Pigment mixture

Abstract

The present invention relates to a pigment mixture based on spherical particles having a defined particle-size distribution, and to the use thereof in paints, coatings, printing inks, security printing inks, plastics, ceramic materials, glasses, in cosmetic formulations, as tracer, as filler and for the preparation of pigment preparations and dry preparations.

Claims

1. A pigment mixture consisting of components A and B: component A consists of spherical base particles having a particle-size distribution D.sub.90 of 0.5-15 m and coating layers, wherein the coating layers consist of a TiO.sub.2 layer, a SiO.sub.2 layer, and optionally an outer protective layer, wherein said spherical base particles are completely covered on their surface firstly with the TiO.sub.2 layer and subsequently with the SiO.sub.2 layer, and component B consists of spherical base particles having a particle-size distribution D.sub.90 of 0.5-15 m and coating layers, wherein the coating layers consist of a TiO.sub.2 layer, an iron oxide layer or with a layer of a mixture of TiO.sub.2 and iron oxide, and optionally an outer protective layer, said spherical base particles are completely covered on their surface firstly with the TiO.sub.2 layer and subsequently with the iron oxide layer or with the layer of the mixture of TiO.sub.2 and iron oxide.

2. The pigment mixture according to claim 1, wherein the spherical base particles of component A and component B are magnesium silicate, aluminum silicate, alkali-metal aluminum silicates, alkaline-earth metal aluminum silicates, SiO.sub.2 spheres, glass beads, hollow glass beads, nylon, aluminum oxide beads, polymeric beads comprising ethylene-acrylic acid copolymers, ethylene-methacrylate copolymers, HDI-trimethylol hexyl lactone copolymers, nylon, polyacrylates, polymethyl methacrylate copolymers, polyethylene, polymethylsilsesquioxanes or mixtures thereof.

3. The pigment mixture according to claim 1, wherein the spherical base particles of component A and/or the spherical base particles of component B are SiO.sub.2.

4. The pigment mixture according to claim 1, wherein the spherical base particles of component A and the spherical base particles of component B each consist of SiO.sub.2.

5. The pigment mixture according to claim 1, wherein, in component B, the iron oxide of the iron oxide layer or of the layer of the mixture of TiO.sub.2 and iron oxide is Fe.sub.2O.sub.3.

6. The pigment mixture according to claim 1, wherein, in component A, the TiO.sub.2 of the TiO.sub.2 layer is TiO.sub.2 in anatase modification.

7. The pigment mixture according to claim 1, wherein the TiO.sub.2 layer of component A has a layer thickness of 10-500 nm.

8. The pigment mixture according to claim 1, wherein the SiO.sub.2 layer of component A has a layer thickness of 10-500 nm.

9. The pigment mixture according to claim 1, wherein, in component B, the TiO.sub.2 of the TiO.sub.2 layer is TiO.sub.2 in anatase modification.

10. The pigment mixture according to claim 1, wherein the TiO.sub.2 layer of component B has a layer thickness of 50-400 nm.

11. The pigment mixture according to claim 1, wherein, in component B, the coating layers consist of the TiO.sub.2 layer, the iron oxide layer, and optionally the outer protective layer, and the iron oxide layer of component B has a layer thickness of 5-300 nm.

12. The pigment mixture according to claim 1, wherein, in component B, the coating layers consist of the TiO.sub.2 layer, the layer of the mixture of TiO.sub.2 and iron oxide, and optionally the outer protective layer, and the layer of the mixture of TiO.sub.2 and iron oxide of component B has a layer thickness of 55-700 nm.

13. The pigment mixture according to claim 1, wherein components A and B are mixed in a weight ratio of 99:1 to 90:10.

14. The pigment mixture according to claim 1, wherein component A and/or component B includes the outer protective layer for increasing light, temperature or weather stability compared to pigment without said layer.

15. The pigment mixture according to claim 1, wherein the spherical base particles of both component A and component B have a D.sub.90 value of 4-15 m.

16. The pigment mixture according to claim 1, wherein the spherical base particles of both component A and component B are having a D.sub.90 value of 4-8 m.

17. In paints, coatings, printing inks, security printing inks, plastics, ceramic materials, glasses, in cosmetic formulations, tracers, fillers or dry preparations comprising a pigment, the improvement wherein the pigment comprises a pigment of claim 1.

18. A formulation comprising the pigment mixture according to claim 1, and at least one absorbent, astringent, antimicrobial substance, antioxidant, antiperspirant, antifoaming agent, antidandruff active compound, antistatic, binder, biological additive, bleach, chelating agent, deodorizer, emollient, emulsifier, emulsion stabilizers, dye, humectant, film former, filler, fragrance, flavor, insect repellent, preservative, anticorrosion agent, cosmetic oil, solvent, oxidant, vegetable constituent, buffer substance, reducing agent, surfactant, propellant gas, opacifier, UV filter, UV absorber, denaturing agent, viscosity regulator, perfume or vitamin.

19. A process for the preparation of the pigment mixture according to claim 1, comprising covering the spherical base particles of components A and B with the coating layers by wet-chemical coating or by a CVD or PVD process, and component A and component B are subsequently mixed with one another.

20. The process according to claim 19, further comprising, after mixing component A and component B with one another, subjecting the mixture to calcination at a temperature of between 250 and 1100 C.

21. The process according to claim 19, further comprising, after mixing component A and component B with one another, subjecting the mixture to calcination at a temperature of between 35 and 900 C.

Description

EXAMPLES

Example 1

(1) Preparation of Component A

(2) 200 g of the spherical SiO.sub.2 particles having a D.sub.90 value of 4-8 m are coated with 300-330 g of TiCl.sub.4 solution (400 g of TiCl.sub.4/l) at a pH of 2-2.5 and subsequently with 300-310 g of sodium water-glass (13-15% by weight of SiO.sub.2) at a pH of 7.8-8.2, and the mixture is subsequently stirred. The precipitated amounts of TiO.sub.2 and SiO.sub.2 are in each case 12-16% by weight, based on the total weight of the coated white particles.

(3) Preparation of Component B

(4) In parallel, 100 g of the spherical SiO.sub.2 particles having a D.sub.90 value of 4-8 m are coated in another reaction vessel with 200 g of TiCl.sub.4 solution (400 g of TiCl.sub.4/l) at a pH of 2-2.5 and subsequently with 100-130 g of FeCl.sub.3 solution (218 g of FeCl.sub.3) at a pH of 3-3.5, and the mixture is subsequently stirred. The desired color is set (from ochre-yellow to reddish) by in-situ measurements of the Lab values. The precipitated amounts of TiO.sub.2 and Fe.sub.2O.sub.3 are 16-19% by weight and 7-10% by weight respectively, based on the total weight of the coated yellow/reddish particles.

(5) After the coating, the suspension is washed until salt-free, and the particles are filtered off and dried at 110 C. and sieved.

(6) Depending on the desired color of the end product, 2-10% by weight, based on the weight of component A, of these yellow/reddish spherical particles (component B) are added to the suspension of component A, and the mixture is stirred for at least 15 min. After components A and B have settled, the supernatant solution is decanted off, the spherical particles are filtered off and washed until salt-free. After drying at 110 C., 100 g of the end product are calcined at 600 C. for 45 min and sieved.

(7) Depending on the content of component B, hues from apricot (2-4% by weight) via pale pink (5-6% by weight) to strong pink (7-10% by weight) can be set.

(8) The mixing ratio of component A and component B can also be set by weighing out the dry pigments.

Example 2

(9) The mixtures of component A and component B as described in Example 1 can be adjusted in color through the choice of the calcination temperature. Starting at temperatures of 600 to 750 C., the hue shifts increasingly from pink/brownish/apricot into yellowish until the end product appears yellowish/white from 700 C. Pseudobrookite (Fe.sub.2TiO.sub.5) formation commences here.

USE EXAMPLES

Example A1: Eye Shadow Gel

(10) TABLE-US-00001 Raw material INCI [%] Phase A Timiron Super (1) MICA, CI 77891 (TITANIUM 15.00 Gold DIOXIDE) Pigment mixture 7.00 from Example 1 Carbopol Ultrez 21 (2) Acrylates/C10-30 Alkyl 0.30 Acrylate crosspolymer Aloe vera powder (3) Aloe Barbadensis 0.05 regular 200 Citric acid (1) Citric Acid 0.00 monohydrate Water, Aqua (Water) 55.87 demineralized Phase B Triethanolamine (4) Triethanolamine, Aqua 0.78 90% Care (Water) Germaben II (5) Propylene Glycol, Diazolidinyl 1.00 Urea, Methylparaben, Propylparaben Glycerin, (1) Glycerin 2.00 anhydrous Water, Aqua (Water) 13.00 demineralized Phase C Lubrajel DV (6) Propylene Glycol, 5.00 Polyglyceryl methacrylate
Preparation:

(11) The aloe vera powder is dissolved in the water of phase A, then all pigments and the pigment mixture and the remaining ingredients apart from the Carbopol are added and the mixture is dispersed. A few drops of citric acid are used in order to reduce the viscosity, then the Carbopol is scattered in with stirring. When completely dissolved, the pre-dissolved phase B is slowly stirred in (the mixture is not homogenized), and subsequently phase C is added. If necessary, the pHis adjusted to between 7.0-7.5 using citric acid solution.

(12) A water-based eye shadow gel formulation containing aloe vera is obtained (extremely fast-drying and easy to apply using the fingers).

(13) Sources of Supply:

(14) (1) Merck KGaA/Rona (2) Noveon (3) Terry Laboratoires, Inc. (4) BASF AG (5) ISP Global Technologies (6) Guardian

Example A2: Creamy Eye Shadow

(15) TABLE-US-00002 Raw material INCI [%] Phase A Colorona Light (1) MICA, CI 77891 (TITANIUM 10.00 Blue DIOXIDE) CI 77510 (FERRIC FERROCYANIDE) Pigment mixture 15.00 from Example 1 Talc (1) Talc 12.00 Phase B Crodamol PMP (2) PPG-2Myristyl Ether 32.80 Propionate Miglyol 812 N (3) Caprylic/Capric Triglyceride 12.00 Syncrowax HGLC (2) C18-36 Acid Triglyceride 10.00 Syncrowax HRC (2) Tribehenin 3.00 Parteck LUB STA (1) Stearic Acid 3.00 Antaron V-216 (4) PVP/Hexadecene Copolymer 2.00 Oxynex K liquid (1) PEG-8, Tocopherol, Ascorbyl 0.10 Palmitate, Ascorbic Acid, Citric Acid Propyl 4-hydroxy- (1) Propylparaben 0.10 benzoate
Preparation:

(16) Phase B is heated to about 80 C. until everything has melted and cooled to 65 C. with stirring. Then the ingredients of phase A are added with stirring, and the composition is poured into the packaging provided at 65 C., and allowed to cool to room temperature.

(17) Sources of Supply:

(18) (1) Merck KGaA/Rona (2) Croda GmbH (3) Sasol Germany GmbH (4) ISP Global Technologies

Example A3: Face Powder

(19) TABLE-US-00003 Raw material INCI [%] Phase A Pigment mixture 20.00 from Example 1 Unipure Yellow LC (1) CI 77492 (Iron Oxides) 1.20 182 Unipure Red LC (1) CI 77491 (Iron Oxides) 0.20 381 Unipure Brown LC (1) CI 77491 (Iron Oxides) CI 0.30 889 77499 (Iron Oxides) Magnesium (2) Magnesium Stearate 2.00 stearate Talc (2) Talc 71.90 Phase B RonaCare (2) Tocopheryl Acetate 0.30 all-rac-alpha- tocopheryl acetate Perfume oil 200 (3) Perfume 0.30 529 Eutanol G (4) Octyldodecanol 3.70 Propyl 4-hydroxy- (2) Propylparaben 0.10 benzoate
Preparation:

(20) The constituents of phase A are added to the mixer (for example La Moulinette from Moulinex) and are mixed for 210 seconds. The mixture is poured into a beaker, phase B is added, and is stirred in advance using a spatula. The mixture of phase A and phase B is added to the mixer and is processed for 310 seconds to give a homogeneous phase.

(21) The pressing pressure for a powder tray having a diameter of 36 mm is about 25 bar.

(22) Sources of Supply:

(23) (1) Les Colorants Wackherr (2) Merck KGaA/Rona (3) Fragrance Resources (4) Cognis GmbH

Example A4: Mattifying Foundation

(24) TABLE-US-00004 Raw material INCI [%] Phase A Water, Aqua (Water) 57.89 demineralized Pigment mixture 6.00 from Example 1 Glycerin (87% (1) Glycerin, Aqua (Water) 5.00 extra pure) RonaCare ectoin (1) Ectoin 0.30 Keltrol CG-SFT (2) Xanthan Gum 0.15 Triethanolamine (3) Triethanolamine, Aqua 0.13 90% Care (Water) Phase B Kronos 1001 (4) CI 77891 (Titanium Dioxide) 4.92 Unipure Yellow (5) CI 77492 (Iron Oxides) 1.60 LC 182 Unipure Red LC (5) CI 77491 (Iron Oxides) 0.20 381 Unipure Brown (5) CI 77491 (Iron Oxides) CI 0.20 LC 889 77499 (Iron Oxides) Unipure Blue LC (5) CI 77007 (Ultramarin Blue) 0.08 686 Phase C Miglyol 812N (6) Caprylic/Capric Triglyceride 7.00 Eutanol G (7) Octyldodecanol 4.00 Montanov 202 (8) Arachidyl Alcohol, Behenyl 4.00 Alcohol, Arachidylglucoside Avocado oil (9) Persea Gratissima (Avocado 2.00 Oil) Eusolex 9020 (1) Butyl 1.50 Methoxydibenzoylmethane Hydrolite-5 (10) Pentylene Glycol 1.20 Bentone gel (11) Stearalkonium Hectorite, 1.00 GTCC V Propylene Carbonate, Caprylic/Capric Triglyceride RonaCare (2) Tocopheryl Acetate 0.50 all-rac-alpha- tocopheryl acetate Phenonip (12) Phenoxyethanol, 0.40 Butylparaben, Ethylparaben, Propylparaben, Methylparaben Oxynex K liquid (1) PEG-8, Tocopherol, Ascorbyl 0.03 Palmitate, Ascorbic Acid, Citric Acid Phase D Simulgel EG (8) Sodium Acrylate/Sodium 0.60 Acryloyldimethyltaurate Copolymer, Isohexadecane, Polysorbate 80 Phase E Water, Aqua (Water) 1.00 demineralized
Preparation:

(25) Keltrol is added slowly to the water of phase A and is dispersed. The remaining constituents of phase A are scattered in with stirring. The constituents of phase B are added to phase A and homogenized using the Ultra-Turrax T25 (red-blue setting, 13500-20500 rpm) for 3 min and check for agglomerates. Phase A/B and phase C are heated separately to 75 C. Phase C is added to phase A/B with stirring and homogenized for 2 min using the Ultra-Turrax T25 (yellow-green setting, 8000-9500 rpm). Phase D is added at between 55 and 60 C., phase E is added at 40 C., and cooled to room temperature with further stirring; the pH is adjusted to 7.0 using 30% citric acid, and is transferred into suitable containers.

(26) A light, slightly opaque foundation is obtained which is suitable for all skin types. Avocado oil, vitamin E acetate and cell-protecting RonaCare ectoin support the skin-care action.

(27) Sources of Supply:

(28) (1) Merck KGaA/Rona (2) C. P. Kelco (3) BASF AG (4) Kronos International Inc. (5) Les Colorants Wackherr (6) Sasol Germany GmbH (7) Cognis GmbH (8) Seppic (9) Gustav Heess GmbH (10) Symrise (11) Elementis Specialities (12) Clariant GmbH

Example A5: Body Lotion

(29) TABLE-US-00005 Raw material INCI [%] Phase A Aloe vera gel 10 (1) ALOE BARBADENSIS 2.00 decolorised D-Panthenol (2) PANTHENOL 0.40 Pigment mixture 6.00 from Example 1 RonaCare (3) ALLANTOIN 0.20 allantoin Glycerin, (3) GLYCERIN 4.00 anhydrous Water, AQUA (WATER) 67.57 demineralized Phase B Protelan AGL (4) SODIUM COCOYL 6.00 95/C GLUTAMATE Cosmacol EMI (5) DI-C12-13 ALKYL MALATE 3.00 Eutanol G (6) Octyldodecanol 3.00 Jojoba oil (7) SIMMONDSIA CHINENSIS 1.50 (JOJOBA OIL) Tegosoft TN (8) C12-15 Alkyl Alkyl benzoate 1.50 Carbopol ETD (9) Acrylates/C10-30 Alkyl 0.60 2020 Acrylate Crosspolymer Phenonip (10) Phenoxyethanol, Butylparaben, 0.60 Ethylparaben, Propylparaben, Methylparaben RonaCare (3) Bisabolol 0.50 bisabolol RonaCare all- (3) Tocopheryl Acetate 0.50 rac-alpha- tocopheryl acetate Oxynex ST liquid (3) Diethylhexyl 0.50 Syringylidenemalonate, Caprylic/Capric Triglyceride Cremophor RH (11) PEG-40 Hydrogenated Castor 0.30 410 Oil Oxynex K liquid PEG-8, Tocopherol, Ascorbyl 0.03 Palmitate, Ascorbic Acid, Citric Acid Phase C Perfume oil (12) Perfume 0.50 Lifetime DH10255/1 Phase D Water, Aqua (Water) 1.00 demineralized Germal 115 (13) Imidazolidinyl Urea 0.30
Preparation:

(30) The aloe vera and RonaCare allantoin are pre-dissolved in the water of phase A with stirring, then the other constituents of phase A are added and heated to 60 C. The jojoba oil, Oxynex K liquid, Cosmacol EMI, Eutanol G and Tegosoft TN are added into a stirred vessel, then the Carbopol is incorporated homogeneously using the disperser disc (about 700 rpm, 20 min). Then the remaining constituents of phase B are added, and everything is stirred to give a homogeneous mixture, adding the Protelan AGL 95/C right at the end of phase B in order to prevent excessive incorporation of air. Phase A is incorporated into phase B (RT) at 60 C. with the aid of the disperser disc. Add phases C and D, then homogenized for 4 min using the Ultra-Turrax T50, speed 4, and cooled to room temperature.

(31) pH (23 C.)=5.5-6.0

(32) Viscosity: Brookfield DV II+Helipath, spindle C, 5 rpm, 24 C.=11200 mPa.Math.s

(33) Sources of Supply:

(34) (1) Terry Laboratoires (2) Alfa Aesar GmbH & Co. KG (3) Merck KGaA/Rona (4) Zschimmer & Schwarz GmbH & Co. (5) Nordmann, Rassmann GmbH & Co. (6) Cognis GmbH (7) Gustav Heess GmbH (8) Evonik Goldschmidt GmbH (9) Noveon (10) Clariant GmbH (11) BASF AG (12) Parfex (13) ISP Global Technologies

(35) 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.

(36) 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.