COMPOSITIONS COMPRISING AT LEAST ONE ACRYLIC POLYMER AND AT LEAST ONE INSOLUBLE ORGANIC SCREENING AGENT

Abstract

The subject of the present is a composition, in particular a cosmetic composition, comprising at least one photoprotective system capable of screening out UV rays containing at least one insoluble organic UV-screening agent and at least one polymer comprising at least hydroxyethyl acrylate units and acrylate units bearing a lipophilic group, the weight ratio of the sum of all the hydroxyethyl acrylate units to the sum of all the acrylate units bearing a lipophilic group ranging from 1:30 to 1:1 and the polymer having a number-average molecular weight Mn ranging from 2000 to 9000 g/mol.

Claims

1. A composition comprising at least one photoprotective system capable of screening out UV rays comprising at least one insoluble organic UV-screening agent a), characterized in that it also comprises at least one polymer b) comprising monomer units of formulae (A) and (B): ##STR00056## in which: R.sub.1, independently of one another, is chosen from alkyl or alkylene radicals, and at least 60% by weight of the R.sub.1 groups are behenyl radicals, the percentage by weight relating to the sum of all the R.sub.1 groups present in the polymer, and the weight ratio of the sum of all the hydroxyethyl acrylate units to the sum of all the acrylate units bearing the R.sub.1 group ranges from 1:30 to 1:1, and the sum of the total of units A and B is at least 95% by weight of the total weight of the polymer, the polymer having a number-average molecular weight Mn ranging from 2000 to 9000 g/mol.

2. The composition according to claim 1, wherein, in the polymer b), R.sub.1 is constituted of alkyl radicals.

3. The composition according to claim 1, wherein in the polymer b), at least 70% by weight of the R.sub.1 groups are behenyl radicals.

4. The composition according to claim 1, wherein, in the polymer b), all the R.sub.1 groups are behenyl radicals.

5. The composition according to claim 1, wherein, in the polymer b), the weight ratio of the sum of all the hydroxyethyl acrylate units to the sum of all the acrylate units bearing the R.sub.1 group ranges from 1:15 to 1:1.

6. The composition according to claim 1, in which the polymer units present in the polymer b) are constituted of the units (A) and (B).

7. The composition according to claim 1, wherein the polymer b) has a number-average molecular weight Mn ranging from 5000 to 9000 g/mol.

8. The composition according to claim 1, wherein the polymer b) has a melting point ranging from 60 C. to 69 C.

9. The composition according to claim 1, wherein the polymer(s) b) are present in the composition in an amount of active material ranging from 0.1% to 10% by weight, relative to the total weight of the composition.

10. The composition according to claim 1, wherein the insoluble organic UV-screening agent is in the form of particles which have a mean size ranging from 0.01 to 5 m.

11. The composition according to claim 1, wherein the insoluble organic UV-screening agent is chosen in particular from organic UV-screening agents of the oxalanilide type, of the triazine type, of the benzotriazole type; of the vinylamide type; of the cinnamide type; of the type comprising one or more groups which are benzazole and/or benzofuran, benzothiophene or of the indole type; of the aryl vinylene ketone type; of the phenylene bis-benzoxazinone derivative type; of the amide, sulfonamide or acrylonitrile carbamate derivative type, or mixtures thereof.

12. The composition according to claim 1, wherein the insoluble organic UV-screening agent is chosen from: (i) symmetrical triazines substituted with naphthalenyl groups or polyphenyl groups; (ii) the methylenebis(hydroxyphenylbenzotriazole) compounds of formula (IV) below: ##STR00057## in which the radicals T.sub.10 and T.sub.11, which may be identical or different, denote a C.sub.1-C.sub.18 alkyl radical which may be substituted with one or more radicals chosen from C.sub.1-C.sub.4 alkyl, C.sub.5-C.sub.12 cycloalkyl or an aryl residue; (iii) and mixtures thereof.

13. The composition according to claim 12, wherein the methylenebis(hydroxyphenylbenzotriazole) compound of formula (IV) is in the form of an aqueous dispersion of particles having a mean particle size which ranges from 0.01 to 5 m, in the presence of at least one surfactant of structure C.sub.nH.sub.2n+1O(C.sub.6H.sub.10O.sub.5).sub.xH in which n is an integer from 8 to 16 and x is the mean degree of polymerization of the unit (C.sub.6H.sub.10O.sub.5) and ranges from 1.4 to 1.6.

14. The composition according to claim 11 wherein the methylenebis(hydroxyphenylbenzotriazole) compound of formula (IV) is in the form of an aqueous dispersion of particles having a mean particle size which ranges from 0.02 to 2 m in the presence of at least one mono(C.sub.8-C.sub.20)alkyl ester of polyglycerol having a degree of glycerol polymerization of at least 5.

15. The composition according to claim 14, wherein the mono-(C.sub.8-C.sub.20)alkyl ester of polyglycerol is chosen from decaglyceryl caprate, decaglyceryl laurate, decaglyceryl myristate, decaglyceryl oleate, decaglyceryl stearate, decaglyceryl isostearate, hexaglyceryl caprate, hexaglyceryl laurate, hexaglyceryl myristate, hexaglyceryl oleate, hexaglyceryl stearate, hexaglyceryl isostearate, pentaglyceryl caprate, pentaglyceryl laurate, pentaglyceryl myristate, pentaglyceryl oleate, pentaglyceryl stearate, and pentaglyceryl isostearate.

16. The composition according to claim 10, wherein the amount of methylenebis(hydroxyphenylbenzotriazole) compound of formula (IV) in the aqueous dispersion ranges from 10% to 60% by weight relative to the total weight of the dispersion.

17. The composition according to claim 10, wherein the methylenebis(hydroxyphenylbenzotriazole) compound/mono-(C.sub.8-C.sub.2)alkyl ester of polyglycerol weight ratio ranges from 0.05 to 0.5.

18. The composition according to claim 9, wherein the methylenebis(hydroxyphenyl benzotriazole) compound of formula (IV) in the form of an aqueous dispersion is the 2,2-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] compound having the structure below: ##STR00058##

19. The composition according to claim 1, wherein the insoluble organic UV-screening agent(s) of the invention are present at a concentration of active material ranging from 0.1% to 15% by weight relative to the total weight of the composition.

20. The composition according to claim 1, wherein it also comprises at least one soluble organic UV-screening agent which is active in the UV-A range and/or the UV-B range, and/or an inorganic UV-screening agent.

21. The composition according to claim 20, wherein the soluble organic UV-screening agents are chosen in particular from anthranilates; cinnamic derivatives; dibenzoylmethane derivatives; salicylic derivatives; camphor derivatives; triazine derivatives; benzophenone derivatives; ,-diphenylacrylate derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis-benzazolyl derivatives; p-aminobenzoic acid (PABA) derivatives; screening polymers and screening silicones; -alkylstyrene-based dimers; 4,4-diarylbutadienes and mixtures thereof.

22. The composition according to claim 21, wherein the soluble organic UV-screening agents are chosen from: Ethylhexyl salicylate, Butylmethoxydibenzoylmethane, Ethylhexyl methoxycinnamate, Octocrylene, Phenylbenzimidazolesulfonic acid, Terephthalylidenedicamphorsulfonicacid, Benzophenone-3, Benzophenone-4, Benzophenone-5, 4-Methylbenzylidenecamphor, Benzimidazilate, Anisotriazine, Ethylhexyl triazone, Diethylhexyl butamidotriazone, Drometrizole trisiloxane, and mixtures thereof.

Description

EXAMPLES

Example of Preparation of Polymer 1

[0431] Determination of the Molecular Weight by Gel Permeation Chromatography (GPC):

[0432] The sample is prepared by preparing a solution of the polymer at 10 mg/ml in tetrahydrofuran. The sample is placed in an oven at 54 C. for 10 minutes and then in an oscillating shaker for 60 minutes to aid dissolution. After visual inspection, the sample appears to be totally dissolved in the solvent.

[0433] The sample prepared was analysed using two polypore 3007.5 mm columns (manufactured by Agilent Technologies), a Waters 2695 chromatographic system, a tetrahydrofuran mobile phase and detection by refractive index. The sample was filtered through a 0.45 m nylon filter, before being injected into the liquid chromatograph. The standards used for the calibration are the Easi Vial narrow polystyrene (PS) standards from Agilent Technologies.

[0434] Polystyrene standards ranging from 2 520 000 to 162 daltons were used for the calibration.

[0435] The system is equipped with a PSS SECcurity 1260 RI detector. The polystyrene calibration curve was used to determine the average molecular weight. The recording of the diagrams and the determination of the various molecular weights were performed by the Win GPC Unichrom 81 program.

[0436] Determination of the Melting Point by Differential Scanning Calorimetry (or DSC):

[0437] This method describes the general procedure for determining the melting point of polymers by differential scanning calorimetry. This method is based on the standards ASTM E791 and ASTM D 34182 and the DSC calibration is performed according to standard ASTM E 9672.

[0438] Behenyl Acrylate/2-Hydroxyethyl Acrylate Copolymer (Polymer 1):

[0439] In a 4-necked flask equipped with side-blade mixer, an internal thermometer, two funnels, a reflux condenser, and an extension for two other necks, 175 g of behenyl acrylate, 25 g of 2-hydroxyethyl acrylate and 0.4 g of 2,2-azobis(2-methylbutyronitrile) (Akzo Nobel) were added, over the course of 60 minutes at 80 C., to 40 g of isopropanol, with stirring, after having removed the oxygen from the system by means of a nitrogen flush for 20 minutes. The mixture was stirred at 80 C. for 3 hours. The solvent was then eliminated by vacuum distillation, then 1 g of dilauryl peroxide was added and the reaction was continued for 60 minutes at 110 C. The step was repeated. The mixture was then cooled to 90 C., a stream of demineralized water was added and the mixture was then stirred. The water was removed by vacuum distillation.

[0440] Molecular weight: Mn=7300 g/mol, Mw=21 000, Mw/Mn=2.8

[0441] Melting point: 65 C.

Formulation Examples

Examples 1 to 8

[0442] For each composition, the stability over time was studied at various temperatures and/or the sensory aspect was evaluated during and after its application to the skin.

[0443] Study of the Stability Over Time at Various Temperatures

[0444] The stability is studied over time by observing the change in the composition with regard to its macroscopic appearance and its microscopic appearance, at various temperatures such as ambient temperature (AT), 4 C. or 45 C.

[0445] The following compositions were prepared.

TABLE-US-00001 Ex Ex Ex Ex INCI name Ex 1 Ex 2 Ex 3 Ex 4 5* 6* 7* 8* A1 Behenyl Alcohol (and) Glyceryl 3 3 3 3 3 3 3 3 Stearate (and) Disodium Ethylene Dicocamide PEG-15 Disulfate (and) Glyceryl Stearate Citrate A1 Cetyl alcohol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 A1 Octocrylene 5 5 5 5 5 5 5 5 A1 Butyl Methoxydibenzoylmethane 5 5 5 5 5 5 5 5 A1 Ethylhexyl salicylate 5 5 5 5 5 5 5 5 A1 Caprylyl glycol 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 A2 Phenoxyethanol 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 B Disodium EDTA 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 C Ammonium Polyacryloyldimethyl 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Taurate (Hostacerin AMPS) C Xanthan gum 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 A1 Behenyl acrylate/2-hydroxyethyl 2 2 2 2 acrylate copolymer (Polymer 1) as previously synthesized A1 Polystearyl acrylate (IPA-13-1) 2 2 2 2 D Methylene bisbenzotrazolyl 6 3 1 6 3 1 tetramethylbutylphenol (and) Polyglyceryl-10 laurate (concentration of active material) D Methylene bisbenzotriazolyl 6 6 tetramethylbutylphenol (and) Decyl glucoside (Tinosorb M) (concentration of active material) B Water (qs) 100% 100 100 100 100 100 100 100

[0446] Procedure:

[0447] Dissolve the starting materials of the fatty phase (A1) at 75/80 C.

[0448] Dissolve the starting materials of the aqueous phase (B) at AT.

[0449] Add the phenoxyethanol (A2) to A1 just before the emulsification.

[0450] At 65 C., emulsify B in (A1+A2), turbine (3000 rpm)+paddles for 10 min. Add the gelling agents (C), turbine (3000 rpm)+paddles for 10 min.

[0451] Add the remaining water (D), turbine (3000 rpm)+paddles for 10 min while beginning to cool to AT.

[0452] Continue the cooling with paddles.

[0453] At AT, add the insoluble screening agent (E), then operate the turbine at 3000 rpm, then stir with paddles for 5 min.

[0454] Results

[0455] The properties of glide on application and of softness after application were compared for each of the compositions at equivalent screening-agent concentration.

[0456] 50 l of product sampled with a pipette are deposited on the back of the hand (or on SkinFX (reconstructed skin)).

[0457] 15 circular motions are performed on the back of the hand over the course of 15 seconds.

[0458] After having waited 15 seconds, 15 circular motions are again performed over the course of 15 seconds.

[0459] Trained experts evaluate from 1 to 5 with an increment of 0.5 (1=negative limit, 5=positive limit).

[0460] Glide: Tactile evaluation at the end of application. Slide 2 fingers on the skin.

[0461] Tack: Tactile evaluation. Tactile evaluation 45 s after application.

TABLE-US-00002 composition Ex 1 Ex 5* Glide on application 1 2 Softness after 2 3 application

TABLE-US-00003 composition Ex 2 Ex 6* Glide on application 1 2 Softness after 3 4 application

TABLE-US-00004 composition Ex 3 Ex 7* Glide on application 2 3 Softness after 4 5 application

TABLE-US-00005 composition Ex 4 Ex 8* Glide on application 1 2 Softness after 2 3 application

[0462] The compositions comprising an insoluble screening agent and a polymer b) according to the invention have improved cosmetic properties.

Examples 9 to 14

[0463] The following compositions were prepared.

TABLE-US-00006 Ex Ex INCI name (EU) Ex 9 Ex 10 Ex 11 12* 13* Ex14* Homosalate 7 7 7 7 7 7 Octocrylene 5 5 5 5 5 5 Butyl 5 5 5 5 5 5 Methoxydibenzoylmethane Ethylhexyl salicylate 5 5 5 5 5 5 Ethylhexyl triazone 1.5 1.5 1.5 1.5 1.5 1.5 C12-15 Alkyl benzoate 4 4 4 4 4 4 Caprylyl glycol 0.4 0.4 0.4 0.4 0.4 0.4 Phenoxyethanol 0.6 0.6 0.6 0.6 0.6 0.6 Disodium EDTA 0.1 0.1 0.1 0.1 0.1 0.1 Acrylates copolymer 1.2 1.2 1.2 1.2 1.2 1.2 Triethanolamine 0.15 0.15 0.15 0.15 0.15 0.15 Ammonium 0.4 0.4 0.4 0.4 0.4 0.4 acryloyldimethyltaurate/VP copolymer Behenyl acrylate/2- 3 3 3 hydroxyethyl acrylate copolymer (Polymer 1) as previously synthesized Polystearyl acrylate (IPA-13-1) 3 3 3 Methylene bisbenzotrazolyl 6 3 1 6 3 1 tetramethylbutylphenol (and) Polyglyceryl-10 laurate (concentration of active material) AQUA (qsp) 100 100 100 100 100 100 *Example according to the invention

[0464] Procedure:

[0465] Dissolve the SMs of the fatty phase (A1) at 75/80 C.

[0466] Dissolve the starting materials of the aqueous phase (B) at 65 C.

[0467] Add the phenoxyethanol (A2) to A1 just before the emulsification.

[0468] At 65 C., emulsify (A1+A2) in B, turbine (3000 rpm)+paddles for 10 min. Add the gelling agent (C), turbine (3000 rpm)+paddles for 10 min.

[0469] Initiate the cooling to AT while leaving the turbine (2000 rpm) and the paddles until T<40 C.

[0470] At AT, add the insoluble screening agent (D), turbine (3000 rpm)+paddles for 5 min.

[0471] Results

TABLE-US-00007 Ex 9 Ex 10 Ex 11 Ex 12* Ex 13* Ex 14* Macroscopic Granular Granular Granular Smooth cream Smooth cream Smooth cream appearance 24 H Microscopic Broken Broken Broken Fine and Fine and Fine and appearance emulsion emulsion emulsion homogeneous homogeneous homogeneous 24 H emulsion emulsion emulsion Change at 2 Broken Broken Broken Fine and Fine and Fine and months AT emulsion emulsion emulsion homogeneous homogeneous homogeneous and 45 emulsion emulsion emulsion

[0472] The compositions according to the invention are stable, contrary to the compositions not containing the polymer b) according to the invention.

Examples 15 to 17

[0473] The following compositions are prepared.

TABLE-US-00008 INCI name (EU) Ex15 Ex16 Ex17 C12-15 Alkyl benzoate 25 25 10 Phenylene bis- 3% AM benzoxazolyle in isobutene dispersion Caprylyl glycol 0.4 0.4 0.4 Phenoxyethanol 0.6 0.6 0.6 Acrylates copolymer 1.2 1.2 1.2 Triethanolamine 0.15 0.15 0.15 Ammonium 0.4 0.4 0.4 acryloyldimethyltaurate/VP copolymer Behenyl acrylate/2-hydroxyethyl 3 3 3 acrylate copolymer (Polymer 1) as previously synthesized Tris-biphenyl triazine in aqueous 3% AM dispersion (Tinosorb A2B) 1,1-(1,4-piperazinediyl)bis[1- 3% AM [2-[4-(diethylamino)-2- hydroxybenzoyl]phenyl]methanone in aqueous dispersion Eau (qsp) 100% 100% 100%