AU736477B2

AU736477B2 - Combinations of sunscreens and compositions containing them

Info

Publication number: AU736477B2
Application number: AU89778/98A
Authority: AU
Inventors: Alverio Malpede; Giuseppe Raspanti
Original assignee: 3V Sigma SpA
Current assignee: 3V Sigma SpA
Priority date: 1997-07-30
Filing date: 1998-07-21
Publication date: 2001-07-26
Anticipated expiration: 2018-07-21
Also published as: WO1999006014A2; WO1999006014A3; ITMI971823A1; AU8977898A; IT1293508B1

Description

WO 99/06014 PCT/EP98/04518 COMBINATIONS OF SUNSCREENS AND COMPOSITIONS CONTAINING

THEM

The present invention relates.. to combinations of sunscreens and to the compositions containing .them.

It is well known that sun radiations ranging from 280 to 400 nm are noxious for human skin; in particular those with a wavelength from 280 to 320 nm, the socalled UV-B radiation, cause erythema and cutaneous-sunburns, whose severity depends on the kind of the skin and on the duration of the exposition to sunlight.

It has been ascertained that also radiations ranging from 320 to 400 nm, the so called UV-A radiations, which were considered innocuous and onlyresponsible of skin tanning, are, as a matter of fact, harmful, in that they can cause damages to elastine and collagene, with consequent ageing of the skin as well as a number of phototoxic and photoallergic reactions.

A great number of substances are described in the patent and non-patent literature, which are capable of protecting skin from radiations, such substances belonging to a variety of chemical classes (benzophenones, dibenzoylmethane derivatives, benzylidenecamphor derivatives, salicylic acid derivatives, p-aminobenzoic acid derivatives, cyanocrylates, triazinoanilines, benzimidazoles, etc.).

They exert their protective action more or less satisfactorily; however, the practical use thereof in cosmetic or dermatological compositions is not free from problems, due to the poor photostability of some of them (for example, dibenzoylmethane derivatives (Int. J.

SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 2 Cosm. Science, 10, 53, 1988)), to the poor absorbing power at certain wavelengths (for example, benzophenone derivatives show a poor absorption at 290 and 325 nm), and to problems of solubility in the oily or aqueous solvents used in cosmetics or in dermatology for the preparation of the relevant formulations.

Specific combinations of anti UV-A and anti UV-B sunscreens have been proposed in the attempt to prevent the photodegradation of the first ones, -for example combinations of benzylidenecamphor derivatives or cyanocrylates (anti UV-B sunscreens)- and" d-ibenzoylmethane derivatives (anti UV-A sunscreens) are reported in GB 2,198,944, WO 91/11989 and WO 94/04131, and synergistic compositions of anti UV-B sunscreens are described in EP 0,689,828 and EP 0,685,224.

The kind of sunscreens and the amounts at which they are used, alone or in mixtures, are selected depending on the intended protection, as well as on the above mentioned remarks. In particular, an index of this protection is the so-called sun protection factor, (SPF), which is expressed as the ratio of the time of irradiation necessary to reach the erythematogenic threshold in the presence of the UV filter to the time necessary to reach the erythematogenic threshold in the absence of the UV filter.

There is, anyway, a demand for novel, more effective protection systems for those parts of the body which can be damaged by a more or less prolonged exposition to UV radiations, such as skin and hair, which demand is even more felt nowadays in view of the problems deriving from the holes in the ozone layer.

SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 3 Therefore, an object of the present invention are combinations of sunscreens for the protection from ultraviolet radiations, which comprise: a) at least one compound of formula I: NH-U >--COOR 1 R-NH-CO

H-<I

N

NH~i~j COXR 2 wherein: R is a straight or branched (Cl_ 8 alkyl group, (C5_ 12 cycloalkyl, optionally substituted with one or more straight or branched (CI_ 4 alkyl groups; X is an oxygen atom.or. the group R 1 has the same meanings as R, or is hydrogen, a monovalent metal ion, a quaternary ammonium group, or a group of formula II A- O-CH 2

-CH

in which A is a straight or branched (CI_ 8 alkyl, (C 5 12 cycloalkyl, or (C 6 10 aryl optionally substituted with one or more straight or branched (CI_ 4 alkyl groups; R 3 is hydrogen or methyl; n is an integer from 1 to 10; R 2 has the same meaning as R when X is NH-, or has the same meanings as R, when X is oxygen; in combination with at least one or more sunscreens selected from the following classes of compounds: b) benzylidenecamphor derivatives of formula III: SUBSTITUTE SHEET (RULE 26) WO 99/06014 WO 9906014PCT/EP98/04518 R -CH2 R wherein R4 is hydrogen, or the group SO 3 M, in which M is hydrogen, or a monovalent metal ion, or a quaternary amnmonium group, and R 5 is hydrogen, methyl, a group S0 3

M

wherein M is defined as above, or a group of formula IV orV

CH

.3 .1 CIF R- 2 4 whereirn-R 4 is- as-defined above; c) dibenzoylmethane derivatives of formula VI R 6 in which R 6 and R7are selected independently from hydrogen, straight or branched (C 1 8 alkyl and straight or branched (C 1 8 alkoxy; d) alkoxyciinaoic acid esters of formula VII

R

8 -0 CH CH-COOR 9 V11 wherein is a s-traigh-t or, branched (C 1 8 f) alk'%:I. group, SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 and R 9 is selected from hydrogen, a straight or branched (C1- 10 alkyl group, a monovalent metal ion and a quaternary ammonium group; e) triazinoaniline derivatives of formula VIII ROOC -NH-

VIII

NH

COOR

2 in which R, R 1 and- R 2 are. defined as above for formula

(I)

benzophenone derivatives- of formula IX.

HO

R

1 2

O-R

1 0

RII

wherein R10 is hydrogen or a straight or branched (Calkyl group, R 11 is hydrogen or the group SO 3 Q, in which Q is hydrogen, a monovalent metal ion or a quaternary ammonium group, and R12 is hydrogen, hydroxy or straight or branched (C 1 alkoxy; g) diphenylcyanoacrylates of formula X C C COOR 1 3

CN

wherein R 1 3 has the samie meanings as R 1 defined above; SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 6 h) salicylic acid derivatives of formula XI

COOR

1 4 0 o

XI

wherein R14 is a straight or branched (C1- 1 0 alkyl group, a benzyl group optionally substituted with a straight or branched (C 1 alkyl group, a 3,3,5trimethylcyclohexyl residue-, both as a racemate and as any optically active forms, or the group HN+(CH 2 CH20H) 3 i) benzimidazolesulfonic acid derivatives of formula

XII

N

1 5 G O 3 S

N

N XII

H

in which G is hydrogen, or a monovalent iimtal ion, or a quaternary ammonium group; j) p-aminobenzoic acid (PABA) derivatives of formula

XIII

R16 N COOR 17^y xi wherein R 15 and R 16 are independently hydrogen or a straight or branched (C 1 6 alkyl group, optionally substituted with a hydroxyl group, and R17 is selected from hydrogen, a straight or branched (C1- 1 0 alkyl SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCTIEP98/04518 7 group, a monovalent metal ion and a quaternary ammonium group, or R 15 is the group -(CH 2

-CH

2 0)xH, R 16 is the group -(CH 2

-CH

2 0) H and R17 is the group -CH 2

-CH

2

-(OCH

2

CH

2 )zOC 2 H5, in which the sum of x, y and z is k) metal oxides having atomic number ranging from 11 to It is evident from what stated above that the combinations of the present invention are, at least, binary combinations of a component as defined in a) with one of the components as defined in the crasses to In the case of combinations of more than two components as defined in a) to two or more thereof can also be selected within the same class, provided at least one of the components present in the combination is as defined in The choice of the components of the combinations depends on the desired type and degree of protection, as well as on the chemico-physical and photostability characteristics of the selected components.

Examples of alkyl group are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl and isomers thereof.

Examples of cycloalkyl group are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl. Examples of substitutions with alkyl groups are methyl, ethyl, propyl, butyl and isomers thereof at one or more positions of the cycloaliphatic ring.

Examples of monovalent metal ions are the sodium, potassium, lithium ions.

Examples of aryl group are phenyl and naphthyl, optionally bearing one or more alkyl groups, such as SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 8 methyl, ethyl, propyl, butyl and isomers thereof.

Examples of alkoxy group are methoxy, ethoxy, propoxy, butoxy and isomers thereof.

The preferred. o pt~;t of formula I are those in which R: ~itlyl, 2,4,4-trimethyl-pent-2-yl, isopropyl or tert-butyl, R 1 is 2-ethyl-hexyl, isopropyl or ntetradecyl, R 2 is isopropyl or 2-ethyl-hexyl, and X is O or Particularly pref erred is the component in which R is tert-butyl, R 1 and R2 are both 2-ethyl-hexyl and X is oxygen, which will be referred to as component a) in the disclosure and examples. These components are described in EP 0,570,838.

Sunscreens of the classes b) to k) are anti UV-A sunscreens and/or anti UV-B sunscreens well-known in literature; many of them being commercial products.

Preferred components of the class b) are the compounds of formula III in which R4 is hydrogen and R is methyl or the group of formula IV, which are known under the trade names EUSOLEXTM 6300 and MEXORYLTM SO, respectively, and those in which R4 is the group SO 3

M,

wherein M is hydrogen or a monovalent metal ion and R is the group of formula V in which R4 is defined as above, known under the trade name MEXORYLTM SX.

Preferred components of the class c) are those compounds of formula VI in which R 6 is isopropyl or tert-butyl and R 7 is hydrogen or methoxy, known under the trade names EUSOLEXTM 8020 (R 6

=(CH

3 2 CH, R 7 and PARSOLTM 1789 (R6=(CH 3 3 C, R 7

=OCH

3 respectively.

Preferred components of the class d) are those compounds of formula VII, in which R 8 is methyl and R 9 is 2-ethyl-hexyl or the group +NH 2

(CH

2

CH

2

OH)

2 known SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 9 under the trade names PARSOLTM MCX and BERNELTM HYDRO, respectively.

The preferred component of the class e) is the compound of formula VIII in which all of R, R 1 and R 2 are 2-ethyl-hexyl, known under the trade name UVINULTM T 150.

Preferred components of the class f) are those compounds of formula IX in which R10 is hydrogen or methyl, R 1 1 is hydrogen or the group. SO 3 in which.Q. is hydrogen or a monovalent metal ion, and R 12 is hydrogen, known under the trade names UVASORBTM 2QH

(R

10

=R

11

=R

12 UVASORBTM MET (R 10

=CH

3

R

11

=R

12 UVASORBTM S5 (R 10

=CH

3 R 1

=SO

3 Q wherein Q=H, R 12 respectively.

The preferred component of the class is- the compound of formula X in which R 13 is 2-ethyl-hexyl, known under the trade name-UVINULTM N-539.

Preferred components of the class h) are those compounds of formula XI in which R14 is 2-ethyl-hexyl, the residue (+)-3,3,5-trimethylcyclohexyl or the group

HN+(CH

2 CH20H) 3 known under the trade names ESCALOLTM 587, KEMESTERTM HMS and SUNAROMETM W, respectively.

Preferred components of the class i) are those compounds of formula XII in which G is hydrogen or a monovalent metal ion, known under the trade name EUSOLEXTM 232.

Preferred components of the class j) are paminobenzoic acid as it is (formula XIII, R15=R16=R17=H), the compounds of formula XIII in which R15 and R16 are at the same time methyl or 2hydroxypropyl, and R 17 is ethyl or 2-ethyl-hexyl, known SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 under the trade names UVASORBTM DMO (R 15

=R

16

=CH

3

R

17 =2ethyl-hexyl) and AMERSCREENTM P (R15=R6 2hydroxypropyl, R 1 7=ethyl), respectively, and the compound of formula XIII in which R 1 5 is the group CH2-CH 2 R 6is the group (-CH 2 -CH20-) H and R7 is the group -CH 2

-CH

2

-(-OCH

2

-CH

2 -)zOC 2 H5-, in which the sum of x, y and z is 25, known under the trade name UVINULTM Preferred components of the class k) are titanium dioxide (TiO 2 and zinc oxide (ZnO). These oxides are preferably used in micronized form, in which the particles have a size not higher than about 100 nm as.

for TiO 2 and ranging from about 15 to about 300 nm as for ZnO. Most preferably, the size of the Ti02 particles ranges from about 5 to about 50 nin. Titanium dioxide can have an anatase, rutile or amorphous structure. For the purposes of the invention, these micronized metal oxides can be used either as they are or coated with other agents, such as A1 2 0 3 or aluminium salts with C10-18 aliphatic fatty acids. They are easily commercially available products. For example, micronized Ti02 is marketed under the trade name P25 (Degussa), whereas TiO 2 coated with aluminium stearate is marketed as MT100T (Tayka Corp.), and that coated with A1 2 0 3 is known as UFTR (Miyoshi). Micronized ZnO is, in its turn, available as Z-COTETM (sunSMART) or as SPECTRAVEILTM (Tioxide).

Therefore, a preferred aspect of the present invention relates to sunscreens synergistic combinations which contain the component a) in combination with at least one or more of the sunscreens belonging to the SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 11 classes b) to k) and defined above as the preferred ones. As already stated, when the combination comprises more than two sunscreens, the components, in addition to component can.b.e t ed from any of the different classe fs. -t or within the same class. This is also meant when an acidic sunscreen is used as a component: the combination can contain a mixture of the filter in the acidic form and in the salified form with a monovalent metal, or with a quaternary ammonium group.

Representative examples of these preferred combinations of sunscreens are those combinations which comprise the component a) with: 1) at least one preferred- component of the class k), optionally together with one or more of the other preferred components according to the invention; 2) at least.-one preferred component of the class i), optionally together with a preferred component of the class k) and/or one or more of the other preferred components according to the invention; 3) at least one preferred component of the class c) and at least one preferred component of the class optionally together with one or more of the other preferred components according to the invention; 4) at least one preferred component of the class c), the preferred component of the class optionally together with a preferred component of the class k) and/or one or more of the other preferred components according to the invention; 5) at least one preferred component of the class c), the preferred component of the class at least SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 12 one preferred component of the class optionally together with a preferred component of the class k) and/or one or more of the other preferred components according to the.invention; 6) at least one preferred component of.- the class b) and at least one preferred component of the class optionally together with one or more of the other preferred- components according to :.the.

invention; at least one preferred component of the class b), at least one preferred component of the class i) and at least one preferred component of the class optionally together with one or more of the other preferred components according to the invention; 8) at least one preferred component of the class b), at least one preferred component of the class c), optionally together with a preferred component of the class k) and/or one or more of the other preferred components according to the invention; 9) at least one preferred component of the class c), at least one preferred component of the class f) and at least one preferred component of the class optionally together with one or more of the other preferred components according to the invention; at least one preferred component of the class d), at least one preferred component of the class f), optionally together with a preferred component of the class k) and/or one of the other preferred components according to the invention; SUBSTITUTE SHEET (RULE 26) Wo 99/06014 PCT/EP98/04518 11) at least one preferred component of the class e), optionally together with a preferred component of the class i) and/or one or more of the other -preferred components according to the invention; S :12) at least one preferred component of the class c) and at least one preferred component of the class optionally together with one or more of the other preferred components according to the invention; 13) at least one preferred component of the class c) and at least one preferred- component of the class optionally together with one or more of the other preferred components according to theinvention; 14) at least one preferred component of the class c) and at least one preferred component of the class optionally together with one or more of the other preferred components according to the invention.

Other preferred combinations of sunscreens will be evident to those skilled in the art from the disclosure and examples.

The combinations of sunscreens of the present invention can be used both in the protection of human body from the harmful effects of UV radiations, and in the stabilization of the various compositions containing them, for example, cosmetic or dermatological compositions. This stabilizing effect has also been observed when including the above mentioned combinations in photosensitive compositions different from the cosmetic and dermatological ones, such as polymers.

SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCTIEP98/045I8 14 In said compositions, the combination used comprises at least one component a) in amounts ranging from about 0.05 to about 20% of the composition total weight, and at least one of the other components b) to k) in amounts ranging from about 0 to about calculated on the composition total weight, with the proviso that at least one of the components b) to k) is present in a percent amount different from zero. In genera-l, the- amount of the desired combination present in the composition ranges-from about 0.1 to about 35% of the composition total weight. As stated above, the choice of the components of the combinations will depend on the desired type and degree of protection and stabilization, as well as on the chemico-physical and photostability characteristics of the selected components. The above indicated percentages and those reported in the following are percent by weight, and they are calculated on the composition total weight.

The preferred compositions are the cosmetic compositions, which, therefore, are a further object of the present invention.

In a preferred embodiment, the cosmetic compositions comprise a combination of sunscreens according to the invention in cosmetically acceptable excipients, such as oil-in-water, water-in-oil, oil-water-oil, water-oil-water emulsions, oily solutions, lipid fusions, hydro-alcoholic or anhydrous aqueous gels, alcoholic or hydro-alcoholic solutions, and analogues.

When an oily substance is necessary to dissolve or disperse one or more of the components of the selected combination, this substance is a compound advantageously SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 selected from: i) hydrocarbons, such as paraffin, mineral oils, and analogs; ii) oils, butters and natural waxes, such as. avocado oil, sunflower oil, almond oil, apricot-stone oil, karitb butter, evening primrose oil, black currant oil, borage oil, jojoba oil,_ safflower oil, wheat germ oil, macadamia oil, rice bran oil, sesame oil., castor oil, coconut oil; unsaponifiable oils of olive, avocado, soya; cocoa butter, bees-wax, candelilla wax, carnauba wax, and analogs; iii) silicones oils such as dimethicones, cyclomethicones, dimeth-i-conols, alkyldimethicones, and analogs; iv) -esters of straight or branched, saturated or unsaturated aliphatic acids or of aromatic or alkylaromatic acids, having 1 to 25 carbon atoms, said acids being optionally hydroxylated and/or ethoxylated, with mono- or polyhydroxylated aliphatic alcohols, saturated or unsaturated, straight or branched, having 1 to 25 carbon atoms, such as octyldodecyl-neopentanoate, pentaerythritol-dioleate, trimethylolpropan-trioleate, triisostearyl-citrate, diacetin, triacetin, 2-ethylhexyl acetate, neopentylglycol oleate, triethylene glycol diacetate, isopropyl myristate, isopropyl palmitate, bis-diglyceryl-caprylate/caprate/isostearate/stearate/hydroxystearate/adipate, dioctyl maleate, di-(2-ethyl-hexyl) malate, (C12- 15 )alkyl benzoates, cetylstearyl octanoate, cetylstearyl isononanoate, 2-ethyl-hexyl palmitate, 2-ethyl- SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 16 hexyl stearate, C8-10 triglycerid, PEG-7 glyceryl coccoate and analogs; v) amides, such as those mentioned in EP 0,748,623, in particular N,N-diethylmethylbenzamides and ethyl 1- (N-acetyl-N-butyl)-propionate; vi) (C 6

-C

35 alcohols, such as cetyl. alcohol, stearyl alcohol, behenyl alcohol, octyldodecyl alcohol, 3,5,5-trimethylhexyl alcohol, 2-butoxyethanol, 2phenoxyethanol, 2-ethyl-1,3-hexanediol and analogs; vii) ethers of (C 8

-C

40 fatty alcohols, such as di-noctylether; viii) butyl ethers of glycols, such as propylene glycol tert-butyl ether, diethylene glycol butyl ether, a (polypropylene glycol)3_ 53 butyl ether, and analogs; ix) esters of (C 1 6 )alkyl ethers, such as diethylene glycol butyl ether acetate, propylene glycol methylether acetate, and analogs.

For the purposes of the present invention, the substances i) to ix), which are all easily commercially available, can be used either singularly or as mixtures thereof, such as the wax mixtures commercially known under the name CUTINA(

R

(Henkel). Generally, the oily component is used in amounts ranging from about 0.5 to 95% of the composition total weight.

A preferred group of oily components are the esters of saturated or unsaturated, straight or branched aliphatic acids, or of aromatic or alkylaromatic acids, having 1 to 25 carbon atoms, said acids being optionally hydroxylated and/or ethoxylated, with mono- or polyhydroxylated aliphatic alcohols, saturated or SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 17 unsaturated, straight or branched, having 1 to 25 carbon atoms.

Another preferred group of oily components are the N,N-diethyl-methylbenzamides and ethyl 1-(N-acetyl-Nbutyl) -propionate.

A third preferred group of oily components are the mixtures of esters of saturated or unsaturated, straight or branched aliphatic acids, or of aromatic or alkylaromatic acids, having 1 to 25 carbon atoms, said acids being optionally hydroxylated and/or ethoxylated, with mono- or polyhydroxylated aliphatic alcohols, saturated or unsaturated, straight or branched, having 1 to 25 carbon atoms, such as N,N-diethyl-methylbenzamides and/or ethyl 1-(N-acetyl-N-butyl)-propionate.

A fourth preferred group of oily components are the silicones oils.

The cosmetic compositions which comprise emulsions, such as those mentioned above, can also include one or more conventional, commercially available emulsifier.

These can be anionic emulsifiers, such as soaps of fatty acids with alkali metals (for example, potassium stearate), alkaline-earth metals or aliphatic amines; alkylsulfate salts, such as sodium cetylstearyl sulfate (LANETTETM E, Henkel); alkylphosphates salts, optionally ethoxylated, such as potassium cethylphoshate (AMPHISOLTM K, Givaudan); condensates of fatty acids with protein hydrolysates (LAMECREMETM LPM, Henkel); mono- and diglycerides anionic esters (GRINDTEKTM CA-P, Grindsted Products Ltd), and analogs. Amphoteric emulsifiers can be used as well, for example phospholipids such as lecithin, or also non ionic SUBSTITUTE SHEET (RULE 26) WO 99/ 06014 PCT/EP98/0451 8 18 emulsifiers. The latter are, f or example, ethoxylated compounds of natural oil derivatives, such as hydrogenated castor oil (7)OE (ARLACEL.T 989, ICI); mono- and diglycerides of f1atty acids, optionally ethoxylated, such .as 'glyceryl stearate (CUTINATM GMS,., Henkel) and glyceryl(20)OE stearate -(CUTINATM.. E-24, Henkel); sorbitan ethoxylated esters (TWEENTM, ICI and CRILLETTM, Croda) and non-ethoxylated esters (SPANTM,_ ICI and__CRILL7TM,_ croda); polyglycerol. esters with fatty acids, such as triglyceryl diisostearate (LAMEFORMTM TGI, Henkel) and triglyceryl distearate (CITHROLTM 2623, Croda); glucose, methylglucose and saccharose esters with ethoxylated and non-ethoxylated fatty acids, such as methylglucose dioleate (GLUCATETM DO, Amerchol) and methylglucose(20)OE sesquistearate (GLUCAMATETM SS Amerchol);- ethers of glucose and of its oligomers, optionally esterified with (C 10 30 )aliphatic acids, such as triglycerylmethylglucose distereate (Tegodare(R) 450, Goldschmidt) and methyl glucose sesquistearate (Tegodare(R) PS, Goldschmidt), or cetylstearyl glucoside (MONTANOVTM 68, Seppic); ethoxylated fatty acids (MYRJTM, ICI); ethoxylated fatty alcohols (BRIJTM, ICI); lanolin and ethoxylated and non-ethoxylated derivatives, such as lanolin (30)OE (AQUALQSETM L 30. Westbrook); alkylglycols/polyethylene glycols copolymers, such as the copolymer PEG-45/dodecylglycol (ELFACOSTM ST 9, Akzo); silicone emulsifiers (Silicone Fluid 3225 C, Dow Corning; ABILTM W508 and Th. Goldschmidt AG); fluorinated emulsifiers (FOMBLIN(R) Ausimont); polymers of hydroxystearic acid esterified or etherified with polyethyleneglycols (PEG), polypropylene glycols SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 19 (PPG) or copolymers PEG/PPG; and analogs. Instead of these conventional emulsifiers, cross-linked copolymers can also advantageously be used, selected from a) crosslinked copolymers formed by i) acrylic or methacrylic acid, ii) vinyl esters of highly branched trialkylacetic acids of formula XIV

R

0 I II R-C---C-O-CH

=CH

2 I

XIV

Ri 9 in which R18, R19 and R20 are straight alkyl residues, at least one them being methyl, the total sum of the carbon atoms of the acyl residue being preferably and iii) a cross-linking agent such as pentaerythritol triallylether (STABYLEN 30, 3V SIGMA Bergamo, Italy), and b) cross-linked copolymers formed by i) acrylic or methacrylic acid, ii) acrylates or methacrylates of

(C

10 30 )aliphatic alkanols, iii) a cross-linking agent like, for instance, the allyl ethers of saccharose or pentaerythritol, as an example, the products known under the trade name PEMULEN(R) Goodrich).

The amount of emulsifiers which can be used vary from about 0.1 to about 20% of the composition total weight. They can be used singularly or as mixtures thereof. Some of these emulsifiers can advantageously be employed as solvents for the combinations according to the invention.

The cosmetics compositions of the invention can also comprise one or more vitamins, or their precursors, SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 or their analogs. Specifically, the vitamins, or their precursors, or their analogs, which can advantageously be employed are selected from the group consisting of: i) vitamins of A group, including vitamin A 2 and retinal, and their possible esters with straight or branched, saturated or unsaturated (C2_ 20 )aliphatic monocarboxylic acids or (C3- 12 )aliphatic di- or tricarboxyilic acids, said acids being optionally hydroxylated or alkoxylated with PEG, PPG, or copolymers PEG/PPG; or esters-withnicotinic acids;.

ii) a- and P-carotene; iii) vitamins of the B group; iv) vitamin C, and its possible esters with straight or branched, saturated or unsaturated (C2_ 20 )aliphatic monocarboxylic acids or (C 3 12 )aliphatic di- or tricarboxylic acids, said acids being optionally hydroxylated or alkoxylated with PEG, PPG, or copolymers PEG/PPG; or esters with nicotinic acid; v) the natural and synthetic tocopherols, including Vitamin E, as racemates, or in the form of their possible optically active isomers, and their possible esters with straight or branched, saturated or unsaturated (C2_ 20 )aliphatic monocarboxylic acids or (C3_ 12 )aliphatic di- or tri-carboxylic acids, said acids being optionally hydroxylated or alkoxylated with PEG, PPG, or copolymers PEG/PPG; or esters with nicotinic acid; vi) Essential Fatty Acids (EFA); vii) vitamin H; viii) vitamin P complex; and ix) vitamin PP.

SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 21 Generally, the amounts of vitamins, or their precursors, or their analogs, which can be employed, can vary. within wide limits. Preferably, these amounts are comprised between about 0.02. and about 10% by weight, calculated on the composition total weight.

The cosmetic compositions comprising one or more of the above vitamins represent a further object of the present invention.

The cosmetic compositions of the invention can also comprise other conventional components, for example emulsion stabilizers such as sodium chloride or citrate, magnesium sulfate and analogs, in amounts ranging from about 0.1 to about 5% of the composition weight; wetting agents, such as glycerin, propylene glycol or 1,3butylene glycol, in amounts from about 0.1 to about of the composition weight; thickening agents, such as modified celluloses or acrylic acids polymers or copolymers, in amounts not above 4% of the composition weight; sequestering agents, such as EDTA salts, in amounts not higher than 1% of the composition weight; antioxidizers, such as tocopherols and the esters thereof, hydroxytoluene butoxide or butyl hydroxyanisol, in amounts not above 2% of the composition weight; emollients, such as mineral oils, polysiloxanes, almond oil, vaseline, isopropyl myristate or fatty acids triglycerids, in amounts from about 0.1 to about 95% of the composition weight; moisturizing agents in amounts not above 5% of the composition weight; agents for adjusting pH to the desired values, such as sodium or potassium citrate, sodium or potassium hydroxide, or citric acid monohydrate, in amounts not above 1% of the SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 22 composition weight; film-forming agents, such as alkylated polyvinilpyrrolidones or high molecular weight waxes, in amounts not above 5% of the composition weight; preservatiye isuch as 2-bromo-2-nitro- .ropanedi^ $sodium dehydroacetate, isothiazolone, imidazolidinylurea, diazolidinylurea, parabens and hydantoin derivatives (GLYDANTTM, Lonza), sorbic acid, benzoic acid and salts 'thereof, chlorhexidine and the salts thereof, phenoxyethanol, benzyl alcohol and analogs, in amounts not above 10% by composition weight-.

Perfumes, antimicrobial agents, vegetal extracts such as, for instance, the green tea extracts or the walnut extract, depigmenting- agents such as, for instance, magnesium ascorbil..phosphate, and dyes can be added according to what known in the art. Moreover, the compositions of the invention can also contain artificial tanning agents such as dihydroxyacetone (DHA) and its derivatives, optionally in the presence of a iron salt, as described in EP-A- 0,688,203, in order to provide a less yellowish tan than that given by DHA alone. These artificial tanners can be present in amounts ranging from about 0.1 to about 10% of the composition weight.

The cosmetic compositions of the invention can be prepared according to the procedures known to those skilled in the art. Thus, for example, in the case of compositions in which the cosmetically acceptable carrier is an oil-in-water or water-in-oil emulsion, the two phases should, preferably be prepared separately, dissolving or dispersing in any of them the desired components/lipophilic or hydrophilic ingredients, and SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 23 subsequently mixed.

Examples of said compositions are sun-creams, day creams, moisturizing creams, sun-oils, ointments, lipsticks, solutions, lotions, gels, transparent gels, aerosol, foams and analogs. They contain a selected combination of the present invention together with the other ingredients in the above mentioned weight ratios, as well as any other compatible ingredient conventionally used--in- cosmetics. Generally speaking, said compositions will comprise a selected combination of the present invention so as to provide an SPF not lower than 2. The combinations of sunscreens of the present invention have often shown--a- synergistic effect.

The following examples further illustrate the invention. As mentioned above., the.. component a) is the compound of formula I in which R is tert-butyl, R 1 and R2 are both 2-ethyl-n.hexyl and X is oxygen. The amounts of the single components are expressed as weight percentages on the composition total weight.

EXAMPLE 1 A face day-cream is prepared from 1. Cetylstearyl glucoside 2. Glyceryl stearate 3. Cetylstearyl alcohol 4. C 12 -1 5 alkylbenzoate Octyl octanoate 6. Dimethicone 7. Component a) 8. Micronized zinc oxide-component k) 9. Demineralized water q.s. to 100 Imidazolidinyl urea 0.3 SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 24 11. Methyl p-hydroxybenzoate 0.2 12. Glycerin 13. Perfume 0.3 The mixture of components 1 to 6 is melted and.

heated to 70"C, then components 7 and 8 are added, under strong stirring (phase Separately, water is heated to 70C- (phase Phase- A is added to phase B in a homogenizer. The mixture is cooled to room temperature, then glycerin, preservatives and perfume are added.

EXAMPLE 2 A fluid oil-in-water emulsion is prepared from 1. Sorbitan(20)OE stearate 0.25 2. Avocado oil 3. Octyl palmitate 4. Mineral oil Component a) 6. Micronized titanium dioxide-comp. k) 7. Demineralized water q.s. to 100 8. STABYLEN 30 (polymeric emulsifier 0.25 3V SIGMA, Bergamo, Italy) 9. acid comp. i) Sodium hydroxide q.s. to pH 7 11. Diazolidinyl urea 0.3 12. Isothiazolone 0.05 13. Propylene glycol The mixture of components 1 to 4 is heated to then components 5 and 6 are added (phase Separately, component 8 is dispersed in about 90% of water, at under stirring (phase Subsequently, phase A is added to phase B in a homogenizer. Then, Component 9 is SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 dissolved in the residual water at room temperature (phase pH is adjusted to 7 with sodium hydroxide and phase C is added to phase A+B. The mixture is cooled to room temperature ,,,,.then~irdpylene glycol, preservatives S and;'per:f e:are dded.

S EXAMPLE 3 An anhydrous ointment is prepared from 1. Mineral oil q.s. to 100 2. Cetylstearyl isononanoate 30.0 3. C 8 10 triglycerid 30.0 4. Component a) 4-tert-butyl-4 '-methoxy-dibenzoylmethane component c) 6. Micronized titanium dioxidecomponent k) 7. Hydrogenated castor oil 8. Pyrogenic silica 9. Perfume 0.3 The mixture of components 1, 2 and 3 is heated to 60 0 C and components 4 and 5 are added, under stirring.

Components 6, 7 and 8 are then dispersed in the above mixture, under strong stirring. The mixture is finally cooled to room temperature and added with the perfume.

EXAMPLE 4 A fluid water-in-oil emulsion is prepared from 1. Hydrogenated castor oil(7)OE 2. Lanolin alcohols in mineral oil 3. Hydrogenated polyisobutene 4. Octyl octanoate 5. C 8 10 triglycerid 6. Component a) SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 26 7. 4-tert-Butyl-4'-methoxy-dibenzoylmethane-component c) 8. 2-Cyano-3,3-diphenyl-acrylic acid 2-ethyl-hexyl ester component g) 9. Demineralized water to 100 Dimethyl-dimethylol-hydantoin. 0.3 11. Phenoxyethanol and parabens 12. Glycerin 13. Perfume 0.3 The- mixture of components 1 to 5 is heated to and components 6-and-7 are-added, under stirring (phase Component 8 is then dispersed in phase A under strong stirring. Separately, water is heated to 70*C and added to phase A in a homogenizer. The mixture is cooled to room temperature, added with the preservatives mixed in glycerin and with the perfume.

EXAMPLE A high-protection water-in-oil cream is prepared from 1. Triglyceryl diisostearate 2. Bees-wax 3. Mineral oil 10.0 4. Octyl octanoate Cyclomethicone 6. Component a) 7. 2-Cyano-3,3-diphenylacrylic acid 2-ethyl-hexyl ester component g) 8. 4-tert-Butyl-4'-methoxy-dibenzoylmethane-component c) 9. Hydrogenated castor oil Micronized titanium dioxide- SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 component k) 11. Demineralized water q.s. to 100 12. acid component i) 3. 0 13. Triethanolamine q.s. tot pH 14. Sodium dehydroacetate 0.3 Phenoxyethanol and parabens 16. Glycerin 17. Perfume 0.3 The mixture of components 1 to 5 is melted at and, components 6, 7 and 8 are added, under stirring (phase Components 9 and 10 are subsequently dispersed in this phase in a- homogenizer. Separately, about 90% of water is heated to 60*C and added to phase A in a homogenizer. Then, cooling- is started. Component 12 is dissolved in the residual water at room temperature, and the resulting solution is neutralized with 13 (phase Phase C is added to the above prepared emulsion, which is then cooled to room temperature and added with preservatives, glycerin and perfume.

EXAMPLE 6 A fluid oil-in-water emulsion is prepared from 1. Stearic acid (100)OE 2. Cetylstearyl alcohol 3. Avocado oil 4. Jojoba oil Karit& butter 6. Butyl hydroxyanisol 0.1 7. Dimethicone and dimethiconol 8. Component a) SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 28 9. 3-(4-Methylbenzilydene)-camphor component b) Micronized titanium dioxide 11.

12.

component k) Demineralized water SYNTHALEN L (Carbomer 941 q.s. to 100 3V SIGMA, Bergamo, Italy) 13. Potassium cetylphosphate 14. Aminomethyl propanol 0.4 15. Imidazolidinyl urea 0.3 16. Potassium sorbate 17. EDTA disodium 0.1 18. Glycerin 19. Soluble collagene sol.) 20. Perfume 0.3.

The mixture of components 1 to 6 is melted at and components 8, 9 and 10 are added, under strong stirring (phase Separately water is heated to and first component 12, then component 13 are dispersed, under stirring (phase Phase A is added to phase B in a homogenizer, and the resulting mixture is then neutralized (pH 7) with component 14. The mixture is cooled to room temperature and added with preservatives, glycerin, collagene and perfume.

EXAMPLE 7 An oil-in-water cream is prepared from 1. Cetylstearyl alcohol(33)OE 2. Glyceryl stearate(20)OE 3. Behenyl alcohol 4. Isohexadecane Safflower oil 10.0 SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 29 6. Borage oil 7. Butyl hydroxyanisol 0.1 8. Copolymer PVP/eicosene 9. Component a) 10. 3-(4-Methylbenzilidene)-camphor component b) 11. 2-Hydroxy-4-methoxy-benzophenone component f) 12. Micronized zinc oxide component 13. Demineralized water q.s. to 100 14. SYNTHALEN K (Carbomer 940 3V SIGMA, Bergamo, Italy) 0.15 Aminomethyl propanol 0.1 16. Imidazolidinyl urea 0.3 17. Phenoxyethanol and parabens 18. Butylene glycol 19. Perfume 0.3 The mixture of components 1 to 8 is melted at and components 9 to 12 are added, under strong stirring (phase Separately, component 14 is dispersed in water at 70*C, under stirring (phase Phase A is then added to phase B in a homogenizer, and the resulting mixture is then neutralized (pH 7) with component Finally, the mixture is cooled to room temperature and added with preservatives, butylene glycol and perfume.

EXAMPLE 8 A water-in-oil cream is prepared from 1. Methylglucose dioleate 2. Copolymer PEG-45/dodecyl glycol 3. Mineral oil 10.0 SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 4. Paraffin Dioctyl maleate 6. Isopropyl myristate 7. Component a) 8. 3-(4-Methylbenzilidene)-camphor component b) 9. 4-tert-Butyl-4'methoxy-dibenzoylmethane component c) Hydrogenated castor oil 11. Micronized titanium dioxide component- 12. Demineralized water q.s. to 100 13. Magnesium sulfate 14. 2-Bromo-2-nitro-propanediol 0.3 15. Phenoxyethanol and parabens 16. Propylene glycol 17. Tocopherol acetate 18. Perfume 0.3 The mixture of components 1 to 6 is melted at and components 7, 8 and 9 are added, under stirring.

Components 10 and 11 are then dispersed in the fat mixture under strong stirring (phase Separately, water is heated to 70°C, component 13 is added thereto, and the resulting aqueous solution is added to phase A, in a homogenizer. The mixture is cooled to room temperature and added with preservatives, perfume, vitamin and propylene glycol.

EXAMPIE 9 A silicon water-in-oil emulsion is prepared from 1. Cetyl Dimethicone Copolyol 2. Lanolin alcohols in mineral oil SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 3. Cyclomethicone 4. Di-(2-ethyl-hexyl) malate Octyldodecyl neopentanoate 6. Perfume 7. Component a) 8. 4-tert-Butyl-4'-methoxy-dibenzoylmethane component c) 9. 2-Hydroxy-4-methoxy-benzophenone component f) Micronized titanium dioxide comp. k) in isopropyl myristate 10.0 0.3 T1. Demineralized water q.s. to 100 12. Sodium chloride 13. Chlorhexidine digluconate 0.3 14. Methyl paraben 0.2 Glycerin A mixture of components 1 to 6 is prepared, components 7, 8 and 9 are dissolved therein and subsequently, in the resulting mixture, component 10 is dispersed, at room temperature (phase Components 12 to 15 are dissolved in water, at room temperature (phase then phase B is slowly added to phase A, under stirring. Finally, the emulsion is made homogeneous in a homogenizer.

EXAMPLE A sun-oil is prepared from 1. Dioctyl cyclohexane q.s. to 100 2. C 8 1 0 triglycerid 20.0 3. Isopropyl palmitate 30.0 4. Cyclomethicone 10.0 Perfume 0.3 SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 6. Component a) 7. Octyl salicylate component h) 8. 4-tert-butyl-4'-methoxy-dibenzoylmethane component The mixture of components 1, 2 and 3 is heated to and components 6, 7 and 8 are added, under stirring. The- resulting- mixture is cooled to room temperature and added with components 4 and EXAMPLE 11 An oil-in-water cream is prepared with 1. Cetylstearyl alcohol and cetylstearyl glucoside 2. Glyceryl stearate- 3. Cetylstearyl alcohol 4. Propylene glycol dibenzoate

(C

12 -1 5 )alkyl benzoate 6. Dimethicone 7. Component a) 8. 4-tert-Butyl-4'-methoxydibenzoylmethane component c) 9. Demineralized water SYNTHALEN K (Cabomer 940 3V SIGMA, Bergamo, Italy) 11. Potassium cetylphosphate 12. PEG-25 p-aminobenzoic acid component j) 13. Aminomethyl propanol 14. Butylene glycol Phenoxyethanol and parabens 16. Perfume 3.50 1.00 0.50 10.00 7.00 1.00 4.00 2.00 q.s. to 100 0.10 0.50 4.00 0.05 1.50 1.00 0.30 SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 33 The mixture of components 1 to 6 is heated to and, under stirring, is added with components 7 and 8 (phase Separately, component 10 is dispersed into the water, previously heated to 70°C, and the resulting dispersion is added with components 11 and 12 (phase B).

Then, phase A is added to phase B in a homogenizer, the obtained mixture is cooled at room temperature, subsequently neutralized with component 13, and finally added with components 14 to 16.

EXAMPLE 12 An oil-in-water milk is prepared with PEG-4 Polyglyceryl 2-laurate 2.00 2. Dicaprylyl ether 7.50 3. Propylene-glycol dicaprylate/dicaprate 9.50 4. Cetyl lactate 3.00 Cetylstearyl alcohol 0.75 6. Dimethicone 0.50 7. a-tocopheryl acetate 1.50 8. Component a) 4.00 9. 4-tert-Butyl-4'-methoxy-dibenzoylmethane component c) 2.00 Demineralized water q.s. to 100 11. Stabylen 30 (3V SIGMA, Bergamo, Italy) 0.25 12. Trilauryl 40E phosphate 0.80 13. Aminomethyl propanol 0.20 14. Butylene glycol 2.00 Phenoxyethanol and parabens 1.00 16. Disodium EDTA 0.05 17. Perfume 0.30 The mixture of components 1 to 7 is heated to 70*C and, under stirring, is added with components 8 and 9 (phase SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 34 Separately, compound 11 is dispersed into the water, previously heated to 70"C, and the resulting dispersion is .added with component 12 (phase Then phase A is added to phase B in a homogenizer, the obtained mixture is cooled to room temperature, subsequently neutralized with component 13, and finally added with components 14 to 17.

EXAMPLE 13 An oil-in-water cream is prepared with .0 1. PEG-100 Stearate 2.00 2. Glyceryl stearate 1.00 3. Cetearyl alcohol 2.50 4. Stearic acid 5.00 Propylene glycol dicaprylate/dicaprate 9.50 6. Caprylic/Capric triglyceride 3.00 7. Dimethicone 0.50 8. Ascorbyl palmitate 1.00 9. Component a) 4.00 Titanium dioxide MT100T 11.

12.

13.

14.

16.

17.

18.

19.

The (Taika Corp.) component k) 4.00 Isohexadecane 5.00 Cyclomethycone 2.50 Demineralized water q.s. to 100 Potassium cetylphosphate 0.50 Stabylen 30 (3V SIGMA, Bergamo, Italy) 0.15 Butylene glycol 1.50 Imidazolidinyl urea 0.30 Methylparaben 0.20 Propylparaben 0.10 Perfume 0.30 mixture of components 1 to 8 is heated to SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 and subsequently added with component 9 under stirring.

Separately, component 10 is dispersed at room temperature in components 11 and 12, and the resulting dispersion is added to the hot mixture of components 1 to 8 (phase Component 15 is dispersed into the water, previously heated to 70*C, and the resulting dispersion is added-with component 14 (phase Phase A is added to phase B in a homogenizer, the resulting mixture is cooled to room temperature and subsequently added with components 16 to EXAMPLE 14 An oil-in-water cream is prepared with 1. PEG-100 stearate 2.00 2. Gliceryl stearate 1.00 3. Cetearyl alcohol 2.50 4. Stearic acid 5.00 Propylene glycol dicaprylate/dicaprate 9.50 6. (C 18 36 )acid glycol ester 2.00 7. Retinyl palmitate 1.00 8. a-tocopheryl acetate 1.00 9. Component a) 4.00 Titanium dioxide MT100T (Taika Corp.) 11.

12.

13.

14.

16.

17.

18.

component k) 4.00 Isohexadecane 5.00 Cyclomethicone 2.50 Demineralized water q.s. to 100 Potassium cetylphosphate 0.50 Stabylen 30 (3V SIGMA, Bergamo, Italy) 0.15 Butylene glycol 1.50 Green tea extract 1.00 Imidazolidinyl urea 0.30 SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 36 19. Methylparaben 0.20 Propylparaben 0.10 21. Perfume 0.30 The mixture, f. ,compents 1 to 8 is heated to 700C ,and asubsquently added with component 9 under stirring.

Separately, component 10 is dispersed at room temperature in components 11 and 12, and the resulting dispersion-is added to :the hot mixture of components 1 to- (phase Component 15 is dispersed into the water, previously heated to 70°C, and the resulting dispersion is added with component 14 (phase Phase .A is added to phase B in a homogenizer, the resulting mixture is cooled to room temperature and subsequently added with components 16 to 21.

SUBSTITUTE SHEET (RULE 26)

Claims

1. Combinations of sunscreens, which comprise: a) at least one compound of formula I: N N' Q COOR R-NH-CO QNH-(O N N NH COXR 2 wherein: R is a straight or branched (Ci- 8 alkyl group, (C 5 1 2 cycloalkyl, optionally 10 substituted with one of more straight or branched (CI- 4 alkyl groups; X is an oxygen atom or the group -NH- RI has the same meanings as R, or is hydrogen, a monovalent metal ion, a quaternary ammonium group, or a group of formula II 0o SA- O-CH,-CH S 15 R 3 n II I: in which A is a straight or branched (CI- 8 alkyl, (C 5 1 2 cycloalkyl, or (C 6 1 o) aryl optionally substituted with one or more straight or branched (C 1 4 alkyl groups; R 3 is hydrogen or methyl; n is an integer from 1 to 10; R 2 has the same meaining as R when X is or has the same meanings as RI when X is oxygen; in combination with k) metal oxides having atomic number ranging form 21 to 30 and optionally WO 99/06014 PCT/EP98/04518 38 O R4-CH2 CH R 4 III wherein R4 is hydrogen, or the group SO 3 M, in which M is hydrogen, or a monovalent metal ion, or a quaternary ammonium group, and R 5 is hydrogen, methyl, a group SO 3 M wherein M is defined as above, or a group of formula IV or V C"3 I J CH CH 2 R 4 +N -CH CH SO I IV V C3 wherein R4 is as defined above; c) dibenzoylmethane derivatives of formula VI R 6 Q CO-CH 2 -C R in which R 6 and R 7 are selected independently from hydrogen, straight or branched (C 1 alkyl and straight or branched (C 1 8 alkoxy; d) alkoxycinnamic acid esters of formula VII Rg-0- CH CH-COOR 9 wherein R 8 is a straight or branched (C_18) alkyl group, and R9 is selected from hydrogen, a straight or branched SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 39 (C 1 10 alkyl group, a monovalent metal ion and a quaternary ammonium group; e) triazinoaniline derivatives of formula VIII ROOC .NH-O N VII- NH COOR 2 in which R, R 1 and R2 are defined as above for formula (I) benzophenone derivatives-of formula IX HO R 1 2 CO O-R 0 R11 wherein Ri0 is hydrogen or a straight or branched (CI_ alkyl group, R 11 is hydrogen or the group SO 3 Q, in which Q is hydrogen, a monovalent metal ion or a quaternary ammonium group, and R12 is hydrogen, hydroxy or straight or branched (C 1 4 alkoxy; g) diphenylcyanoacrylates of formula X C C COOR 1 3 CN wherein R13 has the same meanings as R 1 defined above; SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 h) salicylic acid derivatives of formula XI COOR 1 4 O 0XI wherein R14 is a straight or branched (C 1 -1 0 alkyl group, a benzyl group optionally substituted with.,a straight or branched (C 1 alkyl group-, a 3,3,5- trimethylcyclohexyl residue, both as a racemate and as any optically active forms, or the groupHN+(CH 2 CH 2 OH) 3 i) benzimidazolesulfonic acid derivatives of formula XII GO 3 S N N XII H in which G is hydrogen, or a monovalent metal ion, or a quaternary ammonium group; j) p-aminobenzoic acid (PABA) derivatives of formula XIII R16 N COOR1 x XIII wherein R15 and R16 are independently hydrogen or a straight or branched (C 1 alkyl group, optionally substituted with a hydroxyl group, and R17 is selected from hydrogen, a straight or branched (C 1 -1 0 alkyl SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 41 group, a monovalent metal ion and a quaternary ammonium group, or- R15 is the group -(CH 2 -CH 2 0)xH, R16 is the group -(CH 2 -CH20) H and R17 is the group -CH 2 -CH 2 -(OCH 2 ,.:CH 2 )zOC 2 H5, in which the sum of x, y and z is metal oxides having atomic number ranging from 11 to

2. A .combination. as claimed in claim 1, wherein compound a) is combined with a compound selected from groups j) and-k).

3. A combination as claimed in claim 1, wherein- compound a) is combined with more compounds selected independently within and/or from groups e), j) and k).

4. A combination as-claimed in any one of claims 1-3, wherein in compounds of formula R is selected from the group consisting of methyl, 2,4,4-trimethyl-pent-2- yl, isopropyl, tert-butyl; R 1 is selected from the group consisting of 2-ethyl-hexyl, isopropyl and n-tetradecyl; R 2 is selected from isopropyl or 2-ethyl-hexyl; X is an oxygen atom or the group -NH-. A combination as claimed in claim 4, wherein in compounds of formula R is tert-butyl; R 1 and R 2 are 2-ethyl-hexyl; X is an oxygen atom.

6. A combination as claimed in any one of claims wherein in compounds of formula (III), R 4 is hydrogen and R5 is methyl or the group formula or R4 is the group SO 3 M, wherein M is hydrogen or a monovalent metal ion and R5 is the group of formula in which R 4 is as defined above.

7. A combination as claimed in any one of claims wherein in compounds of formula R 6 is selected SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 42 from isopropyl and tert-butyl, R 7 is selected from hydrogen and methoxy.

8. A combination as claimed in any one of claims wherein in .compounds of formula (VII), R 8 is methyl and R9 is,,2-ethyl-hexyl or the group +NH 2 (CH 2 CH 2 OH) 2

9. A combination as claimed in any one of claims wherein in compounds of formula (VIII), R, R 1 and R 2 are 2-ethyl-hexyl. A combination as claimed in any one of claims wherein in compounds of formula R 10 is selected from hydrogen and- methyl; R 11 is selected from hydrogen and the group. SO3Q, in which Q is hydrogen or a monovalent metal ion; R 12 is hydrogen.

11. A combination as claimed in any one of claims wherein in compounds of formula R 13 is 2-ethyl- hexyl.

12. A combination as claimed in any one of claims wherein in compounds of formula R 14 is selected from 2-ethyl-hexyl, the residue trimethylcyclohexyl and the group NH(CH 2 CH20H) 3

13. A combination as claimed in any one of claims wherein in compounds of formula (XII), G is selected from hydrogen or a monovalent metal ion.

14. A combination as claimed in any one of claims wherein compound of formula (XIII) is selected from those in which: R 15 R 16 and R17 are hydrogen; R 15 and R16 are at the same time methyl or 2- hydroxypropyl and R17 is ethyl or 2-hetylhexyl; R15 is the group -(-CH 2 -CH 2 R 16 is the group -(-CH 2 -CH 2 R 17 is the group -CH 2 -CH 2 -(-O-CH 2 SUBSTITUTE SHEET (RULE 26) R16\ R1 -COOR1 wherein R 15 and Ri 6 are independently hydrogen or a straight or branched (Ci- 6 alkyl group, optionally substituted with a hydroxyl group, and R 17 is selected from hydrogen, a straight or branched (Ci-lo) alkyl group, a monovalent metal ion and a quaternary ammonium group, or R 15 is the group (CH 2 .CH20) xH, R 16 is the group 10 (CH 2 .CH 2 0) yH, and R17 is the group CH 2 .CH 2 (OCH 2 -CH 2 zOC 2 Hs, in which the sum of x, y and z is k) metal oxides having atomic number ranging from 21 to with vitamins, or their precursors, or their analogs, selected from the group consisting Sof: 15 vitamins of A group, including vitamin A 2 and retinal, and their possible esters with straight or branched, saturated or unsaturated (C 2 20 aliphatic monocarboxylic acids or (C 3 1 2 alipahtic di- or tri- carboxylic acids, said acids being optionally hydroxylated or alkoxylated with PEG, PPG, or copolymers PEG/PPG; or esters with nicotinic acid; (ii) ao- and p-carotene; (iii) vitamins of the B group; (iv) vitamin C, and its possible esters with straight or branched, saturated or unsaturated (C 2 20 aliphatic monocarboxylic acids or (C 3 1 2 alipahtic di- or tri- carboxylic acids, said acids being optionally WO 99/06014 PCT/EP98/04518 44

22. A combination as claimed in any one of claims wherein the combined compound is at least one compound as claimed in claim 6, at least one compound as claimed in claim 13, and optionally at least one compound as claimed in claim

23. A combination as claimed in any one of claims wherein the combined compound is at least one compound as claimed in claim 6, at least one compound as claimed in claim 7, and optionally at least one compound as claimed in claim

24. A combination as claimed in any one of claims wherein the combined compound is at least one compound as claimed in claim 7, at least one compound- as claimed in claim 10, and at least one compound as claimed in claim A combination as claimed in any one of claims wherein the combined compound is at least one compound as claimed in claim 8 at least one compound as claimed in claim 10, and optionally at least one compound as claimed in claim

26. A combination as claimed in any one of claims wherein the combined compound is at least one compound as claimed in claim 9, and optionally at least one compound as claimed in claim 13.

27. A combination as claimed in any of the claims wherein the combined compound is at least one compound as claimed in claim 7, and at least one compound as claimed in claim 8.

28. A combination as claimed in any one of claims wherein the combined compound is at least one compound as claimed in claim 7 and at least one compound as SUBSTITUTE SHEET (RULE 26) WO 99/06014 PCT/EP98/04518 claimed in claim 12.

29. A combination as claimed in any one of claims wherein the combined compound is at. least one compound as claimed., in claim 7 and at least one compound as claimed in claim 14. Cosmetic or dermatological compositions containing a combination as claimed in any one of claims 1-29, in an amount ranging from about 0.1 to 35% by weight on the composition total weight.

31. Compositions as claimed in claim 30, wherein component a) is present in an amount- ranging from about 0.05 to about 20% of the composition total weight and at least one of the other components b) to k) is present in an amount ranging from about 0- to 30% by weight on the composition total weight, with the proviso that at least one of the components b) to k) is present in amounts different from 0.

32. Cosmetic compositions as claimed in claims 30 and 31, which are oil-in- water, water-in-oil, oil-water- oil, water-oil-water emulsions, oily solutions, lipid fusions, hydro-alcoholic or anhydrous aqueous gels, alcoholic or hydro-alcoholic solutions.

33. Cosmetic compositions as claimed in any one of claims 30 to 32, in which the solvent or dispersant of the oily phase is selected from hydrocarbons; oils, butters and natural waxes; silicones oils; esters of straight or branched, saturated or unsaturated aliphatic acids or of aromatic or alkylaromatic acids, having 1 to carbon atoms, said acids being optionally hydroxylated and/or ethoxylated, with mono- or polyhydroxylated aliphatic alcohols, saturated or SUBSTITUTE SHEET (RULE 26) 46 emulsifiers selected from a cross-linked copolymer consisting of i) acrylic or methacrylic acid, ii) vinyl esters of highly branched trialkylacetic acids of formula XIV RI 1 0 I I I 11 R19 CH2 I XIV R 20 in which Rig, R 1 9 and R 20 are straight alkyl residues, at least one of them being methyl, the total sum of the carbon atoms of the acyl residue being preferably 10, and iii) a 10 cross-linking agent, and b) cross-linked copolymers formed by i) acrylic or methacrylic acid, ii) acrylates or methacrylates of (Cio-C 3 0 aliphatic alkanols, iii) a cross-linking agent. 13. Compositions as claimed in claim 5, wherein the vitamins are employed in amounts comprised between about 0.02 and about 10% by weight, calculated on the o 15 composition total weight. *o 14. Composition as claimed in any one of claims 5 or 13, having a sun protecting factor (SPF) not lower than 2. The use of a combination as claimed in any one of claims 1 to 4 for the preparation of a dermatological or cosmetic composition useful for protecting human skin from sun radiations. 16. A method for the stabilization of a photosensitive composition, which comprises including a combination of any one of claims 1-4. 17. A method as claimed in claim 16, wherein said composition is a cosmetic or Sdermatological composition. 47 18. A method as claimed in claim 16, wherein said composition is a composition of one or more polymers. 19. Combinations of sunscreens substantially as hereinbefore described with reference to the accompanying Examples 1 to 14. 20. Cosmetic or dermatological compositions substantially as hereinbefore described with reference to the accompanying Examples 1 to 4. 21. The use of a combination of sunscreens for the preparation of a dermatological or cosmetic composition useful for protecting human skin from sun radiations substantially as hereinbefore described with reference to the accompanying Examples 10 1 to 14. 22. A method for the stabilization of a photosensitive composition substantially as 6* hereinbefore described with reference to the accompanying Examples 1 to 14. DATED THIS 7 TH DAY OF JUNE 2001 15 3V SIGMA S.p.A. 20 By their Patent Attorneys LORD COMPANY PERTH, WESTERN AUSTRALIA