NL8700039A - COSMETIC PREPARATION INTENDED TO PROTECT THE SKIN FROM THE UNDESIRABLE EFFECTS OF ULTRAVIOLET RADIATION. - Google Patents

Description

N.0. 34,269. . 1

Cosmetic preparation, intended to protect the skin against the unwanted effects of ultraviolet radiation.

The invention relates to new cosmetic preparations, intended to protect the skin against the undesired effects of ultraviolet radiation, and in particular against the undesirable effects of sun exposure (burns and possibly tanning of the skin) .

It is known that ultraviolet radiation with a wavelength in the range of about 280-315 ran is responsible for skin inflations or erythema, which are observed when the human body is exposed to the sun's rays without protection. This wavelength region is sometimes referred to as "erythematous region".

It is also known that the ultraviolet rays responsible for skin tanning have a wavelength of about 315-400 nm.

There are known compounds which have the property of absorbing the ultraviolet radiation in the erythematous region, completely passing the radiation responsible for tanning, and the use of such compounds has already been proposed as "sunscreens". "in cosmetic preparations which favorably affect the appearance of a tanning of the skin while avoiding burns and irritations of the skin.

On the other hand, certain users wish to avoid tanning, and it has therefore been proposed to use filters in cosmetic preparations which to a greater extent form a shield for ultraviolet radiation in the wavelength range of 315-400 nm, optionally in combination with compounds that filter UV radiation in the erythematous region to prevent browning and burning of the skin at the same time.

The use of sunscreens, covalently bonded to polymers, has already been recommended, particularly in French patents 73.23254 and 76.23174. The presence in the form of polymers offers the advantage of reducing or eliminating the penetration of the filter compound into the organism through the epidermis, making it possible to avoid any risk of secondary toxic effects.

35 However, the continued investigation of such "anti-solar polymers" has shown that their use has certain drawbacks.

In order to obtain preparations with an increased filtering capacity, it is necessary to use considerable concentrations of the anti-sun polymer and this entails difficulties both at the stage of the preparation of the cosmetic preparations and in the use of these preparations at the skin.

In fact, if one wishes to achieve elevated concentrations, significant difficulties are encountered in solubilizing the polymers, which is a drawback with respect to the formulation. This drawback is all the more pronounced if, in order to obtain an increased filtering effect, the use of polymers of the homopolymer type, of which virtually every unit is substituted by a filter material, is envisaged.

In addition, the anti-sun cosmetic compositions obtained with such increased concentrations of anti-sun polymers are not satisfactory to the user because they are sticky and greasy upon contact, which is unpleasant.

It has now been found that, when appropriate measures are taken in the preparation of the anti-sun polymers, it is possible to obtain new compositions with a large amount of low molecular weight polymer molecules, thanks to which measures the above-described disadvantages can be avoided. .

The present invention relates to new cosmetic preparations, intended to protect the skin against the undesired effects of ultraviolet radiation, which as active ingredient filtering the ultraviolet radiation contains at least one polymer composition containing polymers with acrylamide units covalently bonded to an ultraviolet ray absorbing compound, optionally in combination with units derived from hydrophilic comonomers, the cosmetic compositions being characterized in that the polymers of said polymer composition have a molecular weight distribution such that at least 80% of the polymer molecules have a molecular weight of less than 20,000, the measurement of the molecular weights being carried out according to the size sorting chromatography, comparing with standard polystyrene samples.

The polymer compositions used according to the invention preferably have a molecular weight distribution such that at least 10% of the polymer molecules under the same conditions as indicated above have a molecular weight of more than 40,000. .¾ 3 ten.

The invention relates in particular to cosmetic preparations, as defined above, which are characterized in that the said polymer contains units of the formula 1, wherein X represents an aromatic group which imparts to the polymers an absorption of ultraviolet radiation in the wavelength range. , which can range from 280 to 400 nm, optionally in combination with units derived from hydrophilic comonomers with ethylenic unsaturation, with the proviso that the units of formula 1 make up at least 10% by weight of the polymer.

When the units derived from hydrophilic comonomers are present, the units of the formula 1 may comprise, for example, 10-99% by weight of the polymer.

The polymers present in the polymer composition used according to the invention are therefore, in particular, polymers which only contain units of the formula I, provided that in the same polymer molecule there are several different units corresponding to the different groups X, can be present.

It is known that the solar filters in the cosmetic preparations 20 are in the form of an in oil, in the form of solutions in water or water / alcohol, or in the form of solutions in water and / or oil in preparations in the form of emulsions.

The above-defined polymer compositions, containing only units of the formula I, are sufficiently soluble in the oils, and the preparation, with these polymers, of oil-containing cosmetic preparations does not present any particular difficulties.

On the other hand, in order to obtain a polymer composition which is soluble in water, it is necessary to copolymerize the "filter monomers" corresponding to the units of the formula I with hydrophilic comonomers.

The hydrophilic comonomers are selected in particular from N-vinylpyrrolidone, Ν, Ν-dimethylacryTamide, acrylic acid, methacrylic acid and monomers of the general formula 2, wherein M represents -O- or -NH-, x is a number of 2 or 3, R 1 represents -H or -CH 3 and R 2 represents -CH 3 or -C 2 H 5, with the proviso that the amino groups may be quaternized or in the form of a salt before or after the polymerization.

Among the comonomers of the general formula II, mention may be made, for example, of 2-N, N-dimethylaminoethyl methacrylate, 3-N, N-40 diethylamino-propyl methacrylamide, etc.

8700039; ΐ 4

The amino groups can be brought into the salt form with an inorganic acid such as, for example, hydrogen chloride or an organic acid such as lactic acid. They can also be quaternized with a classic quaternizing agent such as dimethyl sulfate, methyl chloride, chloroacetic acid, etc.

To prepare the polymeric compositions as defined above, monomers of the formula 3 wherein X has the above defined meaning are polymerized in a solution, optionally in the presence of hydrophilic comonomers with an ethylenic unsaturation, in the presence of a polymerization initiator, operating according to known methods to favorably influence the formation of low molecular weight polymer molecules.

Generally, the starting filter monomers of the formula III can be prepared according to known methods, which are described, for example, in French patents 73.23254 and 76.23174.

The process for the preparation of the above polymeric compositions may further have the following features, which may be used individually or in combination with each other: The polymerization initiator is a redox couple, such as, for example, the ascorbic acid-hydrogen peroxide couple; Various known procedures can be used to obtain low molecular weight polymer compositions which are used individually or in combination with one another. Of these regulations, one may mention the use of a significant amount of initiator, the use of so-called chain transfer agents (such as, for example, halogenated compounds, aldehydes, thiol and etc.) or also the use of a significant amount of solvent during the polymerization.

As residues of filter substances, corresponding to the symbol X in formulas 1 and 3, one can particularly mention by way of example the residues represented by formulas 4, 5 and 6, in which R is a methyl or tert octyl group and Z represents a tert-butyl group, ie the residues of 3-benzylidene-dl-camphor, 1 '[2- (2'-hydroxy-5'-tert-octylphenyl)] 2H benzotriazole, r [2- (2, -hydroxy-5l-methyl-35-phenyl)] 2H benzotriazole, respectively. of 4-tert-butyl-4'-methoxy-dibenzoyl methane.

The invention therefore relates to cosmetic preparations intended for protecting the skin against the undesired effects of ultraviolet radiation, which as an active ingredient which filters ultraviolet rays, at least one polymer composition as above 870 0 039 Μ -4 5 defined.

These preparations are preferably in the form of aqueous, water / alcohol or oil containing solutions, aqueous emulsions, lotions, creams, milky preparations, gels, sticks or in the form of aerosol preparations.

These cosmetic preparations contain, in addition to the polymers of the units of the formula I, conventional additives, which are generally present in such preparations, and optionally other substances, which can absorb ultraviolet radiation.

In the cosmetic preparations according to the invention, the concentration of polymer containing the units of the formula 1 is variable because it depends on the degree of protection desired. Generally, the concentration of the polymer can range from 1-20% by weight, based on the total weight of the composition.

The invention also relates to the use of the polymers containing the acrylamide units, which are covalently bonded to an ultraviolet radiation absorbing compound, for the preparation of cosmetic anti-sun preparations, which use is characterized in that at least 80 % of the polymer molecules have a molecular weight of less than 20,000, the measurement of the molecular weights being carried out according to the size sort chromatography method, comparing with standard polystyrene samples.

The absorbing capacity of the filter is expressed in advance using the Ksp value (K-specific), which depends on the amount of the filtering substances present in the sample, on the measured optical density and on a constant, which depends is of the equipment.

30 The definition of Ksp is given in the work "Introduction to electronic absorption Spectroscopy in organic chemistry" by Gillian and Stern, Arnold Ed., London 1954, biz. 10.

K

35 ^ = V.

d with K = “j ~ 40 d = measured optical density 870 0 03 9 i ï 6 c = concentration of the solution (g / ml) 1 = thickness of the cell in cm

Today, the absorbency is defined by the term "specific absorption, ash", defined by the French standard T.01030 (January 1972), which has the following relationship to Ksp: ^ = 1000 ash 10 In the present description, the absorbent power expressed by the specific absorption.

In the following examples, which are not limiting, the invention is further illustrated.

Examples concerning the preparation of the polymers Example I:

Preparation of a polymer derived from 3-benzylidene camphor from purified monomer.

Step 1: Preparation of the monomer [3- (41-acrylamidomethyl-benzylidene)] dl-camphor 20

500 g of pure sulfuric acid 241 g of 3-benzylidene-dl-camphor 1 g of sodium nitrite are introduced into a reactor.

25

After obtaining a solution, the reactor is cooled to 0 ° C using a water and ice bath. Then 110 g of hydroxymethyl acrylic amide as a powder are added and the mixture is then allowed to slowly come to room temperature and stirring is maintained for 48 hours.

The reaction mixture obtained is slowly poured into 5 liters of a mixture of water and ice with stirring; the light beige pasty precipitate formed is collected and washed with water, then dissolved in 2 L of ethyl acetate; the organic solution is washed with water until a neutral pH is obtained, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure (20 mm Hg or about 260 Pa) at a temperature of less than 50 ° C until the weight is constant.

An oily light brown residue is obtained, which crystallizes crude on cooling.

B 7 0 0 0 3 9 * i 7

Analyzes a) - Thin layer chromatography on silica gel with a fluorescent indicator, eluent of ethyl acetate with UV and iodine vapor.

2 main products, Rf = 0.7 and 0.8; 2 by-products, Rf = 0.33 and 0.55; 3-Benzylidene camphor is present in an amount of 5%.

b) - UV spectrum

Arax <CHC13) - 295 «10 Step 2: Purification of the monomer:

50 g of the crude monomer obtained as described above are mixed with 375 ml of diethyl ether. The suspension is stirred vigorously for 30 minutes until a fine white-beige precipitate is obtained.

The precipitate is collected on a frit glass filter, then washed with 150 ml diethyl ether and dried at 25 ° C under reduced pressure for 16 hours.

25 g of a crystalline beige compound are collected.

Analyzes: a) - Thin layer chromatography (TLC), silica gel support with a fluorescence indicator, eluant ethyl acetate, detection with UV and with iodine vapor.

1 main product, Rf = 0.75, 1 by-product, Rf = 0.35, 3-benzylidene camphor is not present 25 b) - UV spectrum

Amax (CHCl 3) * 295 nra aS = 71 Step 3: Recrystallization

The recrystallization is carried out in a mixture of alcohol and water, with 40 cm 2 of H 2 0 and 60 cm 2 of ethanol mixed together.

3 g of the compound obtained as described above are dissolved in 12 ml of the alcohol-water mixture at 6 ° C.

After cooling, the product is obtained in the form of white crystals. After filtration and drying, 1.9 g of the intended compound are obtained.

Analyzes: a) - Thin layer chromatography, silica gel support, with a fluorescence indicator, eluent: ethyl acetate, detection with UV and with iodine vapor.

40 1 single product, Rf = 0.75 S7 0 0 0 3 9 8 b) - NMR spectrum (CDC73 + TMS)

The spectrum is compatible with the presence of the acrylamidomethyl function, bound at the para position of the aromatic ring.

5c) - UV spectrum \ bX (CHC13) = 297 ra as - 80 Step 4: Preparation of the homopolymer

100 g of the monomer obtained according to the previous step, dissolved in 200 g of isopropyl alcohol, and 15 g of a solution containing 30% hydrogen peroxide are mixed. It is heated to 80 ° C with stirring; when this temperature is reached, a solution of 10 g of ascorbic acid in 200 g of water is added at a controlled rate over a period of 3 hours. Stirring is maintained for half an hour. The polymer formed, which is insoluble in the reaction medium, is in the form of oily droplets in suspension. When the reaction is complete and stirring is stopped, the polymer is decanted. The above phase consisting of isopropyl alcohol, water, monomer and the rest of the initiator is removed. The polymer is dissolved in 200 g of dichloromethane. Methanol is added to this solution until the onset of opal escalation, which is obtained by adding 200 g of methanol.

The solution is concentrated under normal pressure at 50 ° C to gradually remove the dichloromethane and effect slow precipitation of the polymer. During the concentration, 200 g of methanol is again added, then the removal of the dichloromethane is continued.

At the end of this treatment, the precipitated oily product is collected, dried and powdered. 70 g of pure polymer are obtained in the form of a pale yellow powder.

Analyzes a) - TLC, support silica gel, with a fluorescence indicator, eluant ethyl acetate, detection by UV.

polymer: Rf = 0 monomer absent (Rf = 0.75). 3-benzylidene camphor absent (Rf = 0.95).

b) - UV spectrum (CHCl3) = 295 nm axis = 68 Example II:

Preparation of a polymer derived from 3-benzylidene camphor from crude monomer.

8700039 9

According to Example I, step 4, the monomer obtained according to Example I, step 1 is polymerized.

Analyzes a) - TLC: identical to that of Example I, step 4.

5b) - UV spectrum max (chct3) = 295 nm axis = 58 c) - Determination of the distribution of the molecular weights

The resulting polymer is characterized in a solution in tetrahydrofuran (THF), by size-chromatography over a number of columns with a porosity of 60, 500, 3,108, 3,10 Angstroms; standard sample: polystyrene »Distribution of molecular weights: M <4000 43% 15 4,000 <M <17,000 46% 17,000 <M <40,000 3% 40,000 <M <68,000 2% 68,000 <M 6% 20 Example III:

Preparation of a polymer derived from 11 [2- (21-hydroxy-51-tert-octylphenyl)] 2H-benzo-triazole.

Step 1: Preparation of the monomer [2- (2'-hydroxy-3'-acrylaminomethyl-5'-tert-octylphenyl)] 2H-benzotriazole.

25

600 g of sulfuric acid and 163 g of [2- (2, -hydroxy-5, -tert-octylphenyl)] 2 H-benzotriazole are introduced into a reactor.

This dissolution proceeds exothermically, the temperature of the mixture reaching a value of 35 ° C. After complete dissolution, the reaction mixture is cooled to 0 ° C and then 60.6 g of hydroxymethyl acrylamide is added in portions over 30 min. And then cooling is stopped. The temperature reaches a value of 30 ° C and is maintained at this value for the entire duration of the reaction.

After a reaction time of 24 hours, it is diluted with 500 ml of ethanol and then poured slowly into 5 l of a mixture of water and ice while stirring vigorously; the white powder obtained is filtered and then washed with water until the pH is 5 8700039

«V

After filtering, the crude product is dissolved in 3 l of chloroform. The remaining water is removed by decantation; after drying over sodium sulfate, the organic phase is concentrated to 250 g and the oily residue is refluxed in 2L of cyclohexane, which is refluxed. The solution is filtered and then cooled: after crystallization, the target product is filtered and dried.

153 g of the intended product, or a yield of 75%, are obtained.

10 Analyzes

Melting point = 156 ° C TLC: si 1icagel carrier LS 254 solvent chloroform eluent: 15 - ethyl acetate 90 - chloroform 10 detection by UV: Rf = 0.66 (starting product: Rf = 0.96) UV spectrum of 1 mg of substance in 100 ml chloroform: \ iax.l = 305 aSl 3 40'8 20 \ iax.2 = 340 ^ aS2 3 37 · 9

Step 2: Preparation of the homopolymer

In a reactor: 35 g [2- (2l-hydroxy-3l-acrylamidomethyl-5'-tert-octyl-phenyl)] 2H-benzotriazole - 70 g of isopropyl alcohol and - 5.25 g of a solution containing 30% H2O2.

The mixture is heated to 80 [deg.] C. and then a solution of 3.5 g of ascorbic acid in 70 ml of water is added at a constant rate over a period of 3 hours, then stirring is continued for a further 30 minutes.

Then it is cooled to 0 ° C. The crude polymer that has settled on the bottom of the reactor is collected by filtration. Quantity obtained: 35 g.

Analyzes a) TLC on silica gel: detection with UV, solvent CHCI3, eluent: diethyl ether.

polymer: Rf = 0 monomer absent (Rf = 0.95) 40 b) UV spectrum (solvent: CHCl3) 8700039 r 9 11 \ iax.l = 304 m axis = 37 »5

Amax. 2 = 340 nm axis = 33> 5 c) Determination of the distribution of the molecular weights under the same conditions as those of Example II, 5 M <4000 44¾ 4,000 <M <17,000 47¾ 17,000 <M <40,000 8¾ 40,000 <M <68,000 4¾ 10 68,000 <M 1%

Example IV:

Preparation of a polymer derived from 4-tert, butyl-4, -methoxy-3'-methyldibenzoylmethane.

Step 1: Preparation of the monomer 4-tert-butyl-31-acrylamidomethyl-41-methoxydi benzoylmethane

600 g of sulfuric acid and 93 g of 4'-tert-butyl-4'-methoxydibenzoylmethane are introduced into a reactor.

This mixture is stirred for 15 minutes to dissolve the solid; after complete dissolution, the reaction mixture is cooled to 0 ° C and then 30.3 g of hydroxy-25-methyl acrylamide are added in portions over a period of 30 min and the reaction mixture is then allowed to cool. The color has changed from orange to red.

After a reaction time of 24 hours, pour slowly into 4 liters of a mixture of ice and water, stirring vigorously. The precipitate is washed with water and filtered, then dissolved in 500 ml of di-chloroethane. The organic phase is washed with water until the washing liquid is neutral, then concentrated to a dry product. The residue is recrystallized in 11 toluene in the presence of bone black.

100 g of the intended product are obtained (yield = 85%). It is a new product which forms part of the invention.

Analysis

Melting point = 164 ° C - TLC

silica gel carrier LS 254 40 solvent chloroform 870 0053 12 eluent diethyl ether detection with UV: main product, Rf: 0.33 by-product, Rf: 0.08 starting product, Rf: 0.86 5 - UV spectrum of a solution of 1 mg substance in 100 ml chloroform: * max = 357 nln as = 86

Step 2: Preparation of the homopolymer 10 In a reactor: - 100 g of 4-tert-butyl-3'-acrylamidomethyl-4'-methoxy-dibenzoylmethane - 200 g of isopropyl alcohol and - 15 g of a solution containing 30% Contains H2O2.

15

The mixture is heated to 80 ° C with stirring.

A solution of 10 g of ascorbic acid in 200 ml of water is added at a constant rate over 3 hours and stirring is then maintained for an additional 30 minutes.

The reaction mixture is cooled to 0 ° C and stirring is stopped.

The precipitated solid polymer is collected by filtration, dissolved in 200 g of dichloromethane and then methanol is added until the onset of opalescence occurs (which still requires about 200 g of methanol). The solution is concentrated under reduced pressure by heating at 50 ° C to remove the dichloromethane. The polymer, which is insoluble in methanol, precipitates while the remaining monomer remains in solution. After drying, 50 g of pure polymer are obtained.

Analyzes 30 TLC on silica gel: detection with UV, solvent CHCl3, eluent: diethyl ether.

polymer: Rf = 0 monomer absent (Rf = 0.5) - UV spectrum 35 ^ max. (CHCl 3) = 356 nm axis = 69> 2 - Determination of the distribution of the molecular weights under the same conditions as those of Example II.

8700039 * * 13

Ff <4000 35% 4,000 <Μ <17,000 63% 17,000 <Μ <40,000 2% 5 40,000 <M imperceptible

Example V:

Copolymer consisting of [3- (4'-acrylamidomethyl-benzylidene)] dl-camphor and [2- (21-hydroxy-31-acrylamidomethyl-51-tert-octylphenyl)] 2H-benzo-10-triazole.

50 g of monomer prepared according to Example 1, step 1, 50 g of monomer prepared according to example 3, step 1, 200 g of isopropyl alcohol and 20 g of ascorbic acid are dissolved in 100 g of water in a reactor. The reaction mixture is refluxed, then 75 g of a 30% hydrogen peroxide solution diluted with 30 g of water are added. During the course of the reaction, the polymer formed is separated from the solvent. When the stirring is stopped after a reaction time of 4 hours, the polymer deposits on the bottom of the reactor. The above phase, consisting of isopropyl alcohol, water, monomers and initiator residues, is removed. The polymer is dissolved in 200 g of dichloromethane and then diisopropyl ether is added until the onset of opalescence. The solution is concentrated under normal pressure at 50 ° C until the dichloromethane is removed, which causes precipitation of the polymer in the form of an oil. This oil is collected, dried and powdered. 80 g of a pale yellow powder are obtained.

Analyzes - TLC: silica gel support with fluorescence indicator; Eluant ethyl acetate or diethyl ether.

Results: residual monomers absent; polymer Rf = 0 - UV spectrum of 1 mg substance in 100 ml CHCl3

Aniax.l * 298 * axis = 42

Amax.2 = 340 ”axis = 18 35 Distribution of the molecular weights: more than 80% of the polymer has a molecular mass of less than 20,000.

Example VI

Homopolymer of [3- (4'-acrylamidomethylbenzylidene)] dl camphor.

15 g of the monomer of Example 1, step 1, 30 g of iso-40 propyl alcohol, 2.25 g of a solution containing 30% hydrogen peroxide, and 0.375 g of dodecyl mercaptan are mixed. The reaction mixture is refluxed and then a solution of 1.5 g of ascorbic acid in 30 ml of water is added at a controlled rate over 3 hours. The termination of the polymerization and the purification of the polymer are carried out as in Example I, step 4.

The polymer is characterized by its UV spectrum measured on a chloroform solution: ^ max "29® nm axis" ^ 9

Molecular weight distribution: more than 80% of the polymer 10 has a molecular weight of less than 20,000.

Example VII

Copolymer consisting of [3- (4'-acrylamidomethyl-benzylidene)] dl-camphor and trimethylammoniopropylmethacrylamide chloride (or MAPTAC)

60 g of the monomer of step 1 according to Example 1, 80 g of a solution of 50% MAPTAC in water, 120 g of isopropyl alcohol and 20 g of ascorbic acid are mixed. This mixture is boiled under nitrogen under reflux of the solvent and then a solution of 75 g of 30% hydrogen peroxide diluted with 30 g of water is added at regular rate over a period of 35 minutes.

At the end of this addition, the reaction is continued for 2.5 hours and then the reaction mixture, which is concentrated to 270 g, is diluted with 55 g of acetone. The opalescent crude polymer solution is slowly poured into 5.5 L of alcohol with vigorous stirring and the precipitated polymer is collected and dried.

66 g of pure polymer, which is soluble in water, are obtained.

TLC: carrier: silica gel; solvent: methanol; eluent: ethyl acetate.

30 Residual filter monomer absent - UV spectrum in water:

Amax = 295 nm axis = 20 NMR ^ H: identical to a composition of 40% filter monomer units and 60% MAPTAC units.

Molecular weight distribution: More than 80% of the polymer has a molecular weight of less than 20,000.

Example VIII

Copolymer consisting of [2- (2'-hydroxy-3'-acrylamidomethyl-5'-tert-octylphenyl)] 2H benzotriazole and MAPTAC.

45 g of the mono monomer prepared according to Example III, step 1, 110 g of a solution of 50% MAPTAC, 5 g of dodecyl mercaptan, 200 g of isopropyl alcohol and 2.5 g of azobis are mixed. isobutyronitrile. This mixture is heated under reflux of the solvent under nitrogen and kept under these conditions for 6 hours. The polymer formed, which is insoluble in the reaction medium, is recovered and dissolved in a mixture of dichloromethane / methanol (50/50) and then precipitated with 6 liters of diethyl ether. After drying, 79 g of a water-soluble polymer are obtained.

TLC: carrier: silica gel solvent: methanol eluent: diethyl ether, residual filter monomer absent.

UV spectrum in water: 15 Amax.l * 300 ™ as * 12> °

Amax.2 = 335 ™ as * 10.7

Molecular weight distribution: More than 80% of the polymer has a molecular weight of less than 20,000.

Example IX

Copolymer consisting of [3- (4'-acrylamidomethyl-benzylidene)] dl-camphor and 2-acrylamido-2-methyl-propanesulfonic acid (AMPS)

95 g of the monomer prepared according to Example 1, step 1, 5 g of AMPS, 200 g of isopropyl alcohol and 20 g of ascorbic acid are dissolved in 100 g of water. This mixture is refluxed with the solvent and a solution of 75 g of 30% hydrogen peroxide diluted with 30 g of water is added at a regular rate over a period of 30 minutes. The polymerization reaction is continued for 2.5 hours. The precipitated polymer is dissolved in 200 ml of tetrahydrofuran and precipitated in 4 L of acetonitrile. After drying, 76 g of pure polymer are obtained.

- TLC: carrier: silica gel solvent: chloroform eluent: ethyl acetate 35 Free filter monomer absent - UV spectrum in chloroform:

^ max = 296 nm axis = 52 Microanalysis: CHNS

Found: 72.9 7.8 4.1 0.6 40 Distribution of the molecular weights: more than 80% of the 5700 039 16

polymer has a molecular weight of less than 20,000. Example X.

Copolymer consisting of [3- (4'-acrylamidomethylbenzylidene)] dl camphor and AMPS.

60 g of the monomer prepared according to Example 1, step 1, 40 g of AMPS, 200 g of isopropyl alcohol and 20 g of ascorbic acid are dissolved in 100 g of water.

This mixture is kept at the reflux temperature of the solvent and then 75 g of a solution of 30 g of hydrogen peroxide diluted with 30 g of water are added over a period of 30 minutes. The polymerization reaction is continued for 2.5 hours. The heterogeneous reaction mixture is homogenized with 50 g of methanol, adjusted to neutral by adding a solution of 5N sodium hydroxide and then precipitated in 4 L of acetonitrile.

15. 63 g of a water-soluble polymer are obtained.

- TLC

carrier: silica gel solvent: methanol eluent: diethyl ether.

20 free filter monomer is absent.

UV spectrum in water:

Xmax = 298 nm axis = 12'5 Microanalysis: CHNS

Found: 46.29 5.77 3.70 5.10 25 Distribution of the molecular weights: more than 80¾ of the polymer has a molecular weight of less than 20,000.

Example XI

Copolymer consisting of [3- (4'-acrylamidomethyl-benzylidene)] dl-camphor and acrylic acid.

10 g of the monomer prepared according to Example I, step 3, 40 g of acrylic acid, 100 g of isopropyl alcohol and 7.5 g of a solution of 30% hydrogen peroxide are mixed. The reaction mixture is refluxed. A solution of 5 g of ascorbic acid in 100 g of water is added at a regular rate over a period of 3 hours. The polymerization reaction is maintained for 4 hours.

The final reaction medium is concentrated and then diluted with acetonitrile until opalescence occurs and finally precipitated in 2 L of acetonitrile.

29 g of dry product are obtained, which neutralization with sodium hydroxide is completely soluble in water.

8700039 .. '17

- TIC

carrier: silica gel solvent: methanol eluent: diethyl ether.

5 residual filter monomer is absent.

UV (for neutralization) in methanol:

Amax * 296 ™ * s * U> 9 Acid number: 470

Microanalysis: C Η N 0 10 (for neutralization)

Found: 53.9 6.5 1.6 35.5

Molecular weight distribution: More than 80¾ of the polymer has a molecular weight of less than 20,000. Example XII

Copolymer consisting of [3- (4'-acrylamidomethyl-benzylidene)] dl-camphor and Ν, Ν-dimethylacryl amide.

4 g of the monomer prepared according to Example I, step 3, 16 g of Ν, Ν-dimethylacryl amide, 40 g of isopropyl alcohol and 3 g of a solution of 30¾ hydrogen peroxide are mixed, the reaction mixture is heated under reflux, and then it is added add a solution of 2 g of ascorbic acid in 40 g of water at a regular rate for 3 hours. The polymerization reaction is maintained for 4 hours. The reaction mixture is concentrated, the residue is dissolved in 100 g of acetone and precipitated in 1 L of ethyl acetate. 13 g of product which is soluble in water, propylene carbonate and sorbitan monostearate are obtained.

- TLC: carrier: silica gel solvent: methanol 30 eluent: ethyl acetate residual filter monomer absent.

UV in methanol:

Amax * 294 "" shaft * 8

Microanalysis: CHNO

35 Found: 56.3 8.4 10.3 23.6

Molecular weight distribution: More than 80% of the polymer has a molecular weight of less than 20,000. Comparative example

The polymer prepared according to Example II is compared with the 40- 8700039 prepared according to Example 6 of French patent 73.23254

V 'V

,. 18 polymer, which has been characterized under the same conditions as described above. The results are as follows: a) Distribution of the molecular weights: 5 M <4000 13% 4,000 <M <17,000 33% 17,000 <M <40,000 20% 40,000 <M <68,000 15% 68,000 <M 19% 10 b) The ease of application:

The polymer prepared according to Example II of the present specification is much easier to formulate than the polymer prepared according to Example 6 of French patent 73.23254. Indeed, it is soluble much faster than the latter polymer in the oil phases of emulsions and at a much lower temperature. These differences are illustrated by comparing the following formulations: mixture of glyceryl mono- and di-stearate, 20 marketed under the designation GELE0L by GATTEF0SSE 2 g mixture of aliphatic alcohols with 12-18 carbon atoms 7 g cetyl alcohol 1 .5 g of petroleum jelly 5 g of 25 benzoate of alcohols with 12-15 carbon atoms, sold under the designation FINS0LV-TN by FINETEX 15 g polymer (ie polymer according to example II or polymer used for comparison).

30 total: 35.5 g

It is noted that the polymer prepared according to Example II is dissolved in 95 minutes at 95 ° C while the polymer prepared according to Example 6 of French patent 73.23254 is dissolved in 20 minutes at the same temperature.

c) Cosmetic properties.

Two creams are prepared in the form of oil-in-water emulsions, the fatty phases of which consist of the oily solutions prepared as described above and 0.5 g of polydimethyl siloxane (Fluid 200 sold by Dow under the designation 40). Corning).

8700039 18 ^

The water phase consists of: glycerol 20 g KATHON-CG (preservative, Rohm and Haas), q.s. perfume, q.s.

Water, qsp 44.5 g

It is found that the cream containing the polymer prepared according to Example II is smoother and less tacky and upon application has an appearance and touch which is less greasy than the cream which is the same as Example 6 of the French patent specification. 73.23254 contains prepared polymer.

Examples of cosmetic preparations Example XIII

According to the method described in the above comparative example, an anti-sun cream (oil-in-water emulsion) is prepared by replacing the polymer of Example II with the polymer of Example I.

Example XIV

In an analogous manner, a cream (water-in-oil emulsion) with the following composition was prepared: - polymer of example II 5 g - magnesium stearate 4 g 25 - octyl dodecanol 10 g

hydrogenated lanolin, under the designation HYDROLAN H

marketed by ONYX 1 g - clear lanolin 4 g 30 - beeswax 6 9 - sorbitan sesquiolate 4.5 g - glycerol monostearate 1 g - oleyl alcohol 5 g - palmitine ester of 2-ethyl hexyl glyceryl ether 2 g 35 - petrolatum oil 20 g - preservative 0.2 g - demineralized water, qsp 100 g

In this example, the polymer of Example II can be replaced by one of the polymers prepared according to Example V or VI.

5700030

- V

19

Example XV

A preparation in the form of a solar oil having the following composition was prepared: 5 - polymer of Example IV 0.5 g - oleyl alcohol 40 g - pentaerythritol tetracaprylate / caprate, marketed by CRODA under the designation CR0DAM0L PTC 10 g 10 - di-tert-butyl-p-cresol 0.05 g - benzoate of alcohols with 12-15 carbon atoms, marketed by FINETEX under the designation FINS0LV TN 49.45 g 15

Example XVI

A preparation in the form of a milk of the following composition has been prepared: 20 - polymer of Example II 5 g - oleyl acetyl alcohol with 30 mol ethylene oxide 8 g - stearyl alcohol 5 g - oleyl alcohol 6 g - palmitine ester of 2-ethyl hexyl glyceryl ether 4 g 25 - petroleum jelly 10 g - polydimethylsiloxane. 1 g - sorbitol, 70% 5 g - preservative (ΚΑΤΗ0Ν CG) 0.2 g - perfume 0.6 g 30 - demineralized water, qsp 100 g

An analogous preparation has been prepared by replacing the polymer of Example II in the above composition with the polymer of Example III.

8700038

. 20 Example XVII

A preparation in the form of a thick oil having the following composition was prepared: 5 - polymer of Example III 1 g - 2-ethylhexyl-paramethoxycinnamate 2 g - myristyl alcohol with 3 moles of propylene oxide, produced by WITCO under the designation WICINOL APM in marketed 5 g of 10 - 2-ethyl hexyl palmitate 10 g - di-tert-butyl-p-cresol 0.05g - silica, marketed by DEGUSSA under the designation AEROSIL R972 6 g of perfume 0.5 g - isostearyl benzoate, qsp 100 g

An analogous preparation has been prepared by replacing in this composition the polymer of example door with the polymer of example IV,

Example XVIII

A preparation in the form of an oil-in-water emulsion having the following composition was prepared: - polymer of Example II 5 g of a 25 - 80/20 mixture of cetyl / stearyl alcohol with 33 moles of ethylene oxide, by HENKEL under the designation SINNOWAX AO marketed 7 g - mixture of glyceryl mono- and di-stearate, 30 marketed by GATTEFOSSE under the designation GELEOL 2 g - cetyl alcohol 1.5 g - petroleum jelly 5 g - benzoate of alcohols with 12-15 carbon atoms, 35 marketed by FINETEX under the designation FINSOLV-TN 15 g - glycerol 20 g - preservative 0.2 g - perfume 0.6 g 40 - demineralized water, qsp 100 g 37 0 0 03 9 v

, "21 Example XIX

A preparation in the form of a stick with the following composition 1 g is prepared: 5 - polymer of example IV 1 g - glyceryl tribehenate 6 g - glyceryl ester of fatty acids with 18-36 carbon atoms, by CRODA marketed under the designation SYNCROWAC HGL-C 8 g 10 - glycol distearate, marketed by the company CRODA under the designation SYNCROWAX ERLC 6 g - triglycerides of ricinoleic acid 10 g - oleyl alcohol 10 g 15 - benzoate of alcohols with 12-15 carbon atoms, marketed by FINETEX under the designation FINSOLV TN 58.9 g - di-tert-butyl-p-cresol 0.1 g 20

Example XX

A formulation in the form of a solar oil having the following composition was prepared: - polymer of Example II 3.5 g - 2-ethyl hexyl-p-aminobenzoate 2.9 g - 2-ethyl hexyl-p-methoxycinnamate 4 g - oleyl alcohol 15 g - isopropyl myristate 20 g 30 - palmitine ester of 2-ethyl hexyl glyceryl ether 6 g - cyclopentadimethylsiloxane 5 g - octamethylcyclotetrasiloxane 5 g - cycTotetradimethylsiloxane, qsp 100 g 870 0 039

; 22 Example XXI

A milk formulation having the following composition was prepared: 5 - polymer of Example III 2 g - oleyl acetyl alcohol with 30 moles ethylene oxide 6 g - stearyl alcohol 4 g - polydlmethylsiloxane 1 g - benzoate of alcohols with 12 -15 carbon atoms, 10 marketed by FINETEX under the designation FINSOLV TN 15 g - oleyl alcohol 4 g - sorbitol, 70¾1s 15 g - preservative (KATHON CG) 0.2 g 15 - perfume 0.2 g - demineralized water, qsp 100 g

An analogous preparation has been prepared by replacing in this composition the polymer of Example III with that of Example IV.

20

Example XXII

A preparation in the form of an oil-in-water emulsion of the following composition has been prepared: 25 - polymer of Example II 3 g - 2-ethyl hexyl-p-methoxycinnamate 3 g - glycerol 5 g - sorbitol, 70 µs 4 g - soy lecithin, 40%, in a surfactant solution, marketed by the company AMERICAN LECITHIN under the designation ALC0LEC 4135 5.5 g - shea butter 4 g - beeswax 4 g - sunflower oil 6 g 35 - isostearyl benzoate 10 g - preservative 0.03g - perfume 0.05g - cetyl alcohol 6 g - stearyl alcohol 2 g 40 - demineralized water, qsp 100 g 870 0039 ', ν' 24

Example XXVI

SUN CREAM (oil-in-water emulsion) - polymer prepared according to example VIII 5.0 g - mixture of cetyl / stearyl alcohol and 5 epoxidized cetyl / stearyl alcohol (33 EO) (80/20) 7.0 g - glyceryl mono- and distearate 2 .0 g - cetyl alcohol 1.5 g - benzoate of alcohols with 12-15 carbon atoms, marketed under the designation FINS0LV TN (WITC0) 15.0 g - glycerol 5.0 g - preservative qs - perfume qs - water, qsp 100.0 g 15

Example XXVII

SUN CREAM (water-in-oil emulsion) - polymer prepared according to Example XI 2.0 g 20 - esters of glycerol / sorbitol and fatty acid, marketed by ATLAS under the designation ARLACEL 481 4.0 g - hydrogenated castor oil, epoxidized with 7 moles of ethylene oxide, marketed by ATLAS under the designation ARLACEL 989 8.0 g - s-hydroxyoctacosanyl-12-hydroxy stearate, marketed by AKZO under the designation ELFACOS C 26 5.0 g - petrolatum oil 15.0 g 30 - isopropyl myristate 4.0 g - NaOH, qs pH »8.0 - water, qsp 100.0 g 870 0 039 23 ·? · 5

Example XXIII SUNSET

- polymer prepared according to example VII 2.5 g - Cellos! PCG 10 (hydroxyethyl cellulose) 1 g 5 - ethanol 12 g - propylene glycol 8 g - preservative qs - perfume qs - water, qsp 100 g 10

Example XXIV

SUN CREAM (oil-in-water emulsion) - polymer prepared according to example XII 4 g - stearic acid 2.5 g 15 - triethanolamine 0.2 g - liquid lanolin 6 g - mixture of glyceryl monostearate and polyethylene glycol stearate (100 EO) 5 g - triglycerides of myristine / palmitine / stearic acid 6 g 20 - stearyl alcohol 2.5 g - petroleum jelly 10 g - propylene glycol 5 g - preservative qs - perfume qs 25 - water, qsp 100 g

Example XXV SOFT MILK

- polymer prepared according to example X 1.5 g 30 - polymer prepared according to example IX 1.5 g - mixture of glyceryl monostearate and polyethylene glycol stearate (100 EO) 50/50 2.5 g - stearyl alcohol 4 g - petrolatum oil 10 g 35 - isopropyl myristate 5 g - Cellos! ze PCG 10 (hydroxyethyl cellulose) 0.5 g - preservative qs - perfume qs - water, qsp 100.0 g 3700039

Claims (10)

25 1. Cosmetic preparations intended to protect the skin 5 from the undesired effects of ultraviolet rays, which as active ingredient for filtering the ultraviolet rays contain at least one polymer composition containing polymers with acrylamide units covalently attached to a UV absorbent compounds are bound, optionally in combination with units derived from hydrophilic comonomers, characterized in that the polymers of the said polymer composition have a molecular weight distribution such that at least 80¾ of the polymer molecules have a molecular weight of less than 20,000 wherein the measurement of the molecular weights was carried out according to the size sort chromatography method, comparing with standard samples of polystyrene. Preparations according to claim 1, characterized in that at least 10¾ of the polymer molecules have a molecular weight of more than 40,000. Preparations according to claim 1 or 2, characterized in that the polymers contain units of the formula 1, wherein X represents an aromatic group which imparts to the polymers an absorption of ultraviolet radiation in the wavelength range, which is from 280 to 400 nm. optionally in combination with units derived from hydrophilic comonomers having an ethylenic unsaturation, provided that the units of formula I make up at least 10% by weight of the polymer. 4. Compositions according to claim 3, characterized in that the units of the formula 1 form 10-99% by weight of the polymer. Preparations according to claim 3 or 4, characterized in that X represents the group of formula 4, 5 and / or 6, wherein R represents a methyl or tert-octyl group and Z represents a tert-butyl group. Preparations according to any one of the preceding claims, characterized in that the hydrophilic comonomers are selected from N-vinylpyrroli-35 don, Ν, Ν-dimethylacryl amide, acrylic acid, methacrylic acid and the monomers of the general formula 2, wherein M-0 - or -NH-, X is a number of 2 or 3, R 1 -H or -CH 3 and R 2 represents -CH 3 or -C 2 H 5, with the proviso that the amino groups present before or after the polymerization are quaternized or the salt form can be brought to 40. 8700039 / '26 N Cosmetic preparations according to any one of the preceding claims, characterized in that the concentration of the polymers can vary from 1 to 20% by weight, based on the total weight of the preparation. Cosmetic preparations according to any one of the preceding claims, characterized in that they can be in the form of aqueous, water / alcohol or oil-containing solutions, aqueous emulsions, lotions, creams, milky preparations, gels, sticks or in the form of compositions for aerosols. 9. Use of polymers containing acrylic units, which are covalently bound to an ultraviolet ray absorbing compound, for preparing cosmetic anti-sun preparations, characterized in that at least 80% of the polymer molecules have a molecular mass of less than 20,000, the molecular weight measurement being carried out by the size sort chromatography method, comparing with standard polystyrene samples. Use according to claim 9, characterized in that said polymers correspond to the polymers defined in any one of claims 2-6. 20 ------ 8700039 '· # ± --- CH - CH-- i CO - ΝΉ - CH2 - X 2. ~ R2 CH. - C - CO-M- (CH-) 2. x R1 R2 LCH2 - CH-CO-NH-CH2-X L o A fr <30 / OH jx CH30 ~ 0 ~ CO- CH2— co -o - * ti 870 0 03 9