AU678911B2

AU678911B2 - Novel sunscreens, photoprotective cosmetic compositions containing them and uses thereof

Info

Publication number: AU678911B2
Application number: AU34380/95A
Authority: AU
Inventors: Alain Lagrange; Madeleine Leduc; Herve Richard
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1994-11-17
Filing date: 1995-10-20
Publication date: 1997-06-12
Anticipated expiration: 2015-10-20
Also published as: CA2163073A1; DE69500729D1; KR100217968B1; EP0712855A1; PL311397A1; CN1050361C; JPH08225582A; CN1133292A; MX9504683A; BR9504923A; EP0712855B1; RU2123006C1; AR000136A1; AU3438095A; HUT74046A; JP2821405B2; DE69500729T2; HU9503279D0; ES2112617T3; PL182416B1

Description

AUSTRALIA

Patents Act 1990 COMHPLETE SPECIFICATION STANnA2RD PATENT gas* #4 0 Applicant:

L'"OREAL

Invention Title: NOVEL SUNSCREENS, PHOTC)PROTECTIVE COSMETIC COMPOSITIONS CONTAINING THEM AND USES THEREOF The following statement is zi full description of this invention, including the best meth.,.d of performing it known to me/us: 1A NOVEL SUNSCREENS, PHOTOPROTECTIVE COSMETIC COMPOSITIONS CONTAINING THEM AND USES THEREOF The present invention relates to novel compounds of the linear or cyclic short-chain diorganosiloxane type, or of the triorganosilane type, having the common characteristic of all having at least one specific and appropriately selected screening unit containing sulphonamide functionality, it being possible for these compounds to be used more particularly as organic sunscreens in cosmetic compositions intended for the protection of the skin and the hair against ultraviolet radiation. The invention also relates to the use of the said compounds in the abovementioned cosmetic application, as well as 15 to the cosmetic compositions with enhanced properties containing them.

It is known that light radiation with wavelengths of between 280 nm and 400 nm permits 0 tanning of the human epidermis, and that light rays 20 with wavelengths more particularly between 280 and 00 320 nm, known as UV-B rays, cause skin burns and erythema which may be harmful to the natural development of the tan; this UV-B radiation should thus be screened out.

0 S 25 It is also known that UV-A rays, with wavelengths of between 320 and 400 nm, which cause tanning of the skin, are liable to induce an adverse change in the latter, especially in the case of L I sensitive skin or of skin which is continually exposed to solar radiation. UV-A rays cause in particular a loss of elasticity of the skin and the appearance of wrinkles, leading to premature skin ageing. They promote triggering of the erythemal reaction or amplify this reaction in certain individuals and may even be the cause of phototoxic or photoallergic reactions. It is thus desirable also to screen out UV-A radiation.

Many compounds intended for the photoprotection (UV-A and/or UV-B) of the skin have been proposed to date.

Most of these are aromatic compounds having an absorption of UV rays in the region between 280 and 315 nm, or in the region between 315 and 400 nm, or 15 alternatively in both of these regions. They are usually formulated in antisun compositions which are in the form of an emulsion of oil-in-water type (that is :0 to say a cosmetically acceptable vehicle consisting of an aqueous dispersing continuous phase and an oily 0 20 disperse discontinuous phase) and which thus contain, in various concentrations, one or more standard organic screening agents containing lipophilic and/or 0* hydrophilic, aromatic functionality, capable of selectively absorbing harmful UV radiation, these 25 screening agents (and the amounts thereof) being selected as a function of the desired protection factor (the protection factor (PF) being expressed mathematically by the ratio of the irradiation time

-L

necessary to reach the erythema-forming threshold with the UV screening agent to the time necessary to reach the erythema-forming threshold without UV screening agent).

Besides their screening power, these compounds with anti-UV activity should also have good cosmetic properties in the compositions which contain them, good solubility in the usual solvents and, in particular, fatty substances such as oils and fats, as well as good resistance to water and to perspiration (remanence).

Among all the aromatic compounds which have been recommended for this purpose, there may in particular be mentioned p-aminobenzoic acid S 15 derivatives, benzylidenecamphor derivatives and in particular 3-benzylidenecamphor derivatives, cinnamic acid derivatives and benzotriazole derivatives.

o.

However, some of these substances do not have all the required properties for a suitable use as UV screening S 20 agents in antisun compositions. In particular, their intrinsic screening power may be insufficient, their solubility in the various types of formulations used as regards sun protection is not always good enough (liposolubility in particular), they may not be 25 sufficiently light-fast (photostability) and they may also have poor resistance to water and to sweat. It is also desirable for these screening substances not to penetrate into the skin.

Thus, in the more specific case of the screening substances of benzotriazole or 3-benzylidenecamphor type, it has been sought to obtain products having improved properties, in particular as regards their liposolubility and their cosmetic nature, by attaching the benzotriazole or 3-benzylidenecamphor screening group by grafting (hydrosilylation) to a macromolecular chain of silicone type (organopolysiloxane) using a connector chain unit of alkylene or alkylenoxy type. This technique, described respectively in Patent Applications EP-A-0,392,883 (benzotriazole) and EP-A-0,335,777 (3benzylidenecamphor), both in the name of the Applicant, do admittedly lead to advantageous compounds (these 15 compounds are known generally as "screening silicones"), but the liposoluble nature of these compounds may still appear to be insufficient and, in o. addition, in ordei to obtain satisfactory screening properties with products of this type, it is often 20 necessary to use relatively large amounts of these screening polymers, which is reflected in poor cosmetic e properties as regards the formulations which contain them.

The present invention is directed towards 25 overcoming the above problems by proposing novel compounds, of screening silicone type, containing specific screening units, which have improved properties, in particular as regards their solubility in fatty substances and their cosmetic properties.

Even more precisely, it has been found, according to the present invention, that by attaching one or more specific screening units chosen from 3-benzylidenecamphor derivatives, benzotriazoles, benzophenones and benzimidazoles, by grafting, in particular by a hydrosilylation reaction, to a suitably selected linear or cyclic silicone chain, or to a suitably selected silane, via a specific connector chain unit containing sulphonamide functionality, it was possible to arrive at novel compounds of the screening silicone type, obviating the drawbacks of the screening silicones of the prior art, these novel compounds having in particular very good screening S 15 properties, either in the UV-A range or in the UV-B range depending on their chemical structure, very good Ssolubility in the usual organic solvents and in particular in fatty substances such as oils, as well as excellent cosmetic properties, making them particularly 20 suitable for use as sunscreens in, or for the 6 preparation of, cosmetic compositions intended for the protection of the skin and/or the hair against ultraviolet radiation.

The first subject of the present invention is 25 thus novel compounds which are characterized in that they correspond to one of the following formulae to LL-l M

I

6 R R B-si -i si- (1) i t R R or I (2) "different, are chosen from C-Co alkyl, phenyl and or 3,3,3-trifluoropropyl radicals, at least 80 in numerical terms, of the radicals R being methyl, in- the groups B, which may be identical or different, are chosen from the above radicals R and the radical A defined below, oeo S- the groups which may be identical or different, are chosen from Cl-C. alkyl radicals, or sophenyl radicals, S15 r is an integer between 0 and 50entical or inclusively, and s is an integer between 0 and inclusivdifferent, with the condition that if a is zero then *C radical A defined below, the groups which may be identical or different, are chosen from C 1

-C

8 alkyl radicals, or phenyl radicals, r is an integer between 0 and inclusively, and s is an integer between 0 and inclusively, with the condition that if s is zero then -n "s 7 at least one of the two symbols B denotes A, u is an integer between 1 and 6 inclusively, and t is an integer between 0 and inclusively, it being understood that t u is equal to or greater than 3, and the symbol A denotes a radical directly attached to a silicon atom, the said radical A corresponding to one of the following formulae to 1) 2 x I(4.1) 0 10 in which formula

X

1 represents a hydrogen atom or a e* S* divalent radical of following formula -SO0-N- CH-CH,- SR2 R

C

15 in which formula

C

SR

1 denotes a hydrogen atom or a

C

1

-C

4 alkyl or hydroxyalkyl radical,

R

2 represents a hydrogen atom or a

C

1

-C

6 alkyl or C 1

-C

6 alkoxy radical, p is an integer between 1 and inclusively,

-II

8 the end -CH 2 group is directly attached to a silicon atom;

X

2 and X 3 which may be identical or different, represent a hydrogen or halogen atom, a CI-C 4 alkyl or alkoxy radical, a divalent radical or a radical Z of following formula (6) X o 0 or alternatively may together form an t,6** 10 alkylidenedioxy group in which the a alkylidene group contains 1 or 2 carbon atoms; it being understood that in this formula 15 one of the three symbols X 1

X

2 and X 3 must '0400 necessarily represent a divalent radical and each of the other two remaining symbols cannot then represent a divalent radical S if X represents a hydrogen atom, X 2 and X 3

S.

are then necessarily different and neither may represent a radical Z, if X 1 represents a divalent radical X 2 ,r I a and X 3 cannot then simultaneously represunt a radical

Z,

if X 1 denotes a hydrogen atom and X 3 represents a divalent radical X 2 is then preferably other than a hydrogen atom; 2) ,xS, s(4.2)

R

3 in which formula

X

4 represents a hydrogen atom, a C -C 8 alkyl radical or a divalent radical 10 X 5 represents a hydrogen or halogen o atom, a CI-C 4 alkyl or alkoxy radical or a divalent radical

R

3 represents a C 1

-C

8 alkyl radical, *it being understood that, in this formula one of the two symbols X 4 and X 5 must necessarily represent a divalent radical it not being possible for the remaining symbol to represent a divalent radical i C~1-~C~C- (4.3) 4) o OH IN 4 (4.4)

OCH

3

Y

In the formulae and above, A thus represents a screening group selected from 3-benzylidenecamphor derivatives (formula benzotriazoles (formula benzimidazoles (formula 4.3) and benzophenones (formula 4.4) which, after attaching to the short starting silicone-containing chain or to the starting silane, imparts absorbent properties to the compounds of linear diorganosiloxane type (formula or cyclic diorganosiloxane type (formula or of triorganosilane type (formula with respect to ultraviolet radiation within a wavelength region which may range from 280 to 400 nm. As indicated above, and as emerges in the definitions of formulae to given above, this group necessarily has at least 15 one sulphonamide function (formula 5) which is provided by the chain unit which ensures anchoring of the screening unit to the silicone chain or to the silane.

One of the advantages attached to the compounds 4 0**0 *c 0 00 C. a

C..

C...D

C

a I-r according to the invention, and more particularly to those for which the screening unit A corresponds to formula or to formula is that it is possible to obtain, depending on the nature and/or the position of the various substituents carried by this screening unit A, agents which either purely screen UV-A or, on the contrary, purely screen UV-B, with particularly high extinction coefficients.

As emerges from the definitions given above, the chain unit -S02-N(R 1

)-(CH

2 )p-CH(R 2

)-CH

2 (that is to say the divalent radical of formula possessing the sulphonamide function) may, according to the present invention, be anchored onto a screening unit derived from 3-benzylidenecamphor, which thus ensures connection of the said unit to the silicon atom of the silicone-containing chain or of the silane, in any one of the positions occupied by the symbols X 1

X

2 and X 3 the -SO2- end part of the said chain unit becoming attached to the unit derived from 3-benzylidenecamphor 20 and its -CH 2 end part becoming attached to a silicon 9.

atom of the silicone-containing chain or of the silane.

Still in the specific case in which the screening unit used is a 3-benzylidenecamphor derivative, it should also be noted that this screening unit may optionally 25 possess two connector chain units (this is effectively possible when X 1 represents a divalent radical and when, simultaneously, X 2 or X 3 represents a radical Z carrying this same divalent radical and may thus l I M be connected to two different silicone-containing chains or to two different silyl units.

In the case of a screening unit of benzotriazole type (formula 4.2) or of benzimidazole type (formula 4.3) or of benzophenone type (formula there can only be a single connector chain unit this chain unit is located at one of the positions occupied by the symbols X 4 and X 5 in the case of benzotriazoles, and in well-defined set positions in the other latter cases.

In the above formulae to the alkyl radicals may be linear or branched and chosen in particular from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-amyl, isoamyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylnexyl and t. tert-octyl radicals. The preferred alkyl radicals R, R' and B according to the invention are the methyl, ethyl, S* propyl, n-butyl, n-octyl and 2-ethylhexyl radicals.

Even more preferably, the radicals R, R' and B are all methyl radicals. As regards the halogens, they may be chosen in particular from chlorine, fluorine and bromine, and are preferably chlorine. The alkoxy radicals may be chosen in particular from the methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and isobutoxy 25 radicals.

Among the compounds of formulae to (3) above, it is preferred to use those corresponding to formula or to formula that is to say linear or I~L~LYa. -C dll 13 cyclic short-chain diorganosiloxanes.

Among the linear or cyclic diorganosiloxanes falling within the scope of the present invention, the random derivatives or well-defined block derivatives having at least one, and more preferably all of the characteristics below (except for the cases of mutual exclusions mentioned above for the three symbols X X 2 and X 3 when the screening unit is a 3benzylidenecamphor derivative, or for the two symbols

X

4 and X 5 when the screening unit is a benzotriazole) are more particularly preferred: R is alkyl and, even more preferably, is methyl, B is alkyl and, even more preferably, methyl (in the case of the linear compounds of formula r is between 0 and 3 inclusively; s is between 0 and 3 inclusively (in the case of the linear compounds of formula t+u is between 3 and 5 (in the case of the cyclic compounds of formula

R

1 is H,

R

2 is H or methyl, p is between 1 and 3 inclusively,

X

1 is H or

X

2 is H, methyl, methoxy, or Z, I I

X

3 is H or

X

4 is tert-butyl or

X

5 is H or

R

3 is methyl or tert-butyl.

The preferred compounds of formula to (3) within the context of the present invention are those which represent screening units A chosen from the 3-benzylidenecamphor derivatives corresponding to formula given above.

In order to prepare the silicone-containing screening agents of formula and it is possible to follow a standard procedure (route 1) using a hydrosilylation reaction: =Si-H CH2=C- =Si-CH2-CH- *I I S• starting with the corresponding silicone in which, for 15 example, all the radicals A are hydrogen atoms. This starting silicone is referred to hereinbelow as derivative containing SiH; the SiH groups may be present in the chain and/or at the ends of the silicone chain. These derivatives containing SiH are well-known S 20 products in the silicone industry and are generally commercially available. They are described, for example, in American Patents US-A-3,220,972, US-A-3,697,473 and US-A-4,340,709.

This derivative containing SiH may thus be

-I

represented, depending on the case, either by the following formula (Ibis): R R -R R B' -Sii- 0 (I bis) R

R

in which R, r and s have the meanings given above for formula and the radicals which may be identical or different, are chosen from the radicals R and a hydrogen atom, or by the following formula (2bis): R

-R

I I S(2bis) t U a.

S* in which R, t and u have the meanings given above for formula *e 10 A standard hyd:osilylation reaction is thus carried out on this derivative containing SiH of formula (Ibis) or (2his), in the presence of a catalytically effective amount of a platinum catalyst, *a which is performed, depending on the case (i.e.

depending on the nature of the screening unit to be grafted) w either on an organic 3-benzylidenecamphor derivative of following formula (4.1bis): x

X

(4.1bis) x

X

0 in which X 1

X

2 and X 3 have the same meanings as those given above for formula except that one of these three radicals, instead of representing a saturated divalent radical of formula defined above, represents in this case the corresponding unsaturated homologous monovalent radical of following formula (CHp -C CH 1112 R R in which R R 2 and p have the same meanings as in 10 formula or on an organic benzotriazole derivative of following formula (4.2bis) o N OH

X

4 N(4.2bis)

X

5

S

0 R3 o in which X 4 and X 5 have the same meanings as those given above for formula except that one of these two III 17 radicals, instead of representing a saturated divalent radical of formula defined above, represents in this case the corresponding unsaturated homologous monovalent radical of formula (5bis) given above; or on an organic benzimidazole derivative of following formula (4.3bis): (4.3bis) in which Y' represents the unsaturated monovalent radical of formula (5bis) given above, a homologue of the saturated diradical of formula or on an organic benzophenone derivative of following formula (4.4bis): o oH (4.4bis) 1 OCH 3

S*Y

1 0 0 in which Y' represents the unsaturated monovalent radical of formula (5bis) given above, the homologue of the saturated diradical of formula 15 Among the above compounds of formula (4.1bis) which fall within the scope of the present invention particularly well, there may in particular be mentioned: a) N-allyl-4-(4,7,7-trimethyl-3-oxobicyclo- 0 a 18 (2.2.lhept-2-ylidenemethyl)benzenesulphonamide b) N-allyl-C-[3-(4-methoxybenzylidene)-7,7dimethyl-2-oxobLiyclo [2.2 .1]hept- l-ylmethanesuiphonamide c) N-allyl-C-(3-benzylidene-7,7-dimethyl-2oxobicyclo[2.2.l]hept-1-yl)methanesulphonamide d) N-allyl-C-(3-benzo[l,3]dioxol-5ylmethylene-7,7-dimethyl-2-oxobicyclo[2.2.1]hept-1yl)methanesulphonamide.

e) N-(2-methyl-allyl)-4-(4,7,,-trimethyl-3oxobicyclo[2.2.llhept-2-ylidenemethyl)benzenesulphonamide.

The products of formulae (4.lbis) to (4.4bis) above may themselves be obtained in a conventional manner (see in particular, in this respect, *too FR-A-2,529,887 as regards the compounds of formula 4.lbis) by reacting the corresponding unsaturated amine of formula *9*9 H -N-R(CH2)-C C'2 R R in which R 1

R

2 and p have the same meanings as in formula 4*4*4* with (ii) the sulphonyl chloride of the screening unit which it is desired to graft, namely, therefore: either a sulphonyl chloride of an organic 3-benzylidenecamphor derivative chosen front those of following formula (4.lter): I-ea I X x (4.1ter) 0 in which X 1

X

2 and X 3 have the same meanings as those given above for formula except that one of these three radicals, instead of representing a divalent radical of formula defined above, represents in this case the monovalent radical -SO 2 Cl; or a sulphonyl chloride of an organic benzotriazole derivative chosen from those of following formula (4.2ter): N

OH

I X 4 oxx (4.2ter) R3 in which X 4 and X 5 have the same meanings as those given *this case the monovalent radical -SO2 or a benzimidazolesulphonyl chloride of 10 above following formula except that one of these two

L..

radicals, instead of representing a saturated divalent radical of formula defined above, represents in this case the monovalent radical -SO 2 Cl; or a benzimidazolesulphonyl chloride of 15 following formula (4.3ter) a~L clo 2 s (4.3ter) or a benzophenonesulphonyl chloride of following formula (4.4ter) 0 OH S(4.4ter)

OCH

3 80201 All of the above sulphonyl chlorides may themselves be obtained conventionally by reaction, in a 5 solvent such as DMF, between the corresponding S" sodium sulphonates (that is to say compounds of formulae 4.1bis, 4.2bis, 4.3bis and 4.4bis in which the 9 radical in this case denotes -SO 3 Na) and (ii) o hionyl chloride (see in particular in this respect the o. 9 abovementioned application FR-A-2,529,887).

The platinum catalysts used to perform the hydrosilylation reaction between the compounds of formula (Ibis) or (2bis) above with the compounds of formulae (4.lbis) to (4.4bis) above are well-known and widely described in the literature. There may in particular be mentioned the complexes of platinum and an organic product described in American Patents US-A-3,159,601, US-A-3,159,602, US-A-3,220,972 and European Patent Applications EP-A-0,057,459, s EP-A-0,188,978 and EP-A-0,190,530 and the complexes of platinum and vinyl organopolysiloxane described in American Patents US-A-3,419,593, US-A-3,377,432 and US-A-3,814,730. In order to react the compounds of formula (Ibis) or (2bis) with the compounds of formulae (4.1bis) to (4.4bis), an amount of platinum catalyst, calculated as weight of platinum metal, of between and 600 ppm, preferably of between 10 and 200 ppm, based on the weight of compounds of formula (ibis) or (2bis) is generally used. The hydrosilylation reaction may take place in bulk or in a volatile organic solvent such as toluene, heptane, xylene, tetrahydrofuran or tetrachloroethylene. It is generally desirable to heat the reaction mixture to a temperature of between 60 and ooe 15 120 0 C for the time required for the reaction to be complete. The compound of formula (Ibis) or (2bis) may be added dropwise to the compound of formula (4.1bis), (4.2bis), (4.3bis) or (4.4bis) in solution in an organic sol "ent containing the catalyst. The compound 20 of formula (Ibis) or (2bis) and the compound of formula (4.lbis) (or (4.2bis) to (4.4bis) respectively) may *i also be added simultaneously to a suspension of catalyst in an organic solvent. t is recommended to check that the reaction -s complete by assaying the residual SiH using alcoholic potassium hydroxide, followed by removal of the solvent, for example by distillation under reduced pressure. The crude oil obtained may be purified, for example by passage

I

22 through an absorbent column of silica.

As regards the preparation of the screening agents of triorganosilane type of formula given above, the process may be performed as indicated above, still by hydrosilylation reaction, this time between a starting silane of formula 3 SiH (formula (3bis), in which R' has the same meaning as for the compound of formula and an organic derivative chosen from (depending on the screening unit desired for the final product) an organic 3-benzylidenecamphor derivative of formula (4.1bis) defined above, an organic benzotriazole derivative of formula (4.2bis) defined above, an organic benzimidazole derivative of formula (4.3bis) defined above, and an organic benzophenone S 15 derivative of formula (4.4bis) defined above.

Another possible synthetic route (route 2) 8 which is suitable for the preparation of the siliconecontaining screening agents of formulae and (2) consists in starting with derivatives corresponding respectively to formula or to formula in which all the radicals A are replaced by the following radical of formula a N-c) R R in which R 1

R

2 and p have the same meanings as in formula The radicals of formula (5quater) may be present in the silicone-containing chain and/or at the ends of the silicone-containing chain. These starting amino siloxane derivatives may thus be represented either by the following formula (Iter) (linear amino siloxane derivative): R R R R I I I 1 B" -si-0- si-- S i-o- ter) R

LCH

CH-R2

(CI

2 p

NH

11

R

in which R, r and s have the meanings given above for formula and the radicals which may be identical Sor different, are chosen from the radicals R and the radical of formula 10 or by the following formula (2ter) (cyclic amino siloxane derivative): 6 o o I I I L R -R _si- I I (2ter)

CH

2 2

CH-R

I

(CM

2 p

NH

I1

R

U

in which R, t and u have the meanings given above for formula The amino siloxane derivatives of formula (Iter) or (2ter) above are well-known products in the S, 5 silicone industry and are generally commercially available. They are, in addition, described in particular in Patent Application DE-A-3,702,631, as regards the short chain silicones.

These amino siloxane derivatives are then reacted with the sulphonyl chloride of the screening unit which it is desired to graft on, namely, therefore: either a sulphonyl chloride of an organic 3-benzylidenecamphor derivative chosen from those of formula (4.1ter) defined above; or a sulphonyl chloride of an organic benzotriazole derivative chosen from those of formula I I -1 (4.2ter) defined above, or a sulphonyl chloride of a benzimidazole of formula (4.3ter) defined above; or a sulphonyl chloride of a benzophenone of formula (4.4ter) defined above.

Compared with the screening silicones of the prior art, and in particular with those described in the abovementioned patent applications EP-A-0,392,883 and EP-A-0,335,777, the screening silicones according to the invention thus have one or more essential structural differences, which are the source of their noteworthy properties, and in particular: the siliconecontaining chains, on which the selected screening S-units are grafted, are firstly much shorter; next, the selected screening unit still carries a sulphonamide function.

As indicated above, the compounds of formulae to above have excellent intrinsic screening power with regard to ultraviolet radiation (IV-A and/or 20 UV-B, depending on the structure of the product). By *q o.S mixing together products of different structure, that is to say, more precisely, by mixing together products in accordance with the invention having purely UV-A activity with products in accordance with the invention having purely UV-B activity, it is thus possible to make available a composition which overall will have a screening activity throughout the harmful UV range (UV-A UV-B), which constitutes a considerable dl advantage. In addition, on account of their highly liposoluble nature, the compounds of formulae to above may be used in high concentrations, thereby imparting very high protection factors to the final compositions; moreover, they distribute themselves uniformly in standard cosmetic vehicles containing at least one fatty phase or one cosmetically acceptable organic solvent, and gray thus be applied to the skin or the hair in order to constitute an effective protective film. Finally, their cosmetic properties are very good, namely, in particular, that these products are less sticky and afford more softness when compared with the screening silicones of the prior art.

The subject of the present invention is thus 15 also a cosmetic composition comprising, in a cosmetically acceptable support preferably containing at least one fatty phase or one organic solvent, an effective amount of at least one compound of formulae to defined above.

20 The compounds of formulae to are generally present in proportions of between 0.1 and 20 by weight, preferably of between 0.5 and 10 by weight, relative to the total weight of the composition.

The cosmetic composition of the invention may be used as a composition for protecting the human epidermis or the hair against ultraviolet rays, as an antisun composition or as a make-up product.

This composition may in particular be in the form of a lotion, a thickened lotion, a gel, a cream, a milk, a powder or a solid stick and may optionally be packaged as an aerosol and be in the form of a foam or a spray.

It may contain the cosmetic adjuvants usually used in the field, such as fatty substances, organic solvents, silicones, thickeners, softeners, complementary sunscreens, anti-foaming agents, moisturizing agents, fragrances, preserving agents, surfactants, fillers, sequestering agents, anionic, cationic, nonionic or amphoteric polymers or mixtures %thereof, propellants, basifying or acidifying agents, dyes, pigments or nanopigments, in particular those S 15 intended to provide a complementary photoprotective effect by physically blocking out ultraviolet radiation, or any other ingredient usually used in cosmetics, in particular for the manufacture of antisun a compositions.

20 Among the organic solvents, there may be mentioned lower alcohols and polyols such as ethanol, isopropanol, propylene glycol, glycerol and sorbitol.

The fatty substances may consist of an oil or of a wax or mixtures thereof, fatty acids, fatty acid esters, fatty alcohols, petrolatum, paraffin, lanolin, hydrogenated lanolin or acetylated lanolin. The oils may be chosen from animal, plant, mineral or synthetic oils and, in particular, hydrogenated palm oil, I- hydrogenated castor oil, liquid petrolatum, liquid paraffin, purcellin oil, volatile or non-volatile silicone oils, and isoparaffins.

When the cosmetic composition according to the invention is more particularly intended for protection of the human epidermis against UV rays or as an antisun composition, it may be in the form of a suspension or a dispersion in solvents or fatty substances, or alternatively in the form of an emulsion (in particular of O/W or W/O type, but preferably of O/W type) such as a cream or a milk, or in the form of a vesicle dispersion, a salve, a gel, a solid stick or *an aerosol foam. The emulsions may additionally contain anionic, nonionic, cationic or amphoteric surfaceo 15 active agents.

*e* When the cosmetic composition according to the invention is used for protection of the hair, it may be in the form of a shampoo, a lotion, a gel or composition to be rinsed, to be applied before or after 20 shampooing, before or after dyeing or bleaching, before, during or after permanent-waving or straightening of the hair, or in the form of a styling or treating lotion or gel, a blow-drying or hairsetting lotion or gel, a hair lacquer, a permanentwaving or hair-straightening composition, or a composition for dyeing or bleaching the hair.

When the cosmetic composition according to the invention is used as a make-up product for the

I-

_I s 29 eyelashes, the eyebrows, the skin or the hair, such as a skin-treatment cream, a foundation, a stick of lipstick, an eye shadow, a blusher, an eye-liner, a mascara or a colouring gel, it may be in solid or pasty and anhydrous or aqueous form, such as oil-in-water or water-in-oil emulsions, suspensions or gels.

The subject of the invention is also a process for the protection of the skin and the hair against ultraviolet radiation, in particular solar radiation, which consists in applying to the skin or the hair an effective amount of the cosmetic composition defined above, or of a compound of formula or as defined above.

The examples which follow illustrate the 15 invention without, however, limiting the scope thereof.

o EXAMPLE 1 o This example illustrates the preparation (according to route 1) of N-3-[1,3,3,3-tetramethyl-1- [(trimethylsilyl)oxy]disiloxanyl]propyl- 4 20 trimethyl)-3-oxobicyclo[2.2.1]hept-2- S" ylidenemethyl)benzenesulphonamide, that is to say of a compound in accordance with the invention corresponding to the formula:

CH

3

CH

3

CH

3 I I I

CH

3 s O i- si- CH 3 I I

I

A CH, I i ,rin which A represents: S0 2

N--CH

2 -CH CH 2 CH3 0 (this product corresponds to a compound of formula (1) for which R B CH 3 r 0, s 1; X 1

X

3

H;

R

1

R

2 H; p 1).

a) First step 34.2 g of the sodium salt of 4-(4,7,7trimethyl-3-oxobicyclo[2.2.13hept-2ylidenemethyl)benzenesulphonic acid and 200 ml of dimethylformamide are introduced into a 500 ml reactor.

13 g of thionyl chloride are then introduced dropwise.

The reaction mixture is then stirred at room temperature for 2 hours. Allylamine (6.3 g) and then a .triethylamine (11.1 g) are next added dropwise and stirring is maintained for 3 hours. The reaction 15 mixture is poured into 300 ml of water. The solid obtained is drained and then dried and, after purification, 21.4 g of N-allyl-4-(4,7,7-trimethyl-3oxobicyclo hept-2ylidenemethyl)benzenesulphonamide, having the following 20 characteristics, are recovered: White powder 131 0

C

Elemental analysis: theory C 67.09 H 7.04 N 3.66 S 8.88 found C 66.82 H 7.01 N 3.90 S 8.92 9 *099 9 b) Second step: 17.97 g of the product obtained above and 50 ml of toluene are loaded into a reactor. The mixture is brought to 80 0 C under nitrogen. The hydrosilylation catalyst (complex containing 3-3.5 of Pt in cyclovinylmethylsiloxane, from Huls Petrarch PC085, 100 is added, followed by 11.24 g of heptamethyltrisiloxane.

After 4 hours at 80 0 C under nitrogen, the reaction medium is concentrated and chromatography is carried out on silica under pressure (eluent: heptane/ EtOAc 97/3). 21.8 g of the desired final product, having the following characteristics, are thus obtained: White powder 73 0

C

Elemental analysis: theory C 55.72 H 8.14 N 2.41 S 5.51 Si 14.48 found C 55.88 H 8.09 N 2.62 S 5.49 Si 14.28 The UV absorption characteristics (measured in ethanol) of this product are as follows: Xmax: 295 nm Emax: 28,900 This product may thus be used very effectively as a sunscreen which is active in the UV-B range.

C-~rsiB EXAMPLE 2 Following the same procedure as that given in Example 1, four other compounds in accordance with the invention (compounds A to D) were prepared, all falling within the scope of the general formula and having the same silicone-containing skeleton below: CH3 CH 3

CH

3 CH3 Si. O -i0 6i-O--O CH3 I i 1 A CH 3 CH3 but in each case having a screening unit A of different nature.

The results are collated in Table I.

9 e e e o .o i, TABLE I UV Elemental (ethanol) Analysis calculated Xmax Cmax found C 54.95 H 8.07, N 2.29, S 5.24, Si 13.77 12 nm 25,950 C 54.95, H 8.08, N 2.42, S 4.99, Si 13.54 C 55.72, H 8.14, N 2.41, S 5.51, Si 14.48 C 55.85, H 8.17, N 2.33, S 5.39, Si 13.93 C 53.72, H 7.57, N 2.24, S 5.12, Si 13.46 C 53.84, H 7.60, N 1.94, S 4.96, Si 13.07 0 2 2 0o m2 ~1- 337 nm 21,220 o O--CB-CH- CH2" 2 N 2 F c C 56.43 H 8.26, I N 2.35, S 5.38, Si 14.14 o. 5 D 295 nm 28,970 C 56.37, H 8.25, C93 N 2.37, S 5.44, Si 13.85

O

o o Compounds A, B, C and D above may thus be used very effectively as sunscreens which are active, respectively, in the UV-A range, the UV-B range, the UV-A range and the UV-B range.

10 EXAMPLE 3 This example illustrates the preparation (according to route 2) of bis-N-{3-[1,3,3,3tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl}- 3,3'-terephthalylidene-10,10'-dicamphorsulphonamide, that is to say of a compound in accordance with the invention corresponding to the formula s I I I C CH 3

CH

3 (this product corresponds to a compound of formula (1) for which R B CH; r 0; s 1; X 1 with R 1

R

2 H and p 1; X 2 Z; X 3

H).

4 g of the disodium salt of 3,3'terephthalylidene-10,10'-dicamphorsulphonic acid and 16 ml of dimethylformamidEc are loaded into a reactor.

1.1 ml of thionyl chloride are then added dropwise thereto and stirring is maintained for half an hour.

e This heterogeneous mixture is added portionwise to a S 10 mixture of triethylamine (3.04 g) and 1-amino-l- [1,3,3,3-tetramethyl-3-[(trimethylsilyl)oxy]disiloxanyl]propane (4.2 The reaction mixture is maintained at room temperature for 3 hours and is then poured into 100 ml of ice-cold water and i3 15 finally extracted with dichloromethane. The organic phase is dried over sodium sulphate and concentrated.

After chromatography on silica (eluent: CH 2 Cl 2 3 g of the desired final product, having the following characteristics, are thus obtained: 20 White powder 176-177 0

C

Elemental analysis: theory C 52.23 H 8.00 N 2.65 S 6.06 Si 15.93 found C 52.92 H 8.12 N 2.43 S 5.94 Si 15.37 The UV absorption characteristics (measured in CHCl 3 of this product are as follows: Xmax: 344 nm <max: 47,100 3~1 I This product may thus be used very effectively as a sunscreen which is active in the UV-A range.

EXAMPLE 4 This example illustrates the preparation (according to route 2) of {N-3-[1,3,3,-tetramethyl-l-[(trimethylsilyl)oxy]disiloxanyl]propyl}sulphonamide, that is to say of a compound in accordance with the invention corresponding to the formula: CH3 CH 3

CH

3 I I I CH"" Si i- CH3 I I I A CH3 CH 3 in which A represents

-CR

2 C 2

C

2 NE 0 2 (this product corresponds to a compound of formula (1) for which R B CH3; r 0; s 1; R= R 2 H and p 1) 100 ml of dry dichloromethane, 60 ml of 15 triethylamine and 67 g of heptamethylaminopropyltrisiloxane (product corresponding to a compound of formula (Iter) in which R B" CH 3 r 0; s 1; R R H; p 1) are loaded into a reactor. 23.4 g of 2-phenyl-lH- 20 benzimidazole-5-sulphonyl chloride are added to this S. mixture, portionwise over half an hour at room temperature. The heterogeneous mixture obtained is then heated at 60°C for 3 hours. After cooling, the reaction mixture is poured into 300 ml of water. After extraction with dichloromethane and purification by chromatography on silica (eluent: heptane/CH 2 Cl1 50/50), L ~IL I 8 g of the desired final product, having the following characteristics, are obtained: White powder 169-170°C The UV absorption characteristics (measured in ethanol) of this product are as follows: Xmax: 305 nm Emax: 29,500 Xmax: 317 nm Emax: 19,675 This product may thus be used very effectively as a sunscreen which is active in the UV-B range.

EXAMPLE Following the same procedure as that given in Example 4, another compound in accordance with the invention was prepared, corresponding to the following formula:

CH

3

CH

3

CH

3 II I

I

C Si -Gi- Si SA

CH

3

CH

3 in which A represents

SO

2

NECH

2 2

CH

2

CH

3 (this product corresponds to a compound of formula (1) for which R B CH 3 r 0; s 1; X 4 with R 1

R

2 H and p 1; X 5 H; R 3 methyl).

The UV absorption characteristics (measured in ethanol) of this product are as follows: Xmax: 294 nm Emax: 12,100 =1 Xmax: 325 nm emax: 7,300 This product may 'hus be used very effectively as a sunscreen which is active in the UV-B and UV-A ranges.

EXAMPLE 6 A concrete formulation of an antisun cosmetic composition in accordance with the invention, namely an antisun cream, is illustrated here.

Compound of Example 1 5 g Mixture of cetylstearyl alcohol and cetylstearyl alcohol oxyethylenated with 33 mol of EO ("SINNOWAX AO" from Henkel) 7 g Mixture of non-self-emulsifiable glyceryl mono- and distearate 2 g Cetyl alcohol 1.5 g

C

12

-C

1 5 alkyl benzoate ("FINSOLV TN" from Witco) 20 g Polydimethylsiloxane 1.5 g Glycerol 17.5 g Fragrance, preserving agent qs Water qs 100 g This cream is prepared according to the standard techniques for the preparation of emulsions, 25 by dissolving the screening agent in the fatty phase containing the emulsifying agents, heating this fatty S. phase to about 70-80 0 C and adding, with vigorous stirring, the water which has been heated to the same temperature. Stirring is maintained for 10 to 15 minutes and, after allowing to cool with moderate stirring, the fragrance and preserving agents are then finally added at about 40 0

C.

e I i -sl

Claims

1. Novel compounds of following formulae to RRR I 1 0. B B- si o 0- -0- L R L R J or R R I t U or 5 A-Si(R') 3 (3) in which formulae to the groups R, which may be identical or different, are chosen from C 1 -C 1 0 alkyl, phenyl and 3,3,3-trifluoropropyl radicals, at least 80 in numerical terms, of the radicals R being methyl, the groups B, which may be identical or different, are chosen from the above radicals R and the radical A def -d below, 15 th roups which may be identical or different, are chosen from CI-C 8 alkyl radicals, or phenyl radicals, r is an integer between 0 and inclusively, and s is an integer between 0 and inclusively, with the condition that if s is zero then at least one of the two symbols B denotes A, u is an integer between I and 6 39 inclusively, and t is an integer between 0 and inclusively, it being understood that t u is equal to or greater than 3, and the symbol A denotes a radical directly attached to a silicon atom, the said radical A corresponding to one of the following formulae to 1) X (4.1) x X 0 in which formula X 1 represents a hydrogen atom or a divalent radical of following formula -SO. Ca-CH,- 1 12 .R R S*e in which formula R 1 denotes a hydrogen atom or a C1-C 4 alkyl or hydroxyalkyl radical, R 2 represents a hydrogen atom or a C -C 6 alkyl or CI-C 6 alkoxy radical, p is an integer between 1 and inclusively, 20 the end -CH 2 group is directly attached to a silicon atom; X 2 and X 3 which may be identical or different, represent a hydrogen or halogen atom, a C 1 -C 4 alkyl or alkoxy radical, a divalent radical or a radical Z of following formula slre_~r, 9 1 I 40 (6) xly 0 or alternatively may together form an alkylidenedioxy group in which the alkylidene group contains 1 or 2 carbon atoms; it being understood that in this formula one of the three symbols X 1 X 2 and X 3 must necessarily represent a divalent radical and each of the other two remaining symbols cannot then represent a divalent radical if X 1 represents a hydrogen atom, X 2 and X 3 are then necessarily different and neither may represent a radical Z, if X 1 represents a divalent radical X 2 and X cannot then simultaneously represent a radical Z, 15 if X denotes a hydrogen atom and X 3 represents a divalent radical X 2 is then preferably other than a hydrogen atom; O RH4 S) I/ (4.2) C* x 0 0 R 3 in which formula X 4 represents a hydrogen atom, a C,-C, alkyl radical or a divalent radical staffhtyankalkospo3438,95.CLAIMS 5.3.97 i ill 41 X 5 represents a hydrogen or halogen atom, a C 1 -C 4 alkyl or alkoxy radical or a divalent radical R 3 represents a C 1 -C 8 alkyl radical, it being understood that, in this formula one of the two symbols X 4 and X 5 must necessarily represent a divalent radical it not being possible for the remaining symbol to represent a divalent radical 3) (4.3) 4) 0 OH S (4.4) *ee VOCH 3

2. Novel compounds according to Claim 1, 0 0 corresponding to formula or to formula characterized in that the radicals R are alkyl radicals. 0*0o 3. Novel compounds according to Claim 2, S 15 characterized in that the radicals R are methyl, ethyl, propyl, n-butyl, n-octyl or 2-ethylhexyl radicals.

4. Novel compounds according to Claim 3, Scharacterized in that the radicals R are methyl radicals.

5. Novel compounds according to any one of the preceding claims, corresponding to formula characterized in that the radicals B are alkyl radicals. s II

6. Novel compounds according to Claim characterized in that the radicals B are methyl, ethyl, propyl, n-butyl, n-octyl or 2-ethylhexyl radicals.

7. Novel compounds according to Claim 6, characterized in that the radicals B are methyl radicals.

8. Novel compounds according to any one of the preceding claims, corresponding to formula characterized in that r is between 0 and 3 inclusively, and s is between 0 and 3 inclusively.

9. Novel compounds according to any one of Claims 1 to 4, corresponding to formula characterized in that t+u is between 3 and inclusively.

10. Novel compounds according to Claim 1, corresponding to formula characterized in that the radicals R' are alkyl radicals chosen from the methyl, ethyl, propyl, n-butyl, n-octyl and 2-ethylhexyl radicals. 20 11. Novel compounds according to Claim characterized in that the radicals R' are methyl .radicals.

12. Novel compounds according to any one of the preceding claims, characterized in that in the 25 divalent radical p is between 1 and 3 inclusively.

13. Novel compounds according to any one of the preceding claims, characterized in that, in the divalent radical R represents hydrogen.

14. Novel compounds according to any one of the preceding claims, characterized in that, in the divalent radical R 2 represents hydrogen or a methyl radical. Novel compounds according to any one of the preceding claims, characterized in that A corresponds to formula

16. Novel compounds according to Claim characterized in that X 2 is hydrogen, methyl, methoxy -r IL I II 43 or-Y-.

17. Novel compounds according to either of Claims and 16, characterized in that X 3 is hydrogen or

18. Novel compounds according to any one of Claims 1 to 14, characterized in that A corresponds to formula

19. Novel compounds according to Claim 18, characterized in that X 4 is tert-butyl or Novel compounds according to either of Claims 18 and 19, characterized in that X 5 is hydrogen or

21. Novel compounds according to any one of Claims 18 to 20, characterized in that R 3 is methyl or tert-butyl

22. Novel compounds according to any one of Claims 1 to 14, characterized in that A corresponds to formula

23. Novel compounds according to any one of Claims 1 to 14, characterized in that A corresponds to formula

24. compounds of formulae as defined in any 20 one of the preceding claims, when used as sunscreens which are active in the UV-A and/or UV-B region.

25. Cosmetic composition, in particular for screening out ultraviolet rays, characterized in that it comprises, in a cosmetically acceptable vehicle, an effective amount 25 of at least one of the compounds defined in any one of Claims 1 to 23.

26. Cosmetic composition according to Claim characterized in that the said cosmetically acceptable vehicle contains at least one fatty phase or one organic solvent.

27. Cosmetic composition according to Claim 26, characterized in that the said vehicle is in the form of an emulsion of oil-in-water or water-in-oil stafvryankkeep/sped134380,95.CLAIMS 5.3,97 II 44 type, preferably of oil-in-water type.

28. Cosmetic composition according to one of Claims 25 to 27, characterized in that the content of screening compound(s) is between 0.1 and 20 by weight relative to the total weight of the composition.

29. Cosmetic composition according to Claim 28, characterized in that the said content is between and 10 by weight. Process for the protection of the skin and/or the hair against ultraviolet radiation, in particular solar radiation, characterized in that it consists in applying to the skin and/or the hair an effective amount of at least one compound or of at least one composition as are defined in any one of the preceding claims. DATED THIS 20TH DAY OF OCTOBER 1995 L'OREAL By its Patent Attorneys: *GRIFFITH HACK CO. Fellows Institute of Patent Attorneys of Australia SIB* o o S 0 e ~dl I IkQ' Lgl ABSTRACT NOVEL SUNSCREENS, PHOTOPROTECTIVE COSMETIC COMPOSITIONS CONTAINING THEM AND USES THEREOF The invention relates to novel compounds of the linear or cyclic short-chain diorganosiloxane type or of the triorganosilane type, having screening units containing sulphonamide functionality, chosen from 3-benzylidenecamphor derivatives, benzotriazoles, benzophenones and benzimidazoles, it being possible for these compounds to be used more particularly as organic sunscreens in cosmetic compositions intended for the protection of the skin and the hair against ultraviolet radiation. The invention also relates to the use of the said compounds in the abovementioned cosmetic application, as well as to the cosmetic compositions with improved properties containing them.