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 so- called UV-B radiation, cause erythema and cutaneous sun- burns, 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 only responsible of skin tanning, are, as a matter of fact, harmful, in that they can cause damages to elastine and collagene, with consequent ayeing 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 (inn. J.

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 dibenzoyl- methane 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 erytheinatogenic 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 he 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 prohlems deriving from the holes in the ozone layer.

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 l: wherein: R is a straight or branched (C1-8) alkyl group, (C5~12) cycloalkyl, optionally substituted with one or more straight or branched (C1~4) alkyl groups; X is an oxygen atom or the group -NH-; R1 has the same meanings as R, or is hydrogen, a monovalent metal ion, a quaternary ammonium group, or a group of formula II in which A is a straight or branched (C1~8) alkyl, (C5 12) cycloalkyl, or (Cg-10) aryl optionally substituted with one or more straight or branched (C1~4) alkyl groups; R3 is hydrogen or methyl; n is an integer from 1 to 10; R2 has the same meaning as R when X is -NH-, or has the same meanings as R1 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 TIT:

wherein R4 is hydrogen, or the group 03M, in which M is hydrogen, or a monovalent metal ion, or a quaternary ammonium group, and R5 is hydrogen, methyl, a group SO3M wherein M is defined as above, or a group of formula TV or V wherein R4 is as defined above; c) dibenzoylmethane derivatives of formula VI in which R6 and R7 are selected independently from hydrogen, straight or branched (C1-8) alkyl and straight or branched (C1~8) alkoxy; d) alkoxycinnamic acid esters of formula VII wherein R8 is a straight or branched (C1-8) alkyl group,

and R9 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 in which R, 1 and R2 are defined as above for formula (I) f) benzophenone derivatives of formula IX wherein R10 is hydrogen or a straight or branched (C1 10) alkyl group, R11 is hydrogen or the group S03Q, in which Q is hydrogen, a monovalent metal ion or a quaternary ammonium group, and R12 is hydrogen, hydroxy or straight or branched (C1-4) alkoxy; g) diphenylcyanoacrylates of formula X wherein R13 has the same meanings as R1 defined above;

h) salicyli.e acid derivatives of formula XI wherein R14 is a straight or branched (C1-10) alkyl group, a benzyl group optionally substituted with a straight or branched (C1-6) alkyl group, a 3,3,5- trimethylcyclohexyl residue, both as a racemate and as any optically active forms, or the group HN+(CH2CH2OH)3; i) benzimidazolesulfonic acid derivatives of formula XII in which G is hydrogen, or a monovalent metal. ion, or a quaternary ammonium group; j) p-aminobenzoic acid (PABA) derivatives of formula XIII wherein P15 ad R16 are independently hydrogen or a straight or branched (C1~6) alkyl group, optionally substituted with a hydroxyl group, and R17 is selected from hydrogen, a straight or branched (C1-10) alkyl

group, a monovalent metal ion and a quaternary ammonium group, or R15 is the group -(CH2-CHSO)H, P16 is the group -(CH2-CH2O) yH and R17 is the group -CH2-CH2-(OCH2- CH2)zOC2H5, in which the sum of x, y and z is 25; k) metal oxides having atomic number ranging from 11 to 40.

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 classes b) to k) @ In the case of combinations of more than two components as defined in a) to k), 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 a). 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

methyl, ethyl, propyl, butyl and isomers thereof.

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

The preferred components of formula I are those in which R is methyl, 2,4,4-trimethyl-pent-2-yl, i.sopropyl. or tert-butyl, R1 is 2-ethyl-hexyl, isopropyl or n- tetradecyl, R2 is isopropyl or 2-ethyl-hexyl, and X is O or -NH-. Particularly preferred is the component in which R is tert-butyl, R1 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 P5 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 SO3M, wherein M is hydrogen or a monovalent metal ion and P5 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 R6 is isopropyl or tert-butyl and R7 is hydrogen or methoxy, known under the trade names EUSOLEXTM 8020 (R6=(CH3)2CH, R7=H) and PARSOLTM 1789 (R6=(CEI3)3C, R7=OCH3), respectively.

Preferred components of the class d) are those compounds of formula VII, in which Rg is methyl and P9 is 2-ethyl-hexyl or the group +NH2(CH2CFi2OH)2, known

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, R1 and R2 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, R11 is hydrogen or the group S03Q, in which Q is hydrogen or a monovalent metal ion, and R12 is hydrogen, known under the trade names UVASORBTM 2QH (R10=R11=R12=H), UVASORBTM MET (R1o=CH3, R1l=Rl2 H), UVASORBTM S5 (R1o=CH3, R11=S03Q wherein Q=H, R12=H), respectively.

The preferred component of the class g) is the compound of formula X in which R13 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+(CH2CH2O}I)3, known under the trade names ESCALOLTM 587, REMESTERTM 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 p- aminobenzoic 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 2- hydroxypropyl, and R17 is ethyl or 2-ethyl-hexyl, known

under the trade names UVASORBTM DMO (R15=Rl6=CH3, R17=2- ethyl-hexyl) and AMERSCREENTM P (R15=Rl6= 2- hydroxypropyl, R17=ethyl), respectively, and the compound of formula XIII in which R15 is the group -(- CH2-CH2O-)X-H, R16 is the group (-CH2-CH20-)H and R17 is the group -CH2-CH2-(-OCH2-CH2-)ZOC2H5-, in which the sum of x, y and z is 25, known under the trade name UVINULTM P25.

Preferred components of the class k) are titanium dioxide (TiO2) 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 TiO2, and ranging from about 15 to about 300 nm as for ZnO. Most preferably, the size of the Tio2 particles ranges from about 5 to about 50 rnn. 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 Al203 or aluminium salts with Cj0-18 aliphatic fatty acids. They are easily commercially available products. For example, micronized TiO2 is marketed under the trade name P25 (Degussa), whereas TiO2 coated with aluminium stearate is marketed as MT1OOT (Tayka Corp.), and that coated with Al203 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

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 a), can be selected from any of the different classes b) to k), 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 lr), 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 k), 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 g), 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 g), 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; 6) at least one preferred component of the class b) and at least one preferred component of the class k), optionally together with one or more of the other preferred components according to the invention; 7) 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 lr), 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 k), optionally together with one or more of the other preferred components according to the invention; 10) 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;

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; 12) at least one preferred component of the class c) and at least one preferred component of the class d), 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 h), optionally together with one or more of the other preferred components according to the invention; 14) at least one preferred component of the class c) and at least one preferred component of the class j), 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.

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 30%, 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 general, 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 composi- tions 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

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, arit 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, dimethiconols, 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, pentaery- thritol--dioleate, trimethylolpropan-trioleate, tri- isostearyl-citrate, diacetin, triacetin, 2-ethyl- hexyl acetate, neopentylglycol oleate, triethylene glycol diacetate, isopropyl myristate, isopropyl palmitate, bis-diglyceryl-caprylate/caprate/iso- stearate/stearate/hydroxystearate/adipate, dioctyl maleate, di-(2-ethyl-hexyl) malate, (C12-15)alkyl benzoates, cetylstearyl octanoate, cetylstearyl isononanoate, 2-ethyl-hexyl palmitate, 2-ethyl-

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) (C6-C35) alcohols, such as cetyl alcohol, stearyl alcohol, behenyl alcohol, octyldodecyl alcohol, 3,5,5-trimethylhexyl alcohol, 2-butoxyethanol, 2- phenoxyethanol, 2-ethyl-1 , 3-hexanediol and analogs; vii) ethers of (C8-C40) fatty alcohols, such as di-n- octylether; 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 (C1-6)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

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-N- butyl)-propionate.

A third preferred group of oily cpmponents 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 (AMPHTSoLTM 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

emulsifiers. The latter are, for example, ethoxylated compounds of natural oil derivatives, such as hydrogenated castor oil (7)OE (ARLACELTM 989, ICI); mono- and diglycerides of fatty acids, optionally ethoxylated, such as glyceryl stearate (CUTINATM GMS, Henkel) and ylyceryl(20)0E stearate (CUTINATM E-24, Henkel); sorbitan ethoxylated esters (TWEENTM, ICI and CRILLETTM, Croda) and non-ethoxylated esters (SPANTM, ICI and CRILLTM, 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)0E sesquistearate (GLUCAMATETM SS E-20.

Amerchol); ethers of glucose and of its oligomers, optionally esterified with (C10-30)aliphatic acids, such as triglycerylmethylglucose distereate (TegoCare(R) 450, Goldschmidt) and methyl glucose sesquistearate (TegoCare(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 (AQUALOSETM 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

(PPG) or copolymers PEG/PPG; and analogs. Instead of these conventional emulsifiers, cross-linked copolymers can also advantageously be used, selected from a) cross- linked copolymers formed by i) acrylic or methacrylic acid, ii) vinyl esters of highly branched trialkylacetic acids of formula XIV in which R P19 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 10, 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 (C10-30)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) (B.F. 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,

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 A2 and retinal, and their possible esters with straight or branched, saturated or unsaturated (C2~20)aliphatic monocarboxylic acids or (C3~12)aliphatic di- or tri- carboxyilic acids, said acids being optionally hydroxylated or alkoxylated with PEG, PPG, or copolymers PEG/PPG; or esters with nicotinic 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 (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; 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.

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 1,3- butylene glycol, in amounts from about 0.1 to about 30% 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

composition weight; film-forming agents, such as alkylated polyvinilpyrrolidones or high molecular weight waxes, in amounts not above 5 of the composition weight; preservatives, such as 2-bromo-2-nitro- propanediol, 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 he 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 he prepared separately, dissolving or dispersing in any of them the desired components/lipophilic or hydrophilic ingredients, and

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 nut 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, R1 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 A face day-cream is prepared from 1. Cetylstearyl glucoside 4.0 2. Glyceryl stearate 1.0 3. Cetylstearyl alcohol t.0 4. C12~15 alkylbenzoate 5.0 5. Octyl octanoate 5.0 6. Dimethicone 0.5 7. Component a) 1.0 8. Micronized zinc oxide-component lr) 1.0 9. Demineralized water q.s. to 100 10. Imidazolidinyl urea n.3

11. Methyl p-hydroxybenzoate 0.2 12. Glycerin 3.0 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 A). Separately, water is heated to 70"C (phase B). 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)0E stearate 0.25 2. Avocado oil 3.0 3. Octyl palmitate 3.0 4. Mineral oil 3.0 5. Component a) 3.0 6. Micronized titanium dioxide-comp. k) 2.0 7. Demineralized water q.s. to 100 8. STABYLEN 30 (polymeric emulsifier 0.25 - 3V SIGMA, Bergamo, Italy) 9. 2-Phenylbenzimidazol-5-sulfonic- acid comp. i) 2.0 10. Sodium hydroxide q.s. to pH 7 11. Diazolidinyl urea 0.3 12. Isothiazolone 0.05 13. Propylene glycol 3.0 The mixture of components 1 to 4 is heated to 60"C then components 5 and 6 are added (phase A). Separately, component 8 is dispersed in about 902 of water, at 60°C, under stirring (phase B). Subsequently, phase A is added to phase B in a homogenizer. Then, Component 9 is

dissolved in the residual water at room temperature (phase C), 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 propylene glycol, preservatives and perfume are added.

EXAMPLE 3 An anhydrous ointment is prepared from 1. Mineral oil q.s. to 100 2. Cetylstearyl isononan.oate 30.0 3. C8~10 triglycerid 30.0 4. Component a) 5.0 5. 4-tert-butyl-4 I -methoxy-diben- zoylmethane component c) 1.0 6. Micronized titanium dioxide- component k) 2.0 7. Hydrogenated castor oil 1.5 8. Pyrogenic silica 1.5 9. Perfume 0.3 The mixture of components 1, 2 and 3 is heated to 60°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.

EXAMPEE 4 A fluid water-in-oil emulsion is prepared from 1. Hydroenate castor oil(7)OE 7.5 2. Lanolin alcohols in mineral oil 2.5 3. Flydrogenated polyisobutene 5.0 4. Octyl octanoate 5.0 5. C8~10 triglycerid 3.0 6. Component a) 5.0

7. 4-tert-Butyl-4' -methoxy-diben- zoylmethane-component c) 2.0 8. 2-Cyano-3 , 3-diphenyl-acrylic acid 2-ethyl-hexyl ester component g) 5.0 9. Demineralized water q.s. to 100 10. Dimethyl-dimethylol-hydantoin 0.3 11. Phenoxyethanol and parabens 1.0 12. Glycerin 5.0 13. Perfume 0.3 The mixture of components 1 to 5 is heated to 70"C and components 6 and 7 are added, under stirring (phase A). 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 5 A high-protection water-in-oil cream is prepared from 1. Triglyceryl diisostearate 4.0 2. Bees-wax 2.0 3. Mineral oil 10.0 4. Octyl octanoate 5.0 5. Cyclomethicone 5.0 6. Component a) 5.0 7. 2-Cyano-3,3-diphenylacrylic acid 2-ethyl-hexyl ester component g) 5.0 8. 4-tert-Butyl-4'-methoxy-dibenzoyl- methane-component c) 2.0 9. Hydrogenated castor oil 0.5 10. Micronized titanium dioxide-

component k) 5.0 11. Demineralized water q.s. to 100 12. 2-Phenylbenzimidazol-5-sulfonic acid - component i) 3.0 13. Triethanolamine q.s. tot pH 6.5 14. Sodium dehydroacetate 0.3 15. Phenoxyethanol and parabens 1.0 16. Glycerin 5.0 17. Perfume 0.3 The mixture of components 1 to 5 is melted at 60"C and, components 6, 7 and 8 are added, under stirring (phase A). Components 9 and 10 are subsequently dispersed in this phase in a homogenizer. Separately, about 902 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 C). 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 2.0 2. Cetylstearyl alcohol 1.0 3. Avocado oil 3.0 4. Jojoba oil 6.0 5. KaritB butter 2.0 6. Butyl hydroxyanisol 0.

7. Dimethicone and dimethiconol 1.0 8. Component a) 3.0

9. 3-(4-Methylbenzilydene)-camphor - component b) 2.0 10. Micronized titanium dioxide - component k) 1.0 11. Demineralized water q.s. to 100 12. SYNTHALEN L (Carbomer 941 - 3V SIGMA, Bergamo, Italy) 0.5 13. Potassium cetylphosphate 1.0 14. Aminomethyl propanol 0.4 15. Imidazolidinyl urea 0.3 16. Potassium sorbate 0.5 17. EDTA disodium 0.1 18. Glycerin 3.0 19. Soluble collagene (12 sol.) 2.0 20. Perfume 0.3.

The mixture of components 1 to 6 is melted at 70"C and components 8, 9 and 10 are added, under strong stirring (phase A). Separately water is heated to 70°C and first component 12, then component 13 are dispersed, under stirring (phase B). 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)0E 3.0 2. Glyceryl stearate(2O)OE 2.0 3. Behenyl alcohol 2.0 4. Isohexadecane 10.0 5. Safflower oil 3.0

6. Borage oil 2.0 7. Butyl hydroxyanisol 0.1 8. Copolymer PVP/eicosene 1.0 9. Component a) 3.0 10. 3- ( 4-Methylbenzilidene ) -cam- phor - component b) 2.0 11. 2-Hydroxy-4-methoxy-benzophe- none - component f) 1.0 12. Micronized zinc oxide - component k) 2.0 13. Demineralized water q.s. to 100 14. SYNTHALEN K (Carbomer 940 - 3V SIGMA, Bergamo, Italy) 0.15 15. Aminomethyl propanol 0.1 16. Imidazolidinyl urea 0.3 17. Phenoxyethanol and parabens 1.0 18. Butylene glycol 2.0 19. Perfume 0.3 The mixture of components 1 to 8 is melted at 70°C and components 9 to 12 are added, under strong stirring (phase A). Separately, component 14 is dispersed in water at 70"C, under stirring (phase B). Phase A is then added to phase B in a homogenizer, and the resulting mixture is then neutralized (pII 7) with component 15.

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 5.0 2. Copolymer PEG-45/dodecyl glycol 3.0 3. Mineral oil 10.0

4. Paraffin 1.0 5. Dioctyl maleate 5.0 6. Isopropyl myristate 5.0 7. Component a) 3.0 8. 3-(4-Methylbenzilidene )-cam- phor - component b) 3.0 9. 4-tert-Butyl-4'methoxy-dibenzoyl- methane - component c) 1.0 10. Hydrogenated castor oil 0.5 11. Micronized titanium dioxide - component l) 2.0 12. Demineralized water q.s. to 100 13. Magnesium sulfate 0.5 14. 2-Bromo-2-nitro-propanediol 0.3 15. Phenoxyethanol and parabens 1.0 16. Propylene glycol 2.0 17. Tocopherol acetate 1.5 18. Perfume 0.3 The mixture of components 1 to 6 is melted at 60"C 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 A). 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.

EXAMPLE 9 A silicon water-in-oil emulsion is prepared from 1. Cetyl Dimethicone Copolyol 3.0 2. Lanolin alcohols in mineral oil 2.5

3. Cyclomethicone 10.0 4. Di-(2-ethyl-hexyl) malate 5.0 5. Octyldodecyl neopentanoate 5.0 6. Perfume 0.3 7. Component a) 3.0 8. 4-tert-Butyl-4'-methoxy-diben- zoylmethane - component c) 1.0 9. 2-Hydroxy-4-methoxy-benzophenone component f) 1.0 10. Micronized titanium dioxide comp. l) in isopropyl myristate 4.0 11. Demineralized water q.s. to 100 12. Sodium chloride 2.0 13. Chlorhexidine digluconate 0.3 14. Methyl paraben 0.2 15. Glycerin 5.0 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 A). Components 12 to 15 are dissolved in water, at room temperature (phase B), then phase B is slowly added to phase A, under stirring. Finally, the emulsion is made homogeneous in a homogenizer.

EXAMPLE 10 A sun-oil is prepared from 1. Dioctyl cyclohexane q.s. to 100 2. C8~l0 triglycerid 20.0 3. Isopropyl palmitate 30.0 4. Cyclomethicone 10.0 5. Perfume 0.3

6. Component a) 3.0 7. Octyl salicylate - component h) 2.0 8. 4-tert-butyl-4'-methoxy-dibenzoyl- methane component c) 1.0 The mixture of components 1, 2 and 3 is heated to 600C and components 6, 7 and 8 are added, under stirring. The resulting mixture is cooled to room temperature and added with components 4 and 5.

EXAMPLE 11 An oil-in-water cream is prepared with 1. Cetylstearyl alcohol and cetylstearyl glucoside 3.50 2. Glyceryl stearate 1.00 3. Cetylstearyl alcohol 0.50 4. Propylene glycol dibenzoate 10.00 5. (C1215)alkyl benzoate 7.00 6. Dimethicone 1.00 7. Component a) 4.00 8. 4-tert-Butyl-4 -methoxy- dibenzoylmethane - component c) 2.00 9. Demineralized water q.s. to 100 10. SYNTHALEN K (Cabomer 940 - 3V SIGMA, Bergamo, Italy) 0.10 11. Potassium cetylphosphate 0.50 12. PEG-25 p-aminobenzoic acid - component j) 4.00 13. Aminomethyl propanol 0.05 14. Butylene glycol 1.50 15. Phenoxyethanol and parabens 1.00 16. Perfume 0.30

The mixture of components 1 to 6 is heated to 70"C and, under stirring, is added with components 7 and 8 (phase A). 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 1. PEG-4 Polyglyceryl 2-laurate 2.00 2. Dicaprylyl ether 7.50 3. Propylene glycol dicaprylate/dicaprate 9.50 4. Cetyl lactate 3.00 5. 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 10. 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 15. 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

A). Separately, compound 11 is dispersed into the water, previously heated to 70"C, and the resulting dispersion is .added with component 12 (phase B). 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 1. PEG-100 Stearate 2.00 2. Glyceryl stearate 1.00 3. Cetearyl alcohol 2.50 4. Stearic acid 5.00 5. 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 10. Titanium dioxide MT100T (Taika Corp.) - component k) 4.00 11. Isohexadecane 5.00 12. Cyclomethycone 2.50 13. Demineralized water q.s. to 100 14. Potassium cetylphosphate 0.50 15. Stabylen 30 (3V SIGMA, Bergamo, Italy) 0.15 16. Butylene glycol 1.50 17. Imidazolidinyl urea 0.30 18. Methylparaben 0.20 19. Propylparaben 0.10 20. Perfume 0.30 The mixture of components 1 to 8 is heated to 70"C

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 A). Component 15 is dispersed into the water, previously heated to 70"C, and the resulting dispersion is added with component 14 (phase B). 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 20.

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 5. Propylene glycol dicaprylate/dicaprate 9.50 6. (C18-36)acid glycol ester 2.00 7. Retinyl palmitate 1.00 8. a-tocopheryl acetate 1.00 9. Component a) 4.00 10. Titanium dioxide MT100T (Taika Corp.) component k) 4.00 11. Isohexadecane 5.00 12. Cyclomethicone 2.50 13. Demineralized water q.s. to 100 14. Potassium cetylphosphate 0.50 15. Stabylen 30 (3V SIGMA, Bergamo, Italy) 0.15 16. Butylene glycol 1.50 17. Green tea extract 1.00 18. Imidazolidinyl urea 0.30

19. Methylparaben 0.20 20. Propylparaben 0.10 21. Perfume 0.30 The mixture of components 1 to 8 is heated to 70'C 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 A). Component 15 is dispersed into the water, previously heated to 70"C, and the resulting dispersion is added with component 14 (phase B). 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.