ANTI-UV COSMETIC COMPOSITION

Abstract

Anti-UV cosmetic compositions in the form of an emulsion may include an emulsifying polymer which is prepared by polymerizing an anionic monomer and a C1-C7 ester of an unsaturated carboxylic acid. Such anti-UV cosmetic compositions may be prepared in the absence of a surfactant. The preparation and use of such anti-UV cosmetic compositions may provide anti-UV cosmetic composition having dual protection for the skin: protection against UV rays and limiting the penetration of UV filters into the skin.

Claims

1. A UV-stabilizing cosmetic composition in the form of an emulsion prepared in the absence of any surface-active compound, the composition comprising, based on total composition weight: 1 to 75 wt % of lipophilic phase particles comprising a lipophilic compound and a UV-stabilizing agent comprising an organic sun filter and/or a mineral particle, wherein the lipophilic phase particles are dispersed in: 25 to 99 wt. % of a continuous hydrophilic phase comprising, based on total hydrophilic phase weight: a hydrophilic compound in a range of from 90 to 99.6 wt. %, and an emulsifying polymer (P) in a range of from 0.4 to 10 wt. %, wherein the emulsifying polymer (P) is prepared by a process comprising polymerizing: (a1) an anionic monomer comprising a polymerizable olefinic unsaturation and a carboxylic acid group, optionally in salt form; and (a2) a C.sub.1-C.sub.7 ester of a compound derived from acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, or crotonic acid.

2. The composition of claim 1, comprising from 1 to 70 wt. % of dispersed lipophilic phase, relative to total continuous hydrophilic phase and dispersed lipophilic phase weight.

3. The composition according to one of claim 1, wherein the lipophilic phase comprises a lipophilic compound comprising a fatty acid, fatty alcohol, ester, butter, wax, oil, terpene, polyterpene, phytosterol, silicone oil, and/or fluorinated oil.

4. The composition of claim 1, wherein the UV-stabilizing agent comprises: a titanium dioxide particle, zinc oxide particle, coated mineral particle, and/or a lipophilic UV-stabilizing agent.

5. The composition of claim 1, wherein the hydrophilic compound comprises water and optionally further comprises a hydrophilic UV-stabilizing agent, glycerol, polyglycerol, glycerol, and/or a moistener.

6. The composition of claim 1, having a pH greater than 4, or a pH less than 13, or a pH in a range of from 4 to 13.

7. The composition of claim 1, wherein the anionic monomer (a1) comprises acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, crotonic acid, an acrylic acid salt, a methacrylic acid salt, a maleic acid salt, a maleic anhydride salt, an itaconic acid salt, a crotonic acid salt, or a combination of two or more of any of these, or wherein the C.sub.1-C.sub.7 ester (a2) is a C.sub.1-C.sub.6 ester, or wherein the polymerization reaction uses, relative to total monomer (a1) and (a2) moles: the anionic monomer (a1) in a range of from 20 to 75 mol. %, and the C.sub.1-C.sub.7 ester (a2) in a range of from 25 to 80 mol.

8. The composition of claim 1, wherein the hydrophilic phase comprises the emulsifying polymer (P) in a range of from 0.4 to 9 wt. % relative to the hydrophilic phase weight.

9. The composition of claim 1, wherein the process for preparing the emulsifying polymer (P) further comprises polymerizing: (a3) a third compound comprising 2-acrylamido-2-methylpropane sulphonic acid, ethoxymethacrylate sulphonic acid, sodium methallyl sulphonate, styrene sulphonate, hydroxyethyl acrylate phosphate, hydroxypropyl acrylate phosphate, hydroxyethylhexyl acrylate phosphate, hydroxyethyl methacrylate phosphate, hydroxypropyl methacrylate phosphate, hydroxyethylhexyl methacrylate phosphate, or a mixture thereof, optionally comprising one or more salts thereof, or (a4) a fourth compound comprising hydroxyethyl-acrylate, hydroxypropyl-acrylate, hydroxyethylhexyl-acrylate, hydroxyethyl-methacrylate, hydroxypropyl-methacrylate, hydroxyethylhexyl-methacrylate, or a mixture thereof, or (a5) a cross-linked monomer or a fifth monomer comprising at least two olefinic unsaturations, or (a6) an associative monomer, preferably chosen among a optionally of formula (III):
R.sup.1-(EO).sub.m-(PO).sub.n—R.sup.2  (III), wherein m and n are independently 0 or an integer or decimal less than 150, wherein m or n is not 0, EO is a CH.sub.2CH.sub.2O group, PO is independently CH(CH.sub.3)CH.sub.2O or CH.sub.2CH(CH.sub.3)O, R.sup.1 is an acrylate group or a methacrylate group, and R.sup.2 is a straight C.sub.6-C.sub.40-alkyl group, a branched C.sub.6-C.sub.40-alkyl group, a phenyl group, or a polyphenyl group.

10. The composition of claim 1, wherein the emulsifying polymer (P) is at least partially neutralized, wherein the emulsifying polymer (P) is at least partially coacervated.

11. A a sunscreen formulation, a makeup formulation, a skin care formulation and a hair care formulation, comprising: a UV-stabilizing cosmetic composition of claim 1.

12. A method of preparing a UV-stabilizing cosmetic composition in the form of an emulsion, prepared in the absence of any surface-active compound, the method comprising: preparing a continuous hydrophilic phase comprising, relative to total hydrophilic phase weight: a hydrophilic compound in a range of from 90 to 99.6 wt. %; and a emulsifying polymer (P) in a range of from 0.4 to 10 wt. %, wherein the emulsifying polymer (P) is prepared by a process comprising polymerizing: (a1) a anionic monomer comprising a polymerizable olefinic unsaturation and a carboxylic acid group or salt thereof; and (a2) 1 C.sub.1-C.sub.7 ester of a compound derived from an acid comprising acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid and/or crotonic acid; preparing of a lipophilic phase comprising a lipophilic compound and a UV-stabilizing agent comprising an organic sun filter and/or a mineral particle; then adding, under stirring and in the absence of any surface-active compound, the lipophilic phase in the hydrophilic phase.

13. The method of claim 12, further comprising: adjusting a final pH of the composition, or wherein the adding is performed at a temperature in a range of from 10° C. to 90° C.

14. A method of preparing, the UV-stabilizing cosmetic of claim 1 in the form of an emulsion, the method comprising: preparing the continuous hydrophilic phase; preparing the lipophilic phase; then adding, under stirring and in the absence of any surface-active compound, the lipophilic phase in the hydrophilic phase.

15. A method of controlling penetration into a hydrophobic substrate of a UV-stabilizing cosmetic composition in the form of an emulsion prepared in the absence of any surface-active compound, the method comprising: preparing the UV-stabilizing cosmetic composition of claim 1; then applying the UV-stabilizing cosmetic composition to a hydrophobic substrate; and, optionally, finally leaching the hydrophobic substrate.

16. A method of controlling or reducing the transfer of a UV-stabilizing cosmetic composition in the form of an emulsion prepared in the absence of any surface-active compound, in a hydrophobic substrate, the method comprising: preparing the UV-stabilizing cosmetic composition of claim 1; then applying the UV-stabilizing cosmetic composition to a hydrophobic substrate; and, optionally, finally leaching the hydrophobic substrate.

17. The method of claim 15, having a V50 value of penetration or of transfer of the UV-stabilizing cosmetic composition of less than 150, measured by a method (M) involving: spreading the UV-stabilizing cosmetic composition on a parafilm substrate using a 200 μm an Elcometer model 3540 wedge, to obtain a coated substrate; drying the coated substrate for 4 hours at room temperature, to obtain a dried coated substrate; manually cleaning a surface of the dried coated substrate using an aqueous solution containing 10% of liquid soap, to obtain a cleaned coated substrate; rinsing the surface of the cleaned coated substrate with water, to obtain a rinsed substrate; drying the rinsed substrate by dabbing with a sheet of paper towel, to obtain a dabbed substrate; placing the dabbed substrate in a Datacolor Tru-Vue2 UV chamber; photographing the dabbed substrate with a Sony Cyber-shot DSC-HX20V device, to obtain an image; and analyzing and processing the image using 2011 ImageJ software, wherein a grayscale distribution of pixels in the image corresponds to an amount of UV-stabilizing agent that has penetrated the hydrophobic substrate, with 0 corresponding to black and to maximum penetration, and 255 corresponding to white and no penetration of the substrate by the UV-stabilizing agent.

18. A cosmetic treatment method, comprising: applying the UV-stabilizing cosmetic composition of claim 1 onto a hydrophobic substrate, optionally followed by the leaching of the hydrophobic substrate.

Description

EXAMPLES

[0138] The following abbreviations are used: [0139] MAA: Methacrylic Acid, [0140] EA: Ethyl Acrylate, [0141] AMPS: 2-acrylamido-2-methylpropanesulphonic acid, [0142] DAP: Diallyl Phthalate, [0143] Clariant Polyglykol B11/50: propylene oxide ethylene oxide monobutyl ether, [0144] Huntsmann Empicol LXVN: sodium lauryl sulphate (SLS), [0145] BASF Texapon NSO: ammonium laureth sulphate in 28% solution or ammonium lauryl ether sulphate in 28% solution (SLES), [0146] Sodium persulphate (NH.sub.4).sub.2S.sub.2O.sub.8, sodium metabisulphite Na.sub.2S.sub.2O.sub.5, [0147] Straight C.sub.16-C.sub.18-(EO)25-alkyl methacrylate (monomer (a6)).

Example 1: Preparation of Polymers (P1), (P2), (P3) and (P4) According to the Invention According to a Semi-Batch Method

[0148] In a stirred 1 L reactor heated using an oil bath, mixture 1 is prepared by introducing deionised water and a sodium lauryl sulphate (SLS) solution or an aqueous solution containing 28% by mass of sodium lauryl ether sulphate (SLES), optionally propylene oxide ethylene oxide monobutyl ether (B11/50) and optionally monomer (a3), 2-acrylamido-2-methylpropane sulphonic acid (AMPS).

[0149] A mixture 2 is prepared in a beaker, called a monomer premixture, comprising in deionised water: [0150] monomer (a1), methacrylic acid (MAA), [0151] monomer (a2), ethyl acrylate (EA), [0152] monomer (a5), diallyl phthalate, [0153] optionally monomer (a3), AMPS, [0154] optionally a 28% solution of sodium lauryl ether sulphate (SLES) or of sodium lauryl sulphate (SLS), [0155] optionally an associative monomer (a6) of formula (III), straight C.sub.16-C.sub.18(EO)25-alkyl methacrylate, [0156] optionally a transfer agent, n-dodecyl mercaptan.

[0157] This premixture is stirred to form a monomer mixture.

[0158] An initiator solution is prepared comprising ammonium persulphate and deionised water and optionally sodium metabisulphite. All reagents and amounts used are listed in Table 1.

[0159] For polymers (P1), (P2) and (P4) used according to the invention, the reactor is heated to 85° C.±1° C. and the initiator solution and monomer premixture are injected in parallel, over 2 hours. This mixture is baked for 30 min at 85° C.±1° C. and then cooled to room temperature.

[0160] For polymer (P3) used according to the invention, the reactor is heated to 74° C.±1° C., all of the initiator solution is injected as soon as the reactor has come to the set temperature and the monomer premixture is injected over 2 hours.

[0161] This mixture is baked for 30 min at 74° C.±1° C. and then cooled to room temperature.

[0162] The polymers according to the invention were prepared under these conditions by varying the monomer compositions of the monomer premixtures. The copolymer compositions obtained are shown in Table 1.

TABLE-US-00001 TABLE 1 Polymer Amount (g) P1 P2 P3 P4 Mixture 1 Deionised water 400 400 359.1 261.7 SLS 2.60 0 2.7 3.8 SLES 0 6.17 0 0 Polyglykol B11/50 1.10 0 0 0 AMPS (a3) 0 0 4.5 0 Premixture Deionised water 173.70 175.00 126.4 343.3 SLS 1.81 0 0.9 3.8 SLES 0 4.29 0 0 Polyglykol B11/50 1.04 0 0 0 MAA (a1) 105.69 88.15 91.30 114.0 EA (a2) 191.28 176.36 156.24 84.5 Diallyl phthalate (a5) 2.75 0.88 0 0 Monomer (a6) 0 22.96 0 29.5 N-dodecyl mercaptan 0 0 0 0.9 Initiator Deionised water 54.32 62.85 24.5 65.2 Ammonium persulphate 0.58 0.41 0.88 0.60 Sodium metabisulphite 0 0 0.08 0 Composition monomer (a1) (mol %) 38.98 32.51 40.13 60.5 Monomer (a2) (mol %) 60.67 55.93 59.05 38.55 Monomer (a3) (mol %) 0 0 0.82 0 Monomer (a5) (mol %) 0.35 0.11 0 0 Monomer (a6) (mol %) 0 0.52 0 0.95 Characteristics Final solids content (% by weight) 30 29 30 30 Particle size (nm) 74 75 120 100

Example 2: Preparation and Evaluation of UV-Stabilizing Cosmetic Compositions (C1 to C4) According to the Invention and Comparative UV-Stabilizing Cosmetic Compositions (CC1 to CC3)

[0163] The hydrophilic phase is prepared in a beaker by stirring, using an lka or Rayneri motorised paddle stirrer, deionised water, butyl ene glycol, di sodium ethylenediaminetetraaceticacid (Na.sub.2EDTA), phenylbenzimidazole sulphonic acid (PBSA, Parsol HS) and a polymer (P1) or (P2) or (P3) or (P4) according to the invention or a surface-active compound alone or in combination with a rheology-modifying polymer. The pH is adjusted to 7±0.5 by adding a 20% sodium hydroxide solution in water.

[0164] The hydrophilic phase of the compositions according to the invention and the comparative compositions is prepared under stirring at 700-1,000 rpm (except composition CC1 at 1,600-2,000 rpm).

[0165] The rheology-modifying polymer in the comparative examples (CC2) and (CC3) is Rheostyl UP (Coatex— INCI: acrylate copolymer).

[0166] Comparative compositions (CC1), (CC2) and (CC3) comprise a surface-active compound (Seppic, Oramix CG 110—INCI: Caprylyl/Capryl Glucoside).

[0167] The lipophilic compounds of the lipophilic phase are: [0168] Cetiol B (INCI: dibutyl adipate), [0169] Dicaprylyl carbonate (INCI: dicaprylyl carbonate), [0170] Parsol 340 (INCI: octocrylene), [0171] Parsol MCX (INCI: ethylhexyl cinnamate) and [0172] Parsol 1789 (INCI: avobenzone).

[0173] The other compounds then added are: [0174] Parsol 50 TX AB (INCI: titanium dioxide with silica and dimethicone [0175] Bioxan E 1,000 UI (INCI: tocopheryl acetate), [0176] Phenoxyethanol (INCI: phenoxyethanol) and [0177] Coconut fragrance (INCI: fragrance).

[0178] The ingredients and amounts are listed in Tables 2 and 3 along with the characteristics and properties of the UV-stabilizing cosmetic compositions obtained.

[0179] Brookfield viscosity is measured at 6 rpm and at 25° C.

[0180] To evaluate the transfer of the UV-stabilizing cosmetic composition comprising UV-stabilizing filters to a hydrophobic substrate, a carrier is used with similar but more restrictive characteristics than those of the skin. Indeed, the hydrophobic substrate used is more hydrophobic than the skin and therefore will allow for easier penetration of the UV-stabilizing agents. Moreover, and contrary to the skin, the hydrophobic substrate used is not porous, so it will enable a more difficult penetration of the UV-stabilizing agents.

[0181] The composition is spread on a parafilm (Bemis flexible packaging) using a 200 μm wedge (Elcometer model 3540) and allowed to dry for 4 hours at room temperature. Then, the surface of the coated parafilm is manually cleaned with an aqueous solution containing 10% of liquid soap, then flushed with water from the loop and dried by lightly dabbing with a paper towel. The parafilm is then placed in a UV chamber (Datacolor Tru-Vue2) and a photo of the parafilm is taken (Sony Cyber-shot DSC-HX20V device) and analysed using ImageJ software (2011).

[0182] The darker the parafilm obtained, the greater the transfer of the UV-stabilizing cosmetic composition and of the UV-stabilizing agent. Image processing makes it possible to identify the grayscale distribution of the pixels in the image (from 0 which corresponds to black to 255 which corresponds to white). The V50 value corresponds to the grey level for which one half of the pixels are lighter and the other half are darker. The results obtained are shown in Tables 2 and 3.

TABLE-US-00002 TABLE 2 Composition according to the invention (g) C1 C2 C3 C4 Hydrophilic phase: deionised water 66.55 66.55 66.55 66.55 Hydrophilic phase: butylene glycol 3 3 3 3 Hydrophilic phase: Na.sub.2EDTA 0.05 0.05 0.05 0.05 Hydrophilic phase: Parsol HS 0.5 0.5 0.5 0.5 Hydrophilic phase: P1 at 30% in water 4 0 0 0 Hydrophilic phase: P2 at 29% in water 0 4 0 0 Hydrophilic phase: P3 at 30% in water 0 0 4 0 Hydrophilic phase: P4 at 30% in water 0 0 0 4 Lipophilic phase: Cetiol B 6 6 6 6 Lipophilic phase: Dicaprylyl carbonate 1 1 1 1 Lipophilic phase: Parsol 340 6 6 6 6 Lipophilic phase: Parsol MCX 5 5 5 5 Lipophilic phase: Parsol 1789 2.5 2.5 2.5 2.5 Other Ingredients: Parsol 50TX AB 4 4 4 4 Other Ingredients: Bioxan E 0.2 0.2 0.2 0.2 Other Ingredients: Phenoxyethanol 1 1 1 1 Other Ingredients: Fragrance 0.2 0.2 0.2 0.2 viscosity (mPa .Math. s) 5,570 11,900 20,400 20,800 pH 7.0 6.9 7.0 6.8 V50 153 156 153 151

TABLE-US-00003 TABLE 3 Comparative composition (g) CC1 CC2 CC3 Hydrophilic phase: deionised water 66.55 63.05 66.55 Hydrophilic phase: butylene glycol 3 3 3 Hydrophilic phase: Na.sub.2EDTA 0.05 0.05 0.05 Hydrophilic phase: Parsol HS 0.5 0.5 0.5 Hydrophilic phase: Oramix CG 110- 4 4 0.5 60% in water Hydrophilic phase: 30% Rheostyl UP 0 3.5 3.5 in water Lipophilic phase: Cetiol B 6 6 6 Lipophilic phase: dicaprylyl carbonate 1 1 1 Lipophilic phase: Parsol 340 6 6 6 Lipophilic phase: Parsol MCX 5 5 5 Lipophilic phase: Parsol 1789 2.5 2.5 2.5 Other Ingredients: Parsol 50TX AB 4 4 4 Other Ingredients: Bioxan E 0.2 0.2 0.2 Other Ingredients: Phenoxyethanol 1 1 1 Other ingredients: Fragrance 0.2 0.2 0.2 Viscosity (mPa .Math. s) 6,900 <100 10,000 pH 7.5 7.0 6.9 V50 148 147 149

[0183] Quite surprisingly, it can be seen that the UV-stabilizing cosmetic compositions according to the invention provide a better resistance to penetration of the UV-stabilizing agents in the hydrophobic substrate than the comparative compositions. It can be seen that this resistance to penetration is not related to the associativity of the polymer or that it is not related to the cross-linking of the polymer.

[0184] The highest resistance to penetration of the UV-stabilizing agents in the hydrophobic substrate of the compositions according to the invention depends neither on the viscosity of the composition nor on its suspensive properties. It does not depend on the use of an associative monomer when preparing the polymer (P) used.

[0185] Thus, polymers (P1), (P2), (P3) and (P4) according to the invention make it possible to prepare UV-stabilizing cosmetic compositions that significantly limit transfers of UV-stabilizing agents to hydrophobic substrates. Furthermore, the use of a surface-active compound in the comparative cosmetic compositions does not make it possible to obtain a UV-stabilizing cosmetic composition that significantly limits transfers of lipophilic UV-stabilizing agents to hydrophobic substrates.

[0186] The UV-stabilizing cosmetic compositions according to the invention therefore offer dual protection: they protect against UV radiation and they significantly limit the transfers of UV-stabilizing agents.