PIGMENT POWDERS

Abstract

Disclosed are pigment powders containing only coated BiOCl flakes, which flakes area) BiOCl flakes having a coating containing yellow iron oxide Fe.sub.2O.sub.3*xH.sub.2O, optionally a colorant, optionally an adjuvant, and optionally SiO.sub.2, b) BiOCl flakes having a coating containing SiO.sub.2, optionally a colorant, and optionally an adjuvant, c) BiOCl flakes having a coating containing a colorant, SiO.sub.2, optionally yellow iron oxide Fe.sub.2O.sub.3*xH.sub.2O, and optionally an adjuvant, or d) BiOCl flakes having a coating containing Fe.sub.3O.sub.4 and optionally SiO.sub.2, to a process for the preparation of the pigment powders, and to the use thereof especially in cosmetic formulations.

Claims

1. A pigment powder consisting of coated BiOCl flakes, which flakes are selected from the group consisting of a) BiOCl flakes having a coating comprising yellow iron oxide Fe.sub.2O.sub.3*xH.sub.2O, optionally a colorant, optionally an adjuvant, and optionally SiO.sub.2, b) BiOCl flakes having a coating comprising SiO.sub.2, optionally a colorant, and optionally an adjuvant, c) BiOCl flakes having a coating comprising a colorant, SiO.sub.2, optionally yellow iron oxide Fe.sub.2O.sub.3*xH.sub.2O, and optionally an adjuvant, and d) BiOCl flakes having a coating comprising Fe.sub.3O.sub.4 and optionally SiO.sub.2.

2. The pigment powder according to claim 1, wherein the coated BiOCl flakes are selected from the group consisting of a) coated BiOCl flakes having a first layer comprising yellow iron oxide Fe.sub.2O.sub.3*xH.sub.2O and, optionally a colorant and optionally an adjuvant, and optionally a second layer comprising SiO.sub.2, b) coated BiOCl flakes having a layer comprising SiO.sub.2, c) coated BiOCl flakes having a first layer comprising a colorant, SiO.sub.2, optionally yellow iron oxide Fe.sub.2O.sub.3*xH.sub.2O, and optionally an adjuvant, and optionally a second layer comprising SiO.sub.2, and d) coated BiOCl flakes having a first layer comprising Fe.sub.3O.sub.4 and optionally a second layer comprising SiO.sub.2.

3. The pigment powder according to claim 1, wherein the coated BiOCl flakes comprise an organic after coating.

4. The pigment powder according claim 1, wherein the coated BiOCl flakes comprise 60-95% by weight of BiOCl flakes and 5-40% by weight of yellow iron oxide Fe.sub.2O.sub.3*xH.sub.2O, where the % by weight are based on the total weight of the coated BiOCl flakes.

5. The pigment powder according claim 1, wherein the coated BiOCl flakes comprise 55-94.99% by weight of BiOCl flakes, 5-40% by weight of yellow iron oxide Fe.sub.2O.sub.3*xH.sub.2O, and 0.01-5% by weight of SiO.sub.2, where the % by weight are based on the total weight of the coated BiOCl flakes.

6. The pigment powder according to claim 1, wherein the coated BiOCl flakes comprise 55-94.98% by weight of BiOCl flakes, 5-35% by weight of yellow iron oxide Fe.sub.2O.sub.3*xH.sub.2O, 0.01-5% by weight of Bi metal, and 0.01-5% by weight of carbon, where the % by weight are based on the total weight of the coated BiOCl flakes.

7. The pigment powder according to claim 1, wherein the coated BiOCl flakes comprise 57 to 89.98% by weight of BiOCl flakes, 0.01-3% by weight of yellow iron oxide Fe.sub.2O.sub.3*xH.sub.2O, 5 to 20% by weight of a colorant, 5-15% by weight of SiO.sub.2, and 0.01-5% by weight of an adjuvant, where the % by weight are based on the total weight of the coated BiOCl flakes.

8. The pigment powder according to claim 1, wherein the coated BiOCl flakes comprise 80-98% by weight of BiOCl flakes and 2-20% by weight of SiO.sub.2, where the % by weight are based on the total weight of the coated BiOCl flakes.

9. The pigment powder according to claim 1, wherein the coated BiOCl flakes comprise 75-95% by weight of BiOCl flakes, 5-20% by weight of Fe.sub.3O.sub.4, and 0-5% by weight of SiO.sub.2, where the % by weight are based on the total weight of the coated BiOCl flakes.

10. The pigment powder according to claim 1, wherein the colorant is an FD&C colorant or an D&C colorant or the lake form of a colorant, or phthalocyanine blue or green.

11. The pigment powder according to claim 1, wherein BiOCl flakes have a particle size <25 m and a thickness <100 nm.

12. A process for the production of the pigment powder according to claim 1, wherein uncoated BiOCl flakes are coated by a wet-chemical method and the resultant coated BiOCl flakes are worked up, subsequently spray-dried or oven dried, and optionally baked at 200 to 400 C. under an inert atmosphere.

13. A composition, comprising a pigment powder according to claim 1.

14. The composition according to claim 13, additionally comprising at least one constituent selected from the group consisting of absorbents, astringents, antimicrobial substances, antioxidants, antiperspirants, antifoaming agents, antidandruff active ingredients, antistatics, binders, biological additives, bleaching agents, chelating agents, deodorants, emollients, emulsifiers, emulsion stabilisers, dyes, humectants, film formers, fillers, odour substances, flavour substances, insect repellents, preservatives, anticorrosion agents, cosmetic oils, solvents, oxidants, vegetable constituents, buffer substances, reducing agents, surfactants, propellant gases, opacifiers, UV filters, UV absorbers, denaturing agents, viscosity regulators, perfume and vitamins.

15. A product selected from the group consisting of cosmetics, paints, coatings, inks, plastics, and films, comprising a pigment powder according to claim 1.

16. The pigment powder according to claim 1, wherein the coated BiOCl flakes are selected from the group consisting of a) BiOCl flakes having a coating consisting of yellow iron oxide Fe.sub.2O.sub.3*xH.sub.2O, optionally a colorant, optionally an adjuvant, and optionally SiO.sub.2, b) BiOCl flakes having a coating consisting of SiO.sub.2, optionally a colorant, and optionally an adjuvant, c) BiOCl flakes having a coating consisting of a colorant, SiO.sub.2, optionally yellow iron oxide Fe.sub.2O.sub.3*xH.sub.2O, and optionally an adjuvant, and d) BiOCl flakes having a coating consisting of Fe.sub.3O.sub.4 and optionally SiO.sub.2.

17. The pigment powder according to claim 1, wherein the coated BiOCl flakes are selected from the group consisting of a) coated BiOCl flakes having a first layer consisting of yellow iron oxide Fe.sub.2O.sub.3*xH.sub.2O and, optionally a colorant and optionally an adjuvant, and optionally a second layer consisting of SiO.sub.2, b) coated BiOCl flakes having a layer consisting of SiO.sub.2, c) coated BiOCl flakes having a first layer consisting of a colorant, SiO.sub.2, optionally yellow iron oxide Fe.sub.2O.sub.3*xH.sub.2O, and optionally an adjuvant, and optionally a second layer consisting of SiO.sub.2, and d) coated BiOCl flakes having a first layer consisting of Fe.sub.3O.sub.4 and optionally a second layer consisting of SiO.sub.2.

18. The pigment powder according to claim 1, which is a dry liquid free powder.

19. The pigment powder according to claim 1, wherein, in the yellow iron oxide Fe.sub.2O.sub.3*xH.sub.2O, x is 0.5 to 1.0.

Description

EXAMPLES

Preparation of Gold Lustered Dry Powder High Lustre BiOCl Composite Pigment

[0090] The iron oxide coating introduces a masstone color and a yellow shade (gold) interference effect which has never been reported before for high lustre BiOCl pigments. Compared to other gold pearlescent pigments the effect is sharper and more brilliant, with more of a metallic effect. Furthermore, it provides enhanced protection against UV induced darkening and also allows easy redispersion.

Example 1

[0091] A slurry of 100 g of high lustre BiOCl flakes (thickness 60 nm; particle size 8-20 m) which is washed free of reaction by-products (salts and surfactant) is brought to a concentration of 3 wt % in deionized water. The temperature is raised to 75 deg C. with constant stirring, vigorous enough to maintain uniform suspension and disperse the feed solutions throughout the reaction vessel. A solution of 85 g of ferric ammonium sulfate dodecahydrate in 300 mL of deionized water is fed via submerged inlet tube into the slurry, allowing the pH to fall from neutral pH to 3.0 over 30-45 minutes during the initial feed rate. The rest of the solution is delivered over 3 hours while maintaining pH near 3.0 by simultaneously co-fed with 5% ammonia solution. The slurry color changes from pearlescent silver to gold. Thereafter a solution of dilute sodium water glass containing 5.5% of SiO2 is slowly delivered over about 4 hours until pH 6.0 is reached. The slurry is continued under agitation and heating to maintain suspension and temperature briefly and then allowed to sediment. The supernatant is decanted to remove by-products from the mother liquor (salt water) and replaced by equal volumes of deionized water. After repeating the sedimentation, decant and backfill process several times, the slurry is allowed to be settled and decanted further to reach 30% by weight and then submitted to spray-drying at 30 g per hour. The gold colored powder is comprised of a microscopic mechanical mixture composite of 100 g of BiOCl, 15 g of yellow iron oxide (as FeOOH) and 5 g of amorphous silica. The product is finely divided and can be employed without further handling as a specialty colorant in many applications.

Example 2

[0092] Procedure in example 1 is repeated but uses 112 grams of ferric ammonium sulfate dodecahydrate instead of 85 g and omits the final neutralization and deposition of SiO2, producing a composite pigment in powder form comprised 100 g of BiOCl and 20 g of iron oxide as FeOOH.

Example 3

[0093] Procedure in example 2 is repeated using 140 grams of ferric ammonium sulfate dodecahydrate instead of 85 g, producing a composite pigment in powder form comprised 100 g of BiOCl, 25 g of iron oxide as FeOOH.

Example 4

[0094] Procedure in example 2 is repeated using 168 grams of ferric ammonium sulfate dodecahydrate producing a composite pigment in powder form comprised 100 g of BiOCl, 30 g of iron oxide as FeOOH.

Example 5

[0095] Procedure in example 2 is repeated using 225 grams of ferric ammonium sulfate dodecahydrate producing a composite pigment in powder form comprised 100 g of BiOCl, 40 g of iron oxide as FeOOH.

Example 6

[0096] Procedure in example 2 is repeated using 56 grams of ferric ammonium sulfate dodecahydrate producing a composite pigment in powder form comprised 100 g of BiOCl, 10 g of iron oxide as FeOOH.

Example 7

[0097] Procedure in example 2 is repeated, but instead of feeding ferric ammonium sulfate, a 300 mL aqueous solution of ferric nitrate nonahydrate 72 g admixed with ammonium nitrate 11.5 g and adjusted to pH 2.50.5 with ammonia, is employed, generating the same composition.

Example 8

[0098] Procedure in example 2 is repeated, but instead of feeding ferric ammonium sulfate, a 300 mL aqueous solution of ferric chloride (calculated as anhydrous) 31 g admixed with ammonium chloride 6 g and adjust to pH 2.50.5 with ammonia, is employed.

Example 9

[0099] Procedure in example 2 is repeated, but instead of feeding ferric ammonium sulfate, a 300 mL aqueous solution of ferrous sulfate heptahydrate 47 g admixed with ammonium sulfate 19 g and neutralized to pH 2.50.5 with ammonia, is employed along with feeding compressed air.

Example 10

[0100] Procedure in example 2 is repeated, but instead of feeding ferric ammonium sulfate, a 300 mL aqueous solution of ferric sulfate hydrate 46 g is employed.

Example 11

[0101] Procedure in example 1 is repeated at 85 degrees Celsius instead of 75.

Example 12

[0102] Procedure in example 1 is repeated using 150 grams of high luster BiOCl flakes.

Example 13

[0103] Procedure in example 1 is repeated using 50 grams of high luster BiOCl flakes.

Example 14

[0104] Procedure in example 1 is repeated replacing 5% ammonia solution with 5% NaOH solution.

Example 15

[0105] Procedure in example 1 is repeated but instead of washing by decanting and back-filling and spray-drying, the final slurry is filtered and washed several times and then oven dried at 110 C., followed by sieving to produce a finely divided powder.

Example 16

[0106] A slurry containing 75 g of HL BiOCl is transferred to a 3-neck round bottom flask. Nine hundred milliliters (900 ml) of deionized water are added to the flask and stirred at 250 rpm for 60 minutes. To this slurry 28 g of ferric ammonium sulfate dodecahydrate [NH.sub.4Fe(SO.sub.4).sub.2 12H.sub.2O], 5 g of magnesium sulfate heptahydrate [MgSO.sub.4 7H.sub.2O] and 40 g urea are added and stirred for another 30 minutes (the pH of slurry is around 3). Temperature of the slurry is raised in 30 min to reflux and continued to reflux for another 60 minutes while stirring. By this time, the slurry turns to a gold yellow color. Heating is stopped and the material is allowed to cool down to room temperature. The sample is filtered, washed with deionized water and dried at 110 C overnight. Dried powder is screened with a 45 micrometer sieve.

Example 17

[0107] A subsequent variation to provide a darkened masstone color is to bake the finely divided powder, from any of the above examples, at low temperatures, 200 to 500 C. under inert atmosphere such as nitrogen, or argon etc. This converts some of the organic substances to carbon black and partially converts some of the BiOCl on the surface to crystalline Bi metal and possibly partially converts some of the iron (III) oxide hydrate (yellow) to red (Fe.sub.2O.sub.3/hematite) by dehydration and/or black iron oxide (Fe.sub.3O.sub.4/magnetite) by partial reduction.

Preparation of Colorant Combination Dry Powder High Luster BiOCl Composite Pigment

[0108] The color combination coating introduces a masstone color and a Silver lustre effect BiOCl pigments. This effect cannot achieve by a mechanical mixture of the two components. This surprisingly also increases the tint strength of the colorant and in some cases very little additional additives are needed to provide a commercially interesting cosmetic formulation.

Example 1

[0109] A slurry of 100 g of high luster (HL) BiOCl flakes (thickness 60 nm; particle size 8-20 m) which is washed free of reaction by-products (salts and surfactant) is brought to a concentration of 3 wt % in deionized water. The temperature is raised to 75 degrees C. with constant stirring, vigorous enough to maintain uniform suspension and disperse the feed solutions throughout the reaction vessel. A solution of 6.6 g ferric ammonium sulfate dodecahydrate in 40 millilitres of deionized water is fed via submerged inlet tube into the slurry, allowing the pH to fall from neutral pH to 2.5 over 30-45 minutes. The rest of the solution is delivered while maintaining pH near 2.5 by simultaneously co-fed with 5% ammonia solution. The addition of 10 grams of colorant D&C Red 30 is accomplished by first dispersing the colorant in 80 ml of propylene glycol by sonication and then transferring it to the aqueous suspension of HL BiOCl treated with iron oxide hydrate. The mixture is then stirred for 15 minutes and 2.3 grams of fatty amine ethoxylate surfactant is added to the slurry. After another 15 minutes of mixing a 350 ml dilute sodium silicate solution, containing 6.0 grams of SiO2, is slowly delivered until pH 6.0. The rest of the solution is delivered while maintaining pH of slurry at 6.0 with 5% HCl solution. The slurry is continued under agitation and heating to maintain suspension and temperature briefly and then allowed to sediment. The supernatant is decanted to remove by-products from the mother liquor (salt water) and replaced by equal volumes of deionized water. After repeating the sedimentation, decant and backfill process several times, the slurry is allowed to be settled and decanted further to reach 30% by weight and then submitted to spray-drying at 30 g per hour. The pink colored powder is comprised of a microscopic mechanical mixture composite of 100 g of BiOCl, 1.2 g of yellow iron oxide (as FeOOH), 10.0 g of D&C Red 30 and 6 g of amorphous silica. The product is finely divided and can be employed without further handling as a specialty colorant in many applications.

Example 2

[0110] A slurry of 100 g of high luster BiOCl flakes (thickness 60 nm; particle size 8-20 m) which is washed free of reaction by-products (salts and surfactant) is brought to a concentration of 3 wt % in deionized water. The temperature is raised to 75 degrees C. with constant stirring, vigorous enough to maintain uniform suspension and disperse the feed solutions throughout the reaction vessel. At this stage the pH of slurry is typically around 5.5. The addition of 10 grams of colorant D&C Red 30 is accomplished by first dispersing the colorant in 80 ml of propylene glycol by sonication and then transferring it to the aqueous suspension of HL BiOCl. After another 30 minutes of mixing a 350 ml dilute sodium silicate solution, containing 6.0 grams of SiO.sub.2, is slowly delivered until pH 6.0. The rest of the solution is delivered while maintaining pH of slurry at 6.0 with 5% HCl solution. The slurry is continued under agitation and heating to maintain suspension and temperature briefly and then allowed to sediment. The supernatant is decanted to remove by-products from the mother liquor (salt water) and replaced by equal volumes of deionized water. After repeating the sedimentation, decant and backfill process several times, the slurry is allowed to be settled and decanted further to reach 30% by weight and then submitted to spray-drying at 30 g per hour. The pink colored powder is comprised of a microscopic mechanical mixture composite of 100 g of BiOCl, 10.0 g of D&C Red 30 and 6 g of amorphous silica. The product is finely divided and can employed without further handling as a specialty colorant in many applications.

Example 3

[0111] Procedure in example 1 is repeated but used 5.0 grams of D&C Red 30 instead of 10 g producing a composite pigment in powder form comprised 100 g of BiOCl, 5 g of D&C Red 30 and 6 g of amorphous silica.

Example 4

[0112] Procedure in example 1 is repeated using 20.0 grams of D&C Red 30 instead of 10 g, producing a composite pigment in powder form comprised 100 g of BiOCl, 20 g of D&C Red 30 and 6 g of amorphous silica.

Example 5

[0113] Procedure in example 1 is repeated, but instead of feeding ferric ammonium sulfate, a 40 mL aqueous solution of ferric nitrate nonahydrate 6 g admixed with ammonium nitrate 1 g is employed, generating the same composition.

Example 6

[0114] Procedure in example 1 is repeated, but instead of feeding ferric ammonium sulfate, a 40 mL aqueous solution of ferric chloride (calculated as anhydrous) 2.4 g admixed with ammonium chloride 0.5 g and adjust to pH 2.50.5 with ammonia, is employed.

Example 7

[0115] Procedure in example 1 is repeated, but instead of feeding ferric ammonium sulfate, a 40 mL aqueous solution of ferrous sulfate heptahydrate 3.6 g admixed with ammonium sulfate 1.5 g and neutralized to pH 2.50.5 with ammonia, is employed along with feeding compressed air.

Example 8

[0116] Procedure in example 1 is repeated, but instead of feeding ferric ammonium sulfate, a 40 mL aqueous solution of ferric sulfate hydrate 3.6 g is employed.

Example 9

[0117] Procedure in example 1 is repeated at 85 degrees Celsius instead of 75.

Example 10

[0118] Procedure in example 1 is repeated using 150 grams of high luster BiOCl flakes and adjusting weights of other chemicals to maintain the composition.

Example 11

[0119] Procedure in example 1 is repeated using 50 grams of high luster BiOCl flakes and adjusting weights of other chemicals to maintain the composition.

Example 12

[0120] Procedure in example 1 is repeated replacing 5% ammonia solution with 5% NaOH solution.

Example 13

[0121] Procedure in example 1 is repeated replacing propylene glycol with n-Propyl alcohol.

Example 14

[0122] Procedure in example 1 is repeated replacing propylene glycol with glycerol.

Example 15

[0123] Procedure in example 1 is repeated replacing propylene glycol with aqueous solution of fatty acid ester or fatty alcohol ethoxylate non-ionic surfactant.

Example 16

[0124] Procedure in example 1 is repeated replacing fatty amine ethoxylate with fatty acid ester ethoxylate or fatty alcohol ether ethoxylate, especially those with cloud-points above room temperature.

Example 17

[0125] Procedure in example 1 is repeated replacing fatty amine ethoxylate or ether ethoxylate with fatty acid ester propoxylate or fatty alcohol ether propoxylate, especially those with cloud-points above room temperature . . . .

Example 18

[0126] Procedure in example 1 is repeated replacing silica solution with trialkoxy alkyl silanes.

Example 19

[0127] Procedure in example 1 is repeated but fatty amine ethoxylate is added to HL crystal slurry together with D&C Red 30 and propylene glycol.

Example 20

[0128] Procedure in example 1 is repeated but organic colorant Blue is added to HL crystal slurry together with D&C Red 30 and propylene glycol.

Example 21

[0129] Procedure in example 2 is repeated but organic colorant D&C Red 30 is replaced with FD&C Blue 1 Aluminum Lake.

Example 22

[0130] Procedure in example 2 is repeated but organic colorant D&C Red 30 is replaced with FD&C Yellow 5 Aluminum Lake.

Example 23

[0131] Procedure in example 2 is repeated but organic colorant D&C Red 30 is replaced with FD&C Red 40 Aluminum Lake.

Example 24

[0132] Procedure in example 1 is repeated replacing sonication with high speed rotor stator agitation.

Example 25

[0133] Procedure in example 1 is repeated replacing D&C Red 30 with pigmentary carbon black.

Example 26

[0134] Procedure in example 1 is repeated but instead of washing by decanting and back-filling and spray-drying, the final slurry is filtered and washed several times and then oven dried at 110 C, followed by sieving to produce a finely divided powder.

Example 27

[0135] A subsequent variation to provide a darkened masstone color is to bake the finely divided powder at low temperatures, 200 to 500 C. under inert atmosphere such as nitrogen, or argon etc. This converts some of the organic substances to carbon black and partially converts some of the BiOCl on the surface to crystalline Bi metal. This is a preferred condition to be applied when the colorant is carbon black.

Preparation of Silver Lustered Dry Powder High Luster BiOCl Composite Pigment

[0136] The silica coating provides a sufficient colloidal and mechanical stability which allows easy redispersion in formulations and use in a fluidized-bed application for treatments. It provides a universal compatibility with wide range of formulations including water-borne, solvent-borne and oil based. A distinct advantage compared to High Luster BiOCl dispersions is an extended shelf-life.

Example 1

[0137] A slurry of 100 g of high luster (HL) BiOCl flakes (thickness 60 nm; particle size 8-20 m) which is washed free of reaction by-products (salts and surfactant) is brought to a concentration of 3 wt % in deionized water. The temperature is raised to 70 degrees C. with constant stirring, vigorous enough to maintain uniform suspension and disperse the feed solutions throughout the reaction vessel. A 350 ml dilute sodium silicate solution, containing 6.0 grams of SiO.sub.2, is slowly delivered until pH of the slurry reached 6.3. The rest of the solution is delivered while maintaining pH at 6.3 with 5% HCl solution. Upon completion of the delivery of sodium silicate solution, the slurry is continued under agitation and heating to maintain suspension and temperature for 30 minutes and then allowed to sediment. The supernatant is decanted to remove by-products from the mother liquor (salt water) and replaced by equal volumes of deionized water. After repeating the sedimentation, decant and backfill process several times, the slurry is allowed to be settled and decanted further to reach 30% by weight and then submitted to spray-drying at 30 g per hour. The white powder is comprised of a microscopic mechanical mixture composite of 100 g of BiOCl and 6 g of amorphous silica. Examination of the powder particles by electron microscope shows that flake particles are at least partially coated by the silica. The product is finely divided and can be employed without further handling as a specialty pigment in many applications.

Example 2-3

[0138] Procedure in example 1 is repeated but used only 4 grams and 5 grams of SiO2 respectively producing a composite pigment in powder form.

Example 4-6

[0139] Procedure in example 1 is repeated but used 8, 10 and 15 grams of SiO.sub.2 respectively producing a composite pigment in powder form.

Example 7

[0140] Procedure in example 1 is repeated but used pH 5.0 instead of 6.3 producing a composite pigment in powder form.

Example 8-10

[0141] Procedure in example 1 is repeated but used pH 7.0, 7.5 or 8.0 instead of 6.3 producing a composite pigment in powder form.

Example 11

[0142] Procedure in example 1 is repeated but the slurry is filtered, washed three times and oven dried at 110 C overnight instead of spray drying producing a composite pigment in powder form.

Example 12-15

[0143] Procedure in example 1 is repeated at 65, 75, 80 and 85 degrees Celsius respectively instead of 70 degrees Celsius.

Example 16

[0144] Procedure in example 1 is repeated using 150 grams of high luster BiOCl flakes and delivering 9 g of SiO.sub.2.

Example 17

[0145] Procedure in example 1 is repeated using 50 grams of high luster BiOCl flakes and delivering 3 g of SiO.sub.2.

Example 18

[0146] Procedure in example 1 is repeated replacing 5% HCl solution with 5% H2SO4 solution.

Example 19

[0147] Procedure in example 1 is repeated replacing 5% HCl solution with 5% HNO3 solution.

Example 20

[0148] A variation of the product in example 1 is produced by adding a silane to the slurry before it is allowed to settle. In this example an alkyl trialkoxy silane at 1 to 5% per weight of BiOCl is slowly delivered into the water suspension after the completion of silica layer. The alkyl group in silane can consist of methyl, n-propyl or n-octyl, with preference to the latter two. Upon completion of the delivery of silane, the slurry is continued under agitation and heating to maintain suspension and temperature for 30 minutes and then allowed to sediment. The supernatant is decanted to remove by-products from the mother liquor (salt water) and replaced by equal volumes of deionized water. After repeating the sedimentation, decant and backfill process several times, the slurry is allowed to be settled and decanted further to reach 30% by weight and then submitted to spray-drying at 30 g per hour. Resulting white powder is finely divided and can be employed as a specialty pigment in many applications.

Example 21

[0149] Another method to produce the material is to use tetraethyl orthosilicate (TEOS) as the silicon source. In this procedure, HL BiOCl crystals are allowed settled and the supernatant is decanted off. Then the crystals are transferred into ethyl acetate (EA) and mixed with a solution of octyl hydroxyl stearate (OHS) and stir to get water and EA into octyl hydroxyl stearate phase. Ethanol is added to the mixture and crystals settle. OSH is decanted off with EA and residue water. Ethanol is added to re-suspend the crystals and required amount of TEOS is added to match the amount of SiO.sub.2 desired. An alcohol water solution is added slowly to hydrolyze TEOS to form an SiO.sub.2 layer. More water is added and the crystals settle. Supernatant is decanted off to remove alcohol and add water and stirred to produce a uniform slurry. The material is filtered washed and oven dried or spray dried to produce a finely divided powder.

Example 22

[0150] As a variation, the dry high luster BiOCl powder is further treated by deposition of metal or metal oxides or metal compounds as coatings in a fluid bed device, e.g. by vapor deposition.

Example 23

[0151] The dry powder high luster can also contain colloidal nano-particles of metals (in elemental form, e.g. bismuth from deposition or reaction of BiOCl using a reducing agent such as NaBH.sub.4 etc.) or metal oxides or metal salts, which are processed by a modification of the above procedure. The added particles would be either covered or occluded in the silica deposit. These coatings can also be capped by the addition of a trialkoxy alkyl silane.

Example 24

[0152] A subsequent variation to provide a darkened masstone color would be to bake the finely divided powder, from any of the above examples, at low temperatures, 200 to 500 C. under inert atmosphere such nitrogen, or argon etc. This converts some of the organic substances to carbon black and partially converts some of the BiOCl on the surface to crystalline Bi metal.

Preparation of Black Iron Oxide Coated Dry Powder High Luster BiOCl Composite Pigment

[0153] Black iron oxide coating introduces a dark grey masstone color which enhances the flop of luster effect. This effect cannot achieve by a mechanical mixture of the two components. This surprisingly provides darker masstone and higher hiding which more closely emulates a metallic luster effect. Additional benefit is the enhanced UV stability against discoloration.

Example 1

[0154] A slurry of 100 g of high luster (HL) BiOCl flakes (thickness 60 nm; particle size 8-20 m) which is washed free of reaction by-products (salts and surfactant) is dispersed in 1000 ml deionized (DI) water in a 3-neck round-bottom flask and agitated at 250 rpm. Eighty-nine grams of ferrous sulfate heptahydrate (FeSO.sub.4.7H.sub.2O), 20 g of magnesium sulfate heptahydrate (MgSO.sub.4.7H.sub.2O), 16 grams of potassium nitrate (KNO.sub.3) and 150 grams of urea are added to the above slurry and stirred for 45 minutes. The slurry is slowly heated to reflux in about 90 minutes while agitating at 300 rpm. Heating and stirring is continued for another 60 minutes. The slurry color changed from light gray to gray and then to black. Agitation is reduced to 135 rpm, heating is stopped and the slurry is allowed to cool down to room temperature. The material is filtered, washed 3 times with DI water and dried at 110 C in an inert atmosphere for 10 hours. Dried material is sieved with 45 um screen to obtain a microscopic mechanical mixture composite of 100 g of BiOCl, 25 g of black iron oxide (as Fe.sub.3O.sub.4). The product is finely divided and can be employed without further handling as a specialty colorant in many applications.

Example 2

[0155] Procedure in example 1 is repeated but optional outside silica layer is deposited by means of delivering a sodium silicate solution while maintaining pH of the slurry at 6 by cofeeding a dilute hydrochloric acid solution.

Example 3

[0156] Procedure in example 2 is repeated but uses tetraethyl orthosilicate (TEOS) as the silica source. In this procedure, HL BiOCl crystals are allowed settled and the supernatant is decanted off. Then the crystals are transferred into ethyl acetate (EA) and mixed with a solution of octyl hydroxyl stearate (OHS) and stirred to get water and EA into octyl hydroxyl stearate phase. Ethanol is added to the mixture and crystals settle. OSH is decanted off with EA and residue water. Ethanol is added to re-suspend the crystals and required amount of TEOS is added to match the amount of SiO.sub.2 desired. An alcohol water solution is added slowly to hydrolyze TEOS to form an SiO.sub.2 layer. More water is added and the crystals settle. Supernatant is decanted off to remove alcohol and water is added and stirred to produce a uniform slurry.

Example 4

[0157] Procedure in example 1 is repeated but uses a combination of soluble components of ferrous and ferric salts fed all at once and gradually deposited by urea decomposition.

Example 5

[0158] Procedure in example 2 is repeated but use concurrent feeds of the iron salt solutions and alkali hydroxides, thus maintaining a relatively high pH.

Example 6

[0159] Procedure in example 1 is repeated but uses potassium persulfate (K.sub.2S.sub.2O.sub.8) in lieu of nitrate as an oxidant to induce ferric oxide deposition. It is also possible to use other oxidizing agents such as hydrogen peroxide, sodium hypochlorite, sodium chlorite, sodium chlorate, sodium perchlorate etc.

Example 7

[0160] Yellow iron oxide layer is deposited using a solution of ferric ammonium sulfate while maintaining slurry pH at 3.0 with a 5% ammonia solution. After filtering, washing and drying, the dried pigment is heated at 400 C. under a flow of 4% H/argon to obtain a black iron oxide coated HL BiOCl powder. Optional silica outside silica layer can also be employed.

Example 8

[0161] Procedure in example 7 is repeated but uses a ferric chloride solution in place of ferric ammonium sulfate to generate a red iron oxide layer instead of a yellow iron oxide.

Example 9

[0162] Procedure in example 1 is repeated but the slurry is concentrated and fed to a spray-dryer instead of oven drying. The spray-dried powder is a finely-divided finished good which can be directly packaged without further mechanical treatment.

Example 10

[0163] Procedure in example 1 is repeated but the washing and dewatering is done by filter press. Filtration can also be accomplished using a belt filter or a drum filter resulting in a wet-cake.

Examples of Cosmetic Applications with New High Luster (HL) BiOCl Powders

1. Eye Shadow Gel

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TABLE-US-00007 Ingredients INCI (US) [%] A Water, demineralized WATER 73.00 New HL BiOCl Powder (Black or Blue) 10.00 Carbopol Ultrez 10 CARBOMER 0.30 B Water, demineralized WATER 13.00 Glycerol, anhydrous GLYCERIN 2.00 RonaCare Triethanolamine- TRIETHANOLAMINE 0.70 Replace by 108372 Triethanolamine, EMPROVE exp. Germaben II PROPYLENE GLYCOL (AND) 1.00 DIAZOLIDINYL UREA (AND) METHYLPARABEN (AND) PROPYLPARABEN

[0165] The range of the new HL BiOCl in the formulation can be 10-15% by weight.

2. Loose Powder Eye Shadow

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TABLE-US-00008 Ingredients INCI (US) [%] A Supra H TALC 38.80 New HL BiOCl Powder 20.00 (Silverwhite) Colorona Magenta MICA (AND) TITANIUM 20.00 DIOXIDE (AND) CARMINE Dry Flo PC ALUMINUM STARCH 10.00 OCTENYLSUCCINATE Kaolin KAOLIN 4.00 Magnesium Stearate. MAGNESIUM STEARATE 2.00 Propylparaben PROPYLPARABEN 0.20 B Eutanol G OCTYLDODECANOL 5.00

3. Lipstick

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TABLE-US-00009 Ingredients INCI (US) [%] A Castor Oil RICINUS COMMUNIS 43.85 (CASTOR) SEED OIL Candelilla Wax EUPHORBIA CERIFERA 5.70 (CANDELILLA) WAX Carnauba Wax COPERNICIA CERIFERA 1.80 (CARNAUBA) WAX Ozokerite Wax SP OZOKERITE 1.50 1028P Microcrystalline Wax MICROCRYSTALLINE WAX 3.00 White 1275 W Myritol 312 CAPRYLIC/CAPRIC 16.00 TRIGLYCERIDE Blandol MINERAL OIL 2.00 Ceraphyl 847 OCTYLDODECYL STEAROYL 5.00 STEARATE Eutanol G OCTYLDODECANOL 5.00 OHlan HYDROXYLATED LANOLIN 1.00 Propylparaben PROPYLPARABEN 0.10 Oxynex K liquid PEG-8 (AND) TOCOPHEROL 0.05 (AND) ASCORBYL PALMITATE (AND) ASCORBIC ACID (AND) CITRIC ACID B Xirona Le Rouge IRON OXIDES (AND) SILICA 4.00 New HL BiOCl Powder (Silverwhite) 11.00

4. Lip Gloss

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TABLE-US-00010 Ingredients INCI (US) [%] A Indopol H-100 POLYBUTENE 30.00 Versagel ME 750 HYDROGENATED 24.00 POLYISOBUTENE (AND) ETHYLENE/PROPYLENE COPOLYMER (AND) BHT Beeswax Yellow BEESWAX 4.00 Myritol 312 CAPRYLIC/CAPRIC 6.00 TRIGLYCERIDE Jarplex SB 10 BUTYROSPERMUM PARKII 3.00 (SHEA) BUTTER Castor Oil RICINUS COMMUNIS 8.85 (CASTOR) SEED OIL Cetiol 868 ETHYLHEXYL STEARATE 10.00 LexFeel Shine PROPYLENE GLYCOL 4.00 DIBENZOATE Oxynex ST DIETHYLHEXYL 0.10 SYRINGYLIDENE MALONATE Oxynex K liquid PEG-8 (AND) TOCOPHEROL 0.05 (AND) ASCORBYL PALMITATE (AND) ASCORBIC ACID (AND) CITRIC ACID Propylparaben PROPYLPARABEN 0.10 B New HL BiOCl Powder 9.90 (Pink or Black)

5. Shampoo

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TABLE-US-00011 Ingredients INCI (US) [%] A New HL BiOCl Powder (Gold or Black) 1.00 Water, demineralized WATER 43.40 Carbopol Aqua SF-1 Carbopol Aqua SF-1 Polymer 8.00 Polymer Texapon NSO UP WATER (AND) SODIUM 40.00 LAURETH SULFATE Sodium Hydroxide, 10% WATER (AND) SODIUM HYDROXIDE 0.00 B Tego Betain F 50 COCAMIDOP ROPYL 5.60 BETAINE Proteol O.A.T. SODIUM LAUROYL OAT 1.00 AMINO ACIDS Euxyl K 500 WATER (AND) DIAZOLIDINYL 1.00 UREA (AND) SODIUM BENZOATE (AND) POTASSIUM SORBATE Fragrance (q.s.) FRAGRANCE 0.00 Dye stuff solution (q.s.) 0.00

6. Nail Polish

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TABLE-US-00012 Ingredients INCI (US) [%] New HL BiOCl Powder (Gold) 2.00 Dispersion of cosmetic colors in 0.00 nitrocell. lacquer (q.s.) Nail lacquer Base 12897 ETHYL ACETATE (AND) 98.00 BUTYL ACETATE (AND) NITROCELLULOSE (AND) PHTHALIC ANHYDRIDE/TRIMELLITIC ANHYDRIDE/GLYCOLS COPOLYMER (AND) ACETYL TRIBUTYL CITRATE (AND) ISOPROPYL ALCOHOL (AND) STEARALKONIUM HECTORITE (AND) ADIPIC ACID/NEOPENTYL GLYCOL/TRIMELLITIC ANHYDRIDE COPOLYMER

7. Pressed Eye Shadow

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TABLE-US-00013 Ingredients INCI (US) [%] A New HL BiOCl Powder (Gold) 30.00 Parteck LUB Talc TALC 50.55 Parteck LUB MST MAGNESIUM STEARATE 2.55 Potato Starch POTATO STARCH 7.65 B Isopropyl Stearate ISOPROPYL STEARATE 7.85 Cetyl Palmitate CETYL PALMITATE 0.45 Ewalin 1751 PETROLATUM 0.45 C Euxyl PE 9010 PHENOXYETHANOL (AND) 0.50 ETHYLHEXYL GLYCERIN
8. Serum with New HL BiOCl Pigment

TABLE-US-00014 Ingredients INCI (US) [%] A Water, demineralized WATER ad 100 Triplex III DISODIUM EDTA 0.05 RonaCare Ectoin ECTOIN 0.25 Carbopol Ultrez 20 ACRYLATES/C10-30 ALKYL 0.80 ACRYLATE CROSSPOLYMER Preservatives PRESERVATIVES q.s. 1,2-Propandiol PROPYLENE GLYCOL 2.00 B RonaCare Triethanolamine TRIETHANOLAMINE 1.00 C New HL BiOCl Powder (Silverwhite) 1.00

9. Dip or Spray Coated Pearl Beads

[0172] Here is an example of using new HL BiOCl powder in coatings applications. It is obtained by dispersing the new HL BiOCl powder to a nitrocellulose coatings system. A person skilled in the art knows how to carry out the steps (wetting/deaerating the powder followed by suitable mixing) to achieve a well dispersed coating formulation. The composition of the formulation shown below is final formulation that is ready to be sprayed or dipped onto plastic or glass bead substrates. Nitrocellulose is a preferred film-forming resin, but other options are possible, especially as combinations. The nitrocellulose resin content can be replaced in part by other solids such as other resins and transparent extenders to enhance features such as gloss and surface smoothness. The solvent can also be optionally replaced with other solvents to slow down or speed up evaporation or with other liquids such as plasticizers for enhanced gloss and flexibility, depending on the coating method, dip or spray. The resulting bead shows a very smooth and intense pearl effect that mimics natural pearls. The concentration of the new HL BiOCl powder in the formulation can vary depending on the final appearance required. Other colorants, either solvent soluble dyes or insoluble particle dispersions, can be added in low concentrations e.g. <1% to the formulation to achieve the desired color. Other optional additives such as UV absorbers can be included at low concentrations e.g. <1%, with the intent to protect the bismuth oxychloride flakes against UV light induced darkening. For optimum results, multiple thin layers of coatings are sprayed repeatedly to achieve a deep and sharp lustered pearl effect. Proper viscosity (lower for spraying and higher for dipping) should be maintained by selection of suitable viscosity grades of nitrocellulose resin.

TABLE-US-00015 Ingredients Description [%] HL BiOCl Powder Bismuth oxychloride and silica 0.1 to 3 (SilverWhite) Resin Nitrocellulose RS to 15 sec 5 to 15 viscosity grades Solvent Isopropanol 2 to 6 Solvent n-Butyl Acetate 76 to 95

[0173] All new HL BiOCl powders (Silverwhite, Black/Silver, Gold with various shades, Blue, Pink) can be used in the above formulations with minor formulation adjustments.

[0174] The results are superior, highly reflective products than substrate based effective pigments. Generally, more metallic and higher reflective appearance and less particulates appearance is observed when comparing to finished products made with other substrate based pigments.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] The entire disclosures of all applications, patents and publications, cited herein and of corresponding U.S. provisional application No. 62/473,581, filed Mar. 20, 2017, are incorporated by reference herein.