Film-forming cosmetic composition comprising polyurethane and cross-linked starch

Abstract

A cosmetic composition comprising, in an aqueous cosmetically acceptable medium: a) from 6% to 50% by weight in active material of at least one aqueous polyurethane dispersion; and b) from 2% to 8% by weight of at least one cross-linked starch, the weight being expressed by weight of the total weight of the composition.

Claims

1. A cosmetic composition comprising, in an aqueous cosmetically acceptable medium: a) from about 6% to 50% by weight in active material of at least one aqueous polyurethane dispersion, wherein the at least one aqueous polyurethane dispersion is the reaction product of: A) a prepolymer according to the formula: ##STR00003## wherein R.sub.1 represents a bivalent radical of a dihydroxyl functional compound, R.sub.2 represents a hydrocarbon radical of an aliphatic or cycloaliphatic polyisocyanate, R.sub.3 represents a radical of a low molecular weight diol, optionally substituted with ionic groups, n is from 0 to 5, and m is >1; B) at least one chain extender according to the formula: H.sub.2N—R.sub.4—NH.sub.2 wherein R.sub.4 represents an alkylene or alkylene oxide radical not substituted with ionic or potentially ionic groups; and C) at least one chain extender according to the formula: H.sub.2N—R.sub.5—NH.sub.2 wherein R.sub.5 represents an alkylene radical substituted with an ionic group selected from diaminosulfonate groups; and b) from 2% to 8% by weight of at least one cross-linked starch selected from the group consisting of a gelatinized hydroxypropylated maize distarch phosphate, monostarch phosphates of the formula Am-O—PO—(OX)2, distarch phosphates of the formula Am-O—PO—(OX)—O-Am and tristarch phosphates of the formula Am-O—PO—(O-Am)2, wherein X denotes alkaline metals; alkaline earth metals, ammonia salts, amine salts; amino-3-propanediol-1,2 salts, ammonium salts derived from basic aminoacids and wherein Am is starch, the weight being expressed by weight of the total weight of the composition; wherein the weight ratio of the at least one aqueous polyurethane dispersion to the at least one cross-linked starch is between 1 and 7; and wherein the at least one aqueous polyurethane dispersion does not comprise any poly(meth)acrylate polymer.

2. The composition according to claim 1, wherein the polyisocyanate is an organic diisocyanate chosen from the group consisting of tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)-methane, 1,3- and 1,4-bis(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, isomers of toluene diisocyanate (TDI), hydrogenated TDI, 4,4′-diisocyanato diphenyl methane and its isomeric mixtures with 2,4′- and optionally 2,2′-diisocyanato diphenylmethane, 1,5-diisocyanato naphthalene and dicyclohexylmethane diisocyanate.

3. The composition according to claim 1, wherein the low molecular weight diol is a diol having a molecular weight from about 62 to 700 and having up to about 20 carbon atoms per molecule, and is chosen from ethylene glycol, diethylene glycol, propane 1,2-diol, propane 1,3-diol, butane 1,4-diol, butylene 1,3-glycol, neopentyl glycol, hexylene glycol, butyl ethyl propane diol, cyclohexane diol, 1,4-cyclohexane dimethanol, hexane 1,6-diol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), dimethylol butanoic acid (DMBA), dimethylol propionic acid (DMBA), adipic acid or carboxyl-containing caprolactone polyester diol.

4. The composition according to claim 1, wherein the at least one chain extender B) is an alkylene diamine chosen from the group consisting of hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine and piperazine; or an alkylene oxide diamine chosen from the group consisting of 3-{2-[2-(3-aminopropoxy)ethoxy]ethoxy}propylamine, 2-methyl-1,5-pentanediamine, hexane diamine, isophorone diamine, and 4,4-methylenedi-(cyclohexylamine), dipropylamine propyleneglycol, dipropylamine dipropyleneglycol, dipropylamine tripropyleneglycol, dipropylamine poly(propylene glycol), dipropylamine ethyleneglycol, dipropylamine poly(ethylene glycol), dipropylamine 1,3-propane diol, dipropylamine 2-methyl-1,3-propane diol, dipropylamine 1,4-butane diol, dipropylamine 1,3-butane diol, dipropylamine 1,6-hexane diol and dipropylamine cyclohexane-1,4-dimethanol.

5. The composition according to claim 1, wherein the at least one chain extender C) is chosen from the group consisting of the sodium salt of N-(2-aminoethyl)-2-aminoethane sulfonic acid, the sodium salt of N-(2-aminoethyl)-3-aminoethane sulfonic acid and the sodium salt of N-(2-aminoethyl)-2-aminopropionic acid.

6. The composition according to claim 1, wherein the at least one aqueous polyurethane dispersion is present in an amount, in active material, ranging from about 6.5 to about 45% by weight based on the total weight of the composition.

7. The composition according to claim 1, wherein the at least one cross-linked starch is selected from distarch phosphates of the formula Am-O—PO—(OX)—O-Am wherein X denotes sodium or potassium; calcium or magnesium; ammonia salts; monoethanolamine, diethanolamine, triethanolamine; amino-3 propanediol-1,2 salts; ammonium salts derived from lysine, arginine, sarcosine, ornithine, or citrulline.

8. The composition according to claim 1, wherein the at least one cross-linked starch is the gelatinized hydroxypropylated maize distarch phosphate.

9. The composition according to claim 1, wherein the at least one cross-linked starch is present in the composition in a content ranging from 3% to 7.5% by weight in relation to the total weight of the composition.

10. The composition according to claim 1, wherein the weight ratio of the at least one aqueous polyurethane dispersion to the at least one cross-linked starch is between 1.1 and 6.5.

11. The composition according to claim 1 which comprises a quantity of water from 30% to 95% by weight in relation to the total weight of the composition.

12. The composition according to claim 1 which further comprises hydrophobic particles.

13. The composition according to claim 1 which is substantially free of cationic surfactants and/or of any compound comprising at least one —NH3.sup.+ group.

14. A cosmetic method for caring of the skin and/or scalp, comprising the application to said skin and/or scalp of the composition according to claim 1.

15. The composition according to claim 2, wherein the at least one chain extender B) is an alkylene diamine chosen from the group consisting of hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine and piperazine; or an alkylene oxide diamine chosen from the group consisting of 3-{2-[2-(3-aminopropoxy)ethoxy]ethoxy}propylamine, 2-methyl-1,5-pentanediamine, hexane diamine, isophorone diamine, and 4,4-methylenedi-(cyclohexylamine), dipropylamine propyleneglycol, dipropylamine dipropyleneglycol, dipropylamine tripropyleneglycol, dipropylamine poly(propylene glycol), dipropylamine ethyleneglycol, dipropylamine poly(ethylene glycol), dipropylamine 1,3-propane diol, dipropylamine 2-methyl-1,3-propane diol, dipropylamine 1,4-butane diol, dipropylamine 1,3-butane diol, dipropylamine 1,6-hexane diol and dipropylamine cyclohexane-1,4-dimethanol.

16. The composition according to claim 3, wherein the at least one chain extender B) is an alkylene diamine chosen from the group consisting of hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine and piperazine; or an alkylene oxide diamine chosen from 3-{2-[2-(3-aminopropoxy)ethoxy]ethoxy}propylamine, 2-methyl-1,5-pentanediamine, hexane diamine, isophorone diamine, and 4,4-methylenedi-(cyclohexylamine), dipropylamine propyleneglycol, dipropylamine dipropyleneglycol, dipropylamine tripropyleneglycol, dipropylamine poly(propylene glycol), dipropylamine ethyleneglycol, dipropylamine poly(ethylene glycol), dipropylamine 1,3-propane diol, dipropylamine 2-methyl-1,3-propane diol, dipropylamine 1,4-butane diol, dipropylamine 1,3-butane diol, dipropylamine 1,6-hexane diol and dipropylamine cyclohexane-1,4-dimethanol.

17. The composition according to claim 2, wherein the chain extender C) is chosen from the group consisting of the sodium salt of N-(2-aminoethyl)-2-aminoethane sulfonic acid, the sodium salt of N-(2-aminoethyl)-3-aminoethane sulfonic acid and the sodium salt of N-(2-aminoethyl)-2-aminopropionic acid.

Description

EXAMPLES

(1) The following raw materials of Table 1 are used:

(2) TABLE-US-00001 TABLE 1 INCI Composition Supplier and brand name POLYURETHANE-34 PU-34 32% COVESTRO (BAYER) (PU-34) Water 68% BAYCUSAN C 1001 POLYURETHANE-35 PU-35 41% COVESTRO (BAYER) (PU-35) Water 59% BAYCUSAN C 1004 POLYURETHANE-32 PU-32 50% COVESTRO (BAYER) (PU-32) Water 50% BAYCUSAN C 1003 POLYURETHANE-2 PU-2 20.7%   EVONIK MATERIALS (and) POLYMETHYL PMMA 19.7%   NETHERLANDS B.V. METHACRYLATE Dimethyl MEA 0.9%  HYBRIDUR 875 (PU-2 and PMMA) Sodium dehydroacetate 0.34%   POLYMER Water 58.360%    DISPERSION PU-2 FILM FORMER PU-2 35% WANHUA CHEMICAL (PU-2) Water 65% GROUP CO., LTD CARFIL 9235 HYDROXYPROPYL HYDROXYPROPYL 88% AKZO NOBEL STARCH PHOSPHATE STARCH PHOSPHATE STRUCTURE XL (crosslinked starch) Water 12% ACRYLATES/C10-30 ACRYLATES/C10-30 ALKYL 90% LUBRIZOL ALKYL ACRYLATE ACRYLATE CROSSPOLYMER CARBOPOL ULTREZ CROSSPOLYMER TRIDECETH-6  5% 21 POLYMER PEG-30 dipolyhydroxystearate  5% POLYACRYLATE POLYACRYLATE 100%  Seppic CROSSPOLYMER-6 CROSSPOLYMER-6 SEPIMAX ZEN

Example 1: Tests with Different Amounts of Polyurethanes (PU)

(3) Formulas 1 to 4 of Table 2 are prepared by mixing PU-35 (Baycusan C 1004 of Covestro), in the quoted amounts, with 6% by weight hydroxypropyl starch phosphate (Structure XL) in water.

(4) Each formula is applied evenly on to the back of the hand with an area of diameter of around 2 cm. After 1-2 min of drying process, pure water was sprayed on the applied area and polyurethane film is turned into white gradually. The possibility to pick up the resulting film in a piece was evaluated, and the continuity of the peeled off film was observed.

(5) The results are in Table 2 below:

(6) The legend of the table is as follows: √: can pick up a film (peel off)/one piece film (film continuity) X: cannot pick up a film (peel off)/cracking (film continuity)

(7) TABLE-US-00002 TABLE 2 PU-35 Hydroxypropyl (% of active starch Peel Film No. material) phosphate off continuity 1   5% 6% x X 2 6.97% 6% √ √ 3 20.5% 6% √ √ 4 38.54%  6% √ √

(8) Thus, compositions comprising at least 6.97% by weight of PU-35 are able to form a film continuity with good peeling off.

Example 2: Tests with Different Amounts of Hydroxypropyl Starch Phosphate

(9) Formulas 5 to 8 of Table 3 are prepared by mixing 20.5% by weight of active material of PU-35 (Baycusan C 1004 of Covestro) with hydroxypropyl starch phosphate (Structure XL), in quoted amounts, in water.

(10) The resulting film is evaluated for water resistance and spreading.

(11) For this purpose, each formula is applied evenly on to the back of the hand. The sensory of spreading was evaluated during application. After 1-2 min of drying process, pure water was sprayed on the applied area. The film color with residual water was observed to evaluate the water resistance.

(12) The results are in Table 3 below:

(13) The legend of the table is as follows:

(14) Spreading: +++ very slippery, ++ slippery, + not so slippery, − not sliperry at all Water resistance: ++ transparent film & residual water droplet (the film repels water), + translucent film & residual water droplet (the film adsorbs water slowly), − white film (the film adsorbs water quickly).

(15) TABLE-US-00003 TABLE 3 PU-35 Hydroxypropyl (% of active starch Water No. material) phosphate resistance Spreading 5 20.5% 1% − +++ 6 20.5% 3% + ++ 7 20.5% 6% ++ + 8 20.5% 9% ++ −

(16) Thus, compositions comprising 3% to 6% by weight of hydroxypropyl starch phosphate (i.e. formulas 6 and 7) are able to show both water resistance and good spreading properties.

Example 3: Comparison Study of Films Comprising PU and Crosslinked Starch, and PU and Polyacrylate Derivatives

(17) Formulas 1 to 12 of Table 4 are prepared as indicated.

(18) The resulting film is evaluated as follows:

(19) Benefit 1: each formula was applied on a plastic plate by elcometer to form a film having a thickness of 50 μm. The film was put in the hood for drying during 24 hours.

(20) Then the contact angle of MilliQ water on the film was measured by contact angle meter. For each formula, 15 μL of water was dropped to the film and the contact angle of this drop of water on the film was recorded immediately after contacting, which is CA0. After 5 min, the contact angle was recorded as CA5 min.
ΔCA=CA0−CA5 min.

(21) CA0, CA5ming and ΔCA are listed in Table 4 as benefit 1.

(22) Benefit 2: film color was observed immediately after wetting. T=transparent, W=white.

(23) Benefit 3: each formula was applied on the human skin, and the resulting film was evaluated for the flakiness appearance after rubbing (which mimics make up gesture).

(24) Formulas 4, 6, 8 and 10-12 are comparative.

(25) The results are in Table 4 below.

(26) It results that the formulas according to the invention (1-3, 5, 7 and 9) are the only ones which provide all three benefits 1 to 3 at the same time.

(27) TABLE-US-00004 TABLE 4 Formula 1 2 3 4* 5 6* 7 8* 9 10* 11* 12* PU (% PU-35 6.97% 20.5% 38.54% 20.5% active (Baycusan material) C 1004 of Covestro) PU-34 20.5% 20.5% (Baycusan C 1001 of Covestro) PU-32 20.5% 20.5% (Baycusan C 1003 of Covestro) PU-2 20.5% 20.5% (Carfil 9235 of Wanhua) PU-2 + 19.5% 19.5% PMMA (Hybridur 875 of Evonik) Hydroxy- 6% 6% 6% 6% 6% 6% 6% propyl starch phosphate (Structure XL) Acrylates/ 1% 1% C10-30 alkyl acrylate (Carbopal Ultrez-21) Poly- 2% 2% 2% acrylate cross- polymer- 6 (Sepi- max Zen) Water 77% 44% — 49% 30% Benefit CA0 75.4 76 76 67.8 81.6 40 75.6 — 71.7 73.3 33 — 1 CA5 min 69.5 71.3 71.7 55 75.7 — 71.4 — 60.7 50.9 — — ΔCA 5.9 4.7 4.3 12.8 5.9 — 4.2 — 11 22.4 — — Benefit Color T T T W T W T W T W T — 2 change imme- diately after wetting Droplet Droplet Droplet Contin- col- imme- col- uous lapsed diately lapsed film not after collapsed after formed ~30 s ~30 s Benefit Skin + + + − + − + − + − + − 3 affinity (NO flakiness+, flakiness−) *= comparative formula

Example 4: Comparison Study of Viscosity Increase of Compositions Comprising PU and Crosslinked Starch

(28) Formulas 1 to 11, A, B and C of Table 5 are prepared as indicated.

(29) Viscosity is evaluated as follows:

(30) The measuring ladle of the viscosimeter RHEOMAT 180 is filled with the analyzed formula while preventing air from entering. The set to zero is done before measurement; then the viscosity of the formula is measured under the following parameters: Mode: MANUAL Measuring system: 75 Rotation speed: 200 rpm

(31) The viscosity value is read after 10 minutes of rotation of the measuring instrument.

(32) It corresponds to the following formula:
Viscosity (measured)=(Ktau×M)/R wherein R=200 rpm, Ktau=5.46 (for system 71 or M1), 54.77 (for system 72 or M2), 318 (for system 73 or M3), 1330.4 (for system 74 or M4), 5159.8 (for system 75).

(33) In details, the inventors first calculate M in the above equation with Ktau (system 75, i.e. Ktau=5159.8) and measured viscosity.

(34) Then, the real viscosity (in mPa.$) could be calculated with proper Ktau and M.

(35) As illustration, if we take formula A of group 2, the measured viscosity with M2 was 20. Thus, by using the above formula, we obtain 20=(5159.8×M)/200, thus M=(20×200)/5159.8=0.775.

(36) Then, real viscosity is equal to (54.77−proper Ktau for M2−x 0.775)/200=0.211 Pa.Math.s, thus 211 mPa.Math.s.

(37) The results are in Table 5 below:

(38) TABLE-US-00005 TABLE 5 Hydroxy- Acrylates/ Poly- PU-35 PU-32 PU-2 + propyl C10- acrylate (Bay- (Bay- PMMA starch 30 alkyl cross- cusan cusan PU-2 (Hybridur phosphate acrylate polymer-6 C C (Carfil 875 of (Structure (Carbopol (Sepimax FLA 1004) 1003) 9235) Evonik) XL) Ultrez-21) Zen) Group 1 6% 1 2 1% 3 20.5% 4 20.5% 6% 5 20.5% 1% Group A 20.5% 2 6 20.5% 6%  7 20.5% 2% Group B 20.5% 3 8 20.5% 6% 9 20.5% 1% Group C 19.5% 4 10  19.5% 6% 11  19.5% 2%  Formula Viscosity (mPa .Math. S) Group 1 2991 1 2 4770 3 94 4 8689 5 4641 Group A 211 2 6 2413 7 2163 Group B 163 3 8 10907 9 5853 Group C 103 4 10  18307 11  6059

(39) The results show that the combination of PU-35 with hydroxypropyl starch phosphate (formula 4 in group 1) shows a higher viscosity than a formula comprising PU-35 dispersion only (formula 3 in group 1) and than a formula comprising hydroxypropyl starch phosphate-water dispersion only (formula 1 in group 1); this demonstrates that both ingredients together achieve a synergy on the increase of viscosity.

(40) To the contrary, the combinations of polyurethane and acrylates/C10-30 alkyl acrylate (formulas 5 of group 1 and 9 of group 3) or of polyurethane and polyacrylate crosspolymer-6 (formulas 7 of group 2 and 11 of group 4) did not show the same way of synergy nor the same strength of viscosity.

Example 5: Comparison Study of Films Comprising PU and Crosslinked Starch, and PU and Polyacrylate Derivatives

(41) Formulas 1 to 12 of Table 4 are prepared as indicated.

(42) The contact angle for each formula was measured as described in example 3. The peel off was evaluated as described in example 1.

(43) The results are in Table 6 below.

(44) It results that the formula according to the invention is the only one which provides peel off and the right contact angle.

(45) TABLE-US-00006 TABLE 6 Cream Film-former Formula CA0 CA5Min Peel off Second skin PU-35 + F1 82.1 76.3 √ cream cross-linked according to starch the invention Lotus cream Sunspheres F2 45 — x powder + silica + Emulium mellifera Gel cream CARBOMER F3 — — x INCI F2 (lotus cream) F1 F3 (gel cream) SODIUM HYDROXIDE 0.06 TETRASODIUM EDTA 0.2 DISODIUM EDTA 0.1 SODIUM HYALURONATE 0.01 BETAINE 2 Genecare OSMS BA, Danisco) DICAPRYLYL CARBONATE 2 (Cetiol CC, Cognis) SILICA 1.5 SILICA SILYLATE 0.5 (VM-2270, Dow Corning) FRAGRANCE 0.14 PVP 0.3 (PVP K30L, ISP) HYDROXYETHYLCELLULOSE 0.4 (Natrosol 250 HHR CS, Ashland) XANTHAN GUM 0.2 (Keltrol CG, CP Kelco) XANTHAN GUM 0.05 (Keltrol CG-T, CP Kelco) CARBOMER 0.3 (Ashland 980 MS Carbomer, ashland) ACRYLATES/C10-30 ALKYL ACRYLATE 0.2 CROSSPOLYMER (Pemulen TR-1, Lubrizol) AMMONIUM POLYACRYLOYLDIMETHYL 0.2 TAURATE (Hostacerin AMPS, Clariant) XANTHAN GUM (and) CERATONIA SILIQUA 0.05 (CAROB) GUM (Nomcort CG, Nisshin Oillio) STYRENE/ACRYLATES COPOLYMER 1 (Sunspheres powder, Rohm & Haas) AMMONIUM 0.9 ACRYLOYLDIMETHYLTAURATE/STEARETH- 25 METHACRYLATE CROSSPOLYMER (Aristoflex HMS, Clariant) POLYURETHANE-35 50 (Baycusan C 1004) HYDROXYPROPYL STARCH PHOSPHATE 6 (Structure XL) Preservatives Qs Qs Qs CYCLOHEXASILOXANE 3 DIMETHICONE (and) DIMETHICONOL 1 DIMETHICONE (and) 1 DIMETHICONE/POLYGLYCERIN-3 CROSSPOLYMER (KSG-710, Shin Etsu) ACRYLATES/POLYTRIMETHYLSILOXYMETH 2 ACRYLATE COPOLYMER (Dowsil FA 4002 ID silicone acrylate, Dow Corning) BUTYLENE GLYCOL 7 ALCOHOL 3 5 5 WATER 58.3 32.35 69.0398 GLYCERIN 5 0.4 8 PROPYLENE GLYCOL 3 CAPRYLYL GLYCOL 0.3 PROPANEDIOL 2.5 PEG-40 HYDROGENATED CASTOR OIL 0.5 (Sympatens-TRH/400 (1), Kolb) DISODIUM STEAROYL GLUTAMATE 0.3 (Amisoft HS 21P, Ajinomoto) POLYGLYCERYL-6 DISTEARATE (and) 3 JOJOBA ESTERS (and) CETYL ALCOHOL (and) POLYGLYCERYL-3 BEESWAX (Emulium Mellifera MB, Gattefosse) TOCOPHERYL ACETATE 0.5 0.5