USE OF SPECIFIC POLYMERS TO BRING ABOUT AN ANTI-POLLUTION EFFECT

Abstract

The present invention relates to the use of a polymer or of a cosmetic product comprising said polymer, and additionally other known cosmetic ingredients, to bring about an anti-pollution effect on human skin or on human hair, especially to protect human skin or human hair from dust, wherein the polymer is a cationic, anionic or non-ionic polymer, and wherein the polymer has a solubility in water of at least 0.01 g of polymer in 100 g of water at 20 C. at least at a pH in the range between 4 and 9.

Claims

1. A polymer or a cosmetic product comprising a polymer and additionally other known cosmetic ingredients for use to bring about an anti-pollution effect on human skin or on human hair, wherein the polymer has a solubility in water of at least 0.01 g of polymer in 100 g of water at 20 C. at least at a pH in the range between 4 and 9, and wherein the polymer is selected from the group consisting of polyacrylic acid, polyacrylic acid comprising at most 1% by weight of repeating units which have been derived from a monomer comprising at least two polymerizable, ethylenically unsaturated double bonds to effect branching or crosslinking, a copolymer of methacrylic acid and ethyl acrylate, which optionally also comprises repeating units which have been derived from at least one monomer selected from the group consisting of acrylic acid, methacrylamide, an alkyl acrylate having 2 to 30 carbon atoms in the alkyl group, and an alkyl methacrylate having 2 to 30 carbon atoms in the alkyl group, an ester of methacrylic acid with a C12- to C30 fatty alcohol, wherein the fatty alcohol has been ethoxylated with 1 to 100 ethylene oxide units, and a monomer comprising at least two polymerizable ethylenically unsaturated double bonds, to effect branching or crosslinking, and a copolymer of vinylpyrrolidone with at least one further ethylenically unsaturated polymerizable monomer, wherein a proportion of vinylpyrrolidone in said copolymer is at most 90% by weight, wherein in the case that the polymer comprises repeating units derived from acrylic acid or methacrylic acid, said repeating units are present as free acids or as salts.

2. The cosmetic product according to claim 1, wherein the monomer comprising at least two polymerizable ethylenically unsaturated double bonds is pentaerythritol triallyl ether.

3. The cosmetic product according to claim 1, wherein the polymer is a copolymer of vinylpyrrolidone with at least one further ethylenically unsaturated polymerizable monomer, wherein the proportion of vinylpyrrolidone in said copolymer is at most 90% by weight, and wherein the at least one further ethylenically unsaturated polymerizable monomer is selected from the group consisting of vinylimidazole, methylvinylimidazolium together with any anion, acrylamide, and methacrylamide.

4. The cosmetic product according to claim 3, wherein the anion is selected from the group consisting of chloride and (H.sub.3COSO.sub.3).sup..

5. The cosmetic product according to claim 1, wherein the polymer preferably has a glass transition temperature of at least 70 C.

6. The cosmetic product according to claim 1, wherein the polymer has an average molar mass (weight average Mw) of at least 100 000 g/mol.

7. The cosmetic product according to claim 1, wherein the polymer is selected from the group consisting of polyacrylic acid comprising at most 1% by weight of repeating units derived from a monomer comprising at least two polymerizable, ethylenically unsaturated double bonds to effect branching or crosslinking, a copolymer composed of 30-60% by weight ethyl acrylate, 30-60% by weight methacrylic acid, 5-30% by weight methacrylamide, 0.1-10% by weight C18-alkyl-(EO)25 methacrylates, and 0.01-1.0% by weight pentaerythritol triallyl ether, a copolymer composed of 30-60% by weight ethyl acrylate and 40-70% by weight methacrylic acid, a copolymer composed of 40-60% by weight ethyl acrylate, 30-50% by weight methacrylic acid, 5-15% by weight acrylic acid, and 0.01-1.0% by weight pentaerythritol triallyl ether, a terpolymer composed of 60-80% by weight tert-butyl acrylate, 5-20% by weight ethyl acrylate, and 10-30% by weight methacrylic acid, a copolymer composed of 40-65% by weight vinylpyrrolidone, 25-35% by weight methacrylamide, 5-20% by weight vinylimidazole, and 5-20% by weight quaternary (methylated) vinylimidazole, and a copolymer composed of 50-70% by weight vinylpyrrolidone, 20-40% by weight methacrylamide and 1-10% by weight vinylimidazole.

8. The cosmetic product according to claim 1 wherein the polymer is present in the product at a concentration of 0.01 to 5% by weight.

9. The cosmetic product according to claim 8, comprising at least water as the additional other known cosmetic ingredient in an amount of at least 20% by weight and wherein the polymer is present completely dispersed, suspended, dissolved, or swollen in water at 20 C.

10. The cosmetic product according to claim 1, wherein the cosmetic product serves to protect, to care for, and/or to cleanse skin or to care for and/or to cleanse hair.

11. The cosmetic product according to claim 1, wherein the cosmetic product is selected from the group consisting of an aqueous polymer solution, an emulsifier-free emulsion, and an emulsion.

12. A method for bringing about an anti-pollution effect on human skin or on human hair, or comprising application of a cosmetic product as defined in claim 1 on human skin or such human hair which require an anti-pollution effect.

13. The method of claim 12 wherein the anti-pollution effect is protected from dust.

14. The method of claim 13 wherein the dust is a fine dust.

Description

EXAMPLES

[0192] A1: Test Methods for Testing the Anti-Pollution Effect

[0193] In order to test whether substances have an anti-pollution effect on human skin, especially protection of human skin from dust, especially fine dust, the test method described below was employed.

[0194] Activated carbon (obtained from Carl Roth GmbH, Karlsruhe, Germany) was used as protection model. Activated carbon is microcrystalline carbon. There is a difference in size between the particles of activated carbon and the particles of fine dust. Nevertheless, activated carbon is a suitable model substance for fine dust. Activated carbon is also suitable for investigations of human subjects since it is toxicologically safe compared to many other substances.

[0195] A test setup was developed for the method in order to be able to investigate the anti-adhesive effect on the skin of the substances to be tested. The apparatus used in this case served the defined application of activated carbon to the underarms of human subjects. In this case, a defined amount of activated carbon was placed in a chamber and, under standardized pressure, applied to the skin of the underarm via an air stream.

[0196] The test substance was applied to the skin precleansed with ethanol. For this purpose, a standardized amount of the test substance was applied to a defined area of the skin of the underarm (if not stated otherwise below, this was 2 mg/cm.sup.2). Firstly, prior to the treatment, each skin site was recorded by a photographic recording. After application of the test substance, a further photograph of the same site was taken. After a drying time of 10 min, the activated carbon was applied by a blast of air. After treatment with activated carbon, a further photograph was recorded. These images served to determine the amount of dirt (activated carbon) adhering to the skin. This process was carried out for each test substance on four different sites of the underarm.

[0197] After the specified measurements on all four sites of the underarm had been carried out, the differences in the ability of the adhering dirt (activated carbon) to be washed off were tested. For this purpose, a defined amount of water was applied to the respective skin sites.

[0198] Consistent light conditions were ensured when recording the photographs. Comparison of the treated areas was conducted by means of a suitable computer program. For this purpose, the average grayscale value was taken as a baseline. The value of the skin with adhering activated carbon was correspondingly subtracted from the value of the same skin site without activated carbon. The higher the difference in value obtained, the more activated carbon had stuck to the skin. Subsequently, the average value and the standard deviation of all subjects (if not stated otherwise below, this was 11), was calculated per subject. The ability to be washed off was determined by subtracting the average grayscale value after washing off from that prior to the washing off. The results were stated relative to the results of untreated skin.

[0199] A1-1: Test Methods for Testing the Anti-Pollution Effect on Hair

[0200] In a similar process, the effect on hair was investigated: individual hairs were treated with a test substance and were then exposed to a defined amount of activated carbon via an air stream in a chamber using an appropriate apparatus. The individual hairs were photographed with a digital microscope and the degree of soiling was quantified by image evaluation. The individual hairs were rinsed with a defined amount of water and photographed again by digital microscopy and the corresponding soiling determined.

[0201] A2: Method for Determining the Glass Transition Temperature Tg

[0202] The glass transition temperature Tg was determined as follows. Polymers, which were present as aqueous dispersions, were freeze-dried prior to measurement. Like all other polymers, they were then subjected to a drying process in the DSC instrument used (TA Instruments DSC Q100). The samples were subjected to an isothermal run at 80 C. for 1 hour. After this run, further 30 minute isothermal runs were carried out until a constant weight of the sample was attained. The determination of the polymer glass transition temperatures Tg was conducted with the same instrument in MDSC mode (DSC measurement). Standard aluminum pans which comprised 2 to 10 mg of the dried polymer were heated in the temperature range of 50 C. to 200 C. with a heating rate of 1 K/min and a modulation rate of 0.5 K/min. The reversible heating signal was evaluated according to the standard glass/step transition of the Universal Analysis 2000 software (Version 4.7A, TA Instruments, Eschborn/Germany). The glass transition temperature was specified as the inflection point of the curve.

[0203] B: Substances Tested

[0204] Polymers 1 to 9 described below were tested. % signifies % by weight.

[0205] First Group: Polymers or Copolymers of Acrylic Acid or of Methacrylic Acid

TABLE-US-00001 Polymer No. Name More accurate designation Polymer 1 Carbomer Acrylic acid, crosslinked (with less than 1% (INCI name by weight crosslinker) for polyacrylic acid) Polymer 2 An acrylate A copolymer composed of ethyl acrylate copolymer (30-60%), methacrylic acid (30-60%), methacrylamide (5-30%), C18-alkyl-(EO)25 methacrylate (0.1-10%), pentaerythritol triallyl ether (0.01-1.0%) Polymer 3 An acrylate A copolymer composed of ethyl acrylate copolymer (30-60%) and methacrylic acid (40-70%) Polymer 3a An acrylate A copolymer composed of ethyl copolymer acrylate (40-60%), methacrylic acid (30-50%), acrylic acid (5-15%), pentaerythritol triallyl ether (0.01-1.0%) Polymer 4 An acrylate A terpolymer composed of tert-butyl acrylate copolymer (60-80%), ethyl acrylate (5-20%) and methacrylic acid (10-30%)

[0206] Note on the designation: Acrylate is understood to mean acrylic acid and methacrylic acid and salts and esters thereof

[0207] Second Group: Cationic Polymers

TABLE-US-00002 Polymer No. Name More accurate designation Polymer Polyquaternium- A copolymer composed of vinylpyrrolidone 5 68 (INCI) (40-65%), methacrylamide (25-35%), vinylimidazole (5-20%) and quaternary (methylated) vinylimidazole (5-20%)

[0208] Third Group: Caprolactam-Containing Polymers

TABLE-US-00003 Polymer No. Name More accurate designation Polymer 6 Polyvinylcaprolactam N-Vinylcaprolactam homopolymer

[0209] Fourth Group: Copolymers of Vinylpyrrolidone (VP), Vinylimidazole (VI) and Optional Further Monomers

TABLE-US-00004 Polymer No. Name More accurate designation Polymer 7 VP/methacrylamide/ A copolymer composed of VI copolymer vinylpyrrolidone (50-70%), methacrylamide (20-40%) and vinylimidazole (1-10%)

[0210] Comparative Group: Polycarbonates and Polyurethanes

TABLE-US-00005 Polymer No. Name More accurate designation Polymer 8 Hydrogenated dimer Hydrogenated dimer dilinoleyl/ dilinoleyl/dimethyl dimethyl carbonate copolymer carbonate copolymer Polymer 9 Polyurethane-39 Polyurethane (INCI)

[0211] C: Properties of the Polymers Tested and Test Results

[0212] (Anti-adhesion/washability measured with samples with 1% by weight polymer in water):

TABLE-US-00006 Fewer Anti-adhesive particulate effect substances on Average compared to the skin after Solubility at molar mass untreated washing (at least at least 100000 g/mol Glass transition skin (at least least 5%) Polymer 0.1 g/100 g (weight temperature 5% lower compared to Number of water average Mw) above 70 C. adhesion) untreated skin 1 yes yes yes yes yes 2 yes yes yes yes yes 3 yes yes yes yes yes 3a yes yes yes yes yes 4 yes yes yes yes yes 5 yes yes yes yes yes 6 yes yes yes yes yes 7 yes yes yes yes yes 8 no no no no no 9 yes no no no no

[0213] These results show that polymers 1 to 7 bring about the desired anti-pollution effect, but polymers 8 and 9 do not. It can be assumed that those polymers that effect protection from dust, also effect continuous and general protection from air pollution, not only from dust, but even from other substances which constitute air pollution.

[0214] C-1: Test Results on Hair

TABLE-US-00007 Anti-adhesive effect compared Fewer particulate substances to untreated hair (at least 5% on the hair after rinsing (at Polymer lower adhesion in comparison least 5%) compared to Number to untreated hair) untreated hair 2 no yes 3 yes yes 5 yes yes 9 no no

[0215] These results show that polymers 3 to 5 bring about the desired anti-pollution effect even on hair, but not the polymer 9.

[0216] D: Formulations

[0217] The following formulations show by way of example how cosmetic products may be composed, comprising the aforementioned polymers, and thus should bring about an anti-pollution effect.

[0218] The numerical figures refer to % by weight.

[0219] Sometimes the polymers are introduced into the formulation already as a solution or in other non-pure form. In these case, the active content of polymer is additionally stated.

[0220] Formulation 1: Semisolid Gel Gel (Cream), Formulation 2-7: Low-Viscosity to Free-Flowing Gel Lotions

TABLE-US-00008 Chemical name/ Constituents compostion (%) 1 2 3 4 5 6 7 Polymer 1 1.00 Polymer 2 3.30 (= 1.0 active content) Polymer 3 3.30 (= 1.0 active content) Polymer 4 1.00 Polymer 5 5.00 (= 1.0 active content) Polymer 6 2.50 (= 1.0 active content) Polymer 7 5.00 (= 1.0 active content) Demin. water Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Cetiol Undecane (and) 2.50 1.00 0.50 Ultimate tridecane Cyclomethicone Cyclomethicone 1.00 1.00 0.50 Tocopherol Tocopherol 0.10 0.20 0.50 (Vitamin E) Cegesoft PS Olus Oil 0.2 0.1 6 Tinosorb M Methylen Bis- 5.00 10.00 Benzotriazolyl Tetramethylbutylphenol (and) Aqua (and) Decyl Gluceside (and) Propylene Glycol (and) Xanthan Gum Z-Cote HP1 Zinc Oxide (nano), 1.00 1.00 4.00 Triethoxycaprylylsilane T-80AS Titanium Dioxide, 10.00 5.00 10.00 2.00 silica, triethoxy caprylylsilane D-Panthenol Panthenol 0.5% USP Glycerol Glycerol 5.00 1.00 5.00 1.00 0.5 1.00 PatcH2O Water (and) glycerol 3.00 1.5 3.00 (and) trehalose (and) urea (and) senne (and) pentylene glycol (and) glyceryl polyacrylate (and) algin (and) caprylyl glycol (and) sodium hyaluronate (and) pullulan (and) disodium phosphate (and) potassium phosphate Hydagen GG Glyceryl glucoside 5.00 12.00 and glycerol PURISOFT Water (and) glycerol 3.00 3.00 3.00 POE LS 9726 (and) Moringa pteryosperma seed extract Talc FM SSA Talc (and) 5.00 1.00 (K.S. Pearl) dimethicone Mearlmica Mica, lauroyl lysine 5.00 1.00 treated SVA Pearl-Glo SF Bismuth oxychloride 5.00 5.00 PG1099 SA-SB-300 Silica 2.00 1.00 (Miyoshi kasei) Dow Corning Dimethicone/vinyl 2.00 1.00 9701 dimethicone Cosmetic crosspolymer (and) powder (Dow Silica Corning) STR-100A-LP Titanium dioxide 5.00 (Sakai (nano), hydrated Chemical silica, dimethicone/ Industry) methicone copolymer, aluminum hydroxide Timica Terra Mica, titanium 1.00 1.00 0.5 1.00 0.5 0.5 1.00 White dioxide MN4501 Timica Terra Mica, iron oxides, 0.1 0.1 Brown titanium dioxide MN4509 Timica Terra Mica, iron oxides, 0.1 0.1 0.1 0.1 Yellow titanium dioxide MN4502 Flamenco Mica, titanium 0.5 1.00 Silk Blue dioxide 630M KOH 20% Potassium to adjust to pH 6.5-7.0 hydroxide Euxyl K 320 2-Phenoxyethanol, 1.00 1.00 1.30 1.30 1.00 methyl 4- hydroxybenzoate, ethyl 4- hydroxybenzoate Protectol PE Phenoxyethanol 1.00 1.00 Sensiva SC Ethylhexylglycerin 0.5 0.50 50 pH 6.8 6.6 6.5 6.4 6.5 6.6

[0221] Formulations 8-13: Gel Lotions that can be Applied by Pump Spray and Aerosol Spray as Skin Protection Agent and/or as Top Coat and/or Base Coat for Additive Use in Skin Care Preparations

TABLE-US-00009 Chemical name/ Constituents compostion (%) 8 9 10 11 12 13 Polymer 3 3.30 (= 1.65 (= 2.20 0.33 (= 1.65 (= 0.33 (= 1.0 active 0.5 active 0.1 active 0.5 active 0.1 active content) content) content) content) content) Tinovis GTC Hydrophobically 0.33 (= 0.33 (= 0.33 (= UP modified copolymers 0.1 active 0.1 active 0.1 of acrylic acid content) content) active Acrylate/Beheneth-25 content) Methacrylate Copolymer ~30% aqueous solution Demin. water Water to 100 to 100 to 100 to 100 to 100 to 100 Cetiol Undecane (and) 1.00 1.00 0.50 Ultimate tridecane Cyclomethicone Cyclomethicone 0.50 Tocopherol Tocopherol (Vitamin 0.10 0.20 0.50 E) Cegesoft PS Olus Oil 0.2 0.1 6 Tinosorb M Methylen Bis- 1.00 1.00 Benzotriazolyl Tetramethylbutylphenol (and) Aqua (and) Decyl Glucoside (and) Propylene Glycol (and) Xanthan Gum Z-Cote HP1 Zinc Oxide (nano), 1.00 1.00 Triethoxycaprylylsilane T-80AS Titanium Dioxide, 1.00 silica, triethoxy caprylylsilane D-Panthenol Panthenol 0.5 0.5 USP Glycerol Glycerol 3.00 5.00 1.00 2.0 1.00 PatcH2O Water (and) glycerol 1.5 3.00 (and) trenalose (and) urea (and) serine (and) pentylene glycol (and) glyceryl polyacrylate (and) algin (and) caprylyl glycol (and) sodium hyaluronate (and) pullulan (and) disodiurn phosphate (and) potassium phosphate Hydagen GG Glyceryl glucoside 5.00 12.00 and glycerol PURISOFT Water (and) glycerol 3.00 1.00 1.50 POE LS 9726 (and) Moringa pteryosperma seed extract Talc FM SSA Talc (and) 1.00 1.00 (K.S. Pearl) dimethicone Mearlmica Mica, Lauroyl Lysine 2.00 1.00 treated SVA Pearl-Glo SF Bismuth oxychloride 1.00 PG1099 SA-SB-300 Silica 0.5 (Miyoshi kasei) Dow Corning Dimethicone/vinyl 2.00 1.00 9701 Cosmetic dimethicone powder (Dow crosspolymer (and) Corning) Silica STR-100A-LP Titanium Dioxide 5.00 (Sakai (nano), Hydrated Chemical Silica, Dimethicone/ Industry) Methicone Copolymer, Aluminum Hydroxide Timica Terra Mica, titanium dioxide 1.00 0.5 1.00 0.5 0.5 White MN4501 Timica Terra Mica, Iron Oxides, 0.1 0.1 Brown Titanium Dioxide MN4509 Timica Terra Mica, Iron Oxides, 0.1 0.1 0.1 Yellow Titanium Dioxide MN4502 Flamenco Silk Mica, titanium dioxide 0.5 1.00 Blue 630M KOH 20% Potassium hydroxide to adjust to pH 6.5-7.0 Euxyl K 320 2-Phenoxyethanol, 1.00 1.30 1.30 1.00 methyl 4- hydroxybenzoate, ethyl 4- hydroxybenzoate Protectol PE Phenoxyethanol 1.00 1.00 Sensiva SC Ethylhexylglycerin 0.50 0.50 50 pH 6.8 6.6 6.5 6.4 6.5 6.6

[0222] Formulations 14-19: Creams

[0223] As Skin Protection Agent for Day Care, Baby Care, Facial Care and Body Care

TABLE-US-00010 Chemical name/ Constituents compostion (%) 14 15 16 17 18 19 Polymer 1 0.2 0.2 0.1 0.5 0.1 0.5 Tinovis GTC Hydrophobically 3.33 (= 1 1.65 (= 1.65 (= 0.33 (= 0.33 (= UP modified copolymers of active 0.1 active 0.5 0.1 0.1 acrylic acid content) content) active active active Acrylate/Beheneth-25 content) content) content) Methacrylate Copolymer ~30% aqueous solution Demin. water Water to 100 to 100 to 100 to 100 to 100 to 100 Emulgade PL Cetearyl Glucoside and 1.00 1.00 68/50 Cetearyl Alcohol Emulgade Sucrose Polystearate 1.50 Sucro Plus and Cetyl Palmitate Eumulgin VL Lauryl Glucoside (and) 1.50 75 Polyglycery1-2 Dipolyhydroxystearate (and) Glycerol Eumulgin Disodium Cetearyl 0.2 Prisma Sulfosuccinate AXOL C 62, Glyceryl Stearate 1.00 Evonik Citrate Cetiol Undecane (and) 2.50 2.50 1.25 5.00 0.50 2.50 Ultimate tridecane Cyclomethicone Cyclomethicone 2.50 0.50 Tocopherol Tocopherol (Vitamin E) 0.10 0.20 0.50 Cegesoft PS 6 Olus Oil 0.20 0.1 Tinosorb M Methylene Bis- 1.00 5.00 Benzotriazolyl Tetramethylbutylphenol (and) Aqua (and) Decyl Glucoside (and) Propylene Glycol (and) Xanthan Gum Z-Cote HP1 Zinc Oxide (nano), 1.00 1.00 Triethoxycaprylylsilane T-80AS Titanium Dioxide, silica, 1.00 triethoxy caprylylsilane D-Panthenol Panthenol 0.50 0.50 USP Glycerol Glycerol 3.00 5.00 1.00 2.00 1.00 PatcH2O Water (and) glycerol 1.50 3.00 (and) trehalose (and) urea (and) serine (and) pentylene glycol (and) glyceryl polyacrylate (and) algin (and) caprylyl glycol (and) sodium hyaluronate (and) pullulan (and) disodium phosphate (and) potassium phosphate Hydagen GG Glyceryl glucoside and 5.00 5.00 glycerol PURISOFT Water (and) glycerol 3.00 1.00 1.50 POE LS 9726 (and) Moringa pteryosperma seed extract Talc FM SSA Talc (and) dimethicone 1.00 1.00 (K.S. Pearl) Mearlmica Mica, Lauroyl Lysine 2.00 1.00 treated SVA Pearl-Glo SF Bismuth oxychloride 1.00 PG1099 KOH 20% Potassium hydroxide to adjust to pH 6.5-7.0 Euxyl K 320 2-Phenoxyethanol, 1.30 1.30 1.00 1.00 methyl 4- hydroxybenzoate, ethyl 4-hydroxybenzoate Protectol PE Phenoxyethanol 1.00 1.00 Sensiva SC Ethylhexylglycerin 0.50 0.50 50 pH 6.8 6.6 6.5 6.4 6.5 6.6