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

Abstract

The invention relates to an absorbent effect pigment including a nonmetallic substrate in platelet form and a coating applied thereto, wherein the coating includes at least one spacer layer. The invention further relates to a process for production of and to the use of the absorbent effect pigment.

Claims

1. An absorbent effect pigment comprising a nonmetallic substrate in platelet form and a coating applied to the substrate, wherein the coating comprises a) optionally a layer 1 comprising or consisting 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, at least one of layers 2 and 3 comprises at least two different metal ions and layers 2 and 3 are interrupted by a spacer layer.

2. The absorbent effect pigment as claimed in claim 1, wherein the nonmetallic substrate in platelet form is selected from the group consisting of natural mica platelets, synthetic mica platelets, iron mica, glass platelets, SiO.sub.2 platelets, Al.sub.2O.sub.3 platelets, kaolin platelets, talc platelets, bismuth oxychloride platelets and mixtures thereof, and the nonmetallic substrate in platelet form has optionally been coated with at least one of metal oxide, metal hydroxide or metal oxide hydrate.

3. The absorbent effect pigment as claimed in claim 1, wherein the effect pigment comprises further layers of high and/or low refractive index and optionally at least one further spacer layer.

4. The absorbent effect pigment as claimed in claim 1, wherein the at least two different metal ions of layers 2 and 3 are selected from the group of metals consisting of Ti, Fe, Sn, Mn, Zr, Ca, Sr, Ba, Ni, Sb, Ag, Zn, Cu, Ce, Cr and Co, and wherein the proportion of noncoloring metal ions selected from the group of the metals consisting of Ti, Sn, Zr, Ca, Sr, Ba and Zn totals ≦40% by weight, and the proportion of coloring metal ions selected from the group of the metals consisting of Fe, Ti, Sn, Mn, Ni, Sb, Ag, Cu, Ce, Cr and Co totals ≧4% by weight, determined by means of XRF in each case, calculated in each case as the elemental metal and based in each case on the total weight of the absorbent effect pigment of the invention.

5. The absorbent effect pigment as claimed in claim 1, wherein a weight ratio, determined by means of XRF and calculated as the elemental metal, of noncoloring metal ions to coloring metal ions in the absorbent effect pigment of the invention is preferably <20.

6. The absorbent effect pigment as claimed in claim 1, wherein the at least one spacer layer is arranged essentially parallel to the surface of the nonmetallic substrate in platelet form.

7. The absorbent effect pigment as claimed in claim 1, wherein the at least one spacer layer has a mean height h.sub.a from a range from 5 nm to 120 nm.

8. The absorbent effect pigment as claimed in claim 1, wherein the at least one spacer layer includes connections and cavities.

9. The absorbent effect pigment as claimed in claim 1, wherein the at least one spacer layer has a network density of <85%.

10. A process for producing the absorbent effect pigment as claimed in claim 1, wherein the process comprises: optionally applying an uncalcined layer comprising or consisting of at least one of tin oxide, tin hydroxide or tin oxide hydrate to the nonmetallic substrate in platelet form, (ii) sequentially applying three uncalcined layers A, B and C each consisting of or comprising at least one of metal oxide, metal hydroxide or metal oxide hydrate, where the layers A, B and C are arranged directly one on top of another and where the at least one metal oxide, metal hydroxide and/or metal oxide hydrate applied in the layer B, in relation to the metal ion, is different than the metal ion(s) of the metal oxides, metal hydroxides and/or metal oxide hydrates of layer A and layer C, (iii) calcining the product obtained in step (ii) at a temperature from a range from 400° C. to 1000° C. to obtain the absorbent effect pigment comprising at least one spacer layer.

11. A process for producing the absorbent effect pigment as claimed in claim 1, wherein the process comprises: (i) sequentially applying two uncalcined layers B and C each consisting of or comprising at least one of metal oxide, metal hydroxide or metal oxide hydrate to a calcined, singly or multiply coated nonmetallic substrate, where the layers B and C are arranged directly one on top of another and where the at least one metal oxide, metal hydroxide and/or metal oxide hydrate applied in the layer B, in relation to the metal ion, is different than the metal ion(s) of the metal oxide, metal hydroxide and/or metal oxide hydrate of layer C and of the layer which directly adjoins layer B in the substrate direction, (ii) calcining the product obtained in step (i) at a temperature from a range from 400° C. to 1000° C. to obtain the absorbent effect pigment comprising at least one spacer layer.

12. The process as claimed in claim 10, wherein the metal ions present in layer B diffuse at least partly into layer A and/or layer C to form the at least one spacer layer in the calcined effect pigment.

13. The process as claimed in claim 10, wherein the two or three sequentially applied metal oxides, metal hydroxides and/or metal oxide hydrates for production of the layers B and C or the layers A, B and C do not comprise any metal ion selected from the group of the 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, writing ink, varnish, powder coating or a material for a functional application comprising introducing the absorbent effect pigment of claim 1 into a cosmetic formulation, plastic, film, textile, ceramic material, glass, paint, printing ink, writing ink, varnish, powder coating or a material for a functional application.

15. An article comprising at least one absorbent effect pigment as claimed in claim 1.

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

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

Description

I PRODUCTION OF THE ABSORBENT EFFECT PIGMENTS OF THE INVENTION

Example 1

[0194] 200 g of synthetic mica platelets (fluorphlogopite platelets) having 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. with turbulent stirring. The pH of the suspension was lowered to pH 2.2. By addition of 75 g of a tin chloride solution of concentration c(Sn)=12 g/L, a layer of tin oxide was deposited on the surface of the glass platelets.

[0195] The pH of the suspension was subsequently lowered to pH 1.9 and then a solution of 570 mL of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) was dosed into the suspension. After the end of the addition, the mixture was stirred for a further 10 minutes and then the pH was adjusted to pH 2.6. Subsequently, 50 mL of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3 were dosed. On completion of dosage, the mixture was stirred for another 10 minutes, the pH was adjusted to pH 1.9, and 630 mL of a solution of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) were dosed into the suspension.

[0196] Thereafter, a further dosage of 40 mL of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3 was added in after 10 minutes. 15 minutes after the addition had ended, the suspension was filtered off and the filtercake was washed. The filtercake was dried and calcined at 850° C. for 60 min. Extremely chromatic, high-gloss gold interfering effect pigments with yellow absorption color and very good hiding capacity were obtained.

Example 2

[0197] The filtercake from example 1 was dried and calcined at 820° C. for 60 minutes under a hydrogen atmosphere. Highly chromatic, high-gloss green/gold interference effect pigments with black absorption color and good hiding capacity were obtained.

Example 3

[0198] 200 g of synthetic mica platelets (fluorphlogopite platelets) having 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. with turbulent stirring. The pH of the suspension was lowered to pH 2.2. By addition of 100 g of a tin chloride solution of concentration c(Sn)=12 g/L, a layer of tin oxide was deposited on the surface of the synthetic mica platelets.

[0199] The pH of the suspension was lowered to pH 1.9 and then a solution of 400 mL of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) was dosed into the suspension. After the end of the addition, the mixture was stirred for a further 10 minutes and then the pH was adjusted to pH 2.6. Subsequently, 30 mL of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3 were dosed in. On completion of addition, the mixture was stirred for another 10 minutes, and 405 mL of a further solution of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) were dosed into the suspension. Thereafter, a further dosage of 40 mL of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3 was added after 10 minutes. 15 minutes after the addition had ended, the suspension was filtered off and the filtercake was washed. The filtercake was dried and calcined at 650° C. for 30 minutes under reducing conditions. Highly chromatic, glossy blue interfering effect pigments with gray absorption color were obtained.

Example 4

[0200] 200 g of glass platelets having 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 DM water (DM=demineralized) and heated to 85° C. with turbulent stirring. The pH of the suspension was lowered to pH 2.2. By addition of 75 g of a tin chloride solution of concentration c(Sn)=12 g/L, a layer of tin oxide was deposited on the surface of the glass platelets.

[0201] Thereafter, the pH was lowered to pH 2.0 with dilute HCl, and then a solution of 148 mL of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) was dosed into the suspension. After the end of the addition, the mixture was stirred for a further 10 minutes and then the pH was adjusted to pH 2.6. Subsequently, 8 mL of an aqueous iron chloride solution having a density of 1.25 g/cm.sup.3 were dosed in. On completion of dosage, the mixture was stirred for another 10 minutes and, by addition of 75 mL of tin chloride solution of concentration c(Sn)=12 g/L, a further thin layer of tin oxide was deposited on the pigment surface. Subsequently, 180 mL of a solution of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) were doesd into the suspension. Thereafter, 20 mL of an aqueous iron chloride solution having a density of 1.25 g/cm.sup.3 were dosed in after 10 minutes. 15 minutes after the addition, the suspension was filtered off and the filtercake was washed. The filtercake was dried and calcined at 750° C. for 60 minutes under reducing conditions. Extremely chromatic, high-gloss gold interfering effect pigments with gray absorption color were obtained.

Example 5

[0202] 200 g of synthetic mica platelets (fluorphlogopite platelets) having 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. with turbulent stirring. The pH of the suspension was lowered to pH 2.6.

[0203] Subsequently, 40 mL of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3 was dosed in. Thereafter, the mixture was stirred for 10 minutes and, at pH 1.9, 560 mL of a solution of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) were dosed into the suspension.

[0204] After adjusting the pH to the initial value, 40 mL of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3 were then added to the suspension. Once more, the pH was adjusted to pH 1.9 and 600 mL of a solution of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) were dosed into the suspension. A further addition of 15 mL of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3 was executed and then the mixture was stirred for a further 120 min and filtered. The washed filtercake was dried and calcined at 800° C. for 45 min. Extremely chromatic, high-gloss gold interfering effect pigments with yellow absorption color and very good hiding capacity were obtained.

Example 6

[0205] 200 g of synthetic mica platelets (fluorphlogopite platelets) having 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. with turbulent stirring. The pH of the suspension was adjusted to pH 2.6. By addition of 500 g of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3, a layer of iron oxide was deposited on the surface of the synthetic mica platelets.

[0206] After the end of the addition, the mixture was stirred for a further 120 minutes and then the pH was adjusted to pH 2.2. Subsequently, 1000 g of a tin chloride solution of concentration c(Sn)=12 g/L were dosed in. On completion of dosage, the mixture was stirred for another 120 minutes and then, by addition of 710 g of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3, a further layer of iron oxide was deposited on the surface of the synthetic mica platelets. 60 minutes after the addition had ended, the suspension was filtered off and the filtercake was washed. The filtercake was dried if appropriate and calcined at 800° C. for 60 minutes under reducing conditions. Extremely chromatic, high-gloss red interfering effect pigments with red absorption color and with very good hiding power were obtained.

Example 7

[0207] 200 g of synthetic mica platelets (fluorphlogopite platelets) having 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. with turbulent stirring. The pH of the suspension was adjusted to pH 2.2. By addition of 100 g of a tin chloride solution of concentration c(Sn)=12 g/L, a layer of tin oxide was deposited on the surface of the synthetic mica platelets.

[0208] The pH of the suspension was lowered thereafter to pH 1.9 and then a solution of 400 mL of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) was dosed into the suspension. After the end of the addition, the mixture was stirred for a further 10 minutes and then the pH was adjusted to pH 2.2. Subsequently, 150 mL of a 20% by weight aqueous zirconium chloride solution were dosed in. On completion of metered addition, the mixture was stirred for a further 40 minutes, and 300 mL of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) were dosed into the suspension. After the addition had ended, the suspension was filtered off and the filtercake was washed. The filtercake was dried and calcined at 800° C. for 60 minutes under reducing conditions. Highly chromatic, highly glossy blue interfering effect pigments with gray absorption color were obtained.

Example 8

[0209] 15 g of pigment from example 6 were suspended in 450 mL of demineralized water. Thereafter, 30 mL of silver salt solution consisting of 50 g of AgNO.sub.3 and 50 mL of 28% by weight ammonia solution were supplemented up to 1 L with demineralized water, and the suspension was added simultaneously and stirred at room temperature for 5 minutes. Subsequently, 9 mL of a 35% by weight formaldehyde solution were added and the mixture was stirred for a further 1 hour. The suspension was then filtered and the pigment cake was dried at 120° C. under reduced pressure.

[0210] Dark blue interfering effect pigments with black absorption color and a silver content of 11.1% were obtained.

Example 9

[0211] 100 g of the effect pigment obtained from example 1 were 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. 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 metered in. At the same time, the pH was kept constant by dropwise addition of a 10% NaOH solution. Once the solution had been added completely, the mixture was stirred for a further hour and the pH was adjusted thereafter to pH 10 with dilute sodium hydroxide solution. Thereafter, 5.7 g of Dynasylan 1146 diluted with 24.3 g of demineralized water were added to the suspension, the suspension was stirred for another 180 minutes and filtered, and the filtercake was washed with demineralized water. The filtercake was dried at 95° C. under reduced pressure.

Example 10

[0212] 200 g of synthetic mica platelets (fluorphlogopite platelets) having 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. with turbulent stirring. The pH of the suspension was adjusted to pH 2.6. By addition of 570 g of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3, a layer of iron oxide was deposited on the surface of the synthetic mica platelets.

[0213] The pH of the suspension was lowered thereafter to pH 1.9 and then a solution of 250 mL of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) was dosed into the suspension.

[0214] Thereafter, the mixture was stirred for another 120 minutes and then, by addition of 600 g of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3, a further layer of iron oxide was deposited on the surface of the synthetic mica platelets. 60 minutes after the addition had ended, the suspension was filtered off and the filtercake was washed. The filtercake was dried if necessary and calcined at 400° C. for 60 minutes. Extremely chromatic, high-gloss red interfering effect pigments with red absorption color and very good hiding power were obtained.

Example 11

[0215] 100 g of the effect pigment obtained from example 6 were 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. 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. At the same time, the pH was kept constant by dropwise addition of a 10% NaOH solution. Once the solution had been added completely, the mixture was stirred for a further hour and the pH was adjusted thereafter to pH 10 with dilute sodium hydroxide solution. Thereafter, 5.7 g of Dynasylan 1146 diluted with 24.3 g of demineralized water were added to the suspension, the suspension was stirred for another 180 minutes and filtered, and the filtercake was washed with demineralized water. The filtercake was dried at 95° C. under reduced pressure.

Example 12

[0216] 300 g of glass platelets having 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 1500 mL of demineralized water and heated to 85° C. with turbulent stirring. The pH of the suspension was lowered to pH 2.2. By addition of 70 mL of a tin chloride solution of concentration c(Sn)=12 g/L, a layer of tin oxide was deposited on the surface of the glass platelets. Thereafter, the pH was lowered to pH 2.0 with dilute HCl, and then a solution of 250 mL of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) was dosed into the suspension. After the end of the addition, the mixture was stirred for a further 10 minutes and then the pH was adjusted to pH 2.6. Subsequently, 100 mL of an aqueous iron chloride solution having a density of 1.25 g/cm.sup.3 were dosed in. Subsequently, 300 mL of a solution of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) were dosed into the suspension. 15 minutes after completion of addition, the suspension was filtered off and the filtercake was washed. The filtercake was dried and calcined at 760° C. for 60 minutes. Extremely chromatic, high-gloss golden effect pigments were obtained.

Comparative Example 1

[0217] 200 g of synthetic mica platelets (fluorphlogopite platelets) having a particle size distribution according to MALVERN Mastersizer MS 2000: D.sub.10=25 μm, D.sub.50=55 μm, D.sub.50=100 μm, span ΔD=1.36 were suspended in 1300 mL of DM water (DM=demineralized) and heated to 85° C. with stirring. The pH of the suspension was lowered to pH 2.2. By addition of 100 g of a tin chloride solution of concentration c(Sn)=12 g/L, a layer of “SnO.sub.2” was deposited on the surface of the synthetic mica platelets. Thereafter, the pH was lowered to pH 1.9 with dilute HCl, and then a solution of 500 mL of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) was metered into the suspension. After the end of the addition, the mixture was stirred for a further 10 minutes and then the pH were adjusted to pH 2.6. Subsequently, 60 mL of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3 was metered in. 15 minutes after completion of addition, the suspension was filtered off and the filtercake was washed. The filtercake was dried and calcined at 700° C. for 60 minutes under reducing conditions. Shiny gold pigments with dark absorption color were obtained.

Comparative Example 2

[0218] Red effect pigment based on natural mica platelets, coated with iron oxide, Iriodin 504 Red, from Merck.

Comparative Example 3

[0219] Red effect pigment based on SiO.sub.2 platelets, coated with iron oxide, Iriodin 4504 Lava Red, from Merck.

II CHARACTERIZATION OF THE ABSORBENT EFFECT PIGMENTS AND PIGMENTS FROM THE COMPARATIVE EXAMPLES

IIa Particle Size Measurement

[0220] The size distribution curve of the absorbent effect pigments of the invention and of the pigments from the comparative examples was determined using the Malvern Mastersizer 2000 instrument according to the manufacturer's instructions. For this purpose, about 0.1 g of the respective pigment was introduced into the sample preparation cell of the measuring instrument by means of a Pasteur pipette as an aqueous solution, without addition of dispersing aids, with constant stirring, and analyzed repeatedly. The individual measurement results were used to form the medians. The scattered light signals were evaluated by the Fraunhofer method.

[0221] The median particle size D.sub.50 in the context of this invention is understood to mean the D.sub.50 of the cumulative frequency distribution of the volume-averaged size distribution function, as obtained by laser diffraction methods. The D.sub.50 indicates that 50% of the pigments have a diameter equal to or less than the value reported, for example 20 μm. Correspondingly, the D.sub.10 and D.sub.90 respectively state that 10% and 90% of the pigments have a diameter equal to or less than the respective measured value. The span ΔD, defined as ΔD=D.sub.90-D.sub.10/D.sub.50, indicates the breadth of the particle size distribution. With regard to the visual appearance of the absorbent effect pigments of the invention, a small value of AD, i.e. a narrow span, is preferred.

TABLE-US-00002 TABLE 2 Particle sizes Example/ D.sub.10 D.sub.50 D.sub.90 comparative example [μm] [μm] [μm] Span Example 1 10.8 22.5 40.6 1.326 Example 2 11.0 22.8 40.8 1.307 Example 3 12.4 23.7 42.1 1.254 Example 4 28.1 53.0 92.7 1.219 Example 5 11.9 22.9 40.9 1.271 Example 6 12.5 23.0 40.4 1.217 Example 7 11.9 22.4 39.9 1.247 Example 8 13.7 24.3 41.3 1.138 Example 9 11.1 22.6 40.8 1.314 Example 10 8.8 20.1 37.6 1.429 Example 12 9.7 21.3 41.3 1.482 Comparative example 1 12.0 22.9 40.8 1.260 Comparative example 2 10.8 21.9 41.5 1.402 Comparative example 3 9.7 19.3 35.5 1.337

IIb Angle-Dependent Color Measurements

[0222] To measure the color and brightness values, the effect pigments of the invention and the pigments from the comparative examples were stirred into a conventional nitrocellulose lacquer (Erco 2615e bronze mixing lacquer colorless; from Maeder Plastiklack AG) at a pigmentation level of 6% by weight, based on the total weight of the wet lacquer. This was done by initially charging the respective pigments and then dispersing them into the lacquer with a brush. The finished lacquer was applied to black/white hiding charts (Byko-Chart 2853, from Byk-Gardner) in a wet film thickness of 40 μm or of 76 μm (example 4) with a spiral applicator on an applicator drawdown apparatus (RK Print Coat Instr. Ltd. Citenco K 101 drawdown apparatus), and subsequently dried at room temperature. The choice of spiral applicator is made according to table A depending on the D.sub.50 of the pigments or substrates to be applied in each case.

[0223] The BYK-mac multi-angle colorimeter (from Byk-Gardner) was used to determine the color values on the black background of the hiding chart at a constant angle of incidence of 45° (according to the manufacturer's instructions) at various observation angles relative to the specular angle. Characterization of the color intensity was accomplished using the chroma value C*15, which was measured at a measurement angle separated by 15° from the specular angle on the black background of the black/white hiding chart.

[0224] Strongly reflecting samples (mirrors in the ideal case) reflect virtually all the incident light at what is called the specular angle. The closer to the specular angle the measurement is made on the lacquer application, the more intense the appearance of the interference color.

TABLE-US-00003 TABLE A Wet film thickness as a function of the D.sub.50 of the pigments or substrates to be applied Spiral D.sub.50 applicator <40 μm 40 μm 40 μm-85 μm 76 μm >85 μm 100 μm 

TABLE-US-00004 TABLE 3 Color and brightness values of gold effect pigments Example/ NC lacquer 6% 40 μm BykMac comparative L 110° a*15° b*15° C* 15° example s.sup.1 s s s Example 1 91.7 −7.1 46.1 46.6 Example 2 84.3 −6.6 35.1 35.7 Example 4 77.4 −10.6 23.3 25.6 Example 5 90.8 −10.9 38.6 40.1 Example 9 92.4 −4.0 48.3 48.5 Example 12 73.74 −3.50 32.84 33.02 Comparative 83.9 1.0 25.3 25.3 example 1

TABLE-US-00005 TABLE 4 Color and brightness values of red effect pigments Example/ NC lacquer 6% 40 μm BykMac comparative L 15° a*15° b*15° C* 15° example s.sup.1 s s s Example 6 57.8 42.3 26.8 50.0 Example 7 72.9 16.6 −29.6 34.0 Example 10 64.2 40.2 27.6 48.8 Comparative 74.5 38.6 11.4 40.2 example 2 .sup.1Measured on the black background of the black/white hiding chart.

[0225] Table 3 indicates the color values for gold interference effect pigments. It is clear from this that the color intensity of the effect pigments of the invention is much higher than the color intensity of the single-layer pearlescent pigment from comparative example 1. An exception to this is example 4, since this involves a much thicker glass substrate.

[0226] The color values for red interference effect pigments that are listed in table 4 for the inventive examples are also well above those of comparative example 2.

IIc Comparison of Hiding

[0227] To determine the hiding quotient D.sub.q, defined as

[00002]$D_q=\frac{L_{\mathrm{black}}^{*25}}{L_{\mathrm{white}}^{*25}},$

the brightness values L*25° of the lacquer applications from IIb were recorded with the BYK-mac multi-angle colorimeter (from Byk-Gardner) at a measurement angle of 25° on the black and white backgrounds of the black/white hiding chart. The 25° measurement geometry, at a constant angle of incidence of 45°, relates to the difference from the specular angle. The viewing angle is measured away from the specular reflection in the plane of illumination.

[0228] The effect pigments of the invention have good hiding power. The hiding quotient D.sub.q thereof is preferably ≧0.41. The hiding quotient D.sub.q of the inventive absorbent effect pigments in platelet form from examples 1 to 10, as can be inferred from table 5, is in each case well above 0.41.

IId Gloss Measurements

[0229] Gloss is a measure of directed reflection. To determine the gloss, the paint applications from IIb on the white background of the black/white hiding chart were analyzed at a measurement angle of 60° based on the vertical with the aid of a Micro-Tri-Gloss gloss meter from Byk-Gardner. The gloss values of the absorbent effect pigments of the invention and of the pigments from the comparative examples are listed in table 5.

[0230] Some of the inventive absorbent effect pigments in platelet form from examples 1 to 10 show distinctly higher gloss values than the pigments having a single-layer coating from comparative examples 2 and 3.

[0231] The gloss measurements from table 5 confirm the very high reflectivity of the pigments of the invention compared to the prior art.

IIe Effect Measurements

[0232] In order to objectively describe the optical effect of the absorbent effect pigments of the invention, effect measurements were conducted with the BYK-mac spectrophotometer (from Byk-Gardner) using the lacquer applications from IIb (cf. Byk-Gardner catalog “Qualitätskontrolle für Lacke and Kunststoffe” [Quality Control for Lacquers and Adhesives], 2011/2012, p. 97/98). The corresponding measurement values for the sparkle intensity S_i, the sparkle area S_a and the graininess G are collected in table 5.

TABLE-US-00006 TABLE 5 Effect measurements, hiding quotient and gloss values Example/ comparative S_i 15° S_a 15° G 60° gloss example (s).sup.1 (s).sup.1 (s).sup.1 D.sub.q 25° (w).sup.2 Example 1 15.44 33.99 9.99 0.607 85.8 Example 2 12.75 33.59 8.59 0.618 70.5 Example 3 6.14 24.72 4.66 0.495 42.3 Example 4 53.95 33.66 13.85 0.522 81.5 Example 5 10.15 32.00 8.15 0.692 49.9 Example 6 6.16 30.01 4.37 0.558 52.6 Example 7 5.62 24.12 5.60 0.440 40.3 Example 8 7.84 33.93 4.04 0.505 48.8 Example 9 14.58 33.75 9.98 0.630 90.8 Example 10 6.35 27.85 4.68 0.505 53.9 Example 12 51.65 34.71 13.17 0.4760 69.1 Comparative 4.70 19.38 4.15 0.661 41.8 example 2 Comparative 4.28 18.57 3.45 0.719 32.3 example 3 .sup.1Measured on the black background of the black/white hiding chart. .sup.2Measured on the white background of the black/white hiding chart.

[0233] The effect values S_i, S_a and G of the inventive absorbent effect pigments in platelet form from examples 1 to 10 and 12 are higher than the values for comparative examples 2 and 3. The achievable optical effects of the inventive absorbent effect pigments in platelet form are much more marked than in the case of conventional effect pigments with a single-layer coating from comparative examples 2 and 3.

IIf Waring Blender

[0234] In industry, many lacquers are processed in circulation systems. In this case, the lacquer components are subjected to high shear forces. The Waring blender test simulates these conditions and serves for assessment of the ring line stability/shear stability. Specifically pigments wherein the coating has not been adequately anchored on the support material exhibit significant deviations in the chroma values in this test compared to the untreated applications. The Waring blender test can thus be regarded as a measure of the mutual adhesion of the pigment coating with respect to shear forces.

[0235] For this purpose, the absorbent effect pigments of the invention or the pigments from the comparative examples were weighed out according to the recipe below and converted stepwise to a paste with a conventional acrylic lacquer in an 880 mL beaker. Thereafter, the viscosity was adjusted with butyl acetate/xylene 1:1 to 17″ in the DIN 4 mm cup. A total of 600 g of lacquer were produced, of which 400 g were introduced into a jacketed water-cooled 1 kg vessel and stirred with a specific attachment under the Dispermat (from Waring Blenders). The stirring time was 8 minutes at 13 500 rpm, then 200 g of lacquer were removed and the rest was stirred for a further 12 minutes.

Recipe: 6% pigment [0236] 8% butyl acetate 85 [0237] 86% acrylic lacquer, colorless [0238] 30% dilution butyl acetate 85/xylene 1:1
200 g each of the untreated and treated lacquers were applied to a test sheet with a spraying machine and the Sata LP-90 spray gun according to the following settings:

Setting: Needle: 1.3.4

[0239] Pressure: 4 bar
Runs: The number of spray runs was chosen such that there was a dry lacquer layer thickness of 15-20 μm.

[0240] Conventionally, effect pigments are regarded as being shear-stable when the gloss differential and the color differential, measured close to the specular angle, is relatively low in the application after the Waring blender test. The ΔC* 15° value relative to the untreated sample should ideally be less than 2. Table 6 shows the change in color ΔC* 15° and the change in gloss Δ60° gloss of the sample that has been subjected to the Waring blender test relative to the untreated sample for inventive examples 5 and 10.

TABLE-US-00007 TABLE 6 Gloss differential and color differential in the Waring blender test ΔC* (15°) Δgloss (60°) Example 5 0.9 −1.3 Example 10 1.3 −0.8

[0241] The absorbent effect pigments of the invention from examples 5 and 10 fulfill the criteria of the test. The color difference is negligibly small. Even under the microscope, it was barely possible to detect any changes such as flaking of the coating or other surface defects that have arisen.

[0242] The absorbent effect pigments of the invention are found to be extremely shear-stable in spite of their spacer layer.

IIg Determination of Chemical Stability

[0243] The chemical stability of the absorbent effect pigments of the invention and of the pigments from the comparative examples was determined with reference to applications of lacquer to plastic panels. 6 g of the respective pigment were stirred into a mixture of 90 g of a conventional colorless acrylic lacquer and 10 g of butyl acetate 85. Thereafter, the viscosity was adjusted with a mixture of butyl acetate 85 and xylene in a ratio of 1:1 to 17″ in the DIN 4 mm cup.

[0244] 100 g of this lacquer in each case were applied to the panels in hiding application analogously to IIf with a spraying machine. After the coating, the panels were baked at 80° C. for 30 minutes. 24 hours later, the panels were immersed to half their height into 10% sodium hydroxide solution. After a contact time of 7 days, the panels were rinsed with demineralized water and then, after drying time of 2 hours, assessed visually for damage and/or discoloration. In addition, discoloration was analyzed with the aid of the BYK-mac (from Byk-Gardner). The change in color was characterized using the ΔE value of the exposed sample versus the corresponding unexposed sample at a measurement angle of 15°. The results are shown in table 7 below.

TABLE-US-00008 TABLE 7 Color change ΔE Example/comparative example ΔE(15°) Example 10 2.40 Comparative example 3 13.31

[0245] Pigments with ΔE(15°)<3 can be regarded as stable to chemicals. The absorbent effect pigments of the invention from example 10 are below the limit, while the pigments from comparative example 3 distinctly exceed it.

IIh X-Ray Fluorescence Analysis (XRF)

[0246] The metal oxide, metal hydroxide and/or metal oxide hydrate contents of the absorbent effect pigments of the invention and of the pigments from the comparative examples were determined by means of x-ray fluorescence analysis (XRF). For this purpose, the respective pigments were incorporated into a lithium tetraborate glass tablet, fixed in solid sample measuring cups and analyzed therefrom. The measuring instrument used was the Advantix ARL system from Thermo Scientific. The measurements are shown in table 8. The figures for the different contents are reported here as TiO.sub.2 for titanium, as Fe.sub.2O.sub.3 for iron, and as SnO.sub.2 for tin.

TABLE-US-00009 TABLE 8 Mean height h.sub.a of the spacer layer and XRF values Example/ SEM XRF (as oxide) comparative example Mean height h.sub.a [nm] Ti[%] Fe[%] Sn[%] Example 1 30 57.7 6.9 0.78 Example 2 28 57.7 6.9 0.78 Example 3 20 47.2 5.8 0.55 Example 4 25 28.6 3.1 0.98 Example 5 38 54.9 10.6  / Example 6 55 / 65.8  4.3  Example 7 51 48.2  0.04 3.1  Example 8 / / / / Example 10 20  9.1 51.1  / Example 12 20 23.9 4.6 1.26 Comparative example 1 no spacer layer / / / Comparative example 2 no spacer layer / / / Comparative example 3 no spacer layer / / /

III CONDENSATE WATER TEST

[0247] To determine condensate water stability, the absorbent effect pigments of the invention and the pigments from the comparative examples were incorporated into a waterborne lacquer system and the test applications were produced by spray painting onto aluminum sheets. The basecoat was overcoated with a conventional one-component clearcoat and then baked. These applications were tested according to DIN 50 017 (water condensation-constant atmospheres). Bond strength was tested by means of cross-cutting according to DIN EN ISO 2409 immediately after the end of the test by comparison with the unexposed sample. In this context, Cc 0 means no change and Cc 5 a very significant change.

[0248] The swelling characteristics were visually assessed immediately after condensate water exposure in accordance with DIN 53230. In this context, the index 0 means no change and the index 5 a very significant change.

[0249] Finally, the DOI (distinctness of image) was determined with the aid of a Wave-scan II from Byk-Gardner.

TABLE-US-00010 TABLE 9 Condensate water results 20° 20° gloss gloss Loss Cross- before after of cutting Swelling Sample CW test CW test gloss DOI immediate visual Example 9 90.3 89.7 <1% 78.2 0 0 Example 11 92.8 90.6 2.4%  80.1 1 0 Comparative 91.2 21.7 76% n.d. 5 4 example 2

[0250] The pigment from comparative example 2 had significant swelling characteristics and poor interlayer adhesion. The DOI was no longer measurable because of the high degree of fine structure after condensate water exposure.

[0251] The absorbent effect pigments of the invention from examples 9 and 11, by contrast, were found to be stable and exhibited virtually no changes before and after the test.

IIj UV Stability

[0252] The UV stability of the absorbent effect pigments of the invention and of the pigments from the comparative examples was determined in accordance with the quick UV test described in EP 0 870 730 A1 for determination of the photochemical UV activity of TiO.sub.2 pigments. For this purpose, 1.0 g of the corresponding pigment were dispersed into 9.0 g of a double bond-rich melamine-containing lacquer. Applicator drawdowns on white cardboard were produced and dried at room temperature. The applicator drawdowns were divided and one of the two sections of each was stored in the dark as an unexposed comparative specimen. Subsequently, the samples were irradiated with UV-containing light (UVA-340 lamp, irradiation intensity 1.0 W/m.sup.2/nm) in a QUV system from Q-Panel for 150 minutes. Immediately after the end of the test, a Minolta CM-508i colorimeter was used to determine color values for the exposed samples relative to the respective reference sample. The resulting ΔE* values, calculated according to the Hunter L*a*b* formula, are shown in table 9.

[0253] In this test, essentially a gray/blue color of the TiO.sub.2 layer of the respective pigment is observed owing to Ti(III) species formed under UV light. A condition for this is that the electron hole has left the environment of the TiO.sub.2 and cannot recombine directly with the remaining electron again—for instance through reaction with olefinic double bonds of the binder. Since a melamine-containing lacquer layer significantly slows the diffusion of water (vapor) and oxygen to the pigment surface, reoxidation of the titanium(III) species takes place at a significantly retarded rate, and so the graying can be measured and the ΔE* value can be used as a measure for the UV stability of the pigments. A relatively large numerical ΔE* value of the exposed sample relative to the unexposed reference sample thus means relatively low UV stability of the pigment examined.

TABLE-US-00011 TABLE 10 UV test results Example/ comparative example ΔE* Example 5 3.23 Example 10 2.96 Comparative example 1 7.28

[0254] The comparative example had a much greater change in color (ΔE*) after corresponding exposure. [0255] IIk Determination of the mean thickness of the nonmetallic substrates in platelet form, the mean layer thickness of layers 2 and 3, the mean layer thickness of the overall coating, the mean height h.sub.a of the spacer layer and the mean height h.sub.H of the cavities

[0256] For this purpose, the absorbent effect pigments of the invention were incorporated in a concentration of 10% into a two-component clearcoat, Autoclear Plus HS from Sikkens GmbH, with a sleeved brush, applied to a film with the aid of a spiral applicator (wet film thickness 26 μm) and dried. After a drying time of 24 h, transverse sections of these applicator drawdowns were produced. The transverse sections were analyzed by SEM, with analysis of at least 100 individual pigments to be statistically meaningful for determination of the mean thickness of the nonmetallic substrates in platelet form. To determine the mean layer thickness of layers 2 and 3, the mean thickness of the overall coating, the mean height h.sub.a of the spacer layer and the mean height h.sub.H of the cavities, the upper and lower substrate surfaces, i.e. the longer side of the nonmetallic substrate in platelet form recognizable in each case in the SEM transverse section, were each used as the baseline. The baseline was drawn here along the surface of the substrate in platelet form in the scanning electron micrograph of the transverse section by connecting the two points of intersection of nonmetallic substrate in platelet form —optional layer 1 or of nonmetallic substrate in platelet form—layer 2 from the left- and right-hand edges of the scanning electron micrograph of the transverse section to one another by means of a straight line. The scanning electron micrographs of transverse images were analyzed with the aid of the AxioVision 4.6.3 image processing software (from Zeiss).

[0257] A sufficient number of parallel lines were drawn at 50 nm intervals at a 90° angle from these two baselines as to place a grid over the complete scanning electron micrograph of the transverse section of the effect pigment (FIG. 4). The magnification of the scanning electron micrograph of the transverse section was preferably at least 50 000-fold, based on Polaroid 545. Proceeding from the respective upper and lower baselines of the nonmetallic substrate in platelet form in the direction of layer 3 in each case, the distances between the points of intersection of these lines at the respective interfaces of the optional layer 1 with layer 2, of layer 2 with the spacer layer, of spacer layer with layer 3 and of layer 3 with the environment were measured manually. It happened here that a line marked at 50 nm intervals was located directly above a connection point or a spacer. In this case, only the respective point of intersection at the interface of line 3 with the environment was recorded. These measurements yielded the layer thicknesses of layers 2 and 3, the thickness of the overall coating, and the height h.sub.a of the spacer layer by formation of differences.

[0258] For the determination of the mean height h.sub.H of the cavities, the points of intersection of these parallel lines with the upper and lower cavity boundaries within the spacer layer were used.

[0259] The individual values of the layer thicknesses, the height h.sub.a and the height h.sub.H that have been determined in this way were used to form the respective arithmetic means in order to determine the above-specified values for the mean layer thicknesses, the mean height h.sub.H and the mean height h.sub.a. To be statistically meaningful, the above-described measurements were conducted on at least 100 lines. The term “mean” in all cases means the arithmetic mean.

[0260] Transverse sections of the pigments from the comparative examples that do not have a spacer layer but may have statistically distributed pores within the coating were likewise examined by the method described above using scanning electron micrographs of transverse sections. In this case, if one of the parallel lines occurred above one or more pores, the height of the pore(s), the pore midpoint(s) thereof and the distance of the pore midpoint(s) from the substrate surface were determined.

[0261] As an alternative to transverse sections, the absorbent effect pigments of the invention can be cut by means of the FIB method (FIB=focused ion beam). For this purpose, a fine beam of highly accelerated ions (for example gallium, xenon, neon or helium) is focused to a point by means of ion optics and guided line by line over the effect pigment surface to be processed. On impact with the effect pigment surface, the ions release most of their energy and destroy the coating at this point, which leads to removal of material line by line. It is also possible using the scanning electron micrographs that have then been recorded, by the method described above, to determine the mean height h.sub.a, the mean layer thickness of layers 2 and 3 and the mean layer thickness of the overall coating. The mean thickness of the nonmetallic substrate in platelet form can also be determined using scanning electron micrographs of the effect pigments that have been cut by the FIB method.

[0262] The advantages of the absorbent effect pigments of the invention are therefore apparent in the sum total of various properties. The absorbent effect pigments of the invention have high transparency, very good mechanical and chemical stability, and high gloss and color intensity. None of the comparative pigments considered overall has all the properties mentioned in a satisfactory manner.

TABLE-US-00012 TABLE 11 Characterization of the coating Example/ d.sub.S2 d.sub.S3 h.sub.ma σh.sub.Rma S.sub.D A.sub.H comparative example [nm] [nm] d.sub.S2/d.sub.S3 [nm] h.sub.Rma [%] n.sub.S [%] [%] Example 1 85 91 0.94 100.4 0.49 3.8 1.1 5.4 94.6 Example 3 66 65 1.02 76.3 0.50 5.1 4.6 16.4 83.6 Example 5 83 105 0.79 94.7 0.52 4.9 3.2 15.9 84.1 Example 6 70 99 0.71 87.6 0.44 6.5 2.2 11.0 89.0 Example 7 55 57 0.96 62.0 0.49 13.5 3.6 18.1 81.9 Example 10 118 82 1.43 128.3 0.58 4.5 6.2 30.9 69.1 Example 12 100 118 0.85 110 0.46 4.9 2.2 11.1 88.9 Comparative example 1 no spacer layer 21.3 18 90.0 10.0 Comparative example 2 no spacer layer 24.7 13 65.0 35.0 d.sub.S2 [nm] = mean layer thickness of layer 2 d.sub.S3 [nm] = mean layer thickness of layer 3 n.sub.S = mean number of bars per μm A.sub.H [%] = area proportion of cavities S.sub.D = network density [%] h.sub.ma = midpoint of the spacer layer (sum total of the layer thickness of the optional layer 1 and of layer 2 and half the height h.sub.a) h.sub.Rma = relative height of the spacer layer σh.sub.Rma [%] = standard deviation of the relative height of the spacer layer

[0263] Table 8 shows the mean height h.sub.a of the spacer layer of the pigments examined. All the absorbent effect pigments of the invention, by contrast with the pigments from comparative examples 1 to 3, have a spacer layer.

[0264] The pigments from comparative examples 1 and 2 do not have a spacer layer, but have a statistical distribution of pores within the coating. In table 11, for comparative examples 1 and 2, the value in the σh.sub.Rma [%] column means the standard deviation of the pore midpoints from the substrate surface. Since the pigment from comparative example 2, however, contains only few statistically distributed pores, the network density SD is 65.0%. The standard deviation of the pore midpoints from the substrate surface is 24.7%, which demonstrates that the pores are statistically distributed within the overall coating. The situation is different for the absorbent effect pigments of the invention from examples 1, 3, 5 to 7 and 10. Here, the standard deviation of the relative height of the midpoint of the spacer layer h.sub.Rma is <14% in each case, which indicates that the respective spacer layer thereof is at a defined position within the coating. The standard deviation of the distances of the pore midpoints from the substrate surface of the pigment from comparative examples 1 and 2 can thus be compared with the standard deviation of the relative height of the midpoint of the spacer layer of the absorbent effect pigments of the invention.

III SCANNING ELECTRON MICROGRAPHS

[0265] The scanning electron micrographs were obtained using transverse sections of the absorbent effect pigments of the invention with the Supra 35 scanning electron microscope (from Zeiss). Energy-dispersive x-ray micro-analysis (EDX analysis) was conducted with the EDAX Sapphire instrument, from EDAX.

III APPLICATION EXAMPLES

Application Example 1: Body Lotion

[0266]

TABLE-US-00013 % by Manufacturer/ INCI name Product name wt. suppli Phase A 85.80 Effect pigment from 0.20 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 indicates data missing or illegible when filed

[0267] The effect pigment from example 1 can be used within a range from 0.1% to 2.5% by weight, based on the total weight of the body lotion formulation. Compensation to 100% by weight of the formulation can be effected with water.

[0268] Keltrol CG-T was dispersed in phase A and heated to 75° C. Phase B was heated separately to 75° C. Subsequently, phase B was added gradually to phase A. The emulsion was cooled down to room temperature while stirring and phase C was added individually.

Application Example 2: Eyeshadow Cream

[0269]

TABLE-US-00014 % by Manufacturer/ INCI name Product name wt. supplier Phase A Microcrystalline Wax TeCero-Wax 1030 K 4.50 Tromm Wachs Copernicia Cerifera Cera LT 124 carnauba 4.50 Tromm Wachs wax 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 3

[0270] The effect pigment from example 3 can be used within a range from 5% to 30.0% by weight, based on the total weight of the eyeshadow formulation. Compensation to 100% by weight of the formulation can be effected with isohexadecane.

[0271] Phase A was mixed and heated to 85° C., then phase B was added to phase A while stirring. After dispensing into an appropriate container, the mixture is cooled to room temperature.

Application Example 3: Shower Gel

[0272]

TABLE-US-00015 % by Manufacturer/ INCI name Product name wt. supplier Phase A Effect pigment from 0.10 example 5 Aqua Water 58.50 Acrylates Copolymer Carbopol Aqua SF-1 5.50 Lubrizol Phase B Sodium Hydroxide NaOH (10% by 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 Spezial 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

[0273] The effect pigment from example 5 can be used within a range from 0.01% to 1.0% by weight, based on the total weight of the shower gel formulation. Compensation to 100% by weight of the formulation can be effected with water.

[0274] Phase A was stirred, then phase B was added and stirred until a homogeneous appearance was achieved. Phase C was weighed out separately, mixed briefly and added to phase AB. Subsequently, the mixture was stirred again and phase D was added individually.

Application Example 4: Eyeshadow Compact

[0275]

TABLE-US-00016 % by 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 Aluminium Starch Agenaflo OS 9051 10.00 Agrana Octenylsuccinate Magnesium Stearate Magnesium Stearate 6.00 VWR Effect pigment from 20.00 example 8 Phase B Cyclomethicone Xiameter PMX-0345 5.00 Dow Corning Octyldodecyl Ceraphyl 847 5.00 Ashland Stearoyl Stearate

[0276] The effect pigment from example 8 can be used within a range from 5.0% to 40.0% by weight, based on the total weight of the eyeshadow formulation. Compensation to 100% by weight of the formulation can be effected with talc.

[0277] Phase A was mixed in a high-speed mixer at 2500 rpm for 30 s. Subsequently, phase B was added and the mixture was mixed in the same mixer at 3000 rpm for 60 s. Finally, the powder mixture was pressed into shape by means of an eyeshadow press at 100 bar for 30 seconds.

Application Example 5: Mascara

[0278]

TABLE-US-00017 % by 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 (and) Emulium Delta 5.00 Gattefosse PEG-75 Stearate (and) Ceteth-20 (and) Steareth-20 C10-18 Triglycerides Lipocire A Pellets 2.00 Gattefosse Ozokerite Kahlwax 1899 2.00 Kahl Glyceryl Behenate Compritol 888 CG 2.00 Gattefosse Pastilles Butylene Glycol Cocoate Cocoate BG 4.00 Gattefosse Phase C Effect pigment 5.00 from example 8 Phenoxyethanol (and) Piroctone Olamine Nipaguard PO5 0.50 Clariant Glycine Soja (Soybean) Oil, Dicaprylyl Ether, Follicusan DP 3.00 CLR Berlin Magnolia Grandiflora Bark Extract, Lauryl Alcohol Water, Hydrolyzed Corn Starch, Beta Vulgaris DayMoist CLR 1.00 CLR Berlin (Beet) Root Extract Linoleic Acid (and) Linolenic Acid Vitamin F forte 0.50 CLR Berlin

[0279] The effect pigment from example 8 can be used within a range from 1.0% to 10.0% by weight, based on the total weight of the mascara formulation. Compensation to 100% by weight of the formulation can be effected with the water from phase A.

[0280] Phase A was stirred under high shear. Phase B was weighed out separately. Phase A and phase B were heated separately to 85° C., then phase B was added to phase A. Subsequently, phase AB was cooled to 45° C. and, during the cooling, phase C was added gradually while stirring.

Application Example 6: Hair Gel

[0281]

TABLE-US-00018 % by 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 6 Citric Acid (and) Water Citric Acid (1 0%) 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

[0282] The effect pigment from example 6 can be used within a range from 0.01% to 2.0% by weight, based on the total weight of the hair gel formulation. Compensation to 100% by weight of the formulation can be effected with water.

[0283] The Laponite XLG was stirred with water until phase A became clear. Then the effect pigment from example 6 was added to phase B while stirring. Subsequently, the rest of the ingredients of phase B were added gradually.

Application Example 7: Body Powder

[0284]

TABLE-US-00019 INCI name % by Manufacturer/ Phase A Product name wt. supplier Synthetic Fluorphlogopite Synafil S 1050 40.00 Eckart Polypropylene Synafil W 1234 8.00 Eckart Bentonite Optigel CK-PC 10.00 BYK Talc Talc Powder 18.00 VWR Magnesium Stearate Magnesium Stearate 4.00 Applichem Effect pigment from 20.00 example 5

[0285] The effect pigment from example 5 can be used within a range from 0.2% to 5.0% by weight, based on the total weight of the body powder formulation. Compensation to 100% by weight of the formulation can be effected with Synafil S 1050.

[0286] Phase A was mixed and then the powder was dispensed into a suitable vessel.

Application Example 8: Lipgloss

[0287]

TABLE-US-00020 % by Manufacturer/ INCI name Product name wt. supplier Phase A Hydrogenated Polyisobutene Versagel 75.30 Penreco (and) Ethylene/Propylene/ ME 750 Styrene Copolymer (and) Butylene/Ethylene/Styrene Copolymer Simmondsia Chinensis Jojoba Oil - 2.00 BioChemica (Jojoba) Seed Oil Natural Caprylyl Trimethicone Silcare 7.00 Clariant Silicone 31M50 Stearyl Dimethicone Silcare 3.20 Clariant Silicone 41M65 Hydrogenated Polydecene Dekanex 4.00 IMCD 2004 FG Isopropyl Myristate Isopropyl 4.50 VWR Myristate Phase B Effect pigment 4.00 from example 6

[0288] The effect pigment from example 6 can be used within a range from 0.10% to 8.00% by weight, based on the total weight of the lipgloss formulation. Compensation to 100% by weight of the formulation can be effected with Versagel ME 750.

[0289] Phase A was heated to 85° C., then the pigment from example 6 was added to phase B and stirred until the consistency was homogeneous, and then dispensed into a lipgloss vessel.

Application Example 9: Lipstick

[0290]

TABLE-US-00021 % by 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) Wax Kahlwax 2442 6.00 Kahl 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 Gattefosse Acacia Decurrens/Jojoba/Sunflower Hydracire S 5.00 Gattefosse Seed Wax/Polyglyceryl-3 Esters Tocopheryl Acetate dl-alpha-Tocopheryl 0.50 IMCD Phase B Effect pigment from 10.00 example 10

[0291] The effect pigment from example 10 can be used within a range from 0.5% to 20.0% by weight, based on the total weight of the lipstick formulation. Compensation to 100% by weight of the formulation can be effected with Eutanol G.

[0292] Phase A was heated to 85° C., then phase B was added to phase A and mixed. Subsequently, this mixture was dispensed into a lipstick mold at a temperature of 75° C.

Application Example 10: Liquid Eyelid Liner

[0293]

TABLE-US-00022 % by 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 5.00 Ineos E Polysorbate 60 Mulsifan CPS 1.50 Zschimmer & 60 Schwarz Phase C Effect pigment 4.00 from example 2 Polyurethane-35 Baycusan C 18.00 Bayer Cosmetics 1004 Aqua and CI 77499 and Methylpropanediol and WorléeBase 8.00 Worlée Ammonium Acrylates Copolymer and AQ 77499/1 Simethicone and Caprylyl Glycol and Phenylpropanol Sodium Acrylates Copolymer Phenoxyethanol, Ethylhexylglycerin Euxyl PE 9010 0.60 Schülke & Mayr

[0294] The effect pigment from example 2 can be used within a range from 0.5% to 8.0% by weight, based on the total weight of the eyelid liner formulation. Compensation to 100% by weight of the formulation can be effected with water.

[0295] 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. Thereafter, phase B was added gradually to phase A while stirring. After cooling to 45° C., the ingredients of phase C were added gradually and the mixture was dispensed into a suitable package.

Application Example 11: Mousse

[0296]

TABLE-US-00023 % by Manufacturer/ INCI name Product name wt. supplier Phase A Cyclopentasiloxane Xiameter PMX-0245 8.60 Dow Corning Cyclosiloxane 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 Oi Jojoba Butter HM 1.00 Desert Whale C30-45 Alkyl Methicone (and) C30- Dow Corning AMS-C30 1.15 Dow Corning 45 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 4 Phase D Phenoxyethanol, Ethylhexylglycerin Euxyl PE 9010 0.40 Schülke & Mayr

[0297] The effect pigment from example 4 can be used within a range from 0.1% to 8.0% by weight, based on the total weight of the mousse formulation. Compensation to 100% by weight of the formulation can be effected with Dow Corning 9041 Elastomer.

[0298] Phase A was mixed and heated until everything had melted. Phase B was weighed out 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 the mixture was mixed again in the mixer at 2400 rpm for 30 s. Subsequently, the remaining portion of phase B was likewise added to phase A and the mixture was mixed again at 2400 rpm for 30 s. Lastly, phase C was added to phase AB and the mixture was mixed again in the high-speed mixer at 2400 rpm for 30 s.

Application Example 12: Nail Varnish

[0299]

TABLE-US-00024 % by Manufacturer/ INCI name Product name wt. supplier Phase A Effect pigment 4.00 from example 6 Phase B Butylacetat (and) International 96.00 International Ethylacetat (and) Lacquers Lacquers Nitrocellulose (and) Nailpolish Isopropyl Alcohol Base 15244

[0300] The effect pigment from example 6 can be used within a range from 0.1% to 8.0% by weight, based on the total weight of the nail varnish formulation. Compensation to 100% by weight of the formulation can be effected with International Lacquers Nailpolish.

[0301] Phase A and phase B were mixed and then dispensed into an appropriate container.

Application Example 13: Nail Varnish with Soft-Touch Effect

[0302]

TABLE-US-00025 % by Manufacturer/ INCI name Product name wt. supplier Phase A Effect pigment 4.00 from example 10 Polypropylene Synafil W 1234 5.00 Eckart Phase B Butylacetat (and) International 91.00 International Ethylacetat (and) Lacquers Lacquers Nitrocellulose (and) Nailpolish Isopropyl Alcohol Base 15244

[0303] The effect pigment from example 10 can be used within a range from 0.1% to 8.0% by weight, based on the total weight of the nail varnish formulation. Compensation to 100% by weight of the formulation can be effected with International Lacquers Nailpolish.

[0304] Phase A was mixed and added to phase B, and then the nail varnish was dispensed into an appropriate container.

Application Example 14: Aqueous Nail Varnish

[0305] The effect pigments from examples 1 to 8 and from example 10 can be used in an aqueous nail varnish according to WO 2007/115675 A2 example 1. The pigmentation level here is 0.1% to 10.0% by weight, based on the total weight of the formulation.

Application Example 15: Liquid Eyeshadow

[0306]

TABLE-US-00026 % by 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 Worlee Micromer CEK 20/50 5.00 Worlee Phase C Effect pigment from example 3 10.00 Divinyldimethicone/ Dow Corning HMW 2220 Non- 6.00 Dow Corning Dimethicone Ionic Emulsion Copolymer C12-C13 Pareth-3, C12-C13 Pareth-23 Phenoxyethanol, Euxyl PE9010 0.80 Schülke & Mayr Ethylhexylglycerin

[0307] The effect pigment from example 3 can be used within a range from 0.10% to 20.00% by weight, based on the total weight of the eyeshadow formulation. Compensation to 100% by weight of the formulation can be effected with water.

[0308] Phase A was stirred, then the ingredients of phase B were added individually to phase A and stirred until the consistency was homogeneous. Thereafter, the ingredients of phase C were added individually to phase AB and the mixture was stirred until the consistency was homogeneous.

[0309] FIG. 1: Scanning electron micrograph of a transverse section of an effect pigment of the invention in 50 000-fold magnification (based on Polaroid 545).

[0310] FIG. 2: Scanning electron micrograph of a transverse section of an effect pigment of the invention in 50 000-fold magnification (based on Polaroid 545).

[0311] FIG. 3: Scanning electron micrograph of a transverse section of an effect pigment of the invention in 20 000-fold magnification (based on Polaroid 545).

[0312] FIG. 4: Detail of the scanning electron micrograph of a transverse section from FIG. 2 with a baseline drawn in at the interface of nonmetallic substrate in platelet form—coating, and lines arranged at right angles to the baseline. “x” marks the points of intersection at the interfaces.

[0313] FIG. 5: Scanning electron micrograph of a transverse section of the titanium dioxide-coated pearlescent pigment SYMIC C261 (from ECKART GmbH) in 20 000-fold magnification (based on Polaroid 545).

[0314] FIG. 6: Schematic diagram of the spacer layer.

[0315] FIG. 7: Schematic diagram of the position of the spacer layer.

[0316] FIG. 8: Concentration profile (line scan) using a transverse section in a scanning electron microscope with energy-dispersive microanalyzer (EDX) of example 12 prior to calcination.

[0317] FIG. 9: Concentration profile (line scan) using a transverse section in a scanning electron microscope with energy-dispersive microanalyzer (EDX) of example 12 after calcination.