Oil-in-water emulsion for caring for and/or making up keratin materials comprising microcapsules encapsulating an oily dispersion of at least one reflective agent

Abstract

The present invention concerns a composition for caring for and/or making up keratin materials comprising, in a physiologically acceptable medium, a) at least one aqueous phase; and b) at least one oily phase dispersed in the said aqueous phase; and c) at least microcapsules comprising: an inner core comprising at least a dispersion of at least one reflective agent, in particular bismuth oxychloride, in at least one oil, and at least one outer shell formed of a wall-forming polymeric material surrounding the said core, the said outer shell comprising i) at least one wall-forming polymer, and ii) optionally at least one plasticizer and/or at least one opaque substance and/:or at least one fatty acid salt.

Claims

1. A composition for caring for and/or making up keratin materials comprising, in a physiologically acceptable medium: a) at least one aqueous phase; b) at least one oily phase dispersed in the said aqueous phase; and c) microcapsules comprising: an inner core comprising a dispersion of at least one reflective agent in at least one oil, wherein the at least one reflective agent is bismuth oxychloride and the at least one oil is a non-volatile polar hydrocarbon-based oil selected from the group consisting of 2-ethylhexyl hydroxystearate, ethylhexyl ethylhexanoate, and mixtures thereof, and at least one outer shell formed of a wall-forming polymeric material surrounding the core, the outer shell comprising i) at least one wall-forming polymer, and ii) optionally at least one plasticizer and/or at least one opaque substance and/or at least one fatty acid salt.

2. The composition according to claim 1, wherein an amount of the reflective agent ranges from 50 % to 90% by weight based on a total weight of the dispersion.

3. The composition according to claim 1, wherein a weight ratio of the reflective agent particles to the oil(s) ranges from 1.5/1 to 5/1.

4. The composition according to claim 1, wherein the dispersion of reflective agent in the at least one oil is a dispersion of bismuth oxychloride in ethylhexyl hydroxystearate.

5. The composition according to claim 1, wherein the wall-forming polymer forming the outer shell(s) is selected from a polyacrylate a polymethacrylate, a cellulose ether or ester, or any combination thereof.

6. The composition according to claim 5, wherein the wall-forming polymer is selected from the group consisting of poly(methyl methacrylate) (PMMA), poly(methyl methacrylate)-co-(methacrylic acid) (PMMA/MA), an acrylate/ammonium methacrylate copolymer, and cellulose acetate.

7. The composition according to claim 1, wherein the outer shell of the microcapsules comprises an opaque substance, the opaque substance being selected from TiO.sub.2, zinc oxide, alumina, boron nitride, talc, mica or any combination.

8. The composition according to claim 1, wherein the outer shell of the microcapsules comprises a fatty acid salt, the fatty acid salt being magnesium stearate.

9. The composition according to claim 1, wherein the microcapsules comprise the inner core in an amount within a range of from 20 %to 90% by weight relative to a total weight of the microcapsules; and the wall-formimg polymer(s) of the outer shell within a range of from 5% to 30% by weight relative to the total weight of the microcapsules; and optionally, the opaque substance(s) in the outer shell in an amount ranging from 1% to 50% by weight, relative to the total weight of the microcapsules; and/or optionally, the fatty acid salt in the outer shell in an amount ranging from 0.05% to 5% by weight, relative to the total weight of the microcapsules; and/or optionally, the plasticizer(s) in the outer shell in an amount ranging from 0.5% to about 30% by weight, relative to the total weight of the microcapsules.

10. The composition according to claim 1, wherein the microcapsules are single-layer microcapsules.

11. The composition according to claim 10, wherein the -single-layer microcapsules comprise: the inner core comprising bismuth oxychloride dispersed in 2-ethylhexyl hydroxystearate in an amount from 60 to 80% by weight, and the outer shell comprising magnesium stearate in an amount ranging from 1.0% to 2.0% by weight, TiO2 in an amount ranging from 1% to 20% by weight, and, as the wall-forming polymer, PMMA, in an amount ranging from 5% to 20% by weight relative to a total weight of the microcapsules.

12. The composition according to claim 10, wherein the single-layer microcapsules comprise: the inner core comprising bismuth oxychloride dispersed in 2-ethylhexyl hydroxystearate in an amount from 60 to 80% by weight, and the outer comprising TiO.sub.2 in an amount ranging from 10% to 50% by weight, and, as the wall-forming polymer, ethyl cellulose, in an amount ranging from 1% to 10% by weight relative to a total weight of the microcapsules, wherein the outer shell does not comprise magnesium stearate.

13. The composition according to claim 10, wherein the-single-layer microcapsules comprise: the inner core comprising bismuth oxychloride dispersed in 2-ethylhexyl hydroxystearate in an amount from 60 to 80% by weight, and the outer shell comprising magnesium stearate in an amount ranging from 1.0% to 2.0% by weight, TiO.sub.2 in an amount ranging from 1% to 20% by weight, and, as the wall-forming polymer, poly(ethyl acrylate)-co-methyl methacrylate-co-trimethyl ammonium ethyl methacrylate chloride, in an amount ranging from 5% to 20% by weight, relative to a total weight of the microcapsules.

14. The composition according to claim 10, wherein the single-layer microcapsules comprise: the inner core comprising bismuth oxychloride dispersed in 2-ethylhexyl hydroxystearate in an amount ranging from 60 to 80% by weight, and the outer shell comprising magnesium stearate in an amount ranging from 1.0% to .0% by weight, TiO.sub.2 in an amount ranging from 1% to 20% by weight, and, as the wall-forming polymer, poly(methyl methacrylate)-co-(methacrylic acid) (PMMA/MA), in an amount ranging from 5 % to 20% by weight, relative to a total weight of the microcapsules.

15. The composition according to claim 10, wherein the -single-layer microcapsules comprise: the inner core comprising bismuth oxychloride dispersed in 2-ethylhexyl hydroxystearate in an amount of from 60 to 80% by weight, and the outer shell comprising a plasticizer, in an amount ranging from 1% to 20% by weight, and, as the wall-forming polymer material, poly(ethyl acrylate)-co-methyl methacrylate-co-trimethyl ammonium ethyl methacrylate chloride, in an amount ranging from 5% to 20% by weight, relative to a total weight of the microcapsules, wherein the outer shell does not comprise magnesium stearate nor TiO.sub.2.

16. The composition according to claim 1, wherein the composition is an oil-in-water emulsion.

17. The composition according to claim 1, further comprising at least one coloring agent.

18. The composition according to claim 1, further comprising at least one mono-alcohol comprising from 2 to 8 carbon atoms, at a concentration of at least 10% by weight relative to a total weight of the composition.

19. The composition according to claim 1, further comprising at least one filler.

20. The composition according to claim 1 further comprising at least one non-emulsifying organopolysiloxane elastomer.

21. The composition according to claim 1, wherein the composition is in the form of an oil-in-water emulsion having oil globules whose number-average size is less than or equal to 200 nm.

22. The composition according to claim 19, wherein the aqueous phase is continuous and the oily phase dispersed on said continuous phase; and the composition further comprises a) a mixture of nonionic surfactants comprising: (i) at least one alkoxylated fatty ester selected from esters formed from 1 to 100 ethylene oxide units and at least one fatty acid chain containing from 16 to 22 carbon atom; and (ii) at least one fatty ester of glycerol selected from esters formed from at least one acid comprising a saturated linear alkyl chain having from 16 to 22 carbon atoms, and 1 to 20 glycerol units; and b) at least one anionic amphiphilic lipid, wherein a weight ration of the amount of oily phase to a total amount of nonionic surfactants and anionic amphiphilic lipid is from 2 to 20.

23. A cosmetic process for caring for and/or making up keratinic materials, comprising applying onto the keratinic materials the composition according to claim 1, wherein the keratinic material is skin.

Description

EXAMPLES

(1) Reference is now made to the following examples, which together with the above descriptions illustrate some embodiments of the invention in a non limiting fashion.

(2) Materials and Methods

(3) Ethyl acetate was obtained from Gadot, Israel. Magnesium stearate was obtained from FACI ASIA PACIFIC PTE Ltd. Titanium oxide, which is also referred to herein throughout as titanium dioxide or TiO.sub.2 RC402, was obtained from Sachtleben Chemie GmbH. Bismuth oxychloride pre-dispersed 2-ethylhexyl hydroxystearate (marketed as Timiron Liquid Silver) was obtained from Merck KGaA, Darmstadt, Germany. Polyvinyl alcohol (PVA) as used was Mowiol 4-88, KSE solution 4%; Kuraray America, Inc., USA. Cellulose acetate 398-10NF was obtained from Eastman, USA. (Poly(ethyl acrylate-co-methyl methacrylate-co-trimethylammonium ethyl methacrylate chloride), EUDRAGIT RS PO, was obtained from Evonik industries, Germany). Size distribution of the microcapsules was determined using HORIBA LA300. Loose Bulk Density of the microcapsules was determined using USP-NF <616>.

Example 1

Preparation of PMMA Microcapsules Containing Bismuth Oxychloride Predispersed 2-ethylhexyl hydroxystearate

(4) 1.1 Preparation of organic phase/master batch (MB)

(5) An organic phase (herein referred to interchangeably as master batch (MB)) was prepared by gradually adding 10 grams of the wall-forming polymer poly(methyl methacrylate) (PMMA) under stirring (10 minutes), into 300 grams of ethyl acetate, heating the obtained mixture to 50 C. and stirring well until the mixture was homogeneous and transparent (about 20 minutes). The obtained polymer solution was cooled to 25 C. One gram of Magnesium Stearate (MgSt) was added to the solution under stirring for about 5 minutes. Ten grams of Titanium dioxide (TiO2) were then added to the solution under stirring for about 5 minutes and then the mixture was homogenized for about 8 minutes.

(6) A mixture of bismuth oxychloride predispersed 2-ethylhexyl hydroxystearate (79 grams) was added to the previous suspension under stirring for about 5 minutes. A list of the components included in the prepared MB is presented in Table 1.

(7) TABLE-US-00001 TABLE 1 Master batch constituents Loading Material for 100 grams MB Poly(methyl methacrylate) 10.0 TiO.sub.2 RC402 10.0 Magnesium stearate 1.0 Bismuth oxychloride dispersed in 2-ethylhexyl 79.0 hydroxystearate Ethyl acetate 300.0
1.2 Preparation of the emulsion

(8) An aqueous solution of 0.25% polyvinyl alcohol (PVA) was prepared by mixing water (1013 grams) with PVA 4% solution (68 grams). Ethyl acetate (120 grams) was added to the aqueous solution, and the master batch of step 1.1 above was thereafter gradually added into the ethyl acetate/water emulsion under stirring at about 400 RPM for 2 minutes. The ratio between the master batch and the emulsion (w/w) was . A list of the components included in the prepared emulsion is presented in Table 2.

(9) TABLE-US-00002 TABLE 2 Emulsion constituents Material Loading (grams) Water 1013 PVA (4% solution) 68 Ethyl Acetate 120 MB 400
1.3 Extraction of the organic solvent

(10) The extraction solution was composed of a mixture of 8775 grams water and 225 grams of PVA solution 4% (final concentration of PVA in the extraction solution was 0.10% PVA). The emulsion of step 1.2 above (1600 grams) was gradually added into the extraction solution in a 15 L pail under stirring at 150 RPM using a manual pump, and the obtained mixture was further stirred for additional 15 minutes. The resulting mixture was left to sediment for about 24 hours at 25 C. A list of the components included in extraction medium is presented in Table 3.

(11) TABLE-US-00003 TABLE 3 Extraction medium constituents Material Loading (grams) Emulsion 1600 Water 8775 4% PVA solution 225
1.4 Washing, Drying and Sifting of the microcapsules

(12) The microcapsules obtained in step 1.3 above were separated either by sedimentation or vacuum filtration, and then dried and sifted.

(13) In the sedimentation procedure, the upper liquid phase from the pail was decanted and the remaining suspension was shaken and transferred to a drying vessel.

(14) In the filtration procedure, the upper phase liquid was decanted from the pail, the remaining suspension was shaken and then filtered, and the sediment was rinsed on the filter with 400 ml water. The suspension was transferred to a drying vessel. In the drying stage, the microcapsules were freeze dried (lyophilized) for 48 hours.

(15) In the sifting stage, the dried microcapsules were sifted using automatic sifter Ari j-Levy, Sifter MIC. 100. The sifted microcapsules were stored in an appropriate container at room temperature or in a refrigerator.

Example 2

Preparation of Cellulose Acetate Microcapsules Containing Bismuth Oxychloride Predispersed 2-ethylhexyl hydroxystearate

(16) 2.1 Preparation of organic phase/master batch (MB) stage

(17) An organic phase (herein referred to interchangeably as master batch (MB)) was prepared by gradually adding 5 grams of the wall-forming polymer Cellulose Acetate 398-10NF (CA) under stirring (10 minutes), into 300 grams of ethyl acetate, and stirring the obtained mixture until the mixture was homogeneous and transparent (about 20 minutes). Thirty grams of Titanium dioxide (TiO2) were then added to the obtained solution under stirring for about 5 minutes and then the mixture was homogenized for about 8 minutes. A mixture of bismuth oxychloride predispersed in 2-ethylhexyl hydroxystearate (60 grams) was thereafter added to the suspension under stirring for about 5 minutes.

(18) A list of the components included in the prepared MB is presented in Table 4.

(19) TABLE-US-00004 TABLE 4 Master batch constituents Material Loading for 100 grams MB Cellulose acetate 398-10NF 5.0 TiO.sub.2 RC402 35.0 Bismuth oxychloride dispersed 60.0 2-ethylhexyl hydroxystearate Ethyl acetate 300.0
2.2 Preparation of the emulsion

(20) An aqueous solution of 0.4% polyvinyl alcohol (PVA) was prepared by mixing water (972 grams) with PVA 4% solution (108 grams). Ethyl acetate (120 grams) was added to the aqueous phase, and the master batch of step 3.1 above was thereafter gradually added into the ethyl acetate/water emulsion under stirring at about 400 RPM for 2 minutes. The ratio between the master batch and the emulsion (w/w) was 1/3. A list of the components included in the prepared emulsion is presented in Table 5.

(21) TABLE-US-00005 TABLE 5 Emulsion constituents Material Loading (grams) Water 972 PVA (4% solution) 108 Ethyl Acetate 120 MB 400
2.3 Extraction of the organic solvent

(22) The extraction solution was composed of a mixture of 8550 grams water and 450 grams of PVA solution 4% (final concentration of PVA in the extraction fluid 0.20% PVA). The emulsion of step 3.2 above (1600 grams) was gradually added to the extraction solution in a 15 L pail under stirring at 150 RPM using a manual pump, and the obtained mixture was further stirred for additional 15 minutes. The resulting mixture was left to sediment for about 24 hours at 25 C. A list of the components included in the prepared extraction medium is presented in Table 6.

(23) TABLE-US-00006 TABLE 6 Extraction medium constituents Material Loading (grams) Emulsion 1600 Water 8550 4% PVA solution 450
2.4 Washing, Drying and Sifting of the microcapsules

(24) The microcapsules obtained in step 3.3 above were separated either by sedimentation or vacuum filtration, dried and sifted, as described hereinabove, for Example 1.

Example 3

Preparation of EUDRAGIT Microcapsules Containing Bismuth Oxychloride Predispersed 2-ethylhexyl hydroxystearate

(25) 3.1 Preparation of organic phase/master batch (MB) stage

(26) An organic phase (herein referred to interchangeably as master batch (MB)) was prepared by gradually adding 10 grams of the wall-forming Poly(ethyl acrylate-co-methyl methacrylate-co-trimethylammonioethyl methacrylate chloride) (EUDRAGIT RS PO) under stirring (10 minutes), into 300.0 grams of ethyl acetate, heating to 50 C. and stirring well until the mixture was homogeneous and transparent (about 20 minutes). The obtained polymer solution was cooled to 25 C. One gram of Magnesium Stearate (MgSt) was added to the solution under stirring for about 5 minutes. Then, bismuth oxychloride predispersed 2-ethylhexyl hydroxystearate (79 grams) was added to the suspension under stirring for about 5 minutes. The components of the MB are presented in Table 7.

(27) TABLE-US-00007 TABLE 7 Master batch constituents Loading for Material 100 grams MB EUDRAGIT RS PO (Poly(ethyl acrylate-co- 10.0 methyl methacrylate-co-trimethylammonioethyl methacrylate chloride) Magnesium Stearate 1.0 Bismuth oxychloride dispersed in 2-ethylhexyl 79.0 hydroxystearate Ethyl acetate 233
3.2 Preparation of the emulsion

(28) An aqueous solution of 0.25% polyvinyl alcohol (PVA) was prepared by mixing water (844 grams) with PVA 4% solution (56 grams). Ethyl acetate (100 grams) was added to the water phase. Ten grams of Titanium dioxide (TiO2) was added to previous step under stirring for about 5 minutes and then the mixture was homogenized for about 8 minutes and then the master batch of step 4.1 above was gradually added into the ethyl acetate/water emulsion under stirring at about 400 RPM for 2 minutes. The ratio between the master batch and the emulsion (w/w) was . The components of the emulsion are presented in Table 8.

(29) TABLE-US-00008 TABLE 8 Emulsion constituents Material Loading (grams) Water 844 PVA (4% solution) 56 Ethyl Acetate 100 TiO.sub.2 RC402 10 MB 323
3.3 Extraction of the organic solvent

(30) The extraction fluid was composed of a mixture of 6923 grams water and 178 grams of PVA solution 4% (final concentration of PVA in the extraction fluid 0.10% PVA). The emulsion of step 4.2 above (1333 grams) was gradually added into the extraction fluid in a 15 L pail under stirring at 150 RPM using a manual pump, and was further stirred for additional 15 minutes. The resulting mixture was left to sediment for about 24 hours at 25 C. The components of the extraction medium are presented in Table 9.

(31) TABLE-US-00009 TABLE 9 Extraction medium constituents Material Loading (grams) Emulsion 1333 Water 6923 4% PVA solution 178
3.4 Washing, Drying and Sifting of the microcapsules

(32) The microcapsules obtained in step 3.3 above were separated either by sedimentation or vacuum filtration, dried and sifted, as described hereinabove, for Example 1.

Example 4

Preparation of PMMA/MA Microcapsules Containing Bismuth Oxychloride Predispersed 2-ethylhexyl hydroxystearate

(33) 4.1 Preparation of organic phase/master batch (MB) stage

(34) An organic phase (herein referred to interchangeably as master batch (MB)) was prepared by gradually adding 10 grams of the wall-forming polymer Poly(methacrylic acid-co-methyl methacrylate) (PMMA/MA) under stirring (10 minutes), into 300.0 grams of ethyl acetate, heating to 50 C. and stirring well until the mixture was homogeneous and transparent (about 20 minutes). The obtained polymer solution was cooled to 25 C. One gram of Magnesium Stearate (MgSt) was added to the solution under stirring for about 5 minutes. Ten grams of Titanium dioxide (TiO2) were thereafter added under stirring for about 5 minutes and then the mixture was homogenized for about 8 minutes. Thereafter, bismuth oxychloride predispersed 2-ethylhexyl hydroxystearate (79 grams) was added to the suspension under stirring for about 5 minutes. The components of the MB are presented in Table 10.

(35) TABLE-US-00010 TABLE 10 Master batch constituents Loading for Material 100 grams MB Poly(methacrylic acid-co-methyl methacrylate) 10.0 (PMMA/MA) TiO.sub.2 RC402 10.0 Magnesium stearate 1.0 Bismuth oxychloride dispersed in 2-ethylhexyl 79.0 hydroxystearate Ethyl acetate 300.0
4.2 Preparation of the emulsion

(36) An aqueous solution of 0.25% polyvinyl alcohol (PVA) was prepared by mixing water (1013 grams) with PVA 4% solution (68 grams). Ethyl acetate (120 grams) was added to the water phase, and then the master batch of step 1.1 above was gradually added into the ethyl acetate/water emulsion under stirring at about 400 RPM for 2 minutes. The ratio between the master batch and the emulsion (w/w) was 1/3. The components of the emulsion are presented in Table 11.

(37) TABLE-US-00011 TABLE 11 Emulsion constituents Material Loading (grams) Water 1013 PVA (KSE 4% solution) 68 Ethyl Acetate 120 MB 400
4.3 Extraction of the organic solvent

(38) The extraction fluid was composed of a mixture of 8775 grams water and 225 grams of PVA solution 4% (final concentration of PVA in the extraction fluid 0.10% PVA). The emulsion of step 1.2 above (1600 grams) was gradually added into the extraction fluid in a 15 L pail under stirring at 150 RPM using a manual pump, and was further stirred for additional 15 minutes. The resulting mixture was left to sediment for about 24 hours at 25 C. The components of the extraction medium are presented in Table 12.

(39) TABLE-US-00012 TABLE 12 Extraction medium constituents Material Loading (grams) Emulsion 1600 Water 8775 4% PVA solution 225
4.4 Washing, Drying and Sifting of the microcapsules

(40) The microcapsules obtained in step 4.3 above were separated either by sedimentation or vacuum filtration, dried and sifted, as described hereinabove, for Example 1.

Example 5

Preparation of EUDRAGIT Microcapsules Containing Bismuth Oxychloride Predispersed 2-ethylhexyl hydroxystearate

(41) 5.1 Preparation of organic phase/master batch (MB) stage

(42) An organic phase (herein referred to interchangeably as master batch (MB)) was prepared by gradually adding 10 grams of the wall-forming polymer Poly(ethyl acrylate-co-methyl methacrylate-co-trimethylammonioethyl methacrylate chloride) (EUDRAGIT RS PO) under stirring (10 minutes), into 185.7 grams of ethyl acetate, heating to 50 C. and stirring well until the mixture was homogeneous and transparent (about 20 minutes). The obtained polymer solution was cooled to 25 C. Ten grams of Triethyl Citrate were added to the solution under stirring for about 5 minutes. Eighty grams of bismuth oxychloride (BiClO) were thereafter added to the mixture under stirring for about 5 minutes and then the mixture was homogenized for about 8 minutes. The components of the MB are presented in Table 13.

(43) TABLE-US-00013 TABLE 13 Master batch constituents Loading for Material 100 grams MB EUDRAGIT RS PO (Poly(ethyl acrylate-co- 10.0 methyl methacrylate-co-trimethylammonioethyl methacrylate chloride) Triethyl Citrate 10.0 Bismuth oxychloride dispersed in 2-ethylhexyl 80.0 hydroxystearate Ethyl acetate 185.7
5.2 Preparation of the emulsion

(44) An aqueous solution of 0.25% polyvinyl alcohol (PVA) was prepared by mixing water (723.2 grams) with PVA 4% solution (48.2 grams). Ethyl acetate (85.7 grams) was added to the water phase, and then the master batch of step 6.1 above was gradually added into the ethyl acetate/water emulsion under stirring at about 400 RPM for 10 minutes. The ratio between the master batch and the emulsion (w/w) was 1:3. The components of the emulsion are presented in Table 14.

(45) TABLE-US-00014 TABLE 14 Emulsion constituents Material Loading (grams) Water 723.2 PVA (4% solution) 48.2 Ethyl Acetate 85.7 MB 285.7
5.3 Extraction of the organic solvent

(46) The extraction fluid was composed of a mixture of 5599 grams water and 144 grams of PVA solution 4% (final concentration of PVA in the extraction fluid 0.10% PVA). The emulsion of step 6.2 above (1449.2 grams) was gradually added into the extraction fluid in a 15 L pail under stirring at 150 RPM using a manual pump, and was further stirred for additional 15 minutes. The resulting mixture was left to sediment for about 24 hours at 25 C. The components of the extraction medium are presented in Table 15.

(47) TABLE-US-00015 TABLE 15 Extraction medium constituents Material Loading (grams) Emulsion 1449.2 Water 5599 4% PVA solution 144
5.4 Washing, Drying and Sifting of the microcapsules

(48) The microcapsules obtained in step 5.3 above were separated either by sedimentation or vacuum filtration, dried and sifted, as described hereinabove, for Example 1.

Example 6

Characterization

(49) Size Distribution:

(50) The size distribution of the microcapsules obtained in Examples 1-5 was measured and the obtained data are indicated below.

(51) Herein throughout, a mean diameter means an average size of the microcapsules. The size of the microcapsules may be measured by a Laser distribution size method and particularly by measuring the values D[50] and D[90]. D50 means the size of which 50% of the microcapsules do not exceed, and D90 means the size of which 90% of the microcapsules do not exceed.

(52) The diameter of the microcapsules obtains as described in Example 1 is in the range of from about 3 microns to about 600 microns, with the mean diameter being about 175 microns, the D50 of the microcapsules being about 155 microns, and the D90 of the microcapsules being about 320 microns.

(53) The diameter of the microcapsules obtains as described in Example 3 is in the range of from about 3 microns to about 500 microns, with the mean diameter being about 120 microns, the D50 of the microcapsules being about 96 microns, and the D90 of the microcapsules being about 237 microns.

(54) The diameter of the microcapsules obtains as described in Example 4 is in the range of from about 3 microns to about 400 microns, with the mean diameter being about 120 microns, the D50 of the microcapsules being about 106 microns, and the D90 of the microcapsules being about 195 microns.

(55) The diameter of the microcapsules obtains as described in Example 5 is in the range of from about 3 microns to about 250 microns, with the mean diameter being about 120 microns, the D50 of the microcapsules being about 96 microns, and the D90 of the microcapsules being about 237 microns.

(56) Loose Bulk Density:

(57) The loose bulk density of the microcapsules obtained in Example 1 was determined as ranging from about 300 to about 450 grams/liter (from about 0.30 to about 0.45 gram/cm.sup.3), or from about 300 to about 380 grams/liter (from about 0.30 to about 0.38 gram/cm.sup.3) or from about 300 to about 340 grams/liter (from about 0.30 to about 0.4 gram/cm.sup.3).

(58) The loose bulk density of the microcapsules obtained in Example 2 was determined as ranging from about 360 to about 460 grams/liter (from about 0.36 to about 0.46 gram/cm.sup.3), or from about 380 to 440 grams/liter (from about 0.38 to about 0.44 gram/cm.sup.3), or from about 400 to 420 grams/liter (from about 0.40 to about 0.42 gram/cm.sup.3).

(59) The loose bulk density of the microcapsules obtained in Example 3 was determined as ranging from about 140 to about 360 grams/liter (from about 0.14 to about 0.36 gram/cm.sup.3), or from about 200 to 300 grams/liter (from about 0.20 to about 0.30 gram/cm.sup.3), or from about 240 to about 260 grams/liter (from about 0.24 to about 0.26 gram/cm.sup.3).

(60) The loose bulk density of the microcapsules obtained in Example 5 was determined as ranging from about 420 to about 560 grams/liter (from about 0.42 to about 0.56 gram/cm.sup.3), or from about 450 to about 530 grams/liter (from about 0.45 to about 0.53 gram/cm.sup.3), or from about 480 to about 500 grams/liter (from about 0.48 to about 0.50 gram/cm.sup.3).

(61) Masking:

(62) Quantitative measurements of the masking effect provided by encapsulating bismuth oxychloride, the X-Rite measurement technique using the CIE Color Systems (based on the CIE L*a*b* color scale, wherein L* defines lightness, a* denotes the red/green value and b* the yellow/blue value) was used. The standard illuminant applied for these measurements was daylight.

(63) Quantitative values were obtained by integrating values/data measured for three visual elements of color: hue (namely, how we perceive an object's color), chroma (the vividness or dullness of a color namely, how close the color is to either gray or the pure hue), and degree of lightness (namely classifying whether a color is light or dark).

(64) Table 16 below presents the shift in lightness on the lightness scale L* of the present microcapsules relative to the bismuth oxychloride-containing raw material Timiron Liquid Silver (DL*). The positive DL* values presented in Table XXX denote a shift on the lightness scale in the direction of substantially lighter, brighter color for the microcapsules of the invention compared to the raw material, which is indicative of the masking effect.

(65) TABLE-US-00016 TABLE 16 DL* relative to Timiron Example No. Liquid Silver Raw material 1 8.45 2 5.71 3 9.96 5 13.47
Light Reflectance:

(66) Light reflectance is measured using polarized goniophotometer system with a halogen lamp. Both input and detected light are polarized. The incident light angle is 45 and a convergent angle ranges over 20-75, with a moving detector. The detection polarizer can be rotated to collect either parallel or perpendicular polarized light. Each quantity of light can be calculated from the quantity of parallel filtered and vertically filtered light.

(67) The quantity of internally reflected light:
linternally reflected light=2lvertical

(68) The quantity of surface-reflected light:
lsurfacereflected light=lparallellvertical

(69) The quantity of totally reflected light:
ltotal=linternally+lsurface=lparallel+lvertical

(70) lcrossed: the quantity of light passing through the crossed polarized filters.

(71) lparallel: the quantity of light passing through the parallel polarized filters.

Examples 6A, 6B, 6C

Oil/Water Emulsions

(72) TABLE-US-00017 6A 6B 6C Phase Ingredients (comparative) (comparative) (invention) CA1 CETYL ALCOHOL 0.50 0.50 0.50 BEHENYL ALCOHOL 1.00 1.00 1.00 PEG-100 STEARATE 0.30 0.30 0.30 CETEARYL ALCOHOL (and) 0.32 0.32 0.32 CETEARYL GLUCOSIDE ISOPROPYL ISOSTEARATE 1.50 1.50 1.50 OCTOCRYLENE 2.00 2.00 2.00 BUTYL 2.00 2.00 2.00 METHOXYDIBENZOYLMETHANE ETHYLHEXYL SALICYLATE 4.00 4.00 4.00 CAPRYLOYL SALICYLIC ACID 0.10 0.10 0.10 OCTYLDODECANOL 0.50 0.50 0.50 A2 TITANIUM DIOXIDE (and) 0.50 0.50 0.50 STEARIC ACID (and) ALUMINA AMMONIUM 0.50 0.50 0.50 ACRYLOYLDIMETHYLTAURATE/ STEARETH-25 METHACRYLATE CROSSPOLYMER CARBOMER 0.07 0.07 0.07 A3 TOCOPHERYL ACETATE 0.20 0.20 0.20 B WATER qsp 100 qsp 100 qsp 100 NIACINAMIDE 3.50 3.50 3.50 PHENOXYETHANOL 0.60 0.6 0.6 PANTHENOL 0.20 0.20 0.20 DISODIUM EDTA 0.10 0.10 0.10 DISODIUM STEAROYL 0.50 0.50 0.50 GLUTAMATE GLYCERIN 5.00 5.00 5.00 C WATER 30.00 30.00 30.00 D POLYACRYLAMIDE (and) C13-14 1.30 1.30 1.30 ISOPARAFFIN (and) LAURETH-7 E DIMETHICONE (and) 2.50 2.50 2.50 DIMETHICONOL F WATER 5.00 5.00 5.00 TRIETHANOLAMINE 0.75 0.75 0.75 PHENYLBENZIMIDAZOLE 1.00 1.00 1.00 SULFONIC ACID G WATER 3.00 3.00 3.00 ASCORBYL GLUCOSIDE 0.20 0.20 0.20 H METHYLISOTHIAZOLINONE 0.10 0.10 0.10 HYDROXYPROPYL 0.50 0.50 0.50 TETRAHYDROPYRANTRIOL RETINYL LINOLEATE 0.05 0.05 0.05 ZINGIBER OFFICINALE (GINGER) 0.05 0.05 0.05 ROOT EXTRACT HYDROLYZED RICE PROTEIN 0.20 0.20 0.20 I PTFE 0.30 0.30 0.30 DIMETHICONE/VINYL 0.50 0.50 0.50 DIMETHICONE CROSSPOLYMER J ALCOHOL DENAT. 2.00 2.00 2.00 K ENCAPSULATED BISMUTH 0 3.00 OXYCHLORIDE OILY DISPERSION OF EXAMPLE 1 BISMUTH OXYCHLORIDE 3.00 DISPERSION IN ETHYLHEXYL HYDROXYSTEARATE (TIMIRON LIQUID SILVER- MERCK) BISMUTH 3.00 OXYCHLORIDE POWDER ENCAPSULATED IN ACRYLATES/ AMMONIUM METHACRYLATE COPOLYMER CAPSULES (RONAFLAIR LF-2000)
Process:

(73) In a 1 liter baker the phase B was prepared at 65 C. under stirring until complete solubilization. At room temperature the phases F and G were prepared. The Phase A was completely melted in the main kettle at 80 C. A2 was added. After 5 minutes of mixing, A3 was added under stirring. The phase B was introduced into the phase A under stiring (Rayneri) with a vigourous stirring (emulsion). The phase C was added to cool and dilute. The phases D and E were added. The cooling was started with ice bath. The phases F, G, H and I were finally added. The phase J was added at 40 C. The phase K was added at the end under Rayneri.

(74) The quantities of the ingredients are expressed in percentages by weight relative to the total weight of the composition.

(75) Evaluation:

(76) Contrarily to the compositions 6B and 6C, it was difficult to make the composition 6A as the phase K was difficult to add. A lot of grey spots appeared after few minutes into the mass bulk. By visual observation, the obtained product was not homogeneous.

(77) Compared to the comparative example 6B, the Example 6C according to the invention containing microcapsules encapsulating bismuth oxychloride in ethylhexyl hydroxystearate was considered cosmetically better for a panel 7 women, glider, fresher and with a better pearly brightening finish.

Examples 7A and 7B in the Form of Liquid O/W Emulsion (Serum)

(78) TABLE-US-00018 Example 7A Example 7B Ingredients (comparative) (invention) A1 WATER 22.30 22.30 BUTYLENE GLYCOL 7.00 7.00 PHENOXYETHANOL 0.50 0.50 DISODIUM EDTA 0.20 0.20 B1 GLYCERYL STEARATE (and) PEG-100 0.60 0.60 STEARATE STEARIC ACID 1.00 1.00 CETYL ALCOHOL 0.50 0.50 C12-15 ALKYL BENZOATE 2.00 2.00 ETHYLHEXYL METHOXYCINNAMATE 4.00 4.00 B2 BISMUTH OXYCHLORIDE 0.20 0.20 C WATER 11.16 11.16 D DIMETHICONE 5.00 5.00 XANTHAN GUM 0.25 0.25 E POLYACRYLAMIDE (and) C13-14 1.00 1.00 ISOPARAFFIN (and) LAURETH-7 F WATER 17.00 17.00 SODIUM CITRATE 0.72 0.72 G WATER 1.00 1.00 TRIETHANOLAMINE 0.01 0.01 H POTASSIUM HYDROXIDE 0.70 0.70 I ALCOHOL DENAT. 2.00 2.00 F1 Iron oxide pigments 7 7 F2 GLYCERIN 7.00 7.00 F3 WATER QS QS G BISMUTH OXYCHLORIDE DISPERSION IN 3 ETHYLHEXYL HYDROXYSTEARATE (TIMIRON LIQUID SILVER-MERCK) MICROCAPSULES CONTAINING 3 BISMUTH OXYCHLORIDE OILY DISPERSION OF EXAMPLE 1
Protocol of Preparation 1. Phase A1 was solubilized at 75 C. and homogenized. 2. Phase A1 was introduced into phase B pre-heated to 75 C. in a beaker, the mixture is stirred during 10 minutes. 3. Phase C was introduced 4. Phase D (pre-mixed with a magnetic bar stirrer at about 40 C.) was introduced and the mixture agitated for 10 minutes. 5. Phase E was introduced. 6. Phase F (once pre-mixed with a magnetic bar stirrer) was slowly introduced and the mixing speed is reduced (ajouts des phases sous agitation?) 7. Phase G (pre-mixed with a magnetic bar stirrer) at 30-35 C.) was introduced, then phase H is introduced, after which phase I is added. 8. The pigments (phase F1) with glycerin (phase F2) and ground in a 3 roller mill. 9. Once the pigments grind was homogenous, the water (phase F3) was incorporated. 10. The pigments were introduced into the beaker containing the other phases under agitation for 5 minutes. 11. The water was added to get 98% with gentle stirring 12. The Phase G was introduced at the end of the preparation at room temperature and weak agitation. The quantities of the ingredients are expressed in percentages by weight relative to the total weight of the composition

(79) The composition of example 7B has been compared with compositions 7A on 7 women. The composition of examples 7B was satisfying in terms of make-up results. It offered better coverage, more homogeneous make-up results, ameliorated playtime and comfort than the comparative composition 7 A. The mass bulk was also more homogeneous with less grey small spots.