Gold-Coloured Effect Pigments Having High Chroma and High Brilliancy, Method for the Production and Use Thereof

Abstract

The present invention relates to gold-colored 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 gold-colored effect pigment.

Claims

1. A gold-colored 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, where the metal ion comprises or is at least one metal ion selected from the group of metals consisting of Fe, Sn, Ti and Zr, and c) a layer 3 comprising at least one of metal oxide, metal hydroxide or metal oxide hydrate, where the metal ion comprises or is at least one metal ion selected from the group of metals consisting of Fe, Sn, Ti and Zr, at least one of layers 2 and 3 comprises at least two different metal ions and at least one of the two different metal ions is an iron ion, and layers 2 and 3 are interrupted by a spacer layer.

2. The gold-colored 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, glass platelets, iron oxide platelets, SiO.sub.2 platelets, Al.sub.2O.sub.3 platelets, kaolin platelets, talc platelets, graphite platelets, bismuth oxychloride platelets and mixtures thereof, and the nonmetallic substrate in platelet form has optionally been coated and calcined with at least one of metal oxide, metal hydroxide or metal oxide hydrate.

3. The gold-colored effect pigment as claimed in claim 1, wherein the effect pigment comprises further layers of high and low refractive index and at least one further spacer layer.

4. The gold-colored effect pigment as claimed in claim 1, wherein the proportion of iron oxide, iron hydroxide and/or iron oxide hydrate in the gold-colored effect pigment is within a range from 1% by weight to 45% by weight, determined by means of XRF, calculated in each case as the metal oxide and based on the total weight of the gold-colored effect pigment.

5. The gold-colored effect pigment as claimed in claim 1, wherein the proportion of metal oxide, metal hydroxide and/or metal oxide hydrate, where the at least one metal ion comprises or is a metal ion selected from the group of metals consisting of Sn, Ti and Zr, is within a range from 10% to 75% by weight in total and the proportion of iron oxide, iron hydroxide and/or iron oxide hydrate is within a range from 1.5% by weight to 25% by weight, determined in each case by means of XRF, calculated in each case as the metal oxide and based in each case on the total weight of the gold-colored effect pigment.

6. The gold-colored effect pigment as claimed in claim 1, wherein layers 2 and 3 do not include any tin oxide, tin hydroxide and/or tin oxide hydrate and the proportion of tin oxide, tin hydroxide and/or tin oxide hydrate in the gold-colored effect pigment is within a range from 0.01% by weight to 1.5% by weight, determined by means of XRF as tin dioxide and based on the total weight of the gold-colored effect pigment.

7. The gold-colored effect pigment as claimed in claim 1, wherein the spacer layer includes connections and cavities.

8. The gold-colored effect pigment as claimed in claim 1, wherein the at least one spacer layer has a mean height h.sub.a in each case from a range from 5 nm to 120 nm.

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

10. A process for producing the gold-colored effect pigment as claimed in claim 1, wherein the process comprises: i. 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 metal oxide, metal hydroxide and/or metal oxide hydrate, where the metal ion comprises or is at least one metal ion selected from the group of metals consisting of Fe, Sn, Ti and Zr and where at least one of these metal ions is an iron ion, 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 450° C. to 990° C. to obtain the gold-colored effect pigment comprising at least one spacer layer.

11. A process for producing the gold-colored 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 metal ion comprises or is at least one metal ion selected from the group of metals consisting of Fe, Sn, Ti and Zr and where at least one of these metal ions is an iron ion, where layers B and C may be arranged directly one on top of another, and where the at least one metal oxide, metal hydroxide and/or metal oxide hydrate applied in layer B, in relation to the metal ion, is different than the metal ion(s) of the metal oxide, metal hydroxide and/or metal oxide hydrate of layer C and the layer that directly adjoins layer B in the substrate direction, ii. calcining the product obtained in step (i) at a temperature from a range from 450° C. to 990° C. to obtain the gold-colored 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 gold-colored 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 gold-colored 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 GOLD-COLORED EFFECT PIGMENTS OF THE INVENTION

Example 1

[0201] 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.90=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 tin oxide 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 250 mL of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) was dosed to 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, 12 mL of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3 were added therein. After completion of dosage, the mixture was stirred for another 10 minutes and, by addition of 100 mL of tin chloride solution of concentration c(Sn)=12 g/L, a further thin layer of tin oxide was deposited. Subsequently, 250 mL of a solution of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) were dosed to the suspension. Thereafter, 12 mL of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3 were dosed after 10 minutes. 15 minutes after completion of addition, the suspension was filtered off and the filtercake was washed. The filtercake was dried and calcined at 900° C. for 60 minutes. Extremely chromatic, high-gloss gold-colored effect pigments were obtained.

Example 2

[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 stirring. The pH of the suspension was lowered to pH 2.2. By addition of 60 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. The pH of the suspension was subsequently lowered to pH 1.9 and then a solution of 500 mL of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) were 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, 65 mL of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3 were added therein. After completion of dosage, the mixture was stirred for another 10 minutes, 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. Thereafter, a further addition of 35 mL of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3 were dosed 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 minutes. Extremely chromatic, high-gloss gold-colored effect pigments with very good hiding capacity were obtained.

Example 3

[0203] 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 demineralized water and heated to 85° C. with 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. 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) were added 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 added. After completion of addition, 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 layer were deposited. Subsequently, 180 mL of a solution of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) were dosed 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 last addition, the suspension was filtered off and the filtercake was washed. The filtercake was dried and calcined at 750° C. for 60 minutes. Extremely chromatic, high-gloss gold-colored effect pigments were obtained.

Example 4

[0204] 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 stirring. The pH of the suspension was lowered to pH 1.9 and then a solution of 580 mL of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) were 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, 80 mL of an aqueous iron chloride solution having a density of 1.25 g/cm.sup.3 were dosed in. After completion of addition, the mixture was stirred for another 10 minutes, and, thereafter, 630 mL of a solution of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) were dosed into the suspension. Thereafter, a further addition of 70 mL of an aqueous iron chloride solution having a density of 1.25 g/cm.sup.3 were dosed after 10 minutes. On completion of addition, the mixture was stirred for a further 10 minutes, and, thereafter, 300 mL of a solution of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) were dosed into the suspension. Thereafter, a further addition of 40 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 had ended, the suspension was filtered off and the filtercake was washed. The filtercake was dried and calcined at 850° C. for 60 minutes. Extremely chromatic, high-gloss gold-colored effect pigments with very good hiding capacity were obtained.

Example 5

[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 stirring. The pH of the suspension was lowered to pH 2.6. Subsequently, 40 mL of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3 were added 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 added into the suspension. 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. Thereafter, at a pH of 1.9, 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 were dosed and then the mixture was stirred for a further 120 minutes and filtered. The washed filtercake was dried and calcined at 800° C. for 45 minutes. Extremely chromatic, high-gloss gold-colored effect pigments with very good hiding capacity were obtained.

Example 6

[0206] 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 stirring. By addition of 75 g of a tin chloride solution of concentration c(Sn)=12 g/L at pH 2.2, a layer of tin oxide was deposited on the surface of the substrate. The pH of the suspension was lowered to pH 1.9 and then a solution of 500 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, 360 mL of an aqueous iron chloride solution having a density of 1.25 g/cm.sup.3 were added. On completion of added dosage, the mixture was stirred for another 10 minutes, and, thereafter, 500 mL of a solution of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) were added to the suspension. After the addition had ended, the mixture was stirred for another 2 hours, the suspension was filtered and the filtercake was washed. The filtercake was dried and calcined at 850° C. for 60 minutes. Extremely chromatic, high-gloss gold-colored effect pigments with very good hiding capacity 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=5 μm, D.sub.50=12 μm, D.sub.90=25 μm were suspended in 1300 mL of demineralized water and heated to 85° C. with stirring. The pH of the suspension was lowered to pH 2.2. By addition of 70 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. The pH of the suspension was subsequently lowered to pH 1.8 and then a solution of 800 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 1.42 g/cm.sup.3 were dosed in. After completion of added dosage, the mixture was stirred for another 10 minutes, the pH was adjusted to pH 1.8, and 400 mL of a solution of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) were dosed into the suspension. Thereafter, a further addition of 25 mL of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3 were dosed 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 880° C. for 45 minutes. Extremely chromatic, high-gloss gold-colored effect pigments with very good hiding capacity were obtained.

Example 8

[0208] 100 g of the gold-colored effect pigment obtained in example 2 were suspended in 850 mL of demineralized water and heated to 85° C. with turbulent stirring. The pH was lowered to 4.2 with dilute hydrochloric acid. Then a solution consisting 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 1 hour and the pH was adjusted thereafter to 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 and the suspension was stirred for another 180 minutes and then filtered, and the filtercake was washed with demineralized water. The filtercake was dried at 95° C. under reduced pressure.

Example 9

[0209] 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. 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 gold-colored effect pigments were obtained.

Comparative Example 1

[0210] 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.90=100 μm, span ΔD=1.36 were suspended in 1300 mL of demineralized water 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 tin oxide 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 added 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, 60 mL of an aqueous iron chloride solution having a density of 1.42 g/cm.sup.3 were added. 15 minutes after completion of addition, the suspension was filtered off and the filtercake was washed. The filtercake was dried and calcined at 870° C. for 60 minutes. Shiny gold pigments were obtained.

Comparative Example 2

[0211] Multilayer pigment based on natural mica platelets, Iriodin 307 Star Gold, from Merck.

Comparative Example 3 (Based on Example 1 of DE 1959998 A1)

[0212] 100 g of natural mica platelets (muscovite platelets) having a particle size distribution according to MALVERN Mastersizer MS 2000: D.sub.10=8 μm, D.sub.50=20 μm, D.sub.90=43 μm were suspended in 1010 mL of demineralized water and heated to 70° C. with stirring. The pH of the suspension was adjusted to pH 2.0 with a TiCl.sub.4 solution in hydrochloric acid 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. Thereafter, a mixture of 11.33 g of FeCl.sub.3.6H.sub.2O dissolved in 6.7 mL of hydrochloric acid (density 1.19 g/cm.sup.3), 66.7 mL of demineralized water and 240 mL of a 25% solution of TiCl.sub.4 in hydrochloric acid was allowed to flow into the suspension at a rate of 60 mL/h with constant pH. After the end of the addition, at the same pH, a solution of 380 mL of TiCl.sub.4 (200 g of TiO.sub.2/L of demineralized water) was introduced into the suspension. After the addition had ended, the mixture was stirred for a further 2 to 4 hours. In the course of this, the pH of the suspension was raised gradually from 5 to 7 with sodium hydroxide solution. Subsequently, the suspension was filtered and the filtercake was washed. The resulting pigment was dried at 120° C. and then calcined at 950° C. for 60 min. A brown, highly agglomerated pigment with no gloss was obtained. No spacer layer is apparent in scanning electron micrographs of transverse sections.

Comparative Example 4 (Based on Claim 1 of CN 101289580 A)

[0213] 100 g of natural mica platelets (muscovite platelets) having a particle size distribution according to MALVERN Mastersizer MS 2000: D.sub.10=8 μm, D.sub.50=20 μm, D.sub.90=43 μm were suspended in 900 mL of demineralized water and heated to 85° C. with stirring. The pH of the suspension was adjusted to pH 2.25 with hydrochloric acid and then a solution of 3940 mL of TiCl.sub.4 having a content of 102.5 g/L was added into the suspension. Thereafter, the pH of the suspension was adjusted to 4.0 and then a mixture of 1006 mL of FeCl.sub.3 solution (FeCl.sub.3 content 80 g/L) and 144 mL of TiCl.sub.4 having a content of 102.5 g/L was allowed to flow in. After the addition had ended, the suspension was left to stand and the supernatant was decanted off, and suspension was concentrated to a solids content of 8.0%. Thereafter, the pH of the suspension was adjusted to 1.8, and 150 mL of a SnCl.sub.2 solution having a tin content of 53.2 g/L were added gradually. A further layer was applied by adjusting the pH to 2.25 and then adding a solution of 2300 mL of TiCl.sub.4 having a content of 102.5 g/L into the suspension. After the addition had ended, the mixture was stirred for a further 2 to 4 hours. In the course of this, the pH was kept constant. Subsequently, the suspension was filtered and the filtercake was washed. The moist pigment was dried at 150° C. and then calcined at 820° C. for 60 minutes. A gold pigment with moderate gloss and good hiding powder was obtained. No spacer layer is apparent in scanning electron micrographs of transverse sections.

Comparative Example 5 (Based on Example 2 of WO 2014/094993 A1)

[0214] 100 g of natural mica platelets (muscovite platelets) having a particle size distribution according to MALVERN Mastersizer MS 2000: D.sub.10=4.8 μm, D.sub.50=21.3 μm, D.sub.90=38.9 μm were suspended in 1500 mL of demineralized water and heated to 75° C. with turbulent stirring. The pH of the suspension was adjusted to pH 2.6 with hydrochloric acid and then a mixed solution of 158.6 mL of FeCl.sub.3 solution (density 1.42 g/cm.sup.3), 107.2 mL of TiCl.sub.4 solution in hydrochloric acid with a TiO.sub.2 content of 200 g/L, 11.8 g of AlCl.sub.3.6H.sub.2O and 126.2 mL of demineralized water was added into the suspension. In the course of this, the pH was kept constant with sodium hydroxide solution. Thereafter, the pH of the suspension was adjusted to 1.8, and 805 mL of a SnCl.sub.2 solution having a tin content of 0.91 g/L were added gradually within 300 minutes. Thereafter, the pH of the suspension was raised to 2.6 and 751.7 mL of a mixed solution of 285 mL of FeCl.sub.3 solution (density 1.42 g/cm.sup.3), 196.4 mL of TiCl.sub.4 solution in hydrochloric acid with a TiO.sub.2 content of 200 g/L, 11.8 g of AlCl.sub.3.6 H.sub.2O and 270.3 mL of demineralized water were gradually added into the suspension. In the course of this, the pH was kept constant. Subsequently, the pH was raised to 5.0, the mixture was stirred for a further 15 minutes and then the suspension was filtered. The pigment cake was washed, and the moist pigment was dried at 110° C. for 16 hours and then calcined at 850° C. for 30 minutes. A gold pigment with high hiding power was obtained. No spacer layer is apparent in scanning electron micrographs of transverse sections.

Comparative Example 6 (Based on Example 3 of WO 2014/094993 A1)

[0215] 100 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 2000 mL of demineralized water and heated to 75° C. with turbulent stirring. The pH of the suspension was adjusted to pH 9.0 and then 95 mL of a sodium silicate solution (13.8% by weight of SiO.sub.2) were added in at constant pH within 50 minutes. Thereafter, the pH of the suspension was adjusted to 2.6 and 250 mL of a mixed solution of 142.7 mL of FeCl.sub.3 solution (density 1.42 g/cm.sup.3), 101.3 mL of TiCl.sub.4 solution in hydrochloric acid with a TiO.sub.2 content of 200 g/L, 3.2 g of AlCl.sub.3.6H.sub.2O and 6 mL of demineralized water were added into the suspension within 60 minutes. Then the pH of the suspension was adjusted to 1.8, and 492 mL of an SnCl.sub.2 solution having a tin content of 24 g/L were added gradually within 4 hours. Thereafter, the pH of the suspension was raised to 2.6 and 250 g of a mixed solution of 142.7 g of FeCl.sub.3 solution (density 1.42 g/cm.sup.3), 101.3 mL of TiCl.sub.4 solution in hydrochloric acid with a TiO.sub.2 content of 200 g/L, 3.2 g of AlCl.sub.3.6 H.sub.2O and 6 mL of demineralized water were gradually added into the suspension within 350 minutes. In the course of this the pH was kept constant. Subsequently, the pH was raised to 5.0, the mixture was stirred for a further 15 minutes and then the suspension was filtered. The pigment cake was washed, and the moist pigment was dried at 110° C. for 16 hours and then calcined at 650° C. for 30 minutes. A gold pigment with good hiding power was obtained. No spacer layer is apparent in scanning electron micrographs of transverse sections.

II CHARACTERIZATION OF THE GOLD-COLORED EFFECT PIGMENTS OF THE INVENTION AND THE PIGMENTS OF THE COMPARATIVE EXAMPLES

IIa Particle Size Measurement

[0216] The size distribution curve of the gold-colored effect pigments of the invention and of the pigments from the comparative examples is 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 suspension, 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.

[0217] 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.

[0218] The span ΔD, defined as

[00003]$\Delta .Math..Math.D=\frac{D_{90}-D_{10}}{D_{50}},$

indicates the breadth of the particle size distribution. With regard to the visual appearance of the gold-colored effect pigments of the invention, a small value of ΔD, i.e. a narrow span, is preferred.

TABLE-US-00002 TABLE 2 Particle sizes Example/ comparative example D10 [μm] D50 [μm] D90 [μm] Span Example 1 19.6 55.5 115.1 1.722 Example 2 10.8 22.5 40.6 1.326 Example 3 28.1 53.0 92.7 1.219 Example 4 11.3 22.3 40.6 1.318 Example 5 10.5 23.6 42.8 1.369 Example 6 11.3 23.6 42.5 1.319 Example 7 7.1 14.5 26.4 1.336 Example 8 10.8 22.6 40.6 1.319 Example 9 9.7 21.3 41.3 1.482 Comparative 12.1 22.8 40.6 1.247 example 1 Comparative 11.5 23.4 43.9 1.380 example 2 Comparative 12.6 24.1 43.0 1.262 example 3 Comparative 9.3 25.9 46.6 1.443 example 4 Comparative 8.5 24.0 44.0 1.480 example 5

IIb Angle-Dependent Color Measurements

[0219] To measure the color and brightness values, the effect pigments of the invention or 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 (examples 1, 3 and 9) 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.

[0220] 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*.sub.15, and characterization of the hue using the hue angle h*.sub.15, each of which was measured at a measurement angle separated by 15° from the specular angle on the black background of the black/white hiding chart.

[0221] 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 D.sub.50 Spiral applicator <40 μm 40 μm 40 μm-85 μm 76 μm >85 μm 100 μm 

TABLE-US-00004 TABLE 3 Color and brightness values at observation angle of 15° relative to the specular angle Example/ comparative example L 15° (s).sup.1) a* 15° (s) b* 15° (s) C* 15° (s) h* 15° (s) Example 1 94.84 −10.38 38.41 39.79 105.13 Example 2 91.75 −7.06 46.11 46.64 98.71 Example 3 65.18 −3.98 28.33 28.61 98.00 Example 4 92.88 −8.24 45.65 46.39 100.23 Example 5 99.58 −10.57 49.09 50.21 102.15 Example 6 93.96 −3.62 51.60 51.72 94.02 Example 7 108.96 −9.50 46.58 47.54 101.52 Example 8 92.36 −3.96 51.33 51.49 94.42 Example 9 73.74 −3.50 32.84 33.02 96.08 Comparative 86.43 1.08 33.97 33.99 88.18 example 1 Comparative 91.92 −0.79 54.67 54.68 90.83 example 2 Comparative 64.23 −4.76 7.39 8.79 122.79 example 3 Comparative 53.03 2.23 12.80 13.00 80.14 example 4 Comparative 66.24 6.53 19.90 20.94 71.84 example 5 Comparative 62.13 7.47 33.38 34.20 77.39 example 6 .sup.1)measured on the black background of the black/white hiding chart.

[0222] The gold-colored effect pigments of the invention from examples 2, 4, 5, 6, 7 and 8 are much more intense in color than comparative examples 1 to 6.

[0223] An exception is comparative example 2. This is a multilayer pigment having the high refractive index/low refractive index/high refractive index structure, which assumes the highest color values because of its structure. The gold pigments 5, 6 and 8 of the invention are barely visually distinguishable from the multilayer pigment from comparative example 2, which is reflected in the virtually comparable C*.sub.15 values.

IIc Comparison of Hiding

[0224] To determine the hiding quotient D.sub.q, defined as

[00004]$D_q=\frac{L_{\mathrm{black}}^{*25}}{L_{\mathrm{white}}^{*25}},$

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.

[0225] 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 gold-colored effect pigments in platelet form from examples 1 to 10, as can be inferred from table 4, is in each case above 0.41.

IId Gloss Measurements

[0226] 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 gold-colored effect pigments of the invention and of the pigments from the comparative examples are listed in table 4.

[0227] Some of the gold-colored effect pigments of the invention from examples 1 to 10 show distinctly higher gloss values than the pigments from comparative examples 1, 3, 4, 5 and 6. The gloss values of the pigments of the invention are in some cases even distinctly higher than the gloss value of a multilayer pigment having the high refractive index/low refractive index/high refractive index structure from comparative example 2.

IIe Effect Measurements

[0228] In order to objectively describe the optical effect of the gold-colored 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 4.

TABLE-US-00005 TABLE 4 Effect measurements, hiding quotient and gloss values Example/ comparative S_i S_a 60° gloss example 15° (s).sup.1 15° (s).sup.1 G (s).sup.1 D.sub.q 25° (w).sup.2 Example 1 26.52 34.28 13.33 0.6450 104.7 Example 2 15.44 33.99 9.99 0.6068 85.8 Example 3 62.36 27.51 16.09 0.4102 105.2 Example 4 22.98 37.07 12.26 0.6059 74.2 Example 5 13.14 32.77 10.38 0.6790 56.0 Example 6 14.31 33.64 9.64 0.6490 90.9 Example 7 8.98 28.07 6.78 0.7267 59.3 Example 8 14.58 33.75 9.98 0.6297 91.6 Example 9 51.65 34.71 13.17 0.4760 69.1 Comparative 8.97 27.68 7.18 0.5538 67.3 example 1 Comparative 13.79 35.47 9.93 0.6103 77.5 example 2 Comparative 5.90 28.28 6.12 0.4660 46.6 example 3 Comparative 5.09 26.10 5.46 0.4860 30.4 example 4 Comparative 11.29 34.03 7.17 0.5290 39.40 example 5 Comparative 11.48 37.13 7.74 0.4460 56.40 example 6

[0229] With the exception of example 7 (owing to the smaller particle size), all effect values (S_i, S_a and G) of the pigments of the invention are higher or comparable to the prior art. The effects achievable are much more marked than in the case of conventional gold-colored effect pigments having yellow absorption color as from comparative example 1. Even compared to multilayer pigments such as comparative example 2, the effects are at least equivalent, but usually distinctly higher.

IIf Waring Blender

[0230] 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 determination 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 brightness values in this test relative to the untreated applications. The Waring blender test can thus be regarded as a measure of the mutual adhesion of the individual coatings with respect to shear forces.

Procedure:

[0231] The pigment paste was weighed out and converted to a paste in a stepwise manner with a conventional wet lacquer based on hydroxy-functional acrylates 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.

[0232] Recipe: [0233] 6% powder (pigment) [0234] 8% butyl acetate 85 [0235] 86% acrylic lacquer, colorless [0236] 30% dilution butyl acetate 85/xylene 1:1

[0237] 200 g each of the untreated and treated lacquers were then applied with a spraying machine and the Sata LP-90 spray gun according to the following settings:

[0238] Setting: [0239] Needle: 1.3.4 [0240] Pressure: 4 bar

[0241] Runs: [0242] The number of spray runs was chosen such that there was a dry lacquer layer thickness of 15-20 μm.

[0243] Conventionally, effect pigments are regarded as being shear-stable when the gloss differential and the color differential, measured by the chroma C*.sub.15 close to the specular angle, is relatively low in the application after the Waring blender test.

[0244] The ΔC*.sub.15 relative to the untreated sample should ideally be less than 2.

[0245] Table 5 shows the change in color ΔC*.sub.15 of the sample that has been subjected to the Waring blender test relative to the untreated sample for inventive example 6.

TABLE-US-00006 TABLE 5 ΔC*(15°) Δgloss (60°) Example 6 1.1 −1.0

[0246] The test sheet of inventive example 6 satisfies the criteria of the test. The color difference is negligibly small. Even under the microscope, it is barely possible to detect any changes such as flaking of the coating or other surface defects that have arisen.

[0247] The gold pigments of the invention are found to be extremely shear-stable in spite of their spacer layer.

IIg Determination of Chemical Stability

[0248] The chemical stability of the gold-colored 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.

[0249] 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 dried at 80° C. for 30 minutes.

[0250] 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 6 below.

TABLE-US-00007 TABLE 6 ΔE(15°) Example 6 2.7 Comparative example 2 44.0

[0251] Pigments with a ΔE(15°)<3 can be regarded as stable to chemicals. The gold-colored effect pigments of the invention from example 6 are well below the limit, while the pigments from comparative example 2 distinctly exceed it.

IIh X-Ray Fluorescence Analysis (XRF)

[0252] The metal oxide, metal hydroxide and/or metal oxide hydrate contents of the gold-colored 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 is the Advantix ARL system from Thermo Scientific. The measurements are shown in table 7. 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-00008 TABLE 7 Mean height h.sub.a of the spacer layer and XRF values Example/ comparative Mean height h.sub.a XRF (as metal oxide) example [nm] from SEM Ti[%] Fe[%] Sn[%] Example 1 26 43.7 3.3 1.3 Example 2 30 57.7 6.9 0.78 Example 3 12 28.6 3.1 0.98 Example 4 34.sup.1 and 38.sup.2 66.3 7.8 1.2 Example 5 24 / / / Example 6 37 49.9 6.9 0.47 Example 7 39 / / / Example 8 50 / / / Example 9 20 23.9 4.6 1.26 Comparative no spacer layer 40.4 4.4 0.46 example 1 Comparative no spacer layer 27.1 18.8 0.39 example 2 Comparative no spacer layer 50.9 1.6 <0.05 example 3 Comparative no spacer layer 66.1 8.9 2.6 example 4 Comparative no spacer layer 50.7 11.8 3.4 example 5 Comparative no spacer layer 24.2 39.5 0.28 example 6 .sup.1= h.sub.a for spacer layer close to substrate .sup.2= h.sub.a for spacer layer remote from substrate

IIi Condensate Water Test

[0253] To determine condensate water stability, the gold-colored 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.

[0254] 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.

[0255] Finally, the DOI (distinctness of image) was determined with the aid of a Wave-scan II from Byk-Gardner.

TABLE-US-00009 TABLE 8 Condensate water results 20° 20° Example/ gloss gloss Loss Cross- comparative before after of cutting Swelling example CW test CW test gloss DOI immediate visual Example 8 98 94  4% 74.4 1 0 Comparative 97 28 71% n.d. 5 5 example 1

[0256] The pigment from comparative example 1 had significant swelling characteristics and poor interlayer adhesion. The gold-colored effect pigment of the invention from example 8, by contrast, was found to be very stable and had virtually no changes before and after the test.

IIj UV Stability

[0257] The UV stability of the gold-colored 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.

[0258] 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-00010 TABLE 9 UV test results Example/ comparative example ΔE* Example 8 3.2 Comparative example 1 7.3

[0259] The pigment from comparative example 1 had more than twice as high a change in color (ΔE*) after corresponding exposure than inventive example 8.

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

[0260] For this purpose, the gold-colored 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.

[0261] 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).

[0262] 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. There was an instance here of one of the lines drawn at 50 nm intervals occurring directly above a connection 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 gave rise to 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.

[0263] 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.

[0264] 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.

[0265] The term “mean” in all cases means the arithmetic mean.

[0266] 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.

[0267] As an alternative to transverse sections, the inventive gold-colored effect pigments can also 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.

TABLE-US-00011 TABLE 10 Example/ d.sub.S2 d.sub.S3 d.sub.S2/ h.sub.ma σh.sub.Rma S.sub.D A.sub.H comparative example [nm] [nm] d.sub.S3 [nm] h.sub.Rma [%] n.sub.S [%] [%] Example 2 85 91 0.94 100 0.49 4.0 1.1 5.4 94.6 Example 5 85 109 0.78 97 0.52 5.1 3.4 17.2 82.8 Example 6 123 113 1.09 142 0.52 4.6 1.5 7.6 92.4 Example 9 100 118 0.85 110 0.46 4.9 2.2 11.1 88.9 Comparative example 1 no spacer layer 0.54 21.3 18 90 10 Comparative example 2 no spacer layer 0.54 20.6 6.9 34.4 65.6 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

[0268] Table 7 shows the mean height h.sub.a of the spacer layer of the pigments examined. All the gold-colored effect pigments of the invention, by contrast with the pigments from the comparative examples, have a spacer layer.

[0269] 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 10, 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. The pigment from comparative example 2 contains pores in statistical distribution and the network density S.sub.D is 34.4%. The standard deviation of the pore midpoints from the substrate surface is 20.6%, which demonstrates that the pores are statistically distributed within the overall coating. The situation is different for the gold-colored effect pigments of the invention from examples 2, 5, 6 and 9. Here, the standard deviation of the relative height of the midpoint of the spacer layer h.sub.Rma is <6% 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 gold-colored effect pigments of the invention.

[0270] In table 10, the network density of the gold-colored effect pigments of the invention is much lower than in the case of the pigment from comparative example 1 with a value of 90%. There is no spacer layer here because of the extremely small number of pores.

IIl Scanning Electron Micrographs

[0271] The scanning electron micrographs were obtained using transverse sections of the gold-colored effect pigments of the invention with the Supra 35 scanning electron microscope (from Zeiss) (for example FIGS. 1-4). 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

[0272]

TABLE-US-00012 Product % by Manufacturer/ INCI name 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

[0273] 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.

[0274] 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

[0275]

TABLE-US-00013 Product % by Manufacturer/ INCI name name wt. supplier Phase A Microcrystalline Wax TeCero-Wax 4.50 Tromm Wachs 1030 K Copernicia Cerifera Cera LT 124 4.50 Tromm Wachs carnauba wax Isohexadecane Isohexadecane 21.00 Ineos Cyclopentasiloxane, Belsil RG 100 8.00 Wacker Dimethicone/Vinyltrimethyl- Silicone siloxysilicate Crosspolymer Elastomer Resin Gel Trimethylsiloxyphenyl Belsil PDM 20 6.00 Wacker Dimethicone Dimethicone Belsil DM 100 14.00 Wacker Caprylic/Capric Triglyceride Miglyol 812 7.00 Sasol Cyclomethicone (and) Tixogel 5.00 BYK Quaternium-90 Bentonite VSP-1438 (and) Propylene Carbonate Phase B Effect pigment 30.00 from example 3

[0276] 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.

[0277] 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

[0278]

TABLE-US-00014 Product % by Manufacturer/ INCI name name wt. supplier Phase A Effect pigment 0.10 from example 5 Aqua Wasser 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 Sectacin 103 2.00 Zschimmmer & Sulfosuccinate Spezial Schwarz Phase D Phenoxyethanol (and) Nipaguard PO 5 0.60 Clariant Piroctone Olamine Fragrance Water Lily OA 0.20 Bell Flavors and Fragrances Sodium Chloride Sodium Chloride 1.60 VWR

[0279] 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.

[0280] 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

[0281]

TABLE-US-00015 Product % by Manufacturer/ INCI name 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 20.00 from example 7 Phase B Cyclomethicone Xiameter PMX-0345 5.00 Dow Corning Octyldodecyl Stearoyl Ceraphyl 847 5.00 Ashland Stearate

[0282] The effect pigment from example 7 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.

[0283] Phase A was mixed in a high-speed mixer at 2500 rpm for 30 s. Subsequently, phase B was added and the mixture was stirred 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

[0284]

TABLE-US-00016 Product % by Manufacturer/ INCI name name wt. supplier Phase A Aqua Water 73.00 Bentonite (and) Xanthan Gum Optigel 2.00 BYK WX-PC Phase B Cetyl Alcohol (and) Glyceryl Emulium 5.00 Gattefosse Stearate (and) PEG-75 Stearate Delta (and) Ceteth-20 (and) Steareth- 20 C10-18 Triglycerides Lipocire A 2.00 Gattefosse Pellets Ozokerite Kahlwax 1899 2.00 Kahl Glyceryl Behenate Compritol 888 2.00 Gattefosse CG Pastilles Butylene Glycol Cocoate Cocoate BG 4.00 Gattefosse Phase C Effect pigment 5.00 from example 2 Phenoxyethanol (and) Piroctone Nipaguard 0.50 Clariant Olamine PO5 Glycine Soja (Soybean) Oil, Follicusan 3.00 CLR Berlin Dicaprylyl Ether, Magnolia DP Grandiflora Bark Extract, Lauryl Alcohol Water, Hydrolyzed Corn Starch, DayMoist 1.00 CLR Berlin Beta Vulgaris (Beet) Root CLR Extract Linoleic Acid (and) Linolenic Vitamin F 0.50 CLR Berlin Acid forte

[0285] The effect pigment from example 2 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.

[0286] 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

[0287]

TABLE-US-00017 Product % by Manufacturer/ INCI name name wt. supplier Phase A Sodium Magnesium Silicate Laponite XLG 2.00 BYK (nano) Aqua Water 94.80 Phase B Effect pigment 0.10 from example 6 Citric Acid (and) Water Citric Acid 0.30 (10%) Glycerin, Water, Avena Strigosa Aquarich 1.50 Rahn AG Seed Extract, Lecithin, Potassium Sorbate, Citric Acid Fragrance Lychee & 0.10 Bell Europe Grape Methylisothiazolinone (and) Optiphen 1.20 Ashland Phenethyl Alcohol (and) MIT Plus PPG-2-Methyl Ether

[0288] 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.

[0289] 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

[0290]

TABLE-US-00018 INCI name Product % by Manufacturer/ Phase A name wt. supplier 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 7

[0291] The effect pigment from example 7 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.

[0292] Phase A was mixed and then the powder was dispensed into a suitable vessel.

Application Example 8: Lipgloss

[0293]

TABLE-US-00019 Product % by Manufacturer/ INCI name 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 4

[0294] The effect pigment from example 4 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.

[0295] 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

[0296]

TABLE-US-00020 Product % by Manufacturer/ INCI name name wt. supplier Phase A Octyldodecanol Eutanol G 42.5 BASF Candelilla Cera Kahlwax 6.00 Kahl 2039 Copernicia Cerifera Kahlwax 6.00 Kahl (Carnauba) Wax 2442 Bis-Diglyceryl Softisan 10.00 Sasol Polyacyladipate-2 649 Polyisobutene Rewopal 10.00 Evonik PIB 1000 Hydrogenated Polydecene Silkflo 364 NF 5.00 Ineos Polydecene C10-18 Lipocire A 5.00 Gattefosse Triglycerides Pellets Acacia Decurrens/ Hydracire S 5.00 Gattefosse Jojoba/Sunflower Seed Wax/Polyglyceryl-3 Esters Tocopheryl Acetate dl-alpha- 0.50 IMCD Tocopheryl Acetate Phase B Effect pigment 10.00 from example 9

[0297] The effect pigment from example 9 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.

[0298] 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

[0299]

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

[0300] The effect pigment from example 1 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.

[0301] 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

[0302]

TABLE-US-00022 Product % by Manufacturer/ INCI name name wt. supplier Phase A Cyclopentasiloxane Xiameter 8.60 Dow Corning PMX-0245 Cyclosiloxane Hydrogenated MC 30 4.00 Sophim Polyisobutene Dimethicone (and) Dow Corning 37.14 Dow Corning Dimethicone Crosspolymer 9041 Silicone Elastomer Blend Squalane Squalane 5.74 Impag Isononyl Isononanoate Dermol 99 10.16 Akzo International Hydrogenated Jojoba Oil Jojoba 2.15 Desert Whale Butter LM Hydrogenated Jojaba Oi Jojoba 1.00 Desert Whale Butter HM C30-45 Alkyl Methicone Dow Corning 1.15 Dow Corning (and) C30-45 Olefin AMS-C30 Cosmetic Wax Stearyl Dimethicone Dow Corning 2503 0.47 Dow Corning Cosmetic Wax Cyclopentasiloxane (and) Dow Corning 5.00 Dow Corning Polypropylsilsesquioxane 670 Fluid Phase B Dimethicone/Vinyl Dow Corning 16.02 Dow Corning Dimethicone Crosspolymer 9506 Powder Silica Dimethyl Silylate Covasilic 15 0.17 LCW Talc Talc Powder 5.00 Sigma-Aldrich Effect pigment 3.00 from example 2 Phase D Phenoxyethanol, Euxyl PE 9010 0.40 Schülke Ethylhexylglycerin & Mayr

[0303] The effect pigment from example 2 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.

[0304] 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 in the mixer 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

[0305]

TABLE-US-00023 Product % by Manufacturer/ INCI name name wt. supplier Phase A Effect pigment 4.00 from example 9 Phase B Butylacetate (and) International 96.00 International Ethylacetate (and) Lacquers Lacquers Nitrocellulose (and) Nailpolish Isopropyl Alcohol Base 15244

[0306] The effect pigment from example 9 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.

[0307] Phase A and phase B were mixed and then dispensed into an appropriate container.

Application Example 13: Nail Varnish with Soft-Touch Effect

[0308]

TABLE-US-00024 Product % by Manufacturer/ INCI name name wt. supplier Phase A Effect pigment 4.00 from example 9 Polypropylene Synafil W 1234 5.00 Eckart Phase B Butylacetate (and) International 91.00 International Ethylacetate (and) Lacquers Lacquers Nitrocellulose (and) Nailpolish Isopropyl Alcohol Base 15244

[0309] The effect pigment from example 9 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.

[0310] 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

[0311] The effect pigments from examples 1 to 7 and from example 9 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

[0312]

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

[0313] 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.

[0314] 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.

[0315] 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)

[0316] 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)

[0317] 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)

[0318] 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.

[0319] 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)

[0320] FIG. 6: Schematic diagram of the spacer layer

[0321] FIG. 7: Schematic diagram of the position of the spacer layer

[0322] FIG. 8: Concentration profile (line scan) using a transverse section in a scanning electron microscope with energy-dispersive microanalyzer (EDX) of example 9 prior to calcination

[0323] FIG. 9: Concentration profile (line scan) using a transverse section in a scanning electron microscope with energy-dispersive microanalyzer (EDX) of example 9 after calcination.