMCD Isopropyl Myristate Isopropyl Myristate 4.50 VWR Phase B Effect pigment from 4.00 Example 1

[0255] The effect pigment from Example 1 can be used in a range of from 0.10 to 8.00 wt.-%, relative to the total weight of the lip gloss formulation. The formulation can be made up to 100 wt.-% with Versagel ME 750.

[0256] Phase A was heated to 85° C., then the effect pigment from Example 1 was added to phase B, stirred until a uniform consistency was formed and then poured into a lip gloss container.

Application-Specific Example 9: Lipstick

[0257]

TABLE-US-00020 Manufacturer/ INCI Name Product name wt.-% Supplier Phase A Octyldodecanol Eutanol G 42.5 BASF Candelilla Cera Kahlwax 2039 6.00 Kahl Copernicia Cerifera (Carnauba) Kahlwax 2442 6.00 Kahl Wax Bis-Diglyceryl Polyacyladipate-2 Softisan 649 10.00 Sasol Polyisobutene Rewopal PIB 1000 10.00 Evonik Hydrogenated Polydecene Silkflo 364 NF polydecene 5.00 Ineos C10-18 Triglycerides Lipocire A Pellets 5.00 Gattefossé Acacia Decurrens/Jojoba/ Hydracire S 5.00 Gattefossé Sunflower Seed Wax/Polyglyceryl- 3 Esters Tocopheryl Acetate dl-alpha-Tocopheryl Acetate 0.50 IMCD Phase B Effect pigment from 10.00 Example 1

[0258] The effect pigment from Example 1 can be used in a range of from 0.5 to 20.0 wt.-%, relative to the total weight of the lipstick formulation. The formulation can be made up to 100 wt.-% with Eutanol G.

[0259] Phase A was heated to 85° C., then phase B was added to phase A and mixed. This mixture was then poured into a lipstick mold at a temperature of 75° C.

Application-Specific Example 10: Liquid Eyeliner

[0260]

TABLE-US-00021 Manufacturer/ INCI Name Product name wt.-% Supplier Phase A Aqua Water 56.90 Bentonite (and) Xanthan Gum Optigel WX-PC 1.40 Phase B Lecithin Emulmetik 100 0.10 Lucas Meyer Copernicia Cerifera Cera Kahlwax 2442 1.00 Kahl Stearic Acid Stearic Acid 3.50 Lipo Chemicals Hydrogenated Polyisobutene Panalane L14 E 5.00 Ineos Polysorbate 60 Mulsifan CPS 60 1.50 Zschimmer & Schwarz Phase C Effect pigment from Example 3 4.00 Polyurethane-35 Baycusan C 1004 18.00 Bayer Cosmetics Aqua and CI 77499 and WorléeBase AQ 77499/1 8.00 Worlée Methylpropanediol and Ammonium Acrylates Copolymer and Simethicone and Caprylyl Glycol and Phenylpropanol Sodium Acrylates Copolymer Phenoxyethanol, Euxyl PE 9010 0.60 Schülke & Mayr Ethylhexylglycerin

[0261] The effect pigment from Example 3 can be used in a range of from 0.5 to 8.0 wt.-%, relative to the total weight of the eyeliner formulation. The formulation can be made up to 100 wt.-% with water. Optigel WX-PC was dispersed in water of phase A and stirred for 10 minutes. Phase A and phase B were heated separately to 80° C. Phase B was then added slowly to phase A under stirring. After cooling to 45° C. the ingredients of phase C were added gradually and poured into suitable packaging.

Application-Specific Example 11: Mousse

[0262]

TABLE-US-00022 Manufacturer/ INCI Name Product name wt.-% Supplier Phase A Cyclopentasiloxane Xiameter PMX-0245 8.60 Dow Corning Cyclosiloxanes Hydrogenated Polyisobutene MC 30 4.00 Sophim Dimethicone (and) Dimethicone Dow Corning 9041 37.14 Dow Corning Crosspolymer Silicone Elastomer Blend Squalane Squalane 5.74 Impag Isononyl Isononanoate Dermol 99 10.16 Akzo International Hydrogenated Jojoba Oil Jojoba Butter LM 2.15 Desert Whale Hydrogenated Jojaba Oil Jojoba butter HM 1.00 Desert Whale C30-45 alkyl methicone (and) C30-45 Dow Corning AMS-C30 1.15 Dow Corning Olefin Cosmetic Wax Stearyl Dimethicone Dow Corning 2503 0.47 Dow Corning Cosmetic Wax Cyclopentasiloxane (and) Dow Corning 670 Fluid 5.00 Dow Corning Polypropylsilsesquioxane Phase B Dimethicone/Vinyl Dimethicone Dow Corning 9506 16.02 Dow Corning Crosspolymer Powder Silica Dimethyl Silylate Covasilic 15 0.17 LCW Talc Talc Powder 5.00 Sigma-Aldrich Effect pigment from 3.00 Example 1 Phase D Phenoxyethanol, Ethylhexylglycerin Euxyl PE 9010 0.40 Schülke & Mayr

[0263] The effect pigment from Example 1 can be used in a range of from 0.1 to 8.0 wt.-%, relative to the total weight of the mousse formulation. The formulation can be made up to 100 wt.-% with Dow Corning 9041 elastomer.

[0264] Phase A was mixed and heated until it was all melted. Phase B was weighed in separately and mixed with a high-speed mixer at 2400 rpm for 60 s. Half of the molten phase A was added to phase B and again mixed in the mixer at 2400 rpm for 30 s. The remainder of phase B was then also added to phase A and again mixed at 2400 rpm for 30 s. Finally, phase C is added to phase AB and again mixed in the high-speed mixer at 2400 rpm for 30 s.

Application-Specific Example 12: Nail Varnish

[0265]

TABLE-US-00023 Manufacturer/ INCI Name Product name wt.-% Supplier Phase A Effect pigment from 4.00 Example 5 Phase B Butylacetate (and) International Lacquers 96.00 International Ethylacetate (and) Nailpolish Base 15244 Lacquers Nitrocellulose (and) Isopropyl Alcohol

[0266] The effect pigment from Example 5 can be used in a range of from 0.1 to 8.0 wt.-%, relative to the total weight of the nail varnish formulation. The formulation can be made up to 100 wt.-% with International Lacquers Nailpolish.

[0267] Phase A and phase B were mixed and then poured into a suitable container.

Application-Specific Example 13: Nail Varnish with “Soft Touch” Effect

TABLE-US-00024 Manufacturer/ INCI Name Product name wt.-% Supplier Phase A Effect pigment from 4.00 Example 2 Polypropylene Synafil W 1234 5.00 Eckart Phase B Butylacetate (and) International Lacquers 91.00 International Ethylacetate (and) Nailpolish Base 15244 Lacquers Nitrocellulose (and) Isopropyl Alcohol

[0268] The effect pigment from Example 2 can be used in a range of from 0.1 to 8.0 wt.-%, relative to the total weight of the nail varnish formulation. The formulation can be made up to 100 wt.-% with International Lacquers Nailpolish.

[0269] Phase A was mixed, added to phase B and the nail varnish was then poured into a suitable container.

Application-Specific Example 14: Aqueous Nail Varnish

[0270] The pigments from Examples 1 to 6 can be used in an aqueous nail varnish according to WO 2007/115675 A2 Example 1. The pigmentation level here is 0.1 to 10.0 wt.-%, relative to the total weight of the formulation.

Application-Specific Example 15: Liquid Eyeshadow

[0271]

TABLE-US-00025 Manufacturer/ INCI Name Product name wt.-% Supplier Phase A Water Aqua 73.80 Glycerin Glycerin 3.00 H. Erhard Wagner Phase B PEG-800 Polyglycol 35000 S 0.60 Clariant Ammonium Aristoflex AVC 0.80 Clariant Acryloyldimehtyltaurate/ VP Copolymer Acrylates Copolymer Worlée Micromer CEK 20/50 5.00 Worlée Phase C Effect pigment from Example 3 10.00 Divinyldimethicone/Dimethicone Dow Corning HMW 2220 6.00 Dow Corning Copolymer C12-C13 Pareth-3, Non-Ionic C12-C13 Pareth-23 Emulsion Phenoxyethanol, Euxyl PE9010 0.80 Schülke & Mayr Ethylhexylglycerin

[0272] The effect pigment from Sample 3 can be used in a range of from 0.10 to 20.00 wt.-%, relative to the total weight of the eyeshadow formulation. The formulation can be made up to 100 wt.-% with water.

[0273] Phase A was stirred, then the ingredients of phase B were added individually to phase A and stirred until a uniform consistency was formed. Then the ingredients of phase C were added individual to phase AB and stirred until a uniform consistency was formed again.

[0274] FIG. 1: Scanning electron microscope polished cross-section photograph of an effect pigment according to the invention magnified 50,000 times (relative to Polaroid 545).

[0275] FIG. 2: Scanning electron microscope polished cross-section photograph of an effect pigment according to the invention magnified 50,000 times (relative to Polaroid 545).

[0276] FIG. 3: Scanning electron microscope polished cross-section photograph of an effect pigment according to the invention magnified 20,000 times (relative to Polaroid 543).

[0277] FIG. 4: Section of the scanning electron microscope polished cross-section photograph from FIG. 2 with base line drawn in at the non-metallic platelet-shaped substrate—coating boundary surface and lines arranged vertical to the base line. The intersections at the boundary surfaces are marked with an “x”.

[0278] FIG. 5: Scanning electron microscope polished cross-section photograph of comparison example 3 magnified 20,000 times (relative to Polaroid 545).

[0279] FIG. 8: Schematic representation of the spacer layer.

[0280] FIG. 9: Schematic representation of the position of the spacer layer.