FIVE-LAYERED PIGMENTS

Abstract

The present invention relates to five-layered pigments based on multi-coated platelet-shaped substrates which comprise a layer sequence comprising (A) a layer of SnO.sub.2 having a layer thickness of 0.1-50 nm, (B) a high-refractive-index coating consisting of TiO.sub.2 in the rutile modification having a layer thickness of 10-800 nm, (C) a colorless coating having a refractive index n1.8 having a layer thickness of 20-800 nm, (D) a high-refractive-index coating consisting of SnO.sub.2 having a layer thickness of 0.1-50 nm, (E) a layer of TiO.sub.2 in the rutile modification having a layer thickness of 10-800 nm,
and optionally (F) an outer protective layer,
and to the use thereof in paints, coatings, powder coatings, printing inks, security printing inks, plastics, ceramic materials, glasses, as dopants for the laser marking of papers and plastics, in cosmetic formulations and for the preparation of pigment preparations and dry preparations.

Claims

1. A pigment comprising a platelet-shaped substrate comprising thereon at least a 5-layer sequence of (A) a layer of SnO.sub.2, having a layer thickness of 0.1-50 nm, (B) a layer of TiO.sub.2 in rutile modification, having a layer thickness of 10-800 nm, (C) a colorless coating having a refractive index n1.8, having a layer thickness of 20-800 nm, (D) a layer of SnO.sub.2, having a layer thickness of 0.1-50 nm, (E) a layer of TiO.sub.2 in the rutile modification, having a layer thickness of 10-800 nm and optionally (F) an outer protective layer.

2. The five-layered pigment according to claim 1, wherein the platelet-shaped substrate is natural or synthetic mica, glass, or Al.sub.2O.sub.3, SiO.sub.2 or TiO.sub.2 platelets.

3. The five-layered pigment according to claim 1, wherein layer (C) is SiO.sub.2, Al.sub.2O.sub.3, AlO(OH), B.sub.2O.sub.3, MgF.sub.2, MgSiO.sub.3 or a mixture thereof.

4. The five-layered pigment according to claim 1, having an outer protective layer (F) increasing light, temperature and weather stability.

5. A process for the preparation of a five-layered pigment according to

1. , comprising coating the substrates by a wet-chemical method with hydrolytic decomposition of metal salts in aqueous medium.

6. In a paint, coating, powder coating, printing ink, security printing ink, plastic, ceramic material, glass, dopants for laser marking of paper or plastic, cosmetic formulation, pigment preparation or dry pigment preparation comprising a luster or effect pigment, the improvement wherein the luster or effect pigment is a five-layered pigment according to claim 1.

7. A pigment preparation comprising at least one binder, and at least one five-layered pigment according to claim 1.

8. A Pigment preparation according to claim 7, which is a dry preparation.

9. The dry preparation according to claim 8, comprising from 0 to 8% by weight of water and/or a solvent or solvent mixture.

10. The dry preparation according to claim 9, in the form of pellets, granules, chips or briquettes.

11. A hydrophilic, hydrophobic or lipophilic cosmetic formulation comprising at least one five-layered pigment according to claim 1.

Description

EXAMPLES

Example 1

5-Layered Pigment having a Pronounced Color Flop

[0048] 100 g of mica having a particle size of 10-60 m are heated to 80 C. in 2 l of demineralised water with stirring. When this temperature has been reached, a solution consisting of 2.3 g of SnCl.sub.45 H.sub.2O and 10 ml of hydrochloric acid (37%) in 70 ml of deionized water is slowly metered into the mica suspension at pH 1.8 with stirring. 220 g of a 32% TiCl.sub.4 solution (400 g of TiCl.sub.4/l) are then metered in at a pH of 1.8, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently raised to 7.5, and 800 ml of sodium water-glass solution (13.0% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant at 7.5 using 10% HCl. After a further stirring time of about 0.5 hour, the pH is lowered to 1.8 using hydrochloric acid (10%), and a solution of 2.3 g of SnCl.sub.45 H.sub.2O and 10 ml of hydrochloric acid (32%) in 70 ml of deionized water is metered in. About 200 ml of TiCl.sub.4 solution (400 g/l of TiCl.sub.4) are subsequently metered in slowly at a pH of 1.8. The pH is in each case kept constant using sodium hydroxide solution (32% by weight). After a further post-stirring time of 0.5 hour at pH 1.8, the coated mica pigment is filtered off, washed and dried at 110 C. for 16 hours. Finally, the pigment is calcined at 850 C. for 0.5 hour.

[0049] A blue interference pigment having a sharp color change from blue to red on changing from a steep to flat viewing angle is obtained.

Example 2

[0050] 100 g of mica having a particle size of 10-60 m are heated to 80 C. in 2 l of demineralised water with stirring. When this temperature has been reached, a solution consisting of 3 g of SnCl.sub.45 H.sub.2O and 10 ml of hydrochloric acid (37%) in 90 g of water is slowly metered into the mica suspension with vigorous stirring. 220 ml of TiCl.sub.4 solution (400 g of TiCl.sub.4/l) are metered in at a pH of 1.8. The pH is then kept constant at 7.5. The pH is subsequently raised to 7.5, and 830 ml of sodium water-glass solution (13% by weight of SiO.sub.2) are slowly metered in at this pH, during which the pH is kept constant at 7.5 using 10% HCl. A solution of 11.5 g of SnCl.sub.45 H.sub.2O and 10 ml of hydrochloric acid (32%) in 350 ml of deionized water is subsequently metered in at pH 1.8. Finally, 220 ml of TiCl.sub.4 solution (400 g of TiCl.sub.4/l) are metered in at pH 1.8. During the addition of the SnCl.sub.45 H.sub.2O solutions and TiCl.sub.4 solutions, the pH is in each case kept constant using NaOH solution (32%).

[0051] For work-up, the coated mica pigment is filtered off, washed and dried at 110 C. for 16 hours. Finally, the pigment is calcined at 850 C. for 0.5 hour.

[0052] A brightly lustrous, green-blue interference pigment whose color is red-violet on viewing at a flat angle is obtained.

USE EXAMPLES

Example A1

Wet Lip Balm Comprising 10% of Pearlescent Pigment

[0053]

TABLE-US-00001 Phase A Five-layered pigment Silica, CI77891 (Titanium dioxide), 10.00% (1) according to Example 1 Mica, Tin oxide Phase B Vegelatum Equiline EU103 11.00% (2) Candelilla Wax Candelilla Cera (Candelilla Wax) 7.00% (3) Beeswax Bleached Cera Alba (Beeswax) 5.00% (1) Myritol 331 Cocoglycerides 8.00% (4) Ozokerite Wax White # 77W Ozokerite 3.00% (3) Isopropyl Myristate Isopropyl Myristate 5.00% (4) Eusolex 2292 Ethylhexyl Methoxycinnamate, BHT 7.00% (1) Eusolex OCR Octocrylene 4.00% (1) Oxynex K Liquid PEG-8, Tocopherol, Ascorbyl Palmitate, 0.10% (1) Ascorbic Acid, Citric Acid Propyl 4-Hydroxybenzoate Propylparaben 0.10% (1) Color dispersion in castor oil 0.50% Castor Oil Ricinus Communis (Castor Oil) 38.80% (5) Phase C Perfume Oil Tendresse # 75418C Perfume 0.50% (6)

[0054] Preparation:

[0055] The constituents of phase B are heated at 75 C. with stirring until everything has melted. Add phase A and stir well. Then introduce the lipstick composition into the casting apparatus held at 65 C., add phase C and stir for 15 minutes. The homogeneous melt is poured into the casting mould pre-warmed to 55 C.

[0056] The moulds are subsequently cooled, and the castings are removed cold. After the lipsticks have been warmed to room temperature, the lipsticks are briefly flame-treated.

[0057] Sources of supply: [0058] (1) Merck KGaA/Rona [0059] (2) Natunola Health Inc. [0060] (3) Ross Waxes [0061] (4) Cognis GmbH [0062] (5) Henry Lamotte GmbH [0063] (6) Haarmann & Reimer GmbH

Example A2

Shower Gel

[0064]

TABLE-US-00002 Phase A Five-layered pigment Silica, CI77891 0.10% (1) according to Example 1 (Titanium dioxide), Mica, Tin oxide Keltrol T Xanthan Gum 0.75% (2) Water, Demineralised Aqua (Water) 64.95% Phase B Plantacare 2000 UP Decyl Glucoside 20.00% (3) Texapon ASV 50 Sodium Laureth Sulfate, 3.60% (3) Sodium Laureth-8 Sulfate, Magnesium Laureth Sulfate, Magnesium Laureth-8 Sulfate, Sodium Oleth Sulfate, Magnesium Oleth Sulfate Bronidox L Propylene Glycol, 0.20% (3) 5-Bromo-5-Nitro-1,3-Dioxane Perfume Oil Everest Perfume 0.05% (4) 79658 SB (deleted) 1% FD&C Blue No. 1 in Aqua (Water), CI 42090 0.20% (5) Water (FD&C Blue No. 1) Phase C Citric Acid Monohydrate Citric Acid 0.15% (1) Water, Demineralised Aqua (Water) 10.00%

[0065] Preparation:

[0066] For phase A, the five-layered pigment is stirred into water. Slowly scatter in the Keltrol T with stirring and stir until it has dissolved. Add phases B and C successively while stirring slowly until everything has distributed homogeneously. Set the pH to from 6.0 to 6.5.

[0067] Sources of Supply: [0068] (1) Merck KGaA/Rona [0069] (2) Kelco [0070] (3) Cognis GmbH [0071] (4) Haarmann & Reimer GmbH [0072] (5) BASF AG

Example A3

Eyeliner Gel

[0073]

TABLE-US-00003 Phase A Five-layered pigment Silica, CI77891 15.00% (1) according to Example 1 (Titanium dioxide), Mica, Tin oxide Mica Black CI 77499 (Iron Oxides), Mica, 5.00% (1) CI 77891(Titanium Dioxide) Ronasphere Silica 2.00% (1) Carbopol ETD 2001 Carbomer 0.40% (2) Citric Acid Monohydrate Citric Acid 0.00% (1) Water, Demineralised 60.00% Phase B Glycerine, Anhydrous Glycerine 4.00% (1) Triethanolamine extra pure Triethanolamine 0.90% (1) Luviskol VA 64 Powder PVPNA Copolymer 2.00% (3) Germaben II Propylene Glycol, 1.00% (4) Diazolidinyl Urea, Methylparaben, Propylparaben Water, Demineralised Aqua (Water) 9.70%

[0074] Preparation:

[0075] The five-layered pigment and the Ronasphere are dispersed in the water of phase A. Acidify using a few drops of citric acid in order to reduce the viscosity, scatter in the Carbopol with stirring. When completely dissolved, slowly stir in the pre-dissolved phase B and adjust the pH to 7.0-7.5.

[0076] Sources of Supply: [0077] (1) Merck KGaA/Rona [0078] (2) BF Goodrich [0079] (3) BASF AG [0080] (4) ISP Global Technologies

Example A4

Eyeshadow

[0081]

TABLE-US-00004 Phase A Five-layered pigment Silica, CI77891 55.0% (1) according to Example 2 (Titanium dioxide), Mica, Tin oxide Biron B 50 CI 77163 3.00% (1) (Bismuth Oxychloride) Colorona Dark Blue Pearlescent pigment: Mica, 10.00% (1) CI 77891 (Titanium Dioxide), CI 77510 (Ferric Ferrocyanide) Magnesium Stearate Magnesium Stearate 2.50% (1) China Clay (deleted) Kaolin 5.00% (1) Hubersorb 600 Calcium Silicate 0.50% (2) Talc Talc 11.00% (1) Phase B Amerchol L 101 Lanolin Alcohol, 10.70% (3) Paraffinum Liquidum (Mineral Oil) Super Hartolan Lanolin Alcohol 1.00% (4) Ewalin 1751 Petrolatum 1.00% (5) Propyl 4-Hydroxybenzoate Propylparaben 0.10% (1) Perfume Oil Elegance # 79228 Perfume 0.20% (6) D MD

[0082] Preparation:

[0083] Combine and pre-mix the constituents of phase A. Subsequently add the molten phase B dropwise to the powder mixture with stirring. The powders are pressed at 40-50 bar.

[0084] Sources of Supply: [0085] (1) Merck KGaA/Rona [0086] (2) J. M. Huber Corp. [0087] (3) Amerchol [0088] (4) Croda GmbH [0089] (5) H. Erhard Wagner GmbH [0090] (6) Haarmann & Reimer GmbH

Example A5

Eyeshadow Gel

[0091]

TABLE-US-00005 Phase A Five-layered pigment Silica, CI77891 15.00% (1) according to Example 1 (Titanium dioxide), Mica, Tin oxide Mica Black CI 77499 (Iron Oxides), Mica, 5.00% (1) CI 77891 (Titanium Dioxide) Ronasphere Silica 3.00% (1) Carbopol ETD 2001 Carbomer 3.00% (2) Citric Acid Monohydrate Citric Acid 0.00% (1) Water, Demineralised Aqua (Water) 60.00% Phase B Glycerine, Anhydrous Glycerine 2.00% (1) Germaben II Propylene Glycol, Diazolidinyl 0.20% (3) Urea, Methylparaben, Propylparaben Triethanolamine extra pure Triethanolamine 0.70% (1) Water, Demineralised Aqua (Water) 13.80%

[0092] Preparation:

[0093] The five-layered pigment and the Ronasphere are dispersed in the water of phase A. Acidify using a few drops of citric acid in order to reduce the viscosity, scatter in the Carbopol with stirring. When completely dissolved, slowly stir in the pre-dissolved phase B.

[0094] Sources of Supply: [0095] (1) Merck KGaA [0096] (2) BF Goodrich GmbH [0097] (3) ISP Global Technologies

Example A6

Shimmering Foundation

[0098]

TABLE-US-00006 Phase A Extender W Mica, CI 77891 9.00% (1) (Titanium Dioxide) Microna Matte Yellow Mica, CI 77492 (Iron Oxides) 4.00% (1) Microna Matte Red CI 77491 (Iron Oxides), Mica 0.40% (1) Microna Matte Black CI 77499 (Iron Oxides), Mica 0.30% (1) Five-layered pigment Silica, CI77891 4.50% (1) according to Example 1 (Titanium dioxide), Mica, Tin oxide Ronasphere Silica 5.00% (1) Phase B Blanose 7 HF Cellulose Gum 0.20% (2) Veegum Magnesium Aluminium 1.00% (3) Silicate Texapon K 1296 Sodium Lauryl Sulfate 0.60% (4) Triethanolamine extra pure Triethanolamine 0.50% (1) Titriplex III Disodium EDTA 0.25% (1) Methyl 4-Hydroxybenzoate Methylparaben 0.15% (1) 1,2-Propanediol Propylene Glycol 10.90% (1) Water, Demineralised Aqua (Water) 42.95% Phase C Isopropyl Myristate Isopropyl Myristate 8.00% (4) Liquid Paraffin Paraffinum Liquidum 3.60% (1) (Mineral Oil) Crodamol SS Cetyl Esters 2.60% (5) Monomuls 60-35 C Hydrogenated Palm Glycerides 1.70% (4) Stearic Acid Stearic Acid 1.50% (1) Eusolex 6300 4-Methylbenzylidene Camphor 1.30% (1) Eusolex 4360 Benzophenone-3 0.50% (1) RonaCare Tocopherol Tocopheryl Acetate 0.10% (1) Acetate Magnesium Stearate Magnesium Stearate 0.10% (1) Propyl 4-Hydroxybenzoate Propylparaben 0.05% (1) Phase D Perfume Oil 200 529 Perfume 0.20% (6) Euxyl K 400 Phenoxyethanol, 0.20% (7) Methyldibromo- Glutaronitrile

[0099] Preparation:

[0100] Melt all constituents of phase C at about 75 C. and stir until everything has melted. Initially introduce the water of phase B cold, homogenize in the Blanose using the Turrax, scatter in the Veegum, and re-homogenize. Warm to 75 C. and dissolve the other constituents therein with stirring. Stir in the constituents of phase A. Add phase C at 75 C. with stirring and homogenize for 2 minutes. Cool the composition to 40 C. with stirring, add phase D. Cool further to room temperature with stirring and adjust to pH 6.0-6.5 (for example using citric acid solution).

[0101] Sources of Supply: [0102] (1) Merck KGaA/Rona [0103] (2) Aqualon GmbH [0104] (3) Vanderbilt [0105] (4) Cognis GmbH [0106] (5) Croda GmbH [0107] (6) Fragrance Resources [0108] (7) Schlke & Mayr GmbH

Example A7

Lip Gloss

[0109]

TABLE-US-00007 Phase A Five-layered pigment Silica, CI77891 10.00% (1) according to Example 2 (Titanium dioxide), Mica, Tin oxide Phase B Indopol H 100 Polybutene 59.90% (2) Bentone Gel MIO V Quaternium-18 Hectorite, 20.00% (3) Propylene Carbonate, Paraffinum Liquidum (Mineral Oil) Eutanol G Octyldodecanol 6.00% (4) RonaCare Tocopherol Tocopheryl Acetate 1.00% (1) Acetate Dow Corning 1403 Fluid Dimethiconol, Dimethicone 3.00% (5) Propyl 4-Hydroxybenzoate Propylparaben 0.05% (1) Rouge Covapate W 3773 Ricinus Communis 0.05% (6) (Castor Oil), CI 15850 (D&C) Red No. 6)

[0110] Preparation:

[0111] All constituents of phase B are weighed out together, heated to 70 C. and stirred well until a homogeneous composition has formed. The pigments are then added and stirred again. The homogeneous mixture is packaged at 50-60 C.

[0112] Sources of Supply: [0113] (1) Merck KGaA/Rona [0114] (2) BP Amoco [0115] (3) Elementis Specialites [0116] (4) Cognis GmbH [0117] (5) Dow Corning [0118] (6) Les Colorants Wackherr

Example A8

EyeshadowCompact Powder

[0119]

TABLE-US-00008 Phase A Five-layered pigment Silica, CI77891 25.00% (1) according to Example 1 (Titanium dioxide), Mica, Tin oxide Colorona Dark Blue Mica, CI 77891 5.00% (1) (Titanium Dioxide), CI 77510 (Ferric Ferrocyanide) Talc Talc 49.50% (1) Potato Starch Solanium Tuberosum 7.50% (2) (Potato Starch) Magnesium Stearate Magnesium Stearate 2.50% (1) Phase B Isopropyl Stearate Isopropyl Stearate 9.14% (3) Cetyl Palmitate Cetyl Palmitate 0.53% (1) Ewalin 1751 Petrolatum 0.20% (4) Perfume Oil Elegance # 79228 Perfume 0.20% (5) D MF Propyl 4-Hydroxybenzoate Propylparaben 0.10% (1)

[0120] Preparation:

[0121] Combine and pre-mix the constituents of phase A. Subsequently add the molten phase B dropwise to the powder mixture with stirring. The powders are pressed at 40-50 bar.

[0122] Sources of Supply: [0123] (1) Merck KGaA [0124] (2) Sdstrke GmbH [0125] (3) Cognis GmbH [0126] (4) H. Erhard Wagner GmbH [0127] (5) Haarmann & Reimer GmbH

Example A9

Loose Eye Powder

[0128]

TABLE-US-00009 Phase A Five-layered pigment Silica, CI77891 (Titanium 50.00% (1) according to Example 1 dioxide), Mica, Tin oxide Phase B Micronasphere M Mica, Silica 5.00% (1) Talc Talc 30.00% (1) China Clay (deleted) Kaolin 8.00% (1) Magnesium Stearate Magnesium Stearate 2.00% (1) Phase C Ceraphyl 368 Ethylhexyl Palmitate 4.90% (2) Propyl 4-hydroxybenzoate Propylparaben 0.10% (1)

[0129] Preparation:

[0130] All constituents of phase B are weighed out together, mixed well and sieved at 100 m. Subsequently add phase A and mix again. Phase C is added dropwise to the composition with stirring.

[0131] Sources of Supply: [0132] (1) Merck KGaA/Rona [0133] (2) ISP Global Technologies

Example A10

Cream Mascara (O/W)

[0134]

TABLE-US-00010 Phase A Mica Black CI 77499 (Iron Oxides), Mica, CI 77891 10.00% (1) (Titanium Dioxide) Five-layered pigment Silica, CI77891 (Titanium dioxide), 5.00% (1) according to Example 2 Mica, Tin oxide Phase B Stearic Acid Stearic Acid 8.00% (1) Beeswax, Bleached Cera Alba (Beeswax) 6.00% (1) Carnauba Wax 2442 L Copernicia Cerifera (Carnauba Wax) 4.00% (2) Eutanol G Octyldodecanol 3.00% (3) Arlacel 83 V Sorbitan Sesquioleate 2.00% (4) Propyl 4-Hydroxybenzoate Propylparaben 0.10% (1) RonaCare Tocopherol Acetate Tocopheryl Acetate 0.50% (1) Phase C Water, Demineralised Aqua (Water) 50.84% Triethanolamine extra pure Triethanolamine 2.30% (1) Water Soluble Shellac SSB 63 Shellac 8.00% (5) Methyl 4-Hydroxybenzoate Methylparaben 0.25% (1) RonaCare Biotin Biotin 0.01% (1)

[0135] Preparation:

[0136] Melt all constituents of phase B together at about 80 C., stir until everything has melted. Stir in the effect pigments of phase A. Dissolve the shellac of phase C in the water, warm to 75 C. Add the remaining constituents of phase C, dissolve. Slowly add phase C to phase A/B at 75 C. with stirring, homogenize for 2 minutes. Cool the composition to room temperature with stirring.

[0137] Sources of Supply: [0138] (1) Merck KGaA/Rona [0139] (2) Kahl & Co. [0140] (3) Cognis GmbH [0141] (4) Uniqema [0142] (5) Paroxite Ltd.

Example A11

Nail Varnish

[0143]

TABLE-US-00011 Phase A Five-layered pigment Silica, CI77891 2.00% (1) according to Example 1 (Titanium dioxide), Mica, Tin oxide Thixotropic Nail Toluene, Ethyl Acetate, 98.00% (2) Varnish Base 1348 Butyl Acetate, Nitrocellulose, Tosylamide/Formaldehyde Resin, Dibutyl Phthalate, Isopropyl Alcohol, Stearalkonium Hectorite, Camphor, Acrylate Copolymer, Benzophenone-1 Color Dispersion with Nitrocellulose Lacquer (q.s.)

[0144] Preparation:

[0145] The five-layered pigment is weighed out together with the varnish base, mixed well by hand using a spatula and subsequently stirred at 1000 rpm for 10 minutes.

[0146] Sources of Supply: [0147] (1) Merck KGaA/Rona [0148] (2) International Lacquers S. A.

Example A12

Shampoo

[0149]

TABLE-US-00012 Phase A Five-layered pigment Silica, CI77891 (Titanium dioxide), 0.05% (1) according to Example 2 Mica, Tin oxide Carbopol ETD 2020 Acrylate/C10-30 Alkyl Acrylate Crosspolymer 0.90% (2) Water, Demineralised Aqua (Water) 59.90% Phase B Triethanolamine extra pure Triethanolamine 0.90% (1) Water, Demineralised Aqua (Water) 10.00% Phase C Plantacare 2000 UP Decyl Glucoside 20.00% (3) Texapon ASV Magnesium Oleth Sulfate, Sodium Oleth 8.00% (3) Sulfate, Magnesium Laureth-8 Sulfate, Sodium Laureth-8 Sulfate, Magnesium Laureth Sulfate, Sodium Laureth Sulfate Bronidox L Propylene Glycol, 0.20% (3) 5-Bromo-5-Nitro-1,3-Dioxane Perfume Oil Everest 79658 SB Perfume 0.05% (4)

[0150] Preparation:

[0151] For phase A, stir the five-layered pigment into the water. Acidify using a few drops of citric acid (10%) in order to reduce the viscosity, and slowly scatter in the Carbopol with stirring. When completely dissolved, slowly add phase B. The constituents of phase C are then added one after the other.

[0152] Sources of Supply: [0153] (1) Merck KGaA [0154] (2) BF Goodrich GmbH [0155] (3) Cognis GmbH [0156] (4) Haarmann & Reimer GmbH

Example A13

Sparkling Body Cream (O/W)

[0157]

TABLE-US-00013 Phase A Five-layered pigment Silica, CI77891 3.00% (1) according to Example 2 (Titanium dioxide), Mica, Tin oxide Carbopol ETD 2001 Carbomer 0.60% (2) Citric Acid Monohydrate Citric Acid (1) Water, Demineralised Aqua (Water) 40.00% Phase B RonaCare Allantoin Allantoin 0.20% (1) 1,2-Propanediol Propylene Glycol 3.00% (1) Euxyl K 400 Phenoxyethanol, 0.10% (3) Methyldibromo-Glutaronitrile Chemag 2000 Imidazolidinyl Urea 0.30% (4) Methyl 4-Hydroxybenzoate Methylparaben 0.15% (1) Water, Demineralised Aqua (Water) 27.65% Phase C Hostaphat KL 340 N Dilaureth-4 Phosphate 3.00% (5) Cetyl Alcohol Cetyl Alcohol 2.00% (1) Liquid Paraffin Paraffinum Liquidum 10.00% (1) (Mineral Oil) Cetiol V Decyl Oleate 6.00% (6) Propyl 4-Hydroxybenzoate Propylparaben 0.05% (1) Phase D Triethanolamine Triethanolamine 0.35% (1) Water, Demineralised Aqua (Water) 3.50% Phase E Perfume Oil 72979 Perfume 0.10% (7)

[0158] Preparation:

[0159] Disperse the five-layered pigment in the water of phase A. If necessary, acidify using a few drops of citric acid in order to reduce the viscosity. Scatter in the Carbopol with stirring. When completely dissolved, slowly stir in the pre-dissolved phase B. Heat phase A/B and phase C to 80 C., stir phase C into phase A/B, homogenize, neutralise using phase D, homogenize again and cool with stirring. Add the perfume oil at 40 C., cool to room temperature with stirring.

[0160] Sources of Supply: [0161] (1) Merck KGaA [0162] (2) BF Goodrich GmbH [0163] (3) Schlke & Mayr GmbH [0164] (4) Chemag AG [0165] (5) Clariant GmbH [0166] (6) Cognis GmbH [0167] (7) Haarmann & Reimer GmbH

Example A14

Plastic

[0168] In each case, [0169] a) 1% of pigment from Example 1 [0170] b) 1% of pigment from Example 2 [0171] c) 1% of pigment from Example 1 and 0.1% of PV True Blue B2G01 (Pigment Blue 15.3)
are added to polypropylene PP Stamylan PPH10 (DSM) or polystyrene 143E (BASF) plastic granules.

[0172] The pigmented granules are subsequently converted into stepped plates in an injection-moulding machine.

Example A15

Printing Ink

[0173] The pigment is stirred into the solvent-containing binder at 600 rpm, and the printing inks are subsequently knife-coated onto black/white cards.

TABLE-US-00014 Ink No. 1: 88.0 g of Gebr. Schmidt 95 MB 011 TW 10.0 g of pigment from Example 1 2.0 g of Gebr. Schmidt 95 MB 022-TW (green) Ink No. 2: 88.0 g of Gebr. Schmidt 95 MB 011 TW 10.0 g of pigment from Example 2 2.0 g of Gebr. Schmidt 95 MB 022-TW (green)

Example A16

Automotive Paint

[0174]

TABLE-US-00015 2.00 g of pigment from Example 1 1.50 g of Heliogen Blue L 6930 0.20 g of Hostaperm Green 8G 0.05 g of carbon black FW 200 66.60 g of basecoat (A4) MP system (solids content = 19%) 29.65 g of thinner mixture

[0175] The entire disclosure[s] of all applications, patents and publications, cited herein and of corresponding German application No. 10229256.6, filed Jun. 28, 2002 and German application No. 10251378.3, filed Nov. 1, 2002 are incorporated by reference herein.

[0176] 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.

[0177] 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.