PIGMENTS

Abstract

Pigments based on particles which are coated with at least one layer which consists of a mixture of amorphous carbon (a-C) and nanocrystalline graphite (nc-graphite) and use of these pigments in, for example, paints, plastics, industrial coatings, automotive coatings, printing inks and cosmetic formulations.

Claims

1. A pigment comprising coated particles wherein the particles are coated with at least one layer which consists of a mixture of amorphous carbon (a-C) and nanocrystalline graphite (nc-graphite).

2. The pigment of claim 1, wherein the ratio a-C/nc-graphite in the at least one a-C/nc-graphite layer is in the range of 60:40 to 80:20.

3. The pigment of claim 1, wherein the at least one a-C/nc-graphite layer has a thickness of 1-10 nm.

4. The pigment of claim 1, wherein the particles are selected from the following group of substrates: natural or synthetic mica, talc, kaolin, Fe.sub.2O.sub.3 flakes, Fe.sub.3O.sub.4 flakes, Al.sub.2O.sub.3 flakes, BiOCl flakes, glass flakes, SiO.sub.2 flakes, TiO.sub.2, flakes, BN flakes, aluminum flakes, Si-oxynitride flakes, Si-/Ti-nitride flakes, graphite flakes, pearl essence, synthetic support-free flakes, glass beads, filler pigments, interference pigments, multilayer pigments, colour flop pigments, goniochromatic pigments, metal effect pigments, silicon particles or mixtures thereof.

5. The pigment of claim 1, wherein the particles are spherical or platelet-shaped.

6. The pigment of claim 1, wherein the particles are further coated with a least one metal oxide and/or metal.

7. The pigment of claim 1, wherein the pigments have one of the following combinations of substrate particle and layers: substrate+a-C/nc-graphite layer; substrate+a-C/nc-graphite layer+TiO.sub.2; substrate+a-C/nc-graphite layer+Fe.sub.2O.sub.3; substrate+a-C/nc-graphite layer+Fe.sub.3O.sub.4; substrate+a-C/nc-graphite layer+Cr.sub.2O.sub.3; substrate+a-C/nc-graphite layer+SiO.sub.2; substrate+a-C/nc-graphite layer+ZrO.sub.2; substrate+a-C/nc-graphite layer+SnO.sub.2; substrate+a-C/nc-graphite layer+ZnO; substrate+a-C/nc-graphite layer+Al; substrate+a-C/nc-graphite layer+Fe; substrate+a-C/nc-graphite layer+Cr; substrate+TiO.sub.2+a-C/nc-graphite layer; substrate+TiO.sub.2/Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+Fe.sub.3O.sub.4+a-C/nc-graphite layer; substrate+TiO.sub.2+Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+TiO.sub.2+Fe.sub.3O.sub.4+a-C/nc-graphite layer; substrate+TiO.sub.2+SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+TiO.sub.2+Al.sub.2O.sub.3+TiO.sub.2+a-C/nc-graphite layer; substrate+TiO.sub.2+MgO*SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+TiO.sub.2+CaO*SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+TiO.sub.2+Al.sub.2O.sub.3*SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+TiO.sub.2+B.sub.2O.sub.3*SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+Fe.sub.2O.sub.3+SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+Fe.sub.2O.sub.3+Al.sub.2O.sub.3+TiO.sub.2+a-C/nc-graphite layer; substrate+Fe.sub.2O.sub.3+MgO*SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+Fe.sub.2O.sub.3+CaO*SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+Fe.sub.2O.sub.3+Al.sub.2O.sub.3*SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+Fe.sub.2O.sub.3+B.sub.2O.sub.3*SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+TiO.sub.2/Fe.sub.2O.sub.3+SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+TiO.sub.2/Fe.sub.2O.sub.3+Al.sub.2O.sub.3+TiO.sub.2+a-C/nc-graphite layer; substrate+TiO.sub.2/Fe.sub.2O.sub.3+MgO*SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+TiO.sub.2/Fe.sub.2O.sub.3+CaO*SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+TiO.sub.2/Fe.sub.2O.sub.3+Al.sub.2O.sub.3*SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+TiO.sub.2/Fe.sub.2O.sub.3+B.sub.2O.sub.3*SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+TiO.sub.2+SiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+TiO.sub.2/Fe.sub.2O.sub.3+SiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+TiO.sub.2/Fe.sub.2O.sub.3+MgO*SiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+TiO.sub.2+Al.sub.2O.sub.3+TiO.sub.2/Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+TiO.sub.2+MgO*SiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+TiO.sub.2+CaO*SiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+TiO.sub.2+Al.sub.2O.sub.3*SiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+TiO.sub.2+B.sub.2O.sub.3*SiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+TiO.sub.2+SiO.sub.2+a-C/nc-graphite layer; substrate+TiO.sub.2+SiO.sub.2/Al.sub.2O.sub.3+a-C/nc-graphite layer; substrate+TiO.sub.2+Al.sub.2O.sub.3+a-C/nc-graphite layer; substrate+SnO.sub.2+a-C/nc-graphite layer; substrate+SnO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+SnO.sub.2+Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+SiO.sub.2+a-C/nc-graphite layer; substrate+SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+SiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+SiO.sub.2+Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+SiO.sub.2+TiO.sub.2+Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+SiO.sub.2+TiO.sub.2+Fe.sub.3O.sub.4+a-C/nc-graphite layer; substrate+SiO.sub.2+TiO.sub.2+SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+SiO.sub.2+Fe.sub.2O.sub.3+SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+SiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3+SiO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+SiO.sub.2+TiO.sub.2+SiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+SiO.sub.2+TiO.sub.2+SiO.sub.2+a-C/nc-graphite layer; substrate+SiO.sub.2+TiO.sub.2+SiO.sub.2/Al.sub.2O.sub.3+a-C/nc-graphite layer; substrate+SiO.sub.2+TiO.sub.2+Al.sub.2O.sub.3+a-C/nc-graphite layer; substrate+a-C/nc-graphite layer+TiO.sub.2+a-C/nc-graphite layer; substrate+a-C/nc-graphite layer+Fe.sub.2O.sub.3+a-C/nc-graphite layer; substrate+a-C/nc-graphite layer+SiO.sub.2+SnO.sub.2+TiO.sub.2+a-C/nc-graphite layer; substrate+a-C/nc-graphite layer+SiO.sub.2+SnO.sub.2+TiO.sub.2+a-C/nc-graphite layer+TiO.sub.2; or substrate+a-C/nc-graphite layer+SiO.sub.2+SnO.sub.2+TiO.sub.2+a-C/nc-graphite layer+Fe.sub.2O.sub.3.

8. The pigment of claim 1, wherein the pigment consists of 90-99 wt. % of the particles and 1-10 wt. % of the a-C/nc-graphite layer(s) based on the total pigment weight.

9. Process for the preparation of a pigment of claim 1, comprising heating the particles in a fluidized bed reactor to a selected reaction temperature in an inert gas atmosphere and, when the selected reaction temperature is reached, adding carbon precursors for the at least one a-C/nc-graphite layer to the fluidization gas and then, after chemical deposition of the at least one a-C/nc-graphite layer, cooling the fluidized bed reaction under inert gas atmosphere until room temperature is reached.

10. Process according to claim 9, wherein the carbon precursors are selected from sugars and organic solvents.

11. Process according to claim 9, wherein the carbon precursors are selected from ethanol, isopropanol, acetone, 2-methyl-3-butin-2-ol, icing sugar, fructose, glycose, dextrose or a mixture thereof.

12. Process according to claim 9, wherein the selected reaction temperature is 200 to <500 C.

13. Process according claim 9, wherein the fluidized bed reactor is a fluidized bed assisted CVD reactor (FBCVD).

14. A composition which is a: paint; coating; automobile coating; automotive refinishing; industrial coating; powder coating; printing ink; security printing ink; plastic; ceramic material; cosmetic; glass; paper; paper coating; toner for electrophotographic printing processes; seed; greenhouse sheeting or tarpaulin; thermally conductive, self-supporting, electrically insulating, flexible sheet for the insulation of machines or devices; absorber in the laser marking of paper and plastics; absorber in the laser welding of plastics; pigment past with water or organic and/or aqueous solvents; in pigment preparation; or dry preparation; composition further comprising a pigment of claim 1.

15. Formulation comprising a pigment of claim 1 in an amount of 0.01-95% by weight, based on the formulation as a whole.

16. Formulation according to claim 15 which additionally comprises at least one component selected from: absorbents, astringents, antimicrobial substances, antioxidants, antiperspirants, antifoaming agents, antidandruff active compounds, antistatics, binders, biological additives, bleaches, chelating agents, deodorisers, emollients, emulsifiers, emulsion stabilisers, dyes, humectants, film formers, fillers, fragrances, flavours, insect repellents, preservatives, anticorrosion agents, cosmetic oils, solvents, water, oxidants, vegetable constituents, buffer substances, reducing agents, surfactants, propellant gases, opacifiers, UV filters or UV absorbers, denaturing agents, aloe vera, avocado oil, coenzyme Q10, green tea extract, viscosity regulators, perfume vitamins, or combinations of these components.

Description

EXAMPLES

Example 1

[0192] 150 g of natural mica flakes of a particle size from 5 to 15 m are dispersed in 2000 ml DI water while stirring. The suspension is then heated up until 75 C. while continuous stirring. Precipitation pH-value of suspension is set to 1.8 by adding a SnCl.sub.4 solution (50%) drop wisely. The remaining SnCl.sub.4 solution is dosed steadily to the suspension. During the procedure the pH value is kept constant at 1.8 by adding sodium hydroxide (32%). After completing adding the solutions the suspension is stirred for another 10 min.

[0193] At a constant pH value of 1.4, 135 g of TiCl.sub.4 solution (25%) are dosed in until the colour end point (blueish silver) has been reached, i. e. 12 wt.-%, TiO.sub.2. Thus, TiO.sub.2 layer thickness of 12 nm is realized. During the precipitation process pH value is kept constant by continuously adding a 32% sodium hydroxide solution. After completion the suspension is stirred for another 10 min, filtered off with suction and washed with DI water until salt-fee. The particulate matter is dried at 120 C. for 24 h. After the drying process a calcination step at 800 C. for 45 min follows.

[0194] The obtained pigments have an intense blueish to light silvery shade.

Example 2

[0195] 150 g of natural mica flakes of a particle size from 5 to 15 m are dispersed in 2000 ml DI water while stirring. The suspension is then heated up until 75 C. while continuous stirring. Precipitation pH-value of suspension is set to 1.8 by adding a SnCl.sub.4 solution (50%) drop wisely. The remaining SnCl.sub.4 solution is dosed steadily to the suspension. During the procedure the pH value is kept constant at 1.8 by adding sodium hydroxide (32%). After completing adding the solutions the suspension is stirred for another 10 min.

[0196] At a constant pH value of 1.4, 201 g of TiCl.sub.4 solution (25%) are dosed in until the colour end point (blueish silver) has been reached, i. e. 18 wt.-% TiO.sub.2. Thus, TiO.sub.2 layer thickness of 18 nm is realized. During the precipitation process pH value is kept constant by continuously adding a 32% sodium hydroxide solution. After completion the suspension is stirred for another 10 min, filtered off with suction and washed with DI water until salt-fee. The particulate matter is dried at 120 C. for 24 h. After the drying process a calcination step at 800 C. for 45 min follows.

[0197] The obtained pigments have a light blueish to intense silvery shade.

Example 3

[0198] 150 g of natural mica flakes of a particle size from 5 to 15 m are dispersed in 2000 ml DI water while stirring. The suspension is then heated up until 75 C. while continuous stirring. Precipitation pH-value of suspension is set to 1.8 by adding a SnCl.sub.4 solution (50%) drop wisely. The remaining SnCl.sub.4 solution is dosed steadily to the suspension. During the procedure the pH value is kept constant at 1.8 by adding sodium hydroxide (32%). After completing adding the solutions the suspension is stirred for another 10 min.

[0199] At a constant pH value of 1.4, 390 g of TiCl.sub.4 solution (25%) are dosed in until the colour end point (blueish silver) has been reached, i. e. 35 wt.-% TiO.sub.2. Thus, TiO.sub.2 layer thickness of 35 nm is realized. During the precipitation process pH value is kept constant by continuously adding a 32% sodium hydroxide solution. After completion the suspension is stirred for another 10 min, filtered off with suction and washed with DI water until salt-fee. The particulate matter is dried at 120 C. for 24 h. After the drying process a calcination step at 800 C. for 45 min follows.

[0200] The obtained pigments have a strong silvery shade with light blueish highlights.

Example 4Chemical Vapour Deposition

[0201] 150 g of the blueish-silvery coloured particles according to Example 1 are heated up in a fluidized bed reactor (DI: 63 mm) up to 490 C. under a constant inert gas atmosphere (N.sub.2). Volumetric flow has been adjusted to reach the minimal fluidization velocity of 2 mm/s, thus excellent mixing and heat and mass transfer properties are guaranteed. As soon as the reaction temperature has been reached the adding of the C precursor acetone is dosed to the fluidization volumetric flow. Due to the elevated reaction temperature the C precursor will decompose in a way that the growth of the C layers on the blueish-silvery coloured pigments surfaces is initiated. The CVD process is run for 60 min in order to achieve a C layer thickness 4 nm. After a cooling phase under inert gas atmosphere the final pigments are removed from the reactor and sieved.

[0202] The dark pigments show a metallic effect with high lustre and high hiding power.

[0203] The deposited C layer consists of a mixture of a-C and nc-graphite with a weight ratio of 90:10. The ratio was determined combining RAMAN spectroscopic investigations according to Ferrari et al. and thermogravimetric analysis according to Mller et. al [Mller, J-O; Su, Dang Sheng; Jentoft, Rolf E.; Krhnert, Jutta; Jentoft, Friederike C.; Schlgl, Robert; Morphology-controlled reactivity of carbonaceous materials towards oxidation, in: Catalysis Today, 102, 2005, S. 259-265.] and Trigueiro et al. [Trigueiro, Joo Paulo C.; Silva, Glaura G.; Lavall, Rodrigo L.; Furtado, Clascdia A.; Oliveira, Srgio; Ferlauto, Andre S.; Lacerda, Rodrigo G.; Ladeira, Luiz O.; Liu, Jiang-Wen; Frost, Ray L.; Purity evaluation of carbon nanotube materials by thermogravimetric, TEM, and SEM methods, in: Journal of nanoscience and nanotechnology, 7, 2007, S. 3477-3486.]

Example 5Chemical Vapour Deposition

[0204] 150 g of the blueish-silvery coloured particles according to Example 2 are heated up in a fluidized bed reactor (DI: 63 mm) up to 490 C. under a constant inert gas atmosphere (N.sub.2). Volumetric flow has been adjusted to reach the minimal fluidization velocity of 2 mm/s, thus excellent mixing and heat and mass transfer properties are guaranteed. As soon as the reaction temperature has been reached the adding of the C precursor 2-methyl-3-butin-2-ol is dosed to the fluidization volumetric flow. Due to the elevated reaction temperature the C precursor will decompose in a way that the growth of the C layers on the particles' surfaces is initiated. The CVD process is run for 60 min in order to achieve a C layer thickness 4 nm. After a cooling phase under inert gas atmosphere the final pigments are removed from the reactor and sieved.

[0205] The dark pigments show a deep metallic effect with high lustre and high hiding power.

[0206] The deposited C layer consists of a mixture of a-C and nc-graphite with a weight ratio of 90:10. The ratio was determined combining RAMAN spectroscopic investigations according to Ferrari et al. and thermogravimetric analysis according to Muller et al.

Example 6Chemical Vapour Deposition

[0207] 150 g of the blueish-silvery coloured pigments particles according to Example 3 are heated up in a fluidized bed reactor (DI: 63 mm) up to 490 C. under a constant inert gas atmosphere (N.sub.2). Volumetric flow has been adjusted to reach the minimal fluidization velocity of 2 mm/s, thus excellent mixing and heat and mass transfer properties are guaranteed. As soon as the reaction temperature of 490 C. has been reached the C precursor acetone is dosed to the fluidization flow. Due to the elevated reaction temperature the C precursor will decompose in a way that the growth of the C layers on the particles' surfaces is initiated. The CVD process is run for 60 min in order to achieve a C layer thickness 4 nm. After a cooling phase under inert gas atmosphere (N.sub.2) the final pigments are removed from the reactor and sieved.

[0208] The dark pigments show a deep metallic effect, high lustre and high hiding power.

[0209] The deposited C layer consists of a mixture of a-C and nc-graphite with a ratio of 90:10. The ratio was determined combining RAMAN spectroscopic investigations according to Ferrari et al. and thermogravimetric analysis according to Mller et al.

Example 7a-C/Nc-Graphite Coating on Commercially Available Blue Interference Pigments

[0210] 1 kg of commercially available blue interference pigment

[0211] Example 7a): Iriodin 7225 Ultra Blue (Merck KGaA; natural mica coated with TiO.sub.2, particle size 10-60 m)

[0212] Example 7b): Timiron Splendid Blue (Merck KGaA; multilayer pigment based on natural mica coated with TiO.sub.2 and SiO.sub.2, particle size 10-60 m)

[0213] Example 7c): Pyrisma Colour Space Blue (Merck KGaA; natural mica coated with TiO.sub.2 and SnO.sub.2, particle size 5-35 m)

[0214] Example 7d): Xirona Caribbean Blue (Merck KGaA, multilayer pigment based on natural mica coated with TiO.sub.2, SiO.sub.2 and SnO.sub.2, particle size 10-60 m)

[0215] Example 7e): Lumina Royal Exterior Blue (BASF, natural mica coated with TiO.sub.2, SiO.sub.2 and SnO.sub.2, d.sub.10=10 m, d.sub.50=19 m, d.sub.90=34 m)

[0216] Example 7f): Mirage Bright Blue (Eckart, borosilicate glass flakes coated with TiO.sub.2 and SnO.sub.2, particle size 10-70 m)

[0217] Example 7g): SynCrystal Blue (Eckart, synthetic mica (fluorophlogopite coated with TiO.sub.2 and SnO.sub.2, particle size 10-50 m)

[0218] Example 7h): XillaMay (Kuncai, synthetic mica coated with TiO.sub.2 and SnO.sub.2, SiO.sub.2 and Ce.sub.2O.sub.3, particle size 6-30 m)

[0219] is heated in a fluidized bed reactor (DI: 100 mm) up to the desired reaction temperature of 480 C. The heating and the C deposition reaction are run in an inert gas atmosphere (N.sub.2). The inert fluidization gas is adjusted in a way that the minimum fluidization velocity of 2 mm/s is maintained throughout the process. If the reaction temperature of 480 C. is reached the C precursor acetone or 2-methyl-3-butin-2-ol is added to the fluidization gas. After a cooling phase under inert gas (N.sub.2) atmosphere the final pigments are removed from the reactor and sieved.

[0220] The deposited C layer consists of a mixture of a-C/nc-graphite:

[0221] Example 7a): a-C/nc-graphite ratio: 85:15, layer thickness: 1-2 nm

[0222] Example 7b): a-C/nc-graphite ratio: 85:15, layer thickness: 1-2 nm

[0223] Example 7c): a-C/nc-graphite ratio: 95:5, layer thickness: 1-2 nm

[0224] Example 7d): a-C/nc-graphite ratio: 90:10, layer thickness: 1-2 nm

[0225] Example 7e): a-C/nc-graphite ratio: 95:5, layer thickness: 1-2 nm

[0226] Example 7f): a-C/nc-graphite ratio: 95:5, layer thickness: 1-2 nm

[0227] Example 7g): a-C/nc-graphite ratio: 90:10, layer thickness: 1-2 nm

[0228] Example 7h): a-C/nc-graphite ratio: 85:15, layer thickness: 1-2 nm

[0229] The coated pigments of Examples 7a)-7h) show a (dark) masstone blue shade. At the same time the hiding power is improved significantly compared to the non-coated pigments. Furthermore, the a-C/nc-graphite coated pigments appear more metallic compared to the pristine (=non-coated) pigments.

[0230] In case of Example 7d) the a-C/nc-graphite layer enhances the colour travel effect, i.e. a very intense colour travel (=multicolour flop of at least three colours) from blue to violet to green. This effect is highly suitable for cosmetic applications, e. g. eyeshadow, lipgloss, lipsticks and nail polish in such a way that a so-called holographic effect can be seen due to the enhanced colour travel.

Example 8Carbon/Graphite Coating on Commercially Available Green Interference Pigments

[0231] 1 kg of commercially available interference pigment green

[0232] Example 8a): Pyrisma Colour Space Turquoise (Merck KGaA; natural mica coated with TiO.sub.2, particle size 5-35 m)

[0233] Example 8b): Timiron Splendid Green (Merck KGaA; multilayer pigment based on natural mica coated with TiO.sub.2 and SiO.sub.2, particle size 10-60 m)

[0234] Example 8c): Xirona Nordic Sunset (Merck KGaA, SiO.sub.2 flakes coated with SnO.sub.2 and TiO.sub.2, particle size: 5-50 m)

[0235] Example 8d): Mirage Dazzling Green (Eckart, borosilicate glass flakes coated with TiO.sub.2 and SnO.sub.2, particle size 150-200 m)

[0236] Example 8e): Adamas AE-791K-OP Splendor Green (CQV, Al.sub.2O.sub.3 flakes coated with TiO.sub.2 and SnO.sub.2, d.sub.10=5 m, d.sub.50=15-19 m, d.sub.90=30 m)

[0237] is heated in a fluidized bed reactor (DI: 100 mm) up to the desired reaction temperature of 450 C. The heating and the C deposition reaction are run in an inert gas atmosphere. The inert fluidization gas is adjusted in a way that the minimum fluidization velocity of 2 mm/s is maintained throughout the process. If the reaction temperature, e. g. 450 C. is reached the C precursor acetone or 2-methyl-3-butine-2-ol is added to the fluidization gas. After a cooling phase under inert gas atmosphere (e. g.: N.sub.2 the final pigments are removed from the reactor and sieved.

[0238] The deposited C layer consists of a mixture of a-C/nc-graphite:

[0239] Example 8a): a-C/nc-graphite ratio: 85:15, layer thickness: 1-2 nm

[0240] Example 8b): a-C/nc-graphite ratio: 85:15, layer thickness: 1-2 nm

[0241] Example 8c): a-C/nc-graphite ratio: 85:15, layer thickness: 1-2 nm

[0242] Example 8d): a-C/nc-graphite ratio: 95:5, layer thickness: 1-2 nm

[0243] Example 8e): a-C/nc-graphite ratio: 85:15, layer thickness: 1-2 nm

[0244] The coated pigments according to Examples 8a) to 8e) show a (dark) masstone green shade and a significantly improved hiding power. Furthermore, the a-C/nc-graphite coated pigments appear more metallic than the pristine (=non-coated) pigments.

[0245] In case of Example 8c) the a-C/nc-graphite layer enhances the colour travel effect and shows a very intense colour travel from silver-green to silver-red to green-gold. This effect can especially be exploited in cosmetic applications, e. g. eyeshadow, lipgloss, lipsticks and nail polish in such a way that a so-called holographic effect can be seen due to the enhanced colour travel.

Examples 9-15a-C/Nc-Graphite Coating on Commercially Available Interference Pigments

[0246] 1 kg of commercially available interference pigments selected from the following table

TABLE-US-00001 Example # Pigment Composition PSD/m Parameter C layer thickness 9a) Iriodin 120 Natural mica + 5-15 T = 490 C., 1-2 nm Luster Satin TiO.sub.2 t = 120 min, 85:15 Merck KGaA Precursor: Aceton, 9b) Iriodin Rutil Natural mica + 5-15 T = 490 C., 1-2 nm Fine Satin TiO.sub.2 t = 120 min, 95:5 Merck KGaA Precursor: 2- Methyl-3- Butin-2-ol 9c) Timiron Natural mica + 5-15 T = 480 C., 1-2 nm SuperSilk TiO.sub.2 t = 120 min, 95:5 MP-1005 Precursor: 2- Merck KGaA Methyl-3- Butin-2-ol 9d) Ronastar Calcium 20-200 T = 480 C., 1-2 nm Noble Sparks Sodium t = 120 min, 95:5 Merck KGaA Borosilicate + Precursor: 2- SiO.sub.2 + TiO.sub.2+ Methyl-3- Butin-2-ol 9e) Xirallic Al.sub.2O.sub.3 flakes + 5-30 T = 490 C., 1-2 nm Crystal Silver SnO.sub.2 + t = 120 min, 85:15 T60-10 TiO.sub.2 Precursor: Merck KGaA Aceton 9f) Adamas Al.sub.2O.sub.3 + SnO.sub.2 d.sub.10 = 5 T = 490 C., 1-2 nm AE-901K-SP TiO.sub.2 +SiO.sub.2 + d.sub.50 = 15- t = 120 min, 85:15 Splendor Silane 19 Precursor: White d.sub.90 = 30 Aceton CVQ 9g) Iriodin 111 Mica + TiO.sub.2 5-15 T = 200 C., 1-2 nm Merck KGaA t = 30 min 99:1 Precursor: Icing Sugar 9h) Timiron Mica + TiO2 + 10-60 T = 450 C., 1-2 nm Arctic Silver SiO2 t = 120 min, 85:15 Precursor: Acetone 10) Iriodin 7215 Natural mica + 10-60 T = 480 C., 1-2 nm Ultra Red TiO.sub.2 t = 120 min, 85:15 Merck KGaA Precursor: 2- Methyl-3- Butin-2-ol 11) Xirona Le Silica + 5-50 T = 450 C., 1-2 nm Rouge Fe.sub.2O.sub.3 t = 60 min, 85:15 Merck KGaA Precursor: Acetone 12) Ronastar Al.sub.2O.sub.3 + 5-50 T = 450 C., 1-2 nm Flaming Fe.sub.2O.sub.3 t = 60 min, 85:15 Lights Precursor: Merck KGaA Acetone 13) Ronastar CaAl 20-200 T = 480 C., 1-2 nm Aqua Sparks Borosilicate + t = 60 min, 85:15 Merck KGaA SiO.sub.2 + SnO.sub.2 + Precursor: TiO.sub.2 Acetone 14) Xirona Mica + TiO.sub.2 + 10-60 T = 480 C., 1-2 nm Volcanic Fire SiO.sub.2 + SnO.sub.2 t = 120 min, 85:15 Merck KGaA Precursor: Acetone 15) Xirona CaAl 20-200 T = 480 C., 1-2 nm Moonlight Borosilicate + t = 60 min, 85:15 Sparks TiO.sub.2 + SiO.sub.2 + Precursor: Merck KGaA SnO.sub.2 Acetone

[0247] is heated in a fluidized bed reactor (DI: 100 mm) up to the desired reaction temperature. The heating and the C deposition reaction are run in an inert N.sub.2-gas atmosphere. The N.sub.2 inert gas fluidization is adjusted in a way that the minimum fluidization velocity of 2 mm/s is maintained throughout the process. If the reaction temperature is reached the C precursor is added to the fluidization gas. After a cooling phase under inert gas atmosphere (N.sub.2) the final pigments are removed from the reactor and sieved.

[0248] The C coating of Examples 9b) and 9c) leads to a liquid metal effectespecially in cosmetic applications, e. g. lipsticks, lipgloss, nailpolish. These three C coated pigments have a Liquid Metal Index of 8.58 (Fop Index=18.09, Graininess=2.11). So far, such effects could only be achieved by the use of aluminium flakes which are not allowed to be used in lipgloss, lipsticks and eyeshadows to regulatory constraints.

Application Examples

Use Example A1Coating

[0249] The a-C/nc-graphite coated pigments according to Example 4 are incorporated in a base coat MIPA WBC 000 (MIPA SE, Germany) by stirring in. Depending on the desired colour shade a certain concentration of pigment has to be used. To achieve a full shade of the pigment of Example 4 1 wt. % of pigment on formulation is used. If necessary, the coating is adjusted to spray viscosity of 70-75 mPa.Math.s at 1000 s.sup.1 by dilution with deionized water. The pigmented base coat is applied on black-white metal panels (Metopac T21G, purchased at company Leneta) by spray coating. For application an automated spray application Oerter APL 4.6 with a spray gun DeVilbiss AGMD2616 is used (nozzle 1.4 mm, cap 767c). Spray pressure is 4200 mbar, material feeding is about 110 ml/min, distance between spray gun and substrate is approx. 30 cm. The spray gun moves with 0.45 m/s, three layers with an intermediate flash off time of 30 s between each layer are applied. The resulting dry film thickness is 10-20 m, preferably 11-15 m. It is also possible to apply only one layer with dry film thickness of 1-3 m in case the carbon content of the pigment is high enough. After predrying of the pigmented layer at room temperature with air circulation a clearcoat is applied on top of this basecoat and the complete coating is stoved.

Use Example A2Coating

[0250] The a-C/nc-graphite coated pigments according to Example 5 are incorporated in a base coat MIPA WBC 000 (MIPA SE, Germany) by stirring in. Depending on the desired colour shade a certain concentration of pigment has to be used. To achieve a full shade of the pigment of Example 4 1 wt. % of pigment on formulation is used. If necessary, the coating is adjusted to spray viscosity of 70-75 mPa.Math.s at 1000 s.sup.1 by dilution with deionized water. The pigmented base coat is applied on black-white metal panels (Metopac T21G, purchased at company Leneta) by spray coating. For application an automated spray application Oerter APL 4.6 with a spray gun DeVilbiss AGMD2616 is used (nozzle 1.4 mm, cap 767c). Spray pressure is 4200 mbar, material feeding is about 110 ml/min, distance between spray gun and substrate is approx. 30 cm. The spray gun moves with 0.45 m/s, three layers with an intermediate flash off time of 30 s between each layer are applied. The resulting dry film thickness is 10-20 m, preferably 11-15 m. It is also possible to apply only one layer with dry film thickness of 1-3 m in case the carbon content of the pigment is high enough. After predrying of the pigmented layer at room temperature with air circulation a clearcoat is applied on top of this basecoat and the complete coating is stoved.

Use Example A3Lipstick

[0251]

TABLE-US-00002 Ingredients INCI (CTFA) [wt. %] Phase A Interference Pigment according (1) 15.00 to Example 6, Phase B Oxynex K liquid (1) PEG-8, TOCOPHEROL, 0.05 ASCORBYL PALMITATE, ASCORBIC ACID, CITRIC ACID Sensiva PA 20 (2) PHENETHYL ALCOHOL, 1.00 ETHYLHEXYL GLYCERIN Paraffin viscous (1) PARAFFINUM LIQUIDUM 2.10 (MINERAL OIL) Adeps Lanae (3) LANOLIN 3.50 Paracera C 44 (4) COPERNICIA CERIFERA CERA 5.25 (COPERNICIA CERIFERA (CARNAUBA) WAX), CERESIN Isopropyl Myristate (5) ISOPROPYL MYRISTATE 5.60 Wax white (1) CERA ALBA (BEESWAX) 8.75 Castor Oil (3) RICINUS COMMUNIS SEED OIL 58.55 Phase C Fragrance Pearl FEMA (6) PARFUM 0.20

Procedure

[0252] Heat the ingredients of phase B up to 75 C. and stir until completely melted. Add phase A and stir until all ingredients are evenly dispersed. Cool down to 65 C., stir until the phase is air free, add phase C and pour into lipstick molds preheated to 55 C. Store the molds in a freezer for approx. 1 hour, remove the sticks and insert them into lipstick mechanics. Flame the lipsticks carefully.

Suppliers

[0253]

TABLE-US-00003 (2) Schlke & Mayr GmbH (3) Henry Lamotte Oils GmbH (4) Azelis Germany GmbH (5) BASF AG (6) Cosnaderm GmbH

Use Example A4Lipstick

[0254]

TABLE-US-00004 Ingredients INCI (CTFA) [wt. %] Phase A Dark Green Interference (1) 15.00 Pigment according to Example 8b Phase B Oxynex K liquid (1) PEG-8, TOCOPHEROL, 0.05 ASCORBYL PALMITATE, ASCORBIC ACID, CITRIC ACID Sensiva PA 20 (2) PHENETHYL ALCOHOL, 1.00 ETHYLHEXYL GLYCERIN Paraffin viscous (1) PARAFFINUM LIQUIDUM 2.10 (MINERAL OIL) Adeps Lanae (3) LANOLIN 3.50 Paracera C 44 (4) COPERNICIA CERIFERA CERA 5.25 (COPERNICIA CERIFERA (CARNAUBA WAX), CERESIN Isopropyl Myristate (5) ISOPROPYL MYRISTATE 5.60 Wax white (1) CERA ALBA (BEESWAX) 8.75 Castor Oil (3) RICINUS COMMUNIS SEED OIL 58.55 Phase C Fragrance Pearl FEMA (6) PARFUM 0.20

Procedure

[0255] Heat the ingredients of phase B up to 75 C. and stir until completely melted. Add phase A and stir until all ingredients are evenly dispersed. Cool down to 65 C., stir until the phase is air free, add phase C and pour into lipstick molds preheated to 55 C. Store the molds in a freezer for approx. 1 hour, remove the sticks and insert them into lipstick mechanics. Flame the lipsticks carefully.

Suppliers

[0256]

TABLE-US-00005 (2) Schlke & Mayr GmbH (3) Henry Lamotte Oils GmbH (4) Azelis Germany GmbH (5) BASF AG (6) Cosnaderm GmbH

Use Example A5Lipstick

[0257]

TABLE-US-00006 Ingredients INCI (CTFA) [wt. %] Phase A Dark Green Interference (1) 15.00 Pigment according to Example 8a) Phase B Oxynex K liquid (1) PEG-8, TOCOPHEROL, 0.05 ASCORBYL PALMITATE, ASCORBIC ACID, CITRIC ACID Sensiva PA 20 (2) PHENETHYL ALCOHOL, 1.00 ETHYLHEXYL GLYCERIN Paraffin viscous (1) PARAFFINUM LIQUIDUM 2.10 (MINERAL OIL) Adeps Lanae (3) LANOLIN 3.50 Paracera C 44 (4) COPERNICIA CERIFERA CERA 5.25 (COPERNICIA CERIFERA (CARNAUBA) WAX), CERESIN Isopropyl Myristate (5) ISOPROPYL MYRISTATE 5.60 Wax white (1) CERA ALBA (BEESWAX) 8.75 Castor Oil (3) RICINUS COMMUNIS SEED OIL 58.55 Phase C Fragrance Pearl FEMA (6) PARFUM 0.20

Procedure

[0258] Heat the ingredients of phase B up to 75 C. and stir until completely melted. Add phase A and stir until all ingredients are evenly dispersed. Cool down to 65 C., stir until the phase is air free, add phase C and pour into lipstick molds preheated to 55 C. Store the molds in a freezer for approx. 1 hour, remove the sticks and insert them into lipstick mechanics. Flame the lipsticks carefully.

Suppliers

[0259]

TABLE-US-00007 (2) Schlke & Mayr GmbH (3) Henry Lamotte Oils GmbH (4) Azelis Germany GmbH (5) BASF AG (6) Cosnaderm GmbH

Use Example A6Lipstick

[0260]

TABLE-US-00008 Ingredients INCI (CTFA) [wt. %] Phase A Dark Blue Interference Pigment (1) 15.00 according to Example 7b) Phase B Oxynex K liquid (1) PEG-8, TOCOPHEROL, 0.05 ASCORBYL PALMITATE, ASCORBIC ACID, CITRIC ACID Sensiva PA 20 (2) PHENETHYL ALCOHOL, 1.00 ETHYLHEXYL GLYCERIN Paraffin viscous (1) PARAFFINUM LIQUIDUM 2.10 (MINERAL OIL) Adeps Lanae (3) LANOLIN 3.50 Paracera C 44 (4) COPERNICIA CERIFERA CERA 5.25 (COPERNICIA CERIFERA (CARNAUBA) WAX), CERESIN Isopropyl Myristate (5) ISOPROPYL MYRISTATE 5.60 Wax white (1) CERA ALBA (BEESWAX) 8.75 Castor Oil (3) RICINUS COMMUNIS SEED OIL 58.55 Phase C Fragrance Pearl FEMA (6) PARFUM 0.20

Procedure

[0261] Heat the ingredients of phase B up to 75 C. and stir until completely melted. Add phase A and stir until all ingredients are evenly dispersed. Cool down to 65 C., stir until the phase is air free, add phase C and pour into lipstick molds preheated to 55 C. Store the molds in a freezer for approx. 1 hour, remove the sticks and insert them into lipstick mechanics. Flame the lipsticks carefully.

Suppliers

[0262]

TABLE-US-00009 (2) Schlke & Mayr GmbH (3) Henry Lamotte Oils GmbH (4) Azelis Germany GmbH (5) BASF AG (6) Cosnaderm GmbH

Use Example A7Eye Shadow

[0263]

TABLE-US-00010 Ingredients INCI (CTFA) [wt. %] Phase A Interference Pigment according (1) 30.00 to Example 6 Parteck LUB Talc (1) TALC 10.00 Phase B RonaCare AP (1) BIS-ETHYLHEXYL 0.50 HYDROXYDIMETHOXY BENZYLMALONATE Oxynex K liquid (1) PEG-8, TOCOPHEROL, 0.10 ASCORBYL PALMITATE, ASCORBIC ACID, CITRIC ACID all-rac-alpha-Tocopheryl (1) TOCOPHERYL ACETATE 0.50 acetate Parteck LUB STA 50 (1) STEARIC ACID 3.00 SP Crodamol PMP MBAL-LQ- (2) PPG-2 MYRISTYL ETHER 30.90 (MH) PROPIONATE Syncrowax HGLC (2) C18-36 ACID TRIGLYCERIDE 10.00 Miglyol 812N (3) CAPRYLIC/CAPRIC 8.00 TRIGLYCERIDE Syncrowax HRC (2) TRIBEHENIN 3.00 Ganex V-216 (4) PVP/HEXADECENE 2.00 COPOLYMER Sunflower Oil, refined (5) HELIANTHUS ANNUUS SEED 1.00 OIL (HELIANTHUS ANNUUS (SUNFLOWER) SEED OIL) Sensiva PA 20 (6) PHENETHYL ALCOHOL, 1.00 ETHYLHEXYL GLYCERIN

Procedure

[0264] Heat phase B to 80 C. until all ingredients are melted. Cool down to 65 C. and add the ingredients of phase A while stirring. Fill the bulk into the desired packaging at 65 C. Cool down to room temperature.

Suppliers

[0265]

TABLE-US-00011 (2) Croda (3) IOI Oleo GmbH (4) Ashland (5) Gustav Heess GmbH (6) Schlke & Mayr GmbH

Use Example A8Lip balm

[0266]

TABLE-US-00012 Ingredients INCI (CTFA) [wt. %] Phase A Metallic reddish/brownish (1) 15.00 interference pigments according to Example 11 Phase B Oxynex K liquid (1) PEG-8, TOCOPHEROL, 0.05 ASCORBYL PALMITATE, ASCORBIC ACID, CITRIC ACID Sensiva PA 20 (2) PHENETHYL ALCOHOL, 1.00 ETHYLHEXYL GLYCERIN Paraffin viscous (1) PARAFFINUM LIQUIDUM 2.10 (MINERAL OIL) Adeps Lanae (3) LANOLIN 3.50 Paracera C 44 (4) COPERNICIA CERIFERA CERA 5.25 (COPERNICIA CERIFERA (CARNAUBA) WAX), CERESIN Isopropyl Myristate (5) ISOPROPYL MYRISTATE 5.60 Wax white (1) CERA ALBA (BEESWAX) 8.75 Castor Oil (3) RICINUS COMMUNIS SEED OIL 58.55 Phase C Fragrance Pearl FEMA (6) PARFUM 0.20

Procedure

[0267] Heat the ingredients of phase B up to 75 C. and stir until completely melted. Add phase A and stir until all ingredients are evenly dispersed. Cool down to 65 C., stir until the phase is air free, add phase C and pour into molds. Store the molds in a freezer for approx. 1 hour. The lipstick base is poured into eye shadow pans.

Suppliers

[0268]

TABLE-US-00013 (2) Schlke & Mayr GmbH (3) Henry Lamotte Oils GmbH (4) Azelis Germany GmbH (5) BASF AG (6) Cosnaderm GmbH

Use Example A9Lip balm

[0269]

TABLE-US-00014 Ingredients INCI (CTFA) [wt. %] Phase A Metallic reddish/brownish (1) 15.00 interference pigments according to Example 12 Phase B Oxynex K liquid (1) PEG-8, TOCOPHEROL, 0.05 ASCORBYL PALMITATE, ASCORBIC ACID, CITRIC ACID Sensiva PA 20 (2) PHENETHYL ALCOHOL, 1.00 ETHYLHEXYL GLYCERIN Paraffin viscous (1) PARAFFINUM LIQUIDUM 2.10 (MINERAL OIL) Adeps Lanae (3) LANOLIN 3.50 Paracera C 44 (4) COPERNICIA CERIFERA CERA 5.25 (COPERNICIA CERIFERA (CARNAUBA) WAX), CERESIN Isopropyl Myristate (5) ISOPROPYL MYRISTATE 5.60 Wax white (1) CERA ALBA (BEESWAX) 8.75 Castor Oil (3) RICINUS COMMUNIS SEED OIL 58.55 Phase C Fragrance Pearl FEMA (6) PARFUM 0.20

Procedure

[0270] Heat the ingredients of phase B up to 75 C. and stir until completely melted. Add phase A and stir until all ingredients are evenly dispersed. Cool down to 65 C., stir until the phase is air free, add phase C and pour into molds. Store the molds in a freezer for approx. 1 hour. The lipstick base is poured into eye shadow pans.

Suppliers

[0271]

TABLE-US-00015 (2) Schlke & Mayr GmbH (3) Henry Lamotte Oils GmbH (4) Azelis Germany GmbH (5) BASF AG (6) Cosnaderm GmbH

[0272] Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

[0273] The entire disclosure[s] of all applications, patents and publications, cited herein and of corresponding European application No. 19198681.9, filed Sep. 20, 2019, is [are] incorporated by reference herein.

[0274] The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

[0275] From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.