AU597022B2

AU597022B2 - Cosmetic preparations intended to protect the skin against the undesirable effects of ultraviolet radiation

Info

Publication number: AU597022B2
Application number: AU67484/87A
Authority: AU
Inventors: Bernard Jacquet; Claude Mahieu; Christos Papantoniou
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1986-01-10
Filing date: 1987-01-12
Publication date: 1990-05-24
Anticipated expiration: 2007-01-12
Also published as: CH670950A5; FR2597336B1; CA1292700C; GB2185396A; DE3700531A1; GB8700568D0; NZ218893A; BE1004271A4; IT1201123B; NL8700039A; GB2185396B; FR2597336A1; IT8719043A0; AU6748487A

Description

COMMONWEALT H OF A UST RR LI A PATENT ACT 1952 COMPLETE SPECIFICATION (original) FOR OFFICE USE Class Int Class Application Number: ]lodged: 67 L- 4 Complete Sipec i fication Lodged: Accepted: 1)1bi ishod; ['nrori t y: Rolat-ed Ai-t.:

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Name of Applicn di Addres. 5 of App i (ad t \ctuill In1voit C) (:d Addl-Osi tot fwiVioo: 14'OREAL, 14, rue RoYaler 75008 Paris,

FRANCE

Claude MAIIIEU Christos PAPANTONIOU Bernard JACQUET [)AV I E2 ('M)hI,18N, at ent At tornelYiS 1 Litil i 11 l~.Iet ,Molbo11rn1e, 3000 S* S 55

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C(Jfmpleto e ipee ii I(ioli for the i nventionl en1t.it lod "1COSMETIC PREPARATIONS INTENDED TO PR~OTE~CT THE SKIN AGAINST THlE UNDESIRABLE EFFECTS Or ULTRAVIOLET

RADIATION"

Tlv followinq st-atemient is a full description of this izw-vntion, includingj t~he Jbest: methiod of performning it known to us I

-I-

-la- The object of the present invention is new cosmetic preparations intended to protect the skin against the undesirable effects of ultraviolet radiation, and in particular against the undesirable effects of exposure to the sun (burning and possibly browning of the skin).

It is known that ultraviolet radiation having a wavelength in the range from 280 to about 350 nm is responsible for the inflammation or erythema of the skin observed when the human body is exposed without protection to the sun's rayb. This wavelength range is sometimes known as the "erythematous zone" It is also known that the ultraviolet radiation responsible for bronzing the skin has a wavelength of from 315 to about 400 nm.

*o Preparations are known which have the property of absorb- S ing the ultraviolet in the erythematous zone, while allowing the radiation responsible for bronzing to pass, and the use of such compounds as "solar filters" in cosmetic preparations promoting the bronzing of the skin and preventing burning and irritation of the skin has already been proposed.

o..

In addition, some users wish to avoid browning and the use has therefore been proposed in these cosmetic preparations of "filters" forming a screen, of greater or lessec proportions against ultraviolet radiation in the wavelength range 315-400 nm, possibly in association with cohoounds filtering UV radiation S* in :he erythematous zone, so as to avoid both browning and :urning of the skin.

The use of solar filters bonded covalently to polymers has been recommended, notably in French patents 75.23254 and 76.23174. Presentation in the form of polymers has the advantage of reducing or suppressing the penetration of the filter compound into the organism by passing through the epidermis, which makes it possible to avoid any risk of toxic side-effects.

-j u- I ii ~44- I I _I~n rq -14r

I-

-2- However, continued study of such "anti-solar polymers" showed that the use of them had certain disadvantages.

To obtain preparations having a high filtering power it is necessary to use considerable concentrations of anti-solar polymer, and this raises difficulties both at the stage of the manufacture of cosmetic preparations and at the stage of applying these preparations to the skin.

Indeed, when it is wished to produce high concentrations, considerable difficulties are experienced in bringing the polymers into solution, which represents a disadvantage at the formulation level. This disadvantage is even more pronounced when an attempt is made, in order to produce a high filtering efficiency, polymers of the homopolymer type, practically every group of which is replaced by a filter substance.

In addition, anti-solar cosmetic preparations obtained with such high concentrations of anti-solar polymers are not satisfactory for the user, since they have a sticky and greasy feel which is unpleasant.

it has now been discovered that if appropriate measures *0 are taken on the preparation of the anti-solar polymers, it is S possible to obtain new compositions which have a high proportion of polymer molecules of low molecular weight, by means of which the disadvantages mentioned above may be eliminated.

The present invention has as its object new cosmetic preparations intended to protect the skin against the undesirable effects of ultraviolet radiation which contain as an active ingredient filtering the ultraviolet radiation at least one polymer composition containing polymers with acrylamide groups covalently bonded to a compound absorbing the ultraviolet, possibly in association with groups derived from hydrophilic comonomers, characterized in that the polymers of said I -3polymer composition have a molecular weight distribution such that at least 80% of the polymer molecules have a molecular weight less than 20,000, the molecular weights being measured by the method of size exclusion chromatography, in comparison with standard samples of polystyrene.

The polymer compounds used according to the invention preferably have a molecular weight distribution such that fewer than 10% of the molecules have, under the same conditions as those given above, a molecular weight greater than 40,000.

The invention has in particular as its object cosmetic preparations such as those described previously, characterized in that said polymers contain groups of formula I 4* .CH CH (I) o-*S I NCO NH CH S t* in which X represents an aromatic group imparting to the polymers an ultraviolet absorption in the wavelength zone possibly ranging from 280 to 400 nm, possibly in association with groups derived from hydrophilic ethylen-unsaturated comonomers, it being understood that the groups of formula I represent at least O* 10% by weight of the polymer.

When groups derived from hydrophilic comonomers are present, the groups of formula I may represent, for example, 10 to 99% by weight of the polymer.

The polymers present in the polymer compound used according to the invention are therefore notably polymers containing solely groups of formula I, it being understood that several different groups, corresponding to different X groups, may be present in the same polymer molecule.

r r -4- It is known that solar filters are present in cosmetic preparations either in the form of oily solutions, in the form of aqueous or hydroalcoholic solutions, or else in the form of aqueous and/or oily solutions in compounds in the form of emulsions.

The polymer compounds as described above which contain only groups of formula I are sufficently soluble in oils and the production, with these compounds, of oil-based cosmetic preparations does not present any particular difficulties.

On the other hand, if it is required to obtain a watersoluble polymer compound, it is necessary to polymerize the "filter monomers" corresponding to the groups of formula I with hydrophilic comonomers.

j.

The hydrophilic comonomers are chosen in particular from N-vinylpryyolidone, N,N-dimethylacrylamide, acrylic acid, methacrylic acid and monomers of the general formula: U

R

2 0 CH 2 C CO-M-(CH 2 -N (II) 0 R R where M represents or -NH-, x is a number equal to 2 or 3,

R

1 represents -H or -CH 3 and

R

2 reptesents -CH3 or -C2H it being understood that the amine groups present may be quaternized or salified before or after polymerization.

y1 I I f Amcilg the comonomers of general formula II it is possible to mention by way of example N.,N-2-dimethylamino ethyl, N,N-3diethylaminopropyl methacrylamide, etc.

The amine groups may be salified with a mineral acid, for example hydrochloric acid, or an organic acid such as lactic acid. They may also be quaternized by a conventional quaternization agent such as dimethyl sulphate, methyl chloride, chloroacetic acid, etc.

To prepare the polymer compounds as decribed above, monomers of formula III

CH

2 CH-CO-NH-CH -X (III) where X is defined as previously, are polymerized in solution, possibly in the presence of ethylene-unsaturated hydrophilic comonomers, in the presence of a polymerization initiator, using known methods to promote the formation of polymer mole- 0 cules of low molecular weight.

Generally speaking, the initial filter monomers of formula III may be prepared by known methods described, for example, in to French patents 73.23254 and 76.23174.

The process for preparing said polymer compounds may also have the following characteristics, taken individually or in combination.

The polymerization initiator is a redox pair, for example the pair ascorbic acid hydrogen peroxide; to obtain polymer compounds having low molecular weights it is possible to use various known processes, taken individually or in combination. Among these processes can be mentioned the use of a large quantity of initiator, the use of so-called chain-transfer agents (for example halogenated compounds, aldehydes, thiols, etc.), or else the use of a large quantity of -6solvent during polymerization.

Among the radicals of the filter substances symbolized by X in formulae I and III particular mention will be made, by way of example, of the radicals represented by the following formulae: H3

R

S.N

S* I

.OH

CH 3*5O CH /ely \r e-ia~ ey req n rerset I-uy gruie h aiaso -ez n capo,2-2-yrx -'tetotlp l)2 ezti hnl) 1 izl n 4-etbtl*'ehx diezymtae Spcie Th prsn S..iute oe a sis betcs mei prprain in:ed rtc tesi gis h uneial efe5s ulrvoe0aitonwihcnana anatv nS...Atflein h lrvoltrdaina les n rcmon ecie rvosy -oCr ahySb an 1 -1

V

6ain which R represents a methyl ur -tertiary o)ctyl group of formula f C l l r.z 1 0 11 3 CH 3 IH3 and Z represents a t-butyl group, i.e. the radicals of 3benzylidene dl camphor, [2-(2'-hydroxy-5'-tert-octyl phenyl)] 2H benzotriazole, -hydroxy-5 '-methyl phenyl)] 2Ubenzotri azole and 4-tert-butyl-4'rnethoxy dibenzoylmethane respectively.

The presernt invention therefore has as its object cosmetic preparations intended to protect the skin against the undesirable effects of ultraviolet radiation which contain as an active ingredient filtering the ultraviolet radiation at least one polymer compound as desoribod previously.

These preparations are preferably presented in the form 0 CS

S*

0 0 A 000 21 :0g. 23 24 6 0: 26 27 :0:as 28 29 31 32 33 34 900305.cazdat.073 .loroad,1 6 -7of aqueous, hydroalcoholic or oil solutions, aqueous emulsions, lotions, creams, milks, gels, sticks or in the form of aerosol compositions.

These cosmetic preparations contain, in addition to the polymers having groups of fornula I, the usual adjuvants generally present in such preparations and possibly other substances capable of absorbing ultraviolet radiation.

In the cosmetic preparations of the invention the concentzation of polymer containing groups of formula I is variable, since it depends on the deg':ee of protection which it is required to obtain. Generally speaking, the polymer concentration may vary from 1 to 20% by weight in relation to the total weight of the preparation.

A further object of the invention is the use of polymers containing acrylamide groups bonded covalently to a compound absorbing ultraviolet radiation in the production of anti-solar cosmetic preparations, characterized in that at least 80% of the polymer molecules have a molecular weight less than 20,000, the molecular weights being measured by size exclusion chromato- 0.

graphy, in comparison with standard t'amples of polystyrene.

The absorbent power of the filter was previously expressed by means of the Ksp value (specific which is a function of the quantity of filtering substances contained in the sample, the measured optical density and a constantdepending on the apparatus.

g The definition of Ksp is given in the work "Introduction to Electronic Absorption Spectrcscopy in Organic Chemistry', by Gillian and Stern, Arnold ed., London 1954, page Ksp with K 1 LL i -j I II~ ;i Ly~i I_ _I_ d measured optical density c concentration of the solution (g/ml) 1 thickness of the cell in cm.

At present the absorbent power is defined by the term "specific absorbance a define by French standard T.01030 (January 1972), linked to Ksp by the relationship Ksp 1000 a s In the present application the absorben power is expressed by means of the specific absorbance.

The following examples illustrate the invention, wihtout, however, limiting it in any way.

Examples of the preparation of polymers EXAMPLE 1 Preparatien of a polymer derived from 3-benzylidene .5 camphor from purifie monomer.

Stage 1: Preparation of the monomer [3-(4-acylamidomehtyl o benzylidene)] dl camphor, S 500 g pure sulphuric acid 241 g 3-benzylidene-dl-comphor 1 g sodium nitrite are introduced ito a reactor.

S

S*After obtaining a solution, the reactor is cooled to 0°C by means of a water bath and ice. 110 g of hydroxymethylacylamide in powdered form is then added and the mixture is allowed slowly to return to ambient temperature and stirring is maintained for 48 hours.

The reaction mixture obtainedis poured slowly into five litres of a mixture of water and ice while being stirred; the i- Lai I g *e.a a a a a I J a *0* 4 a A *0 4 a a..

a a a 4 #4 -9light beige, paste-like precipitate formed is collected and washed with water, then dissolved in two litres of ethyl acetate; the organic solution is washed with water until a neutral pH is obtained, dried over anhydrous sodium sulplate, filtered an concentrated at a temperature below 50°C under reduced pressure (20 mm Hg, i.e. about 260 Pa) until the weight is constant.

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

ANALYSES

a) Thin-layer chromatography on silica gel with fluorescence indicator, eluent ethyl acetate development with UV a'\d iodine vapour.

2 main products Rf 0.7 and 0.8 2 secondary products Rf 0.33 and 0.55 presence of 3-benzylidene camphor, b) UV spectrum A max (CIICI 3 295 nm Ste 2: Purification of the. monomer.

q0 g of untreated monomer obined as above is mixed with 375 ml diethyl ether. The suspension is stirred vigorously for 30 minutes until a fine, white-beige precipitate is obtained.

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

g of a beige crystalline compound is collected.

ANALYSES

a) Thin-layer chromatography (TLC), silica gel support with fluorescence indicator, eluont ethyl acetate, devleopment with UV and iodine vapour.

a 4 A 4 a a S S a a* 4 A a a OS a one main product RE 0.75 one secondary product Rf 0.35 Absence of 3-benzylidene camphox b) UV spectrum max CH 3) 295 nm as 71 Stage 3: Recrystallization fecrystallization i~s ected in a water-alcohol mixture in the proportions: 40 cm 3 11 20 60 cm 3 ethyl alcoholi 3 g of the compound obtained as above is dissolved at 600C in 12 ml of the water-ethanol solution.

0060 After cooling theproduqt is obtained in the form of white rystals. After filtration and drying, 1,9 g of the requ~ired stew compound isobtainod.

ANALYSE_11 A ~rchromatography, silica gel support, with fluoresoence indicator, eluent,- ethyl acetate, development with UV and iodine vapour.

S.A single product, Rf b) NMP. spectrum (CD1)0, TMS) TIhe spectrum is compatible with the presenco of the acrylamidomethyl function fixed in the para position of the :aromatic cycle.

tV Opectrum CIIx13 t.1; 297 nm Ia 8 0 4.-,e4 Preparation of the homopolynior 100 q of the moflomoirobtained as in~ the preceding stage, in 0olution in 200 (1 iz -*ropanol and 15 q of a 3W4 siolution of hydroqen peroxide are mixed, The mixture is heated, with stirinqt -to 8 0OC when this tmperature is reached, a tiolution of 10 g ascorbic acid in 200 g water is introduced regularly within 3 hours. Stirring is maintained for half an hour. The polymer formed, which 's insoluble in the reaction medium, is in suspension in the form of oily droplets. When the reaction is completed and the stirring is discontinued the polymer is decanted. The supernatant phase, composed of isopropyl alcohol, water, monomer and initiator residue, is removed. The polymer is dissolved in 200 g methylene chloride. Methanol is added to this solution until the appearance of an incipient opalescence, whirh is obtained by the addition of 200 q methanol, TPhis solution in concentrated a 50"C under normal proosure in order progressively to remove the methylene chloride and to promote a slow precipitation of the polymer. During the concentration 200 g methanol is again introduced antrd the removal of the methylene chloride is continued.

At the end of this operation the oily product precipitatedI Sis collected, dried and pulverized, 70 qi of pure polymer in the form of a liqht yellow powder is obtained.

:.*ANALYSES:

a) TLC silica gel support, with fluore~scence indicator, eluenJt ethylo acetate, development by UV Polymert REf 0 333 Absence of monomer (RE 0.75) Absence of 3-ben?ylidenv camphor (YRf O,9W) b) UV spectrum A i(ClIcl3 295 nm d a; (68 3EX A M P L' 2 3 Preparation of a pvlymer de-~vdfrom 3--bvtv yI. xIm~wrw-tfromi unt~'ea ted monomer, As in example 1, atage, 41 the monoler Obtainod ized as in example 1, stage

I

-i2-

ANALYSES:

a) TLC: identical to exampie 1, stage 4.

b) UV spectrum: max (CHCl 295 nm a s 58 c) Determination of the molecular weight distribution.

The polymer obtained is characterized in solution in tetrahydrofurane (THF) by size exclusion chromatography in a o set of columns of pcrosity 6U, 500, 3 x 103, 3 x 10" A; standards: polystyrene.

Moleculac weight distribution: M< 4000 4,000 M 17,000 17,000 M 40,000 40,000 M 68,000 68,000 M 46% 3% 2% 6% 0eS

S

o o 55 0 00 O 4 5o

BOOO

I b EXAMPLE 3: Preparation of a polymer derived from 211[2-(2',-hydroxy-tbenzotriazole.

Preparation of the monomer 28U2-(2'hydroxy-3'-arylamidomethyl-t-octyl-5'-phenyl)] benzotriazole.

600 g sulphuric 163 g 2H[2-(2'-hydroxy-t-octyl-5'phenyl)]-benzotirazole a: introduced into a reactor.

This bringing into solution is exothermal and the temperature of the mixture reaches 35 0 C. After complete dissolving the reaction mixture is cooled to 0OC60.6 g hydroxymethyl acrylamide is introduced in portions within 30 minutes and cooling is ten stopped. The temperature reaches and remains at 30 0

C

throughout the duration of the reaction.

After 24 hours of reaction the mixture is diluted with L -26- -13- 500 ml ethanol and then poured slowly into 5 litres of a mixture of water and ice with vigorous stirring; the white powder obtained is filtered, then washed with water until a pH of is obtained; after filtration the untreated product is dissolved in 3 litres of chloroform. The residual water is removed by decantation; after drying over sodium sulphate the organic phase is conventrated to 250 g and the oily residue is dissolved in 2 litres of cyclohexane with reflux. The solution is filtered, then cooled: after crystallization the required product is filtered and dried.

153 g of the required product is obtained, i.e. a yield of

ANALYSES

F

0 156 0

C

TLC: LS 254 silica gel support t solvent chloroform eluent; ethyl acetate chloroform UV development Rtf 0.66 (initial product Rf 0.96) I UV spectrum with 1 mq/100 ml in chloroform max 1 305 nm; as 40.8 ax.2 340 nm; as 37.9 STAGE 2: PREPAIATION OF THE HOMOPOLYMER 35 g 2H[2-(2'-hydroxy-3'-acrylamidomethyl-t- 5octyl-5'-phenyl) -benzotriazole 70 g isopropanol 5.25 g of a 30% solution of H2 2 are introduced into a reactor.

The mixture is heated to 80"C and then o solution of g ascorbic acid in 70 ml water is added at a constant rate I 0 RMW- -1 4in 3 hours, and stirring is then continued for a further minutes.

The mixture is then cooled to 0 0 C. The raw polymer deposited at the bottom of the reactor is recovered by filtration.

Quantity obtained: 35 g

ANALYSES:

a) TLC on silica gel; UV development; solvent CHCl 3 eluent ethyl ether.

Polymer: Rf =0 Absence of monomer i.Rf =0.95) b) UV spectrum (solvent: CHC1 3 max.1= 304 nm asl 7.

max.2= 340 nm as= 33.5 C/ Determination of the molecular weight distribution under co~nditions identical to those in example 2.

404.b 44 4 94 p 4.

.4 44.44.

4.

4- 04 4. 4.00 4 4.

400 4,000 17,000 40,000 68,000 M_; 4,000 17,000 40,000 68,000 44% 47-u 04 4 EXAMPLE 4: Preparation of a polymer derived from 4-t-butyl-4'-methoxy-3' -methyl dibenzoylmethane.

04 4 4 4 STAGE Preparation of the monomer 4-t-butyl-3'-acrylamidomethyl-4 '-methoxy dibenzoylmethane 600 g sulphuric ezcid 93 g 4-t-butyl-4'-methoxy dibenzoylmethane are introduced into a reactor.

This mixture is stirred for 15 minutes in order to dissolve the solid; after complete dissolving the reaction mixture I -28is cooled to 0°C, and then, within 30 minutes, 30.3 g hydroxymethylacrylamide is introduced in portions and cooling is stopped. The colour has changed from orange to red.

After 24 hours' reaction the mixture is poured slowly into 4 litres of a mixture of water and ice with vigorous stirring. The precipitate is washed with water and filtered, then dissolved in 500 ml dichloroethane. The organic phase is washed with water until neutral, then concentred dry. The residue is recrystallized in 1 litre of toluene in the presence of animal black.

100 g of the product required is obtained (yield This is a new product which forms part. of the invention.

ANALYSES

FO F 0 i4° 0

C

TLC

support: LS 254 silica gel solvent: chloroform eluent: ethyl ether UV development: main product Rf 0.33 secondary product Rf 0.08 initial product: Rf 0.86 UV spectrum at 1 mg/100 iii in chloroform A 357 nm a 86 max. s STAGE 2: PREPARATION OF THE IIOMOPOLYMER 100 g 4-t-butyl-3'acrylamidomethyl-4'methoxydibenzouylmethane -200 g isopropanol 15 g of a 30% solution of H202 are introduced into a reactor.

The mixture is heated to 80°C with stirring.

A solution of 10 g ascorbic acid in 200 ml water is added at a constant rate in 3 hours and the stirring is continued I -16for a further 30 minutes.

The reaction mixture is cooled to 0 C and the stirring is halted.

The solid polymer deposited is collected by filtration, dissolved in 200 g methylene chloride and methanol is added until the beginning of opalescence (which takes about 200 g methanol). The solution is concentrated at ambient pressure by heating to 50 0 C in order to remove the methylene chloride.

The polymer, which is insoluble in methanol, is precipitated, whereas the residual monomer remains in solution. 50 g pure polymer is obtained after drying.

Analyses: TLC on silica gel; UV development; solvent

CHCI

3 eluent ethyle ether.

Polymer: Rf 0 Absence of monomer (Rf UV spectrum: max (CHC3) 356 nm as= 69.2 *9 Determination of the molecular weight distribution under conditions identical to those in example 2.

M 4,000 S4,000 M <17,000 63% 17,000 M <40,000 2% *9 40,000 M not detectable.

S EXAMPLE Copolymer composed of d1[3-(4'-acrylamidomethyl-benzyidene)] camphor and [2-(2'-hydroxy-3'-acrylamidomethyl-5'-t'octyl phenyl)] S 2H-benzotriazole.

9 g of monomer prepared as in example 1, stage 1, of monomer prepared as in example 3, stage 1, 200 g isopropanol and 20 g ascorbic in solution in 100 g water are introduced into a reactor. The reaction mixture is brought to reflux and I I I- 1 f r -17then 75 g of a 30% hydrogen peroxide solution diluted with g water is introduced. During the reaction the polymer formed is separated from the solvent. On ceasing stirring after a reaction time of 4 hours the polymer is deposited at the bottom of the reactor. The supernatant phase, composed of isopropyl alcohol, water, monomers and iniator residues, is removed. The polymer is dissolved in 200 g methylene chloride and isopropyl ether is then added until there is a beginning of opalescence. The solution is concentrated under normal pressure at 50 0 C until the methylene chloride is removed, which brings about the precipitation of the polymer in the form of an oil. It is collected, dried and pulverized. 80 g of light yellow powder is obtained.

ANALYSES:

TLC: support: silica gel with fluorescence indicator; eluent: ethyl acetate or diethyl ether.

Results: absence of residual monomers; polymer Rf 0 UV spectrum at 1 mg/100 ml in CjuCI 3 max. 298 nm 42 340 nm 18 Molecular weight distribution: more than 80% of the lee.: polymer having a molecular weight less than 20,000.

EXAMPI 6 Homopolymer ofdl[3-(acrylamidomethyl-4'benzylidene)] camphor.

g of the monomer of example 1, stage 1, 30 g isopropanol, 2.25 g of a 30% solution of hydrogen peroxide and 0.375 g dodecy mercaptan are mixed. The reaction mixture is brought to the solvent reflux, and then a solution of 1.5 g ascorbic -18acid in 30 ml water is added. The completion of polymerization and the purification of the polymer are effected as in example 1, stage 4.

The polymer is characterized by its UV spectrum in solution ir chloroform 296 nm a 59 max s Distribution of molecular weights: more than 80% polymer having a molecular weight less than 20,000.

EXAMPLE 7 Copolymer composed of [3-(4'-acrylamidomethyl-benzylidene)] di-camphor and trimethyl ammoniopropyl methacrylamide chloride (or MAPTAC).

I 160 g of the monomer of example 1, stage 1, 80 g of an *o aqueous 50% solution of MAPTAC, 120 g isopropanol and 20 g acetic acid are mixed. This mixture is brought, under nitrogen to solvent reflux and then a solution of 75 of 30% hydrogen peroxide, diluted with 30 g water, is added regularly in minutes.

At the end of this addition the reaction is continued for 2 hours, and them the reaction mixture, concentrated to S 270 g, is diluted with 55 g acetone. The opalescent solution of raw polymer is poured slowly into 5.5 litres of acetone with vigorous stirring and the polymer presipitated is collected and a dried. 66 g of pure polymer which is soluble in water is obtained.

a

TLC

support: silica gel; solvent: methanol; eluent: ethyl acetate.

Absence of residual filter monomer.

-19- UV spectrum in water: -a 295 nm a max s NMR 1H: indicates a composition of 40% filter monomer structural units and 60% MAPTAC structural units.

Molecular weight distribution: more than 80% polymer having a molecular weight less than 20,000.

EXAMPLE 8.

Copolymer composed of 2H-[2-(2'-hydroxy-3'-acryliamidophenyl)]-benzotriazole and MAPTAC.

g of the monomer prepared as in example 3, stage 1, to 110 g of a 50% MAPTAC solution, 5 g dodecyl mercaptan, 200 g isopropanol and 2.5 g azobis-isobutyronitrile are mied together. This mixture, under notrogen, is brought to solvent reflux and held there for 6 hours. The polymer formed, which is insoluble in the reaction medium, is recovered and dissolved in a 50/50 mixture of methylene chloride and methanol, then precipitated with 6 litres diethyl ether. After drying, 79 g of water-soluble polymer is obtained.

L

S TLC.

Support: silica gel; solvent: methanol; eluent: diethyl ether.

Absence of residual filter monomer.

*9 S UV spectrum in water max 1= 300 nm a s 12.0 Amax 2 335 nm a s 10.7 Molecular weight distribution: more than 80% polymer having a molecular weight less than 20,000.

y iLi 1) i___li EXAM!'LE 9 Copolymer composed of [3-(4'-acrylamidomethyl-benzylidene)] dl-camphor and 2-acryla r nido-2-methylpropane sulphonic acid (AMPS).

g of polymer prepared as in example 1, stage 1, 5 g AMPS, 200 g isopropanol and 20 g ascorbic acid in solution in 100 g water are mixed together. This mixture is brought to the solvent reflux and 75 g of a 30% hydrogen peroxide solution diluted with 30 g water is added regularly within 30 minutes.

The polymerization reaction is continued for 2 hours. The precipitated polymer is dissolved in 200 ml tetrahydrofurane and precipitated in 4 litres acetonitrile. After drying 76 g of pure polymer is obtained.

TLC

Support: silica gel; solvent: chloroform; eluent: ethyl acetate.

Absence of free filter monomer.

UV spectrum in chloroform n 296 nm a 52 n s Microanalysis: C H N S ound: 72.9 7.8 4,1 0.6 Molecular weight distribution: more than 80% polymer having a molecular weight 'ess than 20,000.

EXAMPLE Copolymer composed of [3-(4'-acrylamidomethyl-benzylidene] dl-camphor and AMPS.

g monomer prepared as in example i, stage 1, 40 g AMPS, 200 g isopropanol and 20 g ascorbic acid in solution in 100 g water are mixed together.

This mixture is brought to solvent reflux and then 75 g of a 30% hydrogen peroxide solution diluted with 30 g water is -21added within 30 minutes. The polymerization reaction is continued for 2 1 hours. The heterogeneous reaction mixture is homogenized with 50 g methanol, brought to neutrality by the addition of a 5N sodium hydroxide solution and then precipitated in 4 litres acetonitrile.

63 g of water-soluble ploymer is obtained.

TLC

Support: silica gel; solvent: methanol; eluent: diethyl ether Absence of free filter monomer.

UV spectrum in water: a" 298 nm a s 12.5 max s Microanalysis: C H N S *o Found: 46.29 5.77 3.70 5.10 Molecular weight distribution: more than 80% polymer having a molecular weight less than 20,000.

EXAMPLE 11 Copolymer composed of [3-(4'-acrylamidomethyl-benzylidene)] dl-camphor and acrylic acid.

10 g monomer prepared as in example 1, stage 1, 40 g acrylic acid, 100 g isopropanol and 7.5 g of a 300 hydrogen peroxide solution are mixed together. The reaction mixture is brought to reflux, A solution of 5 g ascorbic acid in 100 g water is added regularly within 3 hours. The polymerizatioxi reaction is maintained for 4 hours.

The final reaction medium is concentrated, then diluted with acetonitrile until opalescence appears, then finally recipitated in 2 litres acetonitrile.

29 g of dry product is obtained which, after neutraliz- -34 ilYL1IILii .il- L -22ation with sodium hydroxide, is completely soluble in water.

TLC:

Support: silica gel; solvent: methanol; eluent: diethyl ether Absence of residual filter monomer.

UV specturm (before neutralization) in methanol: A 296 nm a 11.9 max s Acid number: 470 Microanalysis: C H N 0 (before neutralization) Found: 53.9 6.5 1.6 35.5 Molecular weight distribution; more than 80% polymer having a molecular weight less than 20,000.

EXAMPLE 12 Copolymer composed of [3-(4'-acrylamidomethyl-benzylidene] dl-camphor and N,N-dimethylacrylamide.

4g monomer prepared as in example 1, stage 3, 16 g N,Ndimethylacrylamide, 40 g isopropanol a 3 g 30% hydrogen peroxide solution are mixed, the reaction mixture is reflux heated and a solution of 2 g ascorbic acid in 40 g water is added regularly within 3 hours. The polymerization reaction is maintained for 4 hours. The reaction mixture is concentrated, the residue is dissolved in 100 g acetone and precipitated in 1 litre ethyl acetate. 13 g of product soluble in water, propylene carbonate and sorbitol is obtained.

TLC:

Support: silica gel; solvent: methanol; eluent: ethyl acetate.

Absence of residual filter monomer.

UV spectrum in ethanol: max 294 nm a s 8 a) Thin-layer chroma~ogjraphy (TLC) silica gel Fupport with fluorescence indicator, eluent ethyl acetate, devleopment with UV and iodine vapour.

-23- Microanalysis: C H N 0 Found: 56.3 8.4 10.3 23.6 Molecular weight d',.stribution: more than 80% polymer having a molecular weight less than 20,000.

COMPARATIVE EXAMPLE The polymer prepared as in example 2 is compared with the homopolymer prepared as in example 6 of French patent 73,23254, which is characterized under conditions identical to thoqe previously described. The results are as follows, a) molecular weight di4stribution: M 'c 4000 13" 4,000 v Fi s 17,000 33rc 17,000 M 40,000 20 Z .40,000 Fvi 68,000 15 O2 68,000 M1 192, b) Easo of application.

The polymer prepared as in example 2 of the present patent application is more readily formulable than the polymer as in example 6 of French patent 73.23254. It is, in fact, more rapidly soluble than the latter in the oily phases of the emulsions and at lower temperature. These differences are ill.ustrated by a comparison of the following formuLie.

Mixture of glycerol mono- and distearate, marketed by Gattefosse under the name G~~O 1 2 q *.Mixture of C 12 -C is aliphatic alcohols .7 9 Cetyl alcohol.... Vaseline oil 5 g Blenzoate of alcohols with 12 to 15 carbon atoms marketed by V'INETE under the name VINSOIV-MNIS q Polymer Total 35.5 qj *Polymer as in example 2, or comparison polymer.

*e9e 4 4@e* 4 4

S.

0@44

S

4 4 Seq 4O 5 4 0*SS

S.

SS@

*q 4

S.

-24it is found that the polymer prepared as in example 2 is dissolved in 10 minutes at 95*C, whereas the polymer prepared as in example 6 of French patent 73.23254 is dissolved in minutes at the same temperature.

c) Cosmetic properties.

Two creams were prepared in the form of oil-in-water emulsions, the fat phases of which were composed of the oil solutions prepared above and 0.5 g polydimethylsiloxane, marketed by Dow Corning under the name Fluid 200.

The atqueous phase is composed of; 20 q KATI1ON-CG (preservative; Rohm P~id Haas) q, s Perfume, q.s.

Water, q It was found that the cream containing the polymer prepared as in example 2 is more lubricating, is less adhesive and has, on application, a loss greasy cppearance and feel than the cream containing the polymer perpared as in example 6 of French patent 73.23254.

Examples of Cosmetic preparations Examle Using the procedure described i.n the comparative example above, an anti-solar cream was prepared (oil-in-water emulsion) replacing the polymer of example 2 1by the polymer of example, 1, Exaple B In a similar manner a cream (water-in-oil emulsion) was prepared which had the following formulation: 4 4 S. S .5

S

0~,SS**

S

Polymer of example 2 -Magnesium starate.

00tyl dodecanol.

Hlydrogenated lanolin marketed by ONYX under the name 1IYDROtAN It 5 q 4 V C Clear lanolin 4 g -Beeswax 6 g Sorbitol sesquioleate 4.5 g Glycerol monostearate I g Oleic alcohol .5 g 2-ethylhexyl palmitic glyceryl ether palmitic ester 2 g Vasriine oil 20 g Preservative 0.2 g Demineraliz( dj waster, qsp V I 100 g It is possible to replace the polymer of example 2 by one of the polymers prepared as in examples 5 or 6 in this example.

Example C A composition was prepared in the form of a solar oil having the following formilatbion: Polymer of example 4 0* O Oloic alcohol Pentacrythritol tetracaprylate/ Otarate marketed tnder the name cnCRODAM01 PTC y CROO A Ditertiobutyl paacrecol 005q flnzoate of C 1 2

-C

1 5 alcohol, marketed by VIN1E1flX under the name FINSObV TN 49.,45 q S A composition in the form Of a milk w4; prepared having **too: the following formulation -Polymr of examplo2 4 5 q Olcoetylio qlcohol with 30 moles ethylene oxide 3 q -Stearylia aoid 5 q 010ic alcohol 6 g Palmitic eater of other 4 q Vaaeollne oil 10 gf ~ijji p i i-.i c i _ii- i i I i ~il. Y~ -26- .t d t. &n r S 5~ Polydimethyl silane 1 g Sorbitol, 70% 5 g Preservative (KATHON CG). 0.2 g Perfume .0.6 g Demineralized water, qsp. 100 g A similar compositi- was prepared by replacing in the preceding formulation the polymer of example 2 by the polymer of example 3.

Example E A composition was prepared in the form of a thickened oil having the following formulationz -Polymer of example 3 1 g 2-thylheyl paramethoxy cinnamate 2 g MyristLic alcohol with 3 moles propylene oxide marketed by WITCO under the name WITCONOL APM 2-thylhexyl palmitate 10 g Ditertiobutyl paracrosol. 0.059 Silica marketed by DEGUSSA under the name AEROSIL R972 6 g -Perfume.... Isostearyl benzoate, gsp. 100 g A simi:- compound was pr oared by replacing, in this example, the polymer of example 3 by the polymer of example 4.

Example F A composition was prepared in the form of an oi-in-water emulsion having the following formulation: Polymer of example 2 5 g Mixture 80/20 of cetyl/stearylic alcohol wh 33 moles ethylene oxide marketed by IIENIKEL under the name SINNOWAX AO .7 g Mixture of glycerol mono- and distearate marketed by GATTEFOSSE under the name GELEOL 2 g L. -27- Cetyl alcohol. 1.5 g Vascline oil 5 g Benzoate of C 2

-C,

1 alcohols marketed by FINETEX un er He name FINSOLV TN 15 g Glycerine 20 g Preservative. 0.2 g Perfume. 0.6 g Demineralized water, g Example G A composition was prepal,:ed in the form of a stick having thet following formulation: -Polymer of example 4 1 g -Glyceryl tribehenate 6 g -Glyceric ester of C 1

-C

3 fatty acids marketed by CRODA unc er he name *'SYNCROWAX IHGL-C. 8 g -Glycol distearate marketed by CRODA under the name SYNCROWAX ERI 4 C 6 g *-Ricinoleic acid triglycerides .10 g -Oleic alcohol 10 g -Benzoate of C 12 -C alcohols marketed -byFINETEX under the nay PFINSQIN TN 58.9 g Ditertiobutyl paracresoai 0.1 g Example H *A composition was prepared in the form of a solar oil having the following formulation: Polymer of example 2. 2-ethylhexyl para-amino b nzoate. 2 .9 g 2-ethyihexyl paramethoxy cinnamate 4 g Qleic alcohol 15 g Isopropyl myrisitate 20 g Palmitio ester of 2-othylhexyl glyceryl ether 6 g Cyclopentadimethyl siloxane 5 g Octamethylcyclotetra, siloxane .5 g Cyclotetradimthy. siloxane, qsp 100 g -28- Example I A composition was prepared in the form of the following formulation: a milk having Polymer of example 3 7 Oleocerylic alcohol with 30 moles ethylene oxide 6 Stearylic alcohol. 4 Polydimethyl siloxane 1 Benzoate of C 12 C g alcohols marketed byFINETEX und~r t je name FINSOLV TN Oleic alcohol 4 Sorbitol, 70% Preservative (KATHON Perfume 0.2 Deminoralized water, qsp. 100 a.

a a 0e a.

0S** a.

a a.

a a 0O a a 0* a a a a.

a A similar composi tion was prepared by replac.Knq in this formulation the polymer of example 3 by that of example 4.

Example J A composition Nwas prepared in -the form of an emulsion having -the following formulation: oil-in-water -Polymer of example 2 3 g -2-ethylhexyl parame-thoxycinnamate. 3 g g -Sorbitol, 4 g -Soya lecithine, 40%, in surfactant solution marketed by AMERICAN LECITHIN uinder -the natw, ALCO1LEC Shea '.utter. 4 g g -Sunflower oil. 6 g -Isostearyl benzoate. 10 g Preservative 0.03g g Cetyl 6 g Stea-'7l g -Demineralized q .111.1.1-1-1- -29- Example K SOLAR GEL Polymer prepared as in example 7 2.5 g Cellosize PCG 10 (hydroxyethyl cellulose) 1 g Ethyl alcohol 12 g Propylene glycol. 8 g Preservative s Perfume qs Water qsp- 100 g Example I SOLAR CREAM (oil-in-water emulsion) Po'.rrnIer prepared as in example 12 4 g Steairic acid 2.5 g Triethanolaw.ine 0.2 g -Liquid lanolin. 6 g Mixture of glycerol monostearate and polyethylene glycol stearate (100 OE) 5 g Triglycer-4dog of myristic/palmitic! -stearic g -Stearyl alcohol Vaseline oil 10 g Propylene glycol. g if- Preservative qs -Perfume qs 100 g Example M SOLAR LOTION -Polymer prepared as in example 10 .1.5 g -Polymer prepared as in example 9 .1.5 g -Mixture of glycerol monostearate and polyethylene glycol stearate (100 OE) 50/50 2.5 g -Stearyl alcohol 4 g -Vaseline oil 10 g -Isopropyl myristate 5 g -Cellosize PCG (hydroxyethyl cellulose 0.5 g -Preservative. qs -Perfume qs -Water qsp 100.0 g Example N SOLAR CREAM (oil-in--water emulsion) Polymer prepared as in example 8 5.0 g Mixture of cetyl/stearyl alcohol and cetyl/ox:yehtylenated stearyl alcohol (33 OE) g Glycerol mono- and distearate 2.0 g Cetyl g 0:00 -C 1

&-C

1 alc ohol benzoate marketed oboeun er he name FINSOLV TN (WITCO). .15.0 g -Glycerine. 5.0 g -Preservative s Perfume s Water qsp 100.0 g Example 0 SOLAR CREAM (water-in-oil emulsion) -Polymer prepared as in example 11 2.0 g -Esters of glycerine/sorbitol and fatty acid marketed by ATLAS under *the name ARLjACEL 481 4.0 g -Hydrogenated polyoxyethylenated castor oil with 7 moles ethylene oxide marketed by ATLAS under the name ARLACEL hydroxyoctacosanyl- 12-hydroxy- 9 stearate marketed by AZKO under the name ELFACOS C 5.0 g -Vaseline oil. 15.0 g -Isopropyl myristate. 4.0 g -NaOH s pH=;8. 0 -Water splO0O g

Claims

3. Preparations as in claim 2, wherein the hydrophilic comonomer is ethylenically unsaturated.
4. Preparations as in any preceding claim, characterized in that fewer than 10% of the polymer molecules have a molecular weight greater than 40,000.
5. Preparations as in any preceding claims, characterized in that said polymer contains structural units of formula I CH 2 C NI -C -x in which X represents an aromatic group imparting to the polymers an absorption of ultraviolet radiation in the 900305,oudat.073.1orea1, 2.2 v 4
32- 12 13 13 14 16 17 17 18 19 21 22 23 24 26 27 28 29 wavelength zone ranging from 280 to 400 nm, provided that the structural units of formula I represent at least 10% by weight of the polymer. 6. Preparations as in claim 5, characterized in that *he structural units of formula I represent from 10 to 99% by weight of the polymer. 7. Preparations as in claim 5 or claim 6, characterized in that X is selected from the groups of formulae: 0" at C 3 0 ~-CO 2 -CO in which R represents a methyl or tertiary-octyl group of formula O3 H 3 3 and Z represents a t-butyl group. 8. Preparations as in any one of claims 5 to 7, characterized in that said hydrophilic comonomers are selected from N-vinylpyrrolidone, N,N-dimethylacrylamide, 900305, ndat.073.1oreal,l,3 V er
33- acrylic acid, methacrylic acid and monomers of the general formula: R 2 C11 C CO M(CH2) N (11) 0*e V V. V.9. 0r V@* 0 S *5e*~ in which M represents or -NH-, x is a number equal to 2 or 3, R 1 represents -H or -CH 3 and R 2 represents -CH 3 or provided that the amine groups present can be quaternized or salified before or after polymerization. 9. Cosmetic preparations as in any one of the preceding claims, characterized in that the concentration of said polymer is from 1 to 20% by weight in relation to the total weight of the preparation. 10. Cosmetic preparations as in any one of the preceding claims, characterized in that they occur in the form of aqueous, h.droalcoholic or oil solutions, aqueous emulsions, lotions, creams, milks, gels, sticks or in the form of preparations for aerosols. 21 22 23 24 25 26 27 28 29 31 32 33 34 36 900305, c ca at,073, loreal.1 4 I t 34 11. Cosmetic preparations in accordance with claim 1 and substantially as hereinbefore described with reference to the Examples excluding the Comparative Example. 8 9 11 12 13 17 18 18 19 21 22 S 23 24 S 26 27 28 29 31 32 33 34 36 37 38 DATED THIS 5th March, 1990 DAVIES COLLISON Fellows Institute of Patent Attorneys of Australia. Patent Attorneys for the Applicant 900305,cudat.073, loraa4.