COMPOSITIONS COMPRISING MICROPIGMENTS

Abstract

The present invention relates to topical compositions comprising at least one inorganic micropigment and a cetyl phosphate surfactant mixture consisting essentially of mono- and/or dicetyl esters of phosphoric acid or salts thereof and cetylalcohol and inorganic phosphate and heavy metals and water, characterized in that the surfactant mixture contains no organochlorine impurities and has an inorganic phosphate content of less than 0.7 wt.-% and a heavy metal content of less than 12 ppm.

Claims

1. Topical composition comprising at least one inorganic micropigment and a cetyl phosphate surfactant mixture consisting essentially of mono- and/or dicetyl esters of phosphoric acid or salts thereof and cetylalcohol and inorganic phosphate and heavy metals and water, characterized in that the surfactant mixture contains no organochlorine impurities and has an inorganic phosphate content of less than 0.7 wt.-% and a heavy metal content of less than 12 ppm.

2. The topical composition according to claim 1, wherein the mono- and/or dicetyl esters of phosphoric acid or salts thereof are the potassium salts thereof.

3. The topical composition according to claim 1, wherein the cetyl phosphate surfactant mixture is used in an amount selected in the range of 0.1 to 10 wt.-%, based on the total weight of the topical composition.

4. The topical composition according to claim 1, wherein the cetyl phosphate surfactant mixture is used in an amount selected in the range of 0.3 to 8 wt.-%, based on the total weight of the topical composition.

5. The topical composition according to claim 1, wherein the cetyl phosphate surfactant mixture is used in an amount selected in the range of 0.5 to 8 wt.-% based on the total weight of the topical composition.

6. The topical composition according to claim 1, wherein the inorganic micropigment is used in an amount selected in the range of 0.1 to 40 wt.-%, based on the total weight of the composition.

7. The topical composition according to claim 1, wherein the cetyl phosphate surfactant mixture consists essentially of 60-95 wt.-% of monocetyl phosphoric acid or a salt thereof, 0-15 wt.-% of dicetyl phosphoric acid or a salt thereof, 0-20 wt.-% of cetyl alcohol, 0-0.7 wt.-% of inorganic phosphate, 0-12 ppm of heavy metals and 0-4 wt.-% of residual water.

8. The topical composition according to claim 1, wherein the cetyl phosphate surfactant mixture or a salt thereof consists essentially of 70-90 wt.-% of monocetyl phosphoric acid or a salt thereof, 0.5-12 wt.-% of dicetyl phosphoric acid or a salt thereof, 0-15 wt.-% of cetyl alcohol, 0-0.7 wt.-% of inorganic phosphate, 0-12 ppm of heavy metals and 0-3 wt.-% of residual water.

9. The topical composition according to claim 2, wherein the cetyl phosphate surfactant mixture is a potassium cetyl phosphate surfactant mixture consisting essentially of 72-85 wt.-% of monocetyl phosphate, 0.5-10 wt.-% of dicetyl phosphate, 0-15 wt.-% of cetyl alcohol, 7-12 wt.-% of potassium, 0-0.6 wt.-% of inorganic phosphate, 0-11 ppm of heavy metals and 0-2.5 wt.-% of residual water.

10. The topical composition according to claim 1, wherein the inorganic micropigment is an inorganic sunscreening agent or a coloring agent.

11. The topical composition according to claim 10, wherein the inorganic sunscreening agent is a titanium dioxide having an average primary particle size selected in the range of 2 nm to 100 nm and a secondary particle size selected in the of about 0.05 to 50 ?m.

12. The topical composition according to claim 11, wherein the titanium dioxide is a double coated titanium dioxide having an inner inorganic silica coating and an outer organic coating selected from the group consisting of simethicone, methicone, dimethicone, polysilicone-15, stearic acid and mixtures thereof.

13. The topical composition according to claim 10, wherein the coloring agent is an iron oxide or a titanium dioxide having a particle size selected in the range of 0.001 to 150 ?m, preferably in the range of 0.002 to 100 ?m, more preferably in the range of 0.02 to 50 ?m.

14. The topical composition according to claim 1, wherein the topical composition is an oil-in-water (O/W) emulsion comprising an oily phase dispersed in an aqueous phase.

15. The topical composition according to claim 14, wherein the composition is a sunscreen, a mascara or a make-up/foundation composition.

Description

EXAMPLES

[0076] A: Preparation of a Chlorine Free Cetyl Phosphate Surfactant Mixture According to the Present Invention

[0077] 0.09 mol of cetyl alcohol is added into a flask and diluted with 20 ml of cyclohexane and heated to 75? C. Afterwards 0.3 mol of pyrophosphoric acid diluted in 30 ml of cyclohexane is slowly added. After the addition is complete the reaction is stirred for another hour at 75? C. Afterwards water is added and the reaction stirred for 15 min at 70? C. Then the water phase is separated and the organic phase is washed twice with water followed by removal of cyclohexane in vacuo. The thus obtained crude product is neutralised with 10 g of 50% KOH in water at 50? C. Then methanol is added and the crystallized product is filtered off. The resulting product is recrystallized from methanol resulting in 10 g of a cetyl phosphate surfactant mixture according to the present invention (corresponding to Amphisol? L).

[0078] 1. Analytics

[0079] 1. 1. Method for the Determination of Monocetylphosphate by Titration

[0080] 1.5 g (+/?0.1 g) of the respective homogenized potassium cetylphosphate (powder) was weighed into a 150 mL Erlenmeyer flask with stopper. 60 mL of isopropanol/water mixture (20/80, v/v) was added. The suspension was stirred at 80? C. for 30 min in a closed flask. The solution was titrated at 70? C. on a heatable magnetic stirrer using 0.5 M sodium hydroxide solution as titrant.

[0081] 1.2. Method for the determination of Monocetylphosphate and Cetylalcohol by GC-FID

[0082] 3-4 mg (+/?0.01 mg) of the respective homogenized potassium cetylphosphate (powder) was weighted into a 2 mL GC-Vial. 1 mL of a solution prepared by dissolving 140 mg tricosane (internal standard) in a 200 ml flask in 100 mL N,O-bis(trimethylsilyl)-trifluoroacetamide with 1% trimethylchlorosilane and pyridine (to 200 ml volume)) was added. The GC vial was closed and vortexed for 10 sec, followed by heating the vial for 20 min at 120? C. and vortexing the hot GC vial for another 10 sec. After cooling to RT, the samples were subjected to GC analysis in triplicates. (Column: Optima 5 HT, 30 m?0.25 mm 0.1 ?m, Hydrogen flow rate: 2.2 mL/min (constant flow), Oven programme: 200? C. (0 min) Ramp to 360? C. (20? C./min), 360? C. (0 min)).

[0083] 1.3. Method for the Determination of Dicetylphosphate by FIA-MS

[0084] 100 mg (+/?0.01 mg) of the respective homogenized potassium cetylphosphate (powder) was weighted into a 100.0 ml glass volumetric flask. Then, 50.0 ml of tetrahydrofuran/water (70/30, v/v) was added and the mixture was sonicated for dissolution. The volume was adjusted with tetrahydrofuran/water (70/30, v/v). Then, 1 ml of this solution was diluted with an ammonium carbonate solution (300 mg ammonium carbonate in 100 ml water and 900 ml methanol) to 100 ml. Afterwardsm the amount of dicetyl phosphate was analyzed by FIA-MS (HPLC-MS Agilent 1260, No column, T=40? C., 5 ?l, Detector: ESI-MS)

[0085] The amount of dicetyl phosphate in the sample was calculated using an external calibration with dicetyl phosphate.

[0086] 1.3. Method for the Determination of Inorganic Phosphate

[0087] 0.25 g of the respective homogenized potassium cetylphosphate was weighed into a 100 mL volumetric flask. After the addition of 90 mL THF/Water (70/30, v/v) the flask was placed in an ultrasonic bath for dissolution. Afterwards, the flask was filled to volume with THF/Water (70/30, v/v). 1 mL of this solution was pipetted into a 10 mL flask and filled up to volume with demineralised water. The samples were then analyzed in triplicates by IC chrompatography (Dionex ICS-3000, Chromatographic data system: Chromeleon, Detector: CD-3000 conductivity detector, Column: AS19 column (4.0 mm?250 mm) protected with an AG19 precolumn (4.0 mm?50 mm), Eluent: KOH gradient (0-55 mmol), injection volume 25 ?l).

TABLE-US-00001 TABLE 1 Analytical results of various chlorine-free potassium cetyl phosphate surfactant mixtures Sample Inv Ref-1 Ref-2 Ref-3 Monocetyl phosphate (wt.-%) 75.sup.# 79.6.sup.# 47* 73.6.sup.# Dicetyl phosphate wt.-(%) 6.8 10.1 11 22.5 Inorganic phosphate (wt.-%) 0.34 2.12 16.78 0.54 Cetylalcohol (wt.-%) 9.1 0.5 6.1 1.7 heavy metals sum ppm 8.0 12.1 23.1 23.0 .sup.#via Titration; *via GC-FID (potassium cetyl phosphate surfactant mixtures: Inv: Amphisol? L, Ref-1: EverMap 160K by Sino Lion, Ref-2: Crodafos MCK by Croda, Ref-3: Romol AFSK by Suzhou Eleco Chemical Industry Co. Ltd)

[0088] 2. Formulation

[0089] The formulations as outlined in table 2 to 4 were prepared using the different potassium cetyl phosphate surfactant mixtures outlined in table 1. After storage at 22? C. for 6 weeks, respectively 3 months, the respective samples were assessed visually for their appearance. After 3 months additionally, the viscosity was measured for still intact samples using a Rheometer AR550 with plate SST ST 40 mm shear stress 10/s. As can be retrieved from the results outlined in table 2 to 4, only the formulations comprising the cetyl phosphate surfactant mixture according to the present invention led to stable formulations with an acceptable viscosity for the respective product form.

TABLE-US-00002 TABLE 2 Sunscreens (I) comprising different cetyl phosphate surfactant mixtures acc. to table 1 INCI/Name Inv Ref-1 Ref-2 Ref-3 A Cetearyl Alcohol 2.30 2.30 2.30 2.30 Capric/Caprylic Triglycerides 17.50 17.50 17.50 17.50 Diisopropylsebacate 17.50 17.50 17.50 17.50 Titanium Dioxide & Silica & Dimethicone 6.00 6.00 6.00 6.00 (PARSOL TX) B Aqua Ad 100 Ad 100 Ad 100 Ad 100 Potassium Cetyl Phosphate 2.00 2.00 2.00 2.00 C Phenoxyethanol & Ethylhexylglycerin 1.00 1.00 1.00 1.00 Viscosity (mPas) after 12 weeks 4200 32640 33220 Phase separation (6 weeks)

TABLE-US-00003 TABLE 3 Sunscreens (II) comprising different potassium cetyl phosphate surfactant mixtures acc. to table 1 INCI/Name Inv Ref-1 Ref-2 Ref-3 A Cetearyl Alcohol 2.30 2.30 2.30 2.30 Capric/Caprylic Triglycerides 17.50 17.50 17.50 17.50 Diisopropylsebacate 17.50 17.50 17.50 17.50 Titanium Dioxide & Silica & Dimethicone 8.00 8.00 8.00 8.00 (PARSOL TX) B Aqua Ad 100 Ad 100 Ad 100 Ad 100 Potassium Cetyl Phosphate 2.00 2.00 2.00 2.00 C Phenoxyethanol & Ethylhexylglycerin 1.00 1.00 1.00 1.00 Viscosity (mPas) after 12 weeks 6440 21440 32120 Phase separation (12 weeks)

TABLE-US-00004 TABLE 4 Foundations comprising different potassium cetyl phosphate surfactant mixtures acc. to table 1 INCI/Name Inv Ref-1 Ref-2 Ref-3 A Cetyl Alcohol 2.00 2.00 2.00 2.00 Paraffinum Liquidum 14.00 14.00 14.00 14.00 Euphorbia Cerifera (Candelilla) Wax 3.40 3.40 3.40 3.40 Cera Alba 4.40 4.40 4.40 4.40 Potassium Cetyl Phophate 8.00 8.00 8.00 8.00 Steareth-21 0.50 0.50 0.50 0.50 CI 77891 (and) Triethoxycaprylylsilane 10.00 10.00 10.00 10.00 (Unipure White LC 981 AS-EM) C Aqua Ad 100 Ad 100 Ad 100 Ad 100 Glycerin 2.00 2.00 2.00 2.00 Hydroxyethylcellulose 0.50 0.50 0.50 0.50 ACACIA SENEGAL GUM 3.00 3.00 3.00 3.00 D PEG/PPG-18/18 Dimethicone 0.50 0.50 0.50 0.50 Dimethicone 0.50 0.50 0.50 0.50 Phenoxyethanol & Ethylhexylglycerin 0.70 0.70 0.70 0.70 Viscosity (mPas) after 12 weeks 36440 56850 49110 48160

TABLE-US-00005 TABLE 5 Mascara comprising different potassium cetyl phosphate surfactant mixtures acc. to table 1 INCI/Name Inv Ref-2 Ref-3 A Cetyl Alcohol 2.00 2.00 2.00 Paraffinum Liquidum 14.00 14.00 14.00 Euphorbia Cerifera 3.40 3.40 3.40 (Candelilla) Wax Cera Alba 4.40 4.40 4.40 Potassium Cetyl Phophate 8.00 8.00 8.00 Steareth-21 0.50 0.50 0.50 Iron Oxides (Unipure 10.00 10.00 10.00 Black LC989) C Aqua Ad 100 Ad 100 Ad 100 Glycerin 2.00 2.00 2.00 Hydroxyethylcellulose 0.50 0.50 0.50 ACACIA SENEGAL GUM 3.00 3.00 3.00 D PEG/PPG-18/18 Dimethicone 0.50 0.50 0.50 Dimethicone 0.50 0.50 0.50 Phenoxyethanol & 0.70 0.70 0.70 Ethylhexylglycerin Viscosity (mPas) after 12 weeks 38240 64510 47800