GB1579647A

GB1579647A - Anti-sunburn polymers and cosmetic compositions containing these

Info

Publication number: GB1579647A
Application number: GB2122877A
Authority: GB
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1976-07-29
Filing date: 1977-05-19
Publication date: 1980-11-19
Also published as: FR2359857B2; CA1043495A; NL7706415A; DE2734149A1; JPS5316093A; SE432428B; IT1116760B; NL179184C; SE7705635L; JPS5825324B2; CH610338A5; BE854748R; FR2359857A2; NL179184B

Description

(54) ANTI-SUNBURN POLYMERS AND COSMETIC COMPOSITIONS CONTAINING THESE (71) We, L'OREAL, a French Body Corporate, of 14 Rue Royale, 75008 Paris, France, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention provides polymers comprising, in their macromolecular chain, at least one, and preferably several units corresponding to the formula:

in which the substituent F1 represents one of the radicals having the following formulae:

The polymers of the present invention generally have a number average molecular weight of 2,000 to 1,000,000.

These polymers exhibit the characteristic of absorbing not only the radiations of the "erythematous zone" (between 280 and 315 nm) but also the radiations reponsible for bronzing (up to 350 nm), which makes it possible to obtain good protection both against sunburn and against the effect of U.V. rays between 280 and 350 nm.

The polymers according to this invention are preferably copolymers (bipolymers, terpolymers and the like), that is to say they simultaneously contain units of the formula II and one or more other units derived from ethylenically unsaturated monomers.

The ethylenically unsaturated monomers which can be used in producing the copolymers according to the invention can be chosen to impart various properties to the anti-sunburn copolymers.

Amongst the preferred comonomers there may in particular be mentioned N vinylpyrrolidone, N - methacryloyl, D - glucosamine, dimethylaminoethyl methacrylate, stearyl methacrylate, stearyl acrylate and vinyl stearate. The first three comonomers favour solubility in aqueous solutions and the last three favour solubility in oils.

Copolymers according to the invention can be represented by the following general formula:

ana

in which: F, has the same meaning as above, R' represents a hydrogen atom or a methyl radical and Y represents a radical chosen from the group consisting of:

with X representing an optionally quaternised dimethylaminoethyl radical, and C,8H37 or Y represents

A being a glucosamine radical.

According to this invention, the anti-sunburn polymers usually contain from 15 to 100%, and preferably 20 to 80%, by weight of units of the formula 11 relative to the total weight of the polymer.

The present invention also provides a process for the preparation of the new anti-sunburn polymers of the formulae 11 and III which comprises: polymerising a monomer, called "solar filter monomer", of the following formula: CH2-CH-COMNH-CH2-F, (lay) F, having the same meaning as above, alone or with one or more other comonomers.

The solar filter monomer can be prepared by reacting N - methylolacrylamide with the aromatic compound F,H in the presence of sulphuric acid, in the cold.

The polymerisation reaction can be carried out in accordance with the conventional methods of polymerisation, that is to say in bulk, in solution, in suspension or in emulsion, using conventional polymerisation initiators.

The molecular weight of the anti-sunburn polymers according to the invention can be regulated by introducing during the polymerisation, small amounts (e.g. 0.05 to 0.15';/, by weight) of a chain regulator such as aldehydes, for example butyraldehyde, or chlorinated substances, for examples chloroform, bromoform and carbon tetrachloride.

At the end of the polymerisation, the polymers obtained can, if desired, be subjected to a purification, for example by treating them with ion exchange resins.

The present invention also provides anti-sunburn cosmetic compositions-hich contain at least one polymer of this invention as the active substance which filters U.V. rays together with a cosmetically acceptable vehicle.

These cosmetic compositions can be in various forms which depend on the use for which they are intended. Preferably, these compositions are in the form of aqueous emulsions, lotions, creams, milks, gels or aerosols. These compositions can also be in the form of aqueous or aqueous-alcoholic (e.g. ethanolic or isopropanolic) solutions or in the form of oily solutions.

When the compositions according to the invention are in the form of aerosols, the latter are packaged in aerosol containers in the presence of a propellant gas which is preferably halogenated hydrocarbon or a mixture of such hydrocarbons, such as the mixtures of trichlorofluoromethane with dichlorodifluoromethane.

In these cosmetic compositions, the concentration of anti-sunburn polymers as descibed above can vary because it depends on the degree of protection which it is desired to obtain. However, preferably the concentration of anti-sunburn polymers is from 0.2 to 20% by weight based on the total weight of the composition.

The compositions can also contain conventional ingredients such as fatty materials (e.g. oils, fats and waxes), emulsifiers, surface-active products, perfumes, silicone oils, pigments, dyestuffs and preservatives.

The introduction of coloured pigments into the compositions makes it possible to dye the epidermis and to mask skin defects.

On applying the compositions according to the invention to the skin, a film is formed which has a good affinity for the epidermis and provides excellent protection of the skin against sunrays.

In the Examples which follow and which further illustrate the present invention, the absorption power of the filter has been defined in terms of the Ksp, which is a function of the amount of filtering substance contained in the sample, of the measured optical density and of a constant which depends on the apparatus.

The definition of the Ksp is given in "Introduction to Electronic Absorption Spectroscopy in Organic Chemistry" Gillam and Stern, published by Arnold, London, 1954, page 10.

K K specific=Ksp-- c where d K= l and c=concentration of the solution in g/ml d=measured optical density l=thickness of the apparatus cell expressed in cm.

EXAMPLE A Preparation of the filter monomer 2-[(2'-hydroxy-5'-methyl acrylamidomethyl)-phenyl]-2H-benzotriazole of the formula:

192 g of pure sulphuric acid and 72 g of 2 - [(2' - hydroxy - 5' - methyl) phenyl] - 2H - benzotriazole are introduced into a flask under nitrogen. The mixture is cooled to OOC and 31.5 g of N - hydroxymethyl - acrylamide are then added thereto. The mixture is allowed to return to ambient temperature and stirring is continued for 18 hours. The mixture is poured into water and then filtered. After recrystallization from chloroform, 55 g of pure product are obtained.

Yield: 56%.

Melting point=2040C.

#max1 (THF)= 302 nm Ksp = 55,000 #max2 (THF)= 339 nm Ksp =57000 The acrylamidomethyl derivative of 2 - phenyl - benzimidazole can be prepared analogously.

EXAMPLE B Preparation of a copolymer of 2-[(acrylamidomethyl-2'-hydroxy-5'-methyl) phenyl]-2H-benzotriazole and 2-N,N-dimethylaminoethyl methacrylate quaternised with dimethyl sulphate 2 g of anti-sunburn monomer prepared according to Example A, 8 g of 2-N,Ndimethylaminoethyl methacrylate quaternised with dimethyl sulphate, 20 g of dimethylformamide and 1 g of azo-bis-isobutyronitrile are introduced into a flask under nitrogen. The mixture is heated at 800C for 24 hours, then allowed to cool, diluted with 20 ml of methanol and poured dropwise into 500 ml of acetone. The polymer is filtered and dried under reduced pressure. 8 g of water-soluble copolymers are obtained.

Yield: 80%.

Amax"DMF,=298 nm, Ksp=6,200 #max2 (DMF)=335 nm Ksp -5200 A copolymer of the acrylamidomethyl derivative of 2 - phenyl benzimidazole and 2-N,N-dimethylaminoethyl methacrylate quaternised with dimethyl sulphate can be prepared analogously.

EXAMPLE C Preparation of a copolymer of 2[(acrylamidomethyl-2'-hydrnxy-5'-methyl)- phenyl]-2H-benzotriazole and stearyl acrylate.

50 g of filter monomer prepared according to Example A, 33.4 g of stearyl acrylate, 150 g of tetrahydrofurane and 5 g of azo-bis-isobutyronitrile are introduced into a flask. The mixture is heated at 800C for 9 hours and then poured into 7 litres of methanol. After filtering and drying under reduced pressure, 70 g of an oil-soluble copolymer are obtained.

Yield: 85%.

Amax, {THFI=303 nm, Ksp=28.300 Amax2 zTHF)=339 nm, Ksp=28.000 A copolymer of the acrylamidomethyl derivative of 2-phenyl-benzimidazole and stearyl acrylate can be prepared analogously.

EXAMPLE D An anti-sunburn cream was prepared by mixing the following ingredients: Polymer prepared according to Example B 15 g Cetyl/stearyl alcohol 2g Glycerol monostearate 4g Cetyl alcohol 4g "Vaseline" (Registered Trade Mark) oil 5 g Butyl stearate 5g Propylene glycol 7 g Silicone oil 0.125 g Non-ionic polymer of high molecular weight sold by Union Carbide under the Registered Trade Mark "Polyox", as a 5% strength solution in water 3.5 g Methyl p-hydroxybenzoate 0.3 g Perfume 0.5 g Water, q.s.p. 100 g EXAMPLE E An anti-sunburn oil was prepared by mixing the following ingredients: Polymer prepared according to Example C 10 g Perfume 0.4 g Butylated hydroxytoluene 0.0625 g Colza oil, q.s.p. 100 g

Claims

WHAT WE CLAIM IS:1. A polymer which comprises at least one unit of the formula:

in which F, represents a radical having the formula:
2. A polymer according to claim 1 which has a number average molecular weight of from 2,000 to 1,000,000.
3. A polymer according to claim I or 2 which is a copolymer comprising units derived from N-vinyl-pyrrolidone, N-methacryloyl D-glucosamine, dimethylaminoethyl methacrylate, stearyl methacrylate, stearyl acrylate and vinyl stearate.
4. A polymer according to claim 1, 2 or 3 which also comprises at least one unit of the formula:

in which R' represents a hydrogen atom or a methyl radical and Y represents a radical of the formula:

in which X represents an optionally quaternised dimethylaminoethyl radical or a C,8H37 radical, or Y represents a radical of the formula:

A being a glucosamine radical.
5. A polymer according to any one of claims 1 to 4 which contains 15 to 100% by weight of units of formula (II) based on the total weight of the polymer.
6. A polymer according to claim 5 which contains 20 to 80% by weight of units of formula (II), based on the total weight of the polymer.
7. A copolymer of 2 - [(acrylamidomethyl - 2' - hydroxy - 5' - methyl) phenyl] - 2H - benzotriazole and of 2 - N,N - dimethylaminoethyl methacrylate quaternised with dimethyl sulphate.
8. A copolymer of 2 - [(acrylamidomethyl - 2' - hydroxy - 5' - methyl) phenyl] - 2H - benzotriazole and stearyl acrylate.
9. Process for the preparation of a polymer as claimed in any one of the preceding claims which comprises polymerising an unsaturated derivative of the formula:

in which F, is as defined in claim 1 either alone or with one or more comonomers.
10. Process according to claim 9 substantially as hereinbefore described.
Il. A polymer as defined in claim 1 whenever prepared by a process as claimed in claim 9 or 10.
12. A cosmetic composition, which comprises at least one polymer as claimed in any one of claims I to 8 and 11 in a suitable cosmetic vehicle.
13. A composition according to claim 12 which contains the polymer in an amount from 0.2 to 20% by weight based on the total weight of the composition.
14. A composition according to claim 12 or 13 which is in the form of an aqueous or aqueous-alcoholic solution, an oil, a gel, cream, milk or aerosol.
15. A composition according to claim 12 substantially as described in Example D or E.