AU759357B2

AU759357B2 - Material comprising an organic UV-A filter and method for displacing the maximum absorption wavelength

Info

Publication number: AU759357B2
Application number: AU76683/00A
Authority: AU
Inventors: Sandrine Chodorowski; Francis Xavier Quinn; Clement Sanchez
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1999-10-01
Filing date: 2000-09-28
Publication date: 2003-04-10
Anticipated expiration: 2020-09-28
Also published as: JP2003510342A; HUP0300234A2; WO2001024768A3; BR0007188A; PL347767A1; FR2799120A1; FR2799120B1; CZ20011809A3; ZA200104121B; CA2353709A1; EP1235552A2; AU7668300A; WO2001024768A2; KR20010080582A; RU2212881C2; CN1352544A

Description

B 99/1785 EXT (GD/IC) MATERIAL COMPRISING AN ORGANIC UV-A SCREENING AGENT AND PROCESS FOR SHIFTING THE MAXIMUM ABSORPTION WAVELENGTH The present invention generally relates to a material obtained by the sol-gel route exhibiting a maximum absorption wavelength (Xma×) within the range from 370 to 400 nm, to a process for shifting the maximum absorption wavelength of a material comprising an organic UV-A sunscreen agent and to a cosmetic and/or dermatological composition including such a material.

It is known that light radiation with wavelengths of between 280 nm and 400 nm makes possible browning of the human epidermis and that rays with wavelengths of between 280 nm and 320 nm, known under the name of UV-B radiation, result in erythemas and cutaneous burns which can be harmful to the development of natural tanning; this UV-B radiation therefore has to be screened out.

It is also known that UV-A rays with wavelengths of between 320 and 400 nm, which result in browning of the skin, are capable of bringing about a detrimental change in the latter, in particular in the case of sensitive skin or of skin continually exposed to solar radiation. UV-A rays result in particular in a loss of elasticity of the skin and the appearance of wrinkles, leading to premature aging. They promote the triggering of the erythemal reaction or enhance this reaction in some subjects and can even be the cause of phototoxic or photoallergic reactions. It is therefore desirable also to screen out UV-A radiation.

The commonly used sunscreen agents do not include organic screening agents effective in the long UV-A spectral range corresponding to wavelengths ranging from 370 to 400 nm. In other words, antisun protection is not provided in this spectral range. This is all the more serious as this more penetrating radiation is partly responsible for the development of certain skin cancers 2 and of immunosuppression, in addition to cutaneous photoaging.

In the state of the prior art, Patent Applications PCT numbers WO 93/10753 and WO 93/11135 of Slavtcheff et al. respectively disclose a sunscreen agent of metal complex of dibenzoylmethane derivatives type, the maximum absorption wavelength of which is 366 nm, and a process for the preparation of this novel sunscreen agent. Currently, appropriate organic UV-A sunscreen agents exhibiting a maximum absorption wavelength (Xkx) of greater than or equal to 370 nm with a coefficient of extinction E 25 000 mol- 1 .1 1 .cm preferably e 30 000 mol- 1 .1- 1 .cm 1 are unknown.

It has been found, surprisingly, that, by combining an organic UV-A screening agent having a maximum absorption wavelength of less than 370 nm, such as 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol® 1789; max 358 nm), with certain zirconium, titanium and aluminum compounds, it is possible to obtain a material for which the absorption band is shifted and which exhibits a maximum absorption wavelength within the range from 370 to 400 nm, with an value which is not significantly reduced.

A subject matter of the present invention is therefore a material capable of being obtained by the sol-gel route comprising at least one organic UV-A sunscreen agent with a max of less than 370 nm and at least one zirconium, titanium or aluminum compound, the material having a maximum absorption wavelength which is situated in the range from 370 to 400 nm.

The present invention also relates to a process for shifting the maximum absorption wavelength of an organic UV-A sunscreen agent with a Xmx of less than 370 nm into the range from 370 to 400 nm.

A further subject matter of the present invention is cosmetic and/or dermatological compositions for the 3 photoprotection of the skin and/or keratinous substances comprising a material of the invention.

Other characteristics, aspects and advantages of the invention will become more clearly apparent on reading the description and examples which follow.

A subject matter of the present invention is a material capable of being obtained by the sol-gel route which exhibits a maximum absorption wavelength (Xmx) within the range from 370 to 400 nm and which comprises: at least one metal alkoxide chosen from zirconium, titanium and aluminum alkoxides, at least one organic UV-A sunscreen agent, the maximum absorption wavelength of which is less than 370 nm, at least one functionalized organic polymer or one precursor of such a polymer, or at least one functionalized silicone polymer or one precursor of such a polymer, at least one solvent, and an amount of water sufficient for the partial and/or complete hydrolysis of the metal alkoxide and its condensation.

The term "organic UV-A sunscreen agent" is understood to mean any organic compound which absorbs UV radiation within the 320-400 nm wavelength range.

The metal alkoxides are chosen from the group composed of: metalloorganic compounds corresponding to one of the following formulae:

M(ORI)

n (Ia) R-M(ORI)n- 1 (Ib) (R 0)n- IM-R"-M'(ORI)n'- (Ic) R-M(ORI)n-2 (Id)

R'

in which: 4 M and M' represent, independently of one another, a zirconium, titanium or aluminum atom, n and n' denote the respective valencies of the metal atoms represented by M and M', RI represents a saturated or unsaturated and linear or branched C 1 i 30 preferably hydrocarbonaceous group optionally comprising a heteroatom, such as a nitrogen, sulfur, oxygen or phosphorus atom, and more preferably a linear or branched C1-30, preferably C._ 6 alkyl group, R and R' represent, independently of one another, a saturated or unsaturated and linear, branched or cyclic

C

1 30 preferably C2- 20 hydrocarbonaceous group optionally comprising a heteroatom, such as a nitrogen, phosphorus, sulfur or oxygen atom, such as, for example, a linear or branched alkyl group, a cycloalkyl group or an aryl group, it being possible for said R and R' groups to be substituted by groups capable of reacting with the functionalized organic or silicone polymer, such as, for example, halogen atoms, the hydroxyl, acyl, carboxyl, ester, thiol, alkylthioalkyl, epoxy, isocyanate, thiocyanate, ureido, thioureido, urethane, imidazolo, morpholino or pyrrolo groups, groups comprising ethylenic unsaturation, such as the (meth)acrylic and vinyl groups, halogenated groups, such as perfluorinated groups, hydroxylated or carboxylated groups, phosphonic, phosphonate, phosphate, pyrophosphate, phosphonium, sulfonate, amine, quaternary ammonium, amide, amino acid and polypeptide groups, the acetic acid, acetoacetate (ACAC) or ethyl acetoacetate group, or a group deriving from EDTA and its derivatives, and the like, and it being possible for said R and R' groups to additionally comprise a cosmetically or dermatologically active group chosen, for example, from a colorant group, a photochromic group, a group for screening out UV radiation, a group for promoting adhesion to keratinous 5 substances (such as groups of amide, urethane, urea, hydroxyl, carboxyl, amino acid or polypeptide type), a group for facilitating the removal of makeup, a bactericidal group, a chelating group which can in particular complex polyvalent cations, a hydroxy acid, a neurosuppressant, a group for combating hair loss, an antioxidizing group, a group for combating free radicals or a vitamin-carrying group, R" represents a saturated or unsaturated and linear, branched or cyclic divalent C 1 -30, hydrocarbonaceous group optionally comprising a heteroatom, such as a nitrogen, phosphorus, sulfur or oxygen atom, such as, for example, a linear or branched alkylene group, a cycloalkylene group or an arylene group, it being possible for said R" group to be substituted by groups capable of reacting with the organic or silicone polymer, such as those defined above, and it being possible for said R" group additionally to comprise a cosmetically or dermatologically active group, such as those defined above; complexed or chelated metalloorganic compounds corresponding to one of the following formulae:

M(ORI

n -bx(X)x (IIa) R-M(ORI),n--bx(X)x (IIb) (X)x (ORl)n-l.bx M-R"-M'(OR)n.iI-bx(X)x (IIc)

R-M(ORI

n 2 -bx(X)x (IId)

R'

in which: M, n, RI, R, R' and R" have the same meanings as those given for the above formulae (Ia) to (Id), X represents a monodentate ligand or a chelating group comprising a nitrogen atom, a phosphorus atom, a sulfur atom or an oxygen atom which can be covalently bonded to a group capable of reacting with said functionalized organic polymer or said functionalized silicone polymer such as, for example, those defined above, and which 6 can comprise a cosmetically or dermatologically active group, such as, for example, those defined above, x represents the number of X ligands; and b represents the number of bonding atoms of the X ligand.

The term "monodentate ligand" is understood to mean a group comprising a single atom which can bond to the central metal atom.

The term "chelating group" is understood to mean a polydentate ligand bonded to a single central metal atom by more than one doublet-donating atom.

Mention may be made, as examples of such monodentate or polydentate ligands of sulfuric acids, sulfonic acids, phosphonic acids, phosphoric acids, carboxylic acids, ketones, P-diketones, esters, Pketoesters, amines, P-ketoamines, amino acids, preferably a- or P-hydroxylated amino acids, and their derivatives, a- or 3-hydroxy acids, ethers and polyethers, imines, optionally hydroxylated amides, azo compounds, thiols, ureas, thioether sulfoxides, thioether sulfones, optionally cyclic thioethers, di(thioethers), monoalcohols or polyols, dextrin and its derivatives, or thiazolidines.

Mention may in particular be made of diketones, such as 2,4-pentanedione, 2,4-hexafluoropentanedione or 2,2,6,6-tetramethyl-3,5-heptanedione; salicylic acid and its derivatives, such as 4- or ((meth)acrylamino)salicylic [sic] acid; lactic, succinic, acetic and citric acid; (meth)acrylic acid esters, such as acetoxyethyl methacrylate or methyl ahydroxy(meth)acrylate; ethyl acetoacetate, methyl acetoacetate and acetylacetone; EDTA; polyethers of low molecular mass, such as poly(ethylene glycol)s and poly(propylene glycol)s; polyethyleneimines; lysine and its derivatives, such as e-N-(meth)acryloyl-L-lysine; cysteine and its derivatives, such as N-acetylcysteine, carboxymethylcysteine, cystine or N,N'-diacetylcystine; 7 methionine; lactic acid esters or acetic acid esters; triethanolamine; lipoic acids; or dextrin or cyclodextrin.

Preference is very particularly given, among the metal alkoxides mentioned above, to tetra-n-propyl zirconate, tetraisopropyl zirconate, titanium tetraisopropoxide and aluminum tri-sec-butoxide.

The organic UV-A sunscreen agent having a ,ma x of less than 370 nm can be any appropriate organic compound having a maximum absorption wavelength of less than 370 nm.

Mention may be made, among organic UV-A sunscreen agents which can be used according to the invention, of: dibenzoylmethane derivatives; screening agents active in the UV-A region of following formula (IV): R7 R8 RIO

(IV)

R9 0 O in which:

R

7 and R 9 which are identical or different, represent a hydrogen atom, a halogen atom, an OH group, a saturated or unsaturated and linear or branched C 1 -Cl, alkyl group, a saturated or unsaturated and linear or branched Ci-Ci, alkoxy group or an HSO 3 group;

R,

0 represents a hydrogen atom or HSO 3 R, represents a hydroxyl group; an ORn, group where

R

1 1 represents a saturated or unsaturated and linear or branched Cl-Ci alkyl group; or else a group of following structure: 8 in which R 12 represents a hydrogen atom or HSO 3 or else a group of following formula: COOR 3

R

1 4 or else a a [sic] group of following formula: z R16 in which: Z represents an oxygen atom or an -NH- group;

R

13

R

14

R

15 and R 16 which are identical or different, represent a hydrogen atom, a halogen atom, an OH group, a saturated or unsaturated and linear or branched Cj-Co alkyl group; a saturated or unsaturated and linear or branched C 1

-C,

0 alkoxy group; or an HSO 3 group; screening agents which are active in the UV-A region of the benzimidazole or benzoxazole type of following formula

R

1 7 N w W (V)

R

1 i in which: W represents an oxygen atom or an -NH- group;

R

17 represents a hydrogen atom or HSO 3

R

18 represents a linear or branched alkoxy group comprising from 1 to 10 carbon atoms approximately or a 9 group of following formula:

R

19 N f in which: Y represents an oxygen atom or an -NH- group;

R

19 represents a hydrogen atom or HSO 3 benzophenone derivatives, such as those of following formula (VI): O H R 2 4 0 O H C (vI) R23 R22

R

2 1 in which

R

20 represents a hydrogen atom or a saturated or unsaturated and linear or branched Ci-Ci, alkyl group;

R

2 1 and R 22 which are identical or different, represent a hydrogen atom, a halogen atom, an OH group, a saturated or unsaturated and'linear or branched Ci-Cio alkyl group; a saturated or unsaturated and linear or branched Ci-Cjo alkoxy group or an HSO 3 group;

R

23 represents a hydrogen atom, OH, a saturated or unsaturated and linear or branched Ci-Cio alkyl group or a saturated or unsaturated and linear or branched Cj-Cjo alkoxy group;

R

24 represents OH, a hydrogen atom or a saturated or unsaturated and linear or branched Ci-Cjo alkyl group; silane derivatives or polyorganosiloxanes comprising benzophenone group(s), such as those disclosed in documents EP-A-0 389 377, FR-A-2 657 351 and EP-A- 0 655 453; anthranilates; and 10 their mixtures.

Mention may especially be made, among dibenzoylmethane derivatives which are particularly well suited in the context of the present invention, of, without implied limitation: 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 4,4'-diisopropyldibenzoylmethane, 4,4'-dimethoxydibenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane, 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane, 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane.

Preference is in particular given, among the dibenzoylmethane derivatives mentioned above, to 4-tertbutyl-4'-methoxydibenzoylmethane, sold in particular under the trade name of "Par'sol 1789" by Hoffmann- Laroche, this screening agent corresponding to the following expanded formula: 0 0

(CH

3 3 C C OCH 3

CH

2 Another preferred dibenzoylmethane derivative according to the present invention is 4isopropyldibenzoylmethane, sold under the name of "Eusolexo 8020" by Merck and corresponding to the following expanded formula: 11 O

O

I 11 -0

(CH

3 2 CH C C

CH,

The compounds of structures [sic] (IV) above are disclosed respectively in Patent US 4 585 597 and Patent Applications FR 2 236 515, 2 282 426, 2 645 148, 2 430 938 and 2 592 380.

A particularly preferred compound of formula (IV) is benzene-1,4-[di(3-methylidenecamphor-10-sulfonic acid)], such as the product sold under the name Mexoryl® SX by Chimex.

Benzene-1,4-[di(3-methylidenecamphor-10-sulfonic acid)] and its various salts (compound disclosed in particular in Patent Applications FR-A-2 528 420 and FR- A-2 639 347, are screening agents already known per se ("broad band" screening agents) capable in fact of absorbing ultraviolet rays with a wavelength ranging from 280 nm to 400 nm, with absorption maxima between 320 and 370 nm, in particular in the vicinity of 345 nm. These screening agents correspond to the following general formula: 0 +DSq SO D+

O

in which D represents a hydrogen atom, an alkali metal or an NH(R 25 3 group, in which the R 2 5 groups, which can be identical or different, represent a hydrogen atom or a Ci-

C

4 alkyl or hydroxyalkyl group, or an Mn"/n group, M" representing a polyvalent metal cation in which n is 12 equal to 2 or 3 or 4, M" preferably representing a metal cation chosen from Ca 2 Zn 2 Mg 2 Ba 2 A13l and Zr 4 1. It is clearly understood that the compounds of formula (IV) above can give rise to the "cis-trans" isomer about one or more double bond(s) and that all the isomers come within the scope of the present invention.

Mention may be made, as examples of specific benzimidazole or benzoxazole compounds corresponding to the formula of: benzene-1,4-di(benzimidazol-2-yl-5-sulfonic acid), benzene-1,4-di(benzoxazol-2-yl-5-sulfonic acid), and their partially or completely neutralized forms.

Mention may more particularly be made, among benzophenone derivatives of formula of those chosen from the group composed of: 2,4-dihydroxybenzophenone (benzophenone-1), such as the product sold under the name Uvinul® 400 by BASF; 2,2',4,4'-tetrahydroxybenzophenone (benzophenone-2), such as the product sold under the name Uvinul® D50 by

BASF;

2-hydroxy-4-methoxybenzophenone, also known as oxybenzone (benzophenone-3), such as the product sold under the name Uvinul® M40 by BASF; 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, also known as sulisobenzone (benzophenone-4), such as the product sold under the name Uvinul' MS40 by BASF; and its sodium sulfonate form 2,2'-dihydroxy-4,4 '-dimethoxybenzophenone (benzophenone-6), such as the product sold under the name Helisorb® 11 by Norquay; 5-chloro-2-hydroxybenzophenone (benzophenone-7); 2,2'-dihydroxy-4-methoxybenzophenone, also known as dioxybenzone or benzophenone-8, such as the product sold under the name Spectrasorb® UV-24 by American Cyanamid; 13 the disodium salt of 2,2'-dihydroxy-4,4'diacid or benzophenone-9, such as the product sold under the name Uvinulo DS49 by BASF; 2-hydroxy-4-methoxy-4'-methylbenzophenone benzophenone-11, such as the product sold under the name Uvinul® M493 by BASF; 2-hydroxy-4-(octyloxy)benzophenone (benzophenone- 12).

Mention may very particularly be made, among anthranilates which can be used according to the present invention, of menthyl anthranilate, such as the product sold under the name Neo Heliopan MA® by Haarman Reimer.

The functionalized organic or silicone polymer of the material according to the invention can be a homopolymer or random, block and/or graft copolymer chosen from: alkyloxazoline homopolymers and copolymers, such as poly(2-ethyl-2-oxazoline); homopolymers and copolymers of (meth)acrylic acid, of crotonic acid, of maleic acid, of itaconic acid, of styrenesulfonic acid, of 2- (acrylamido)methylpropanesulfonic acid, of 2sulfoethyl methacrylate, of vinylsulfonic acid and/or of vinylphosphonic acid; homopolymers of acrylic or methacrylic esters or amides and their copolymers with comonomers chosen from unsaturated carboxylic acids, sulfonic acids, phosphonic acids, vinyl esters and ethers, olefins, styrene, substituted styrenes, such as hydroxystyrene, fluoro- and perfluoroolefins, perfluoroalkyl (meth)acrylates, fluorovinyl compounds, such as fluorovinyl ethers, and unsaturated organosilanes, organosiloxanes or organopolysiloxanes; 14 vinyl alcohol homopolymers and copolymers; homopolymers of vinyl and/or allyl and/or methallyl esters or amides and their copolymers with comonomers chosen from unsaturated carboxylic acids, sulfonic acids, phosphonic acids, vinyl esters and ethers, olefins, styrene, substituted styrenes, such as hydroxystyrene, fluoro- and perfluoroolefins, perfluoroalkyl (meth)acrylates, fluorovinyl compounds, such as fluorovinyl ethers, and unsaturated organosilanes, organosiloxanes or organopolysiloxanes; polyethers, such as methylene oxide, ethylene oxide, propylene oxide or tetramethylene oxide homopolymers and copolymers; aromatic and/or aliphatic polyesters, and polyesters obtained by ring opening, such as polycaprolactones, polylactides, polyglycolides and their copolymers; homopolymers and copolymers of olefins or of cycloolefins, such as polyethylenes, ethylene/vinyl acetate, ethylene/a-olefin, ethylene/cycloolefin or ethylene/(meth)acrylate copolymers, and propylene, butene, isobutene and norbornene homopolymers and copolymers; polyamides, polyesteramides and polyetheramides; optionally fluorinated polyurethanes and polyureas which can comprise polyether, polyester and/or polyorganosiloxane blocks; fluoropolymers, such as the products sold by Ausimont under the name of "Fombline" (perfluoropolyether); natural polymers and modified natural polymers, such as ether and/or ester derivatives of cellulose or of starch, polysaccharides, glycosaminoglucans and oligosaccharides, natural gums, such as hydroxyalkylated guar gums, such as those which are hydroxypropylated, hydroxypropylated guar gums 15 comprising carboxyl or quaternized functional groups, locust bean gum or xanthan gum, carrageenans, pectins, alginates, polypeptides or proteins, such as collagen, elastin, gelatin or keratin; polyorganosiloxanes, such as polydimethylsiloxanes, polymethylphenylsiloxanes or polyphenylsiloxanes, or polyorganosiloxanes substituted on the chain or at the chain end by amino acid groups, polyoxyethylene chains, amino or polyamino groups, hydroxyl groups, carboxylic acid groups, alkyl chains, vinyl or acrylic grafts or blocks, or fluorinated or perfluorinated grafts or blocks; polyorganophosphazenes; polysilanes, polycarbosilanes or polysilazanes; and mixtures of these polymers.

In a specific embodiment, the hydrocarbonaceous homopolymers and copolymers as mentioned above can possess polysiloxane chains as blocks and/or grafts.

The organic or silicone polymers can also comprise a cosmetically or dermatologically active group, such as those listed above.

In the case where organic or silicone polymers are not functionalized, they can be functionalized either by reaction within the actual composition, such as, for example, in the case of polyorganosiloxanes, or by prior reaction by conventional methods before the formation of the composition.

Mention may in particular be made, among preferred organic or silicone polymers according to the invention, of poly(2-ethyl-2-oxazoline), a terpolymer of vinyl acetate, of vinyl 4-tert-butylbenzoate and of crotonic acid (62/25/10), polydimethylsiloxane-diols, poly(ethylene glycol)s, poly(vinyl alcohol [sic] and poly(vinylpyrrolidone). The most preferred are polydimethylsiloxane-diols.

16 When the material according to the invention comprises a precursor of the organic or silicone polymer, it is essentially one or more monomers capable of resulting in a functionalized organic or silicone polymer by polymerization of unsaturated double bonds or by polycondensation during application of the composition.

The polymerization can be initiated conventionally by a thermal route in the presence of conventional free radical initiators, by irradiation with UV radiation, by electron beams by the ionic route (cationic or anionic) or by any known polymerization technique.

Although this specific embodiment can be carried out according to the invention, it is nevertheless preferred, for practical reasons, to use a functionalized organic or silicone polymer which has already been formed.

The solvent used in the material of the present invention is preferably a linear or branched lower alcohol, better still ethanol.

The amounts of the various components of the material generally used are as follows, expressed with respect to the total weight of the material: from 0.1% by weight to 99% by weight, preferably from 0.5% by weight to 80% by weight and better still from 1% by weight to 70% by weight of metal alkoxide, from 0.1% by weight to 99% by weight, preferably from by weight to 80% by weight and better still from 1% by weight to 70% by weight of functionalized organic or silicone polymer, from 0.1% by weight to 60% by weight, preferably from 0.1% by weight to 30% by weight and better still from 0.1% by weight to 20% by weight of sunscreen agent.

Another subject matter of the present invention relates to a process for shifting, into the range from 370 to 400 nm, the maximum absorption wavelength (Xmay) of 17 an organic UV-A screening agent having a X,,ax of less than 370 nm which consists in combining, with said screening agent, a sol comprising at least one functionalized organic polymer or one precursor of this polymer or at least one functionalized silicone polymer or one precursor of this polymer, at least one metal alkoxide chosen from zirconium, titanium and aluminum alkoxides, at least one solvent and an amount of water sufficient for the partial and/or complete hydrolysis of the metal alkoxide and its condensation. All the components are as defined above.

According to a preferred embodiment of the process of the invention, the metal alkoxide is mixed with a polymer solution before the addition of the screening agent.

An additional subject matter of the present invention is a cosmetic and/or dermatological composition comprising, in a cosmetically and/or dermatologically acceptable vehicle, a material as defined above according to the present invention.

This cosmetic and/or dermatological composition comprises the material according to the invention in an effective amount ranging from 1% by weight to 99% by weight, preferably from 5% by weight to 60% by weight, with respect to the total weight of the composition. The material according to the invention is preferably dried and milled and added in the form of particles to the composition. The mean size of the particles which are obtained after drying and milling lies within the range from 0.1 pm to 50 pm, preferably from 0.1 pm to 20 pm and better still from 0.1 pm to 10 pm.

The cosmetic and/or dermatological compositions targeted by the present invention can, of course, comprise one or more additional sunscreen agents other than the organic UV-A sunscreen agents defined above, these additional sunscreen agents being water-soluble, 18 fat-soluble or insoluble in the cosmetic solvents commonly used. These additional screening agents can be chosen in particular from cinnamic acid derivatives, salicylic derivatives, camphor derivatives other than those corresponding to the formula triazine derivatives, such as those disclosed in Patent Applications US-4 367 390, EP 0 863 145, EP 0 517 104, EP 0 570 838, EP 0 796 851, EP 0 775 698, EP 0 878 469, EP 0 933 376 and EP 0 893 119, 3,P'-diphenylacrylate derivatives, benzimidazole derivatives, bisbenzoazolyl derivatives, such as those disclosed in Patents EP 0 669 323 and US 2 463 264; methylenebis(hydroxyphenylbenzotriazol) derivatives, such as those disclosed in Applications US-5 237 071, US-5 166 355, GB-2 303 549, DE-19 726 184 and EP 0 893 119, p-aminobenzoic acid derivatives, and the screening hydrocarbonaceous and screening silicone polymers disclosed in Application WO- 93/04665.

Mention may be made, as examples of additional active sunscreen agents, of: p-aminobenzoic acid, ethoxylated (25 mol) p-aminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, N-propoxylated ethyl p-aminobenzoate, glyceryl p-aminobenzoate, homomenthyl salicylate, 2-ethylhexyl salicylate, triethanolamine salicylate, 4-isopropylbenzyl salicylate, 2-ethylhexyl 4-methoxycinnamate, methyl diisopropylcinnamate, isoamyl 4-methoxycinnamate, diethanolamine 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, ethyl 2-cyano-3,3-diphenyl acrylate, 3-(4'-methylbenzylidene)-d,1-camphor, 19 3-benzylidene-d,1-camphor, 2,4,6-tris[p-(2'-ethylhexyl-1'-oxycarbonyl)anilino]-1,3,5-triazine, (p-(tert-butylamido)anilino]-4,6-bis[(p-(2'ethylhexyl-1'-oxycarbonyl)anilino]-1,3,5triazine [sic], 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine [sic] (Tinosorb® S, Ciba-Geigy), the polymer of and (2-oxoborn-3yliden)methyl]benzyl]acrylamide [sic], 1,4-bis(benzimidazolyl)phenylen-3,3',5,5'tetrasulfonic [sic] acid and its soluble salts, polyorganosiloxanes comprising a benzalmalonate functional group, polyorganosiloxanes comprising a benzotriazole functional group, such as drometrizole trisiloxane, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4- (1,1,3,3-tetramethylbutyl)phenol] in the dissolved form, such as the product sold under the trade name Mixxim® BB/100 by Fairmount Chemical, or else in the insoluble micronized form, such as the product sold under the trade name Tinosorb® M by Ciba-Geigy, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4- (methyl)phenol] in the dissolved form, such as the product sold under the trade name Mixxim® BB/200 by Fairmount Chemical.

The cosmetic and/or dermatological compositions according to the invention can also comprise agents for the artificial tanning and/or browning of the skin (selftanning agents), such as, for example, dihydroxyacetone

(DHA).

The cosmetic and/or dermatological compositions according to the invention can also comprise pigments or 20 alternatively nanopigments (mean size of the primary particles: generally between 5 nm and 100 nm, preferably between 10 and 50 nm) formed of coated or uncoated metal oxides, such as, for example, nanopigments formed of titanium oxide (amorphous or crystalline titanium oxide in the rutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide or cerium oxide, which are all photoprotective agents well known per se which act by physical blocking (reflection and/or scattering) of UV radiation. Conventional coating agents are, furthermore, alumina and/or aluminum stearate. Such nanopigments formed of coated or uncoated metal oxides are disclosed in particular in Patent Applications EP-A-0 518 772 and EP-A-0 518 773.

The cosmetic and/or dermatological compositions in accordance with the present invention can additionally comprise conventional cosmetic adjuvants chosen in particular from fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, agents for combating free radicals, opacifiers, stabilizers, emollients, silicones, a-hydroxy acids, antifoaming agents, moisturizing agents, vitamins, fragrances, preservatives, surfactants, fillers, sequestering agents, polymers, propellants, basifying or acidifying agents, dyes or any other ingredient commonly used in the cosmetics and/or dermatological field, in particular for the manufacture of antisun compositions in the form of emulsions.

The fatty substances can be composed of an oil or a wax or their mixtures. The term "oil" is understood to mean a compound which is liquid at ambient temperature.

The term "wax" is understood to mean a compound which is solid or substantially solid at ambient temperature and with a melting point generally of greater than Mention may be made, as oils, of mineral oils (liquid petrolatum); vegetable oils (sweet almond, 21 macadamia, blackcurrant seed or jojoba oil); synthetic oils, such as perhydrosqualene, fatty alcohols, acids or esters (such as the benzoate of C 12

-C,

1 alcohols sold under the name "Finsolv TN" by Finetex, octyl palmitate, isopropyl lanolate or triglycerides, including those of capric/caprillic acids), or ethoxylated or propoxylated fatty esters and ethers; silicone oils (cyclomethicone, preferably comprising 4 or 5 silicon atoms, or polydimethylsiloxane); fluorinated oils; or polyalkylenes.

Mention may be made, as waxy compounds, of paraffin wax, carnauba wax, beeswax or hydrogenated castor oil.

Mention may be made, among organic solvents, of lower alcohols and polyols.

The thickeners can be chosen in particular from crosslinked polyacrylic acids, modified or unmodified guar and cellulose gums, such as hydroxypropylated guar gum, methylhydroxyethylcellulose or hydroxypropylmethylcellulose, and silicone gums, such as, for example, a polydimethylsiloxane derivative.

The cosmetic and/or dermatological compositions according to the invention can be prepared according to techniques well known to a person skilled in the art, in particular those intended for the preparation of emulsions of oil-in-water or water-in-oil type.

This cosmetic and/or dermatological composition can be provided in particular in the form of a simple or complex emulsion W/O, O/W/O or such as a cream or a milk, or in the form of a gel or of a cream gel, of a powder or of a solid stick and can optionally be packaged as an aerosol and be provided in the form of a foam or of a spray.

The cosmetic and/or dermatological compositions according to the invention are preferably provided in the form of an oil-in-water emulsion.

22 When it is an emulsion, the aqueous phase of the latter can comprise a nonionic vesicular dispersion prepared according to known processes (Bangham, Standish and Watkins, J. Mol. Biol., 13, 238 (1965), FR 2 315 991 and FR 2 416 008) The cosmetic and/or dermatological composition according to the invention is used as composition for protecting the skin or keratinous substances against ultraviolet rays, as antisun composition or as makeup product.

When the cosmetic composition according to the invention is used for protecting the hair, it can be provided in the form of a shampoo, lotion, gel, emulsion or nonionic vesicular dispersion and can constitute, for example, a rinse-out composition, to be applied before or after shampooing, before or after dyeing or bleaching, or before, during or after perming or hair straightening, a styling or treating lotion or gel, a lotion or a gel for blow drying or hairsetting, or a composition for perming or straightening or for dyeing or bleaching the hair.

By way of indication, for antisun formulations in accordance with the invention which exhibit a vehicle of oil-in-water emulsion type, the aqueous phase (comprising in particular hydrophilic screening agents) generally represents from 50 to 95% by weight, preferably from to 90% by weight, with respect to the entire formulation, the oily phase (comprising in particular lipophilic screening agents) from 5 to 50% by weight, preferably from 10 to 30% by weight, with respect to the entire formulation and the (co)emulsifier(s) from 0.5 to 20% by weight, preferably from 2 to 10% by weight, with respect to the entire formulation.

The examples are given by way of illustration of the present invention and are not understood in any way to be limiting.

23 Example 1 A material according to the invention is prepared from: Tetra-n-propyl zirconate 9.36 g Absolute ethanol 2.83 g Polydimethylsiloxane-diol (PDMS-diol) 6.24 g Parsol® 1789 0.08 g Water 0.02 g the tetra-n-propyl zirconate originating from Fluka, the Parsol® 1789 (4-tert-butyl-4'-methoxydibenzoylmethane) being sold by Hoffmann-Laroche and the PDMS-diol exhibiting a weight-average molar mass of 550 (ABCR, reference DMS-S12).

The PDMS-diol is diluted in ethanol. The tetra-npropyl zirconate is subsequently added and the mixture is stirred for 5 minutes. The Parsol® 1789 is subsequently added with stirring. The novel material is ready for use.

Application and evaluation The novel material is deposited on a glass sheet (microscope slide). A film is formed on the sheet after evaporation of the volatile components of the mixture.

The drying time of the film is fast, that is to say between 1 and 3 minutes.

The absorption band of the novel material is evaluated by UV visible absorption spectrometry. The \max value has shifted to 378 nm with respect to the Amax of 358 nm of Parsolo 1789 before the preparation of the material. The effectiveness of the novel material is not significantly reduced. This novel material is able to form a film, is entirely persistent toward water and ethanol and is not released under these conditions and in polar and nonpolar cosmetic oils.

24 Example 2 A material according to the invention is prepared from: Titanium tetraisopropoxide 2.27 g Absolute ethanol 0.50 g Polydimethylsiloxane-diol (PDMS-diol) 0.40 g Parsol® 1789 1.10 g Tetrahydrofuran (THF) 2.25 g the titanium tetraisopropoxide originating from Fluka, the Parsolo 1789 (4-tert-butyl-4'-methoxydibenzoylmethane) being sold by Hoffmann-Laroche, the PDMS-diol exhibiting a weight-average molar mass of 550 (ABCR, reference DMS- S12) and the tetrahydrofuran originating from Fluka.

The titanium tetraisopropoxide is diluted in ethanol. The Parsolo 1789, dissolved in the THF, is subsequently added to the solution with stirring over minutes and then the PDMS-diol is added. The mixture is left to stir at ambient temperature for 60 minutes. The novel material is then ready for use.

Application and evaluation The application and evaluation are carried out in the same way as in Example 1. The Xma. value was shifted to 385 nm with respect to the Ama, of 358 nm of Parsol® 1789 before the preparation of the material. The effectiveness of the novel material was not significantly reduced. This novel material is able to form a film, is entirely persistent toward water and ethanol and is not released under these conditions and in polar and nonpolar cosmetic oils.

Example 3 A material according to the invention is prepared from: 004213925v7.doc Aluminum tri-sec-butoxide at 75% in sec-butanol 0.36 g Polydimethylsiloxane-diol (PDMS-diol) 0.44 g Parsol" 1789 0.23 g Tetrahydrofuran (THF) 2.25 g the aluminum tri-sec-butoxide originating from ABCR, the Parsol® 1789 (4-tertbutyl-4'-methoxydibenzoylmethane) being sold by Hoffman-Laroche, the PDMSdiol exhibiting a weight-average molar mass of 550 (ABCR, reference DMS-S12) and the tetrahydrofuran originating from Fluka.

The Parsol® 1789, dissolved in the THF, is added, with stirring over minutes, to the solution of aluminum tri-sec-butoxide in sec-butanol and then the PDMS-diol is added. The mixture is left to stir at ambient temperature for minutes. The novel material is then ready for use.

Application and evaluation The application and evaluation are carried out in the same way as in 15 Example 1. The Xmax value was shifted to 370 nm with respect to the Xmax of 358 nm of Parsol® 1789 before the preparation of the material. The effectiveness of the novel material was not significantly reduced. This novel material is able to form a film, is entirely persistent toward water and ethanol and is not released under these conditions and in polar and nonpolar cosmetic oils.

It will be understood that the invention disclosed and defined in this specification extends to all alternative combinations of two or more of the individual features mentioned or evident from the text or drawings. All of these different combinations constitute various alternative aspects of the invention.

It will also be understood that the term "comprises" (or its grammatical variants) as used in this specification is equivalent to the term "includes" and should not be taken as excluding the presence of other elements or features.

Claims

1. Material capable of being obtained by the sol-gel route comprising: at least one metal alkoxide chosen from zirconium, titanium and aluminum alkoxides, at least one organic UV-A sunscreen agent having a maximum absorption wavelength of less than 370 nm, at least one functionalized organic polymer or one precursor of such a polymer, or at least one functionalized silicone polymer or one precursor of such a polymer, 0 at least one solvent, and an amount of water sufficient for the partial and/or complete hydrolysis of the metal alkoxide and its condensation, said material having a maximum absorption wavelength (Xmax) which is situated in the range from 370 to 400 nm. 5 2. Material according to Claim 1, characterized in that the metal alkoxide is chosen from the group composed of: metalloorganic compounds corresponding to one of the following formulae: M(OR 1 )n R-M(OR 1 )n-1 (R1O)n-1M-R"-M'(ORi)n.1 R-M(OR1)n-2 I R' (la) (Ib) (Ic) (Id) in which: 25 M and M' represent, independently of one another, a zirconium, titanium or aluminum atom, n and n' denote the respective valencies of the metal atoms represented by M and M', R 1 represents a saturated or unsaturated and linear or branched C1-30, hydrocarbonaceous group optionally comprising a heteroatom, such as a nitrogen, sulfur, oxygen or phosphorus atom, R and R' represent, independently of one another, a saturated or 004213925v4.doc 27 unsaturated and linear, branched or cyclic C1-30, hydrocarbonaceous group optionally comprising a heteroatom, such as a nitrogen, phosphorus, sulfur or oxygen atom, it being possible for said R and R' groups to be substituted by groups capable of reacting with the organic or silicone polymer and it being possible for said R and R' groups to additionally comprise a cosmetically or dermatologically active group, R" represents a saturated or unsaturated and linear, branched or cyclic divalent C1-30, hydrocarbonaceous group optionally comprising a heteroatom, such as a nitrogen, phosphorus, sulfur or oxygen atom, it being possible for said R" group to be substituted by groups capable of reacting with the organic or silicone polymer and it being possible for said R" group additionally to comprise a cosmetically or dermatologically active group; complexed or chelated metalloorganic compounds corresponding to one of the following formulae: M(OR)n-bx(X)x (Ila) R-M(ORi)n-l-bx(X)x (lib) (X)x(ORi)n-l-bxM-R"-M'(OR1)n'-I-bx(X)x (lic) R-M(OR)n-2-bx(X)x (lid) R' in which: M, n, R 1 R, R' and R" have the same meanings as those given for the above formulae (la) to (Id), X represents a monodentate ligand or a chelating group comprising a nitrogen atom, a phosphorus atom, a sulfur atom or an oxygen atom which can be 25 covalently bonded to a group capable of reacting with said functionalized organic polymer or said functionalized silicone polymer and which can comprise a cosmetically or dermatologically active group, x represents the number of X ligands; and b represents the number of bonding atoms of the X ligand.

3. Material according to Claim 2, wherein R, represents a Ci-C6 hydrocarbonaceous group.

4. Material according to Claim 2 or 3, wherein R 1 represents an alkyl 004213925v4.doc 28 group. Material according to any one of Claims 2 to 4, wherein R and R' represent a C2-20 hydrocarbonaceous group.

6. Material according to Claim 2 or 5, wherein R and R' represent a linear or branched alkyl group, a cycloalkyl group or an aryl group.

7. Material according to any one of Claims 2 to 6, wherein R" represents a linear or branched alkylene group, a cycloalkylene group or arylene group.

8. Material according to any one of Claims 2 to 7, characterized in that said group capable of reacting with the functionalized organic polymer or the functionalized silicone polymer carried by the R, R' or R" group and/or by the X ligand can be chosen from halogen atoms, the hydroxyl, acyl, carboxyl, ester, thiol, alkylthioalkyl, epoxy, isocyanate, thiocyanate, ureido, thioureido, urethane, imidazolo, morpholino or pyrrolo groups, groups comprising ethylenic S 15 unsaturation, such as the (meth)acrylic and vinyl groups, halogenated groups, such as perfluorinated groups, hydroxylated or carboxylated groups, phosphonic, phosphonate, phosphate, pyrophosphate, phosphonium, sulfonate, amine, quaternary ammonium, amide, amino acid and polypeptide groups, the acetic acid, acetoacetate (ACAC) or ethyl acetoacetate group, or a group deriving from 20 EDTA and its derivatives.

9. Material according to any one of Claims 2 to 8, characterized in that the monodentate or polydentate ligand X is chosen from sulfuric acids, sulfonic acids, phosphonic acids, phosphoric acids, carboxylic acids, ketones, P-diketones, esters, -ketoesters, amines, p-ketoamines, amino acids, preferably a- or P- hydroxylated amino acids, and their derivatives, a- or 3-hydroxy acids, ethers and polyethers, imines, optionally hydroxylated amides, azo compounds, thiols, ureas, thioether sulfoxides, thioether sulfones, optionally cyclic thioethers, di(thioethers), S monoalcohols or polyols, dextrin and its derivatives, or thiazolidines. 004213925v4.doc 29 Material according to any one of the preceding claims, characterized in that the metal alkoxide is chosen from tetra-n-propyl zirconate, tetraisopropyl zirconate, titanium tetraisopropoxide and aluminum tri-sec-butoxide.

11. Material according to any one of the preceding claims, characterized in that the metal alkoxide is present in an amount ranging from 0.1% by weight to 99% by weight, with respect to the total weight of the material.

12. Material according to Claim 11, wherein the metal alkoxide is present in an amount ranging from 0.5% to 80% by weight.

13. Material according to any one of the preceding claims, characterized in that the organic UV-A sunscreen agent is chosen from: dibenzoylmethane derivatives, camphor derivatives, benzimidazole derivatives, I- benzoxazole derivatives, 15 benzophenone derivatives, silane or polyorganosiloxane derivatives comprising benzophenone group(s), anthranilates, and their mixtures. *0 20 14. Material according to any one of the preceding claims, characterized 0.g in that the organic UV-A sunscreen agent is chosen from: 0 0 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 4,4'-diisopropyldibenzoylmethane, 4,4'-dimethoxydibenzoylmethane, /x.AL 4-tert-butyl-4'-methoxydibenzoylmethane, 004213925v4.doc 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane

15. Material according to any one of the preceding claims, characterized in that the organic UV-A sunscreen agent is 4-tert-butyl-4'- methoxydibenzoylmethane.

16. Material according to any one of the preceding claims, characterized in that the organic UV-A sunscreen agent is present in an amount ranging from 0.1% by weight to 60% by weight, with respect to the total weight of the material.

17. Material according to Claim 16 wherein the sunscreen agent is present in an amount ranging from 0.1% to 30% by weight.

18. Material according to any one of the preceding claims, characterized in that the functionalized organic or silicone polymer is a homopolymer or random, •S 15 block and/or graft copolymer chosen from: alkyloxazoline homopolymers and copolymers; homopolymers and copolymers of (meth)acrylic acid, of crotonic acid, of maleic acid, of itaconic acid, of styrenesulfonic acid, of 2- (acrylamido)methylpropanesulfonic acid, of 2-sulfoethyl 20 methacrylate, of vinylsulfonic acid and/or of vinylphosphonic acid; homopolymers of acrylic or methacrylic esters or amides and their copolymers with comonomers chosen from unsaturated carboxylic acids, sulfonic acids, phosphonic acids, vinyl esters and ethers, olefins, styrene, substituted styrenes, fluoro- and perfluoroolefins, perfluoroalkyl (meth)acrylates, fluorovinyl compounds and unsaturated organosilanes, organosiloxanes or organopolysiloxanes; vinyl alcohol homopolymers and copolymers; homopolymers of vinyl and/or allyl and/or methallyl esters or amides and their copolymers with comonomers chosen from unsaturated RL Qcarboxylic acids, sulfonic acids, phosphonic acids, vinyl esters and 004213925v4.doc 31 ethers, olefins, styrene, substituted styrenes, fluoro- and perfluoroolefins, perfluoroalkyl (meth)acrylates, fluorovinyl compounds, and unsaturated organosilanes, organosiloxanes or organopolysiloxanes; polyethers; polyesters; homopolymers and copolymers of olefins or of cycloolefins; polyamides and polyesteramides; polyurethanes and polyureas which can comprise polyether, polyester and/or polyorganosiloxane blocks; fluoropolymers; natural polymers and modified natural polymers; polyorganosiloxanes; polyorganophosphazenes; 15 polysilanes, polycarbosilanes or polysilazanes; and mixtures of these polymers.

19. Material according to any one of the preceding claims, characterized in that the functionalized organic or silicone polymer is chosen from poly(2-ethyl-2- oxazoline), a terpolymer of vinyl acetate, of vinyl 4-tert-butylbenzoate and of crotonic acid (62/25/10), polydimethylsiloxane-diols, poly(ethylene glycol)s, poly(amyl [sic] alcohol) and poly(vinylpyrrolidone). Material according to Claim 19, characterized in that the functionalized organic or silicone polymer is a polydimethylsiloxane-diol.

21. Material according to any one of the preceding claims, characterized in that the functionalized organic or silicone polymer is present in an amount ranging from 0.1% by weight to 99% by weight, with respect to the total weight of the material.

22. Material according to Claim 21, wherein the functionalised organic or silicone polymer is present in an amount ranging from 0.5% to 80% by weight. 004213925v4.doc 32

23. Material according to any one of the preceding claims, characterized in that the solvent is an alcohol.

24. Material according to Claim 23, characterized in that the alcohol is a linear or branched lower alcohol.

25. Material according to Claim 24, characterized in that the alcohol is ethanol.

26. Process for shifting the maximum absorption wavelength (Xmax) of an organic UV-A sunscreen agent having a Xmax of less than 370 nm into the range from 370 to 400 nm, characterized in that it comprises the combination of this screening agent with a sol comprising at least one functionalized organic polymer or one precursor of such a polymer, or at least one functionalized silicone polymer or one precursor of such a polymer, at least one metal alkoxide chosen from zirconium, titanium and aluminum alkoxides, at least one solvent and an amount of water sufficient for the partial and/or complete hydrolysis of the metal alkoxide 15 and its condensation.

27. Process according to Claim 26, characterized in that the metal alkoxide is chosen from the group composed of: metalloorganic compounds corresponding to one of the following *formulae: 20 M(ORi)n (la) R-M(OR 1 )n-1 (Ib) (R10)n-1 (Ic) R-M(ORi)n-2 (Id) R' in which: M and M' represent, independently of one another, a zirconium, titanium or aluminum atom, n and n' denote the respective valencies of the metal atoms represented by a, M and M', 3 R 1 represents a saturated or unsaturated and linear or branched C1-3 0 004213925v4.doc 33 hydrocarbonaceous group optionally comprising a heteroatom, such as a nitrogen, sulfur, oxygen or phosphorus atom, R and R' represent, independently of one another, a saturated or unsaturated and linear, branched or cyclic C1- 3 o, hydrocarbonaceous group optionally comprising a heteroatom, such as a nitrogen, phosphorus, sulfur or oxygen atom, it being possible for said R and R' groups to be substituted by groups capable of reacting with the organic or silicone polymer and it being possible for said R and R' groups to additionally comprise a cosmetically or dermatologically active group, R" represents a saturated or unsaturated and linear, branched or cyclic divalent C1- 30 hydrocarbonaceous group optionally comprising a heteroatom, such as a nitrogen, phosphorus, sulfur or oxygen atom, it being possible for said R" group to be substituted by groups capable of reacting with the organic or silicone polymer and it being possible for said R" group additionally to comprise a S: 15 cosmetically or dermatologically active group; complexed or chelated metalloorganic compounds corresponding to one of the following formulae: M(ORi)n-bx(X)x (Illa) R-M(ORj)n-1-bx(X)x (lib) (X)x(OR1)n-1 bxM-R"-M'(ORl)n'- 1 bx(X)x (Ilc) R-M(OR)n-2-bx(X)x (lid) I R' in which: M, n, R 1 R, R' and R" have the same meanings as those given for 25 the above formulae (la) to (Id), X represents a monodentate ligand or a chelating group comprising a nitrogen atom, a phosphorus atom, a sulfur atom or an oxygen atom which can be covalently bonded to a group capable of reacting with said functionalized organic polymer or said functionalized silicone polymer and which can comprise a cosmetically or dermatologically active group, x represents the number of X ligands; and b represents the number of bonding atoms of the X ligand. 28 Process according to Claim 27, wherein R 1 represents a Ci-C 6 004213925v4.doc 34 hydrocarbonaceous group.

29. Process according to Claim 27 or 28, wherein R 1 represents an alkyl group. Process according to any one of Claims 27 to 29, wherein R and R' represent a C2- 2 0 hydrocarbonaceous group.

31. Process according to Claim 27 or 30, wherein R and R' represent a linear or branched alkyl group, a cycloalkyl group or an aryl group.

32. Process according to any one of Claims 27 to 31, wherein R" represents a linear or branched alkylene group, a cycloalkylene group or arylene group.

33. Process according to any one of Claims 27 to 32, characterized in that said group capable of reacting with the functionalized organic polymer or the functionalized silicone polymer carried by the R, R' or R" group and/or by the X ligand can be chosen from halogen atoms, the hydroxyl, acyl, carbonyl, ester, thiol, alkylthioalkyl, epoxy, isocyanate, thiocyanate, ureido, thioureido, urethane, imidazolo, morpholino or pyrrolo groups, groups comprising ethylenic unsaturation, such as the (meth)acrylic and vinyl groups, halogenated groups, such as perfluorinated groups, hydroxylated or carboxylated groups, phosphonic, phosphonate, phosphate, pyrophosphate, phosphonium, sulfonate, amine, 20 quaternary ammonium, amide, amino acid and polypeptide groups, the acetic acid, acetoacetate (ACAC) or ethyl acetoacetate group, or a group deriving from "EDTA and its derivatives.

34. Process according to any one of Claims 27 to 33, characterized in that the monodentate or polydentate ligand X is chosen from sulfuric acids, sulfonic acids, phosphonic acids, phosphoric acids, carboxylic acids, ketones, P-diketones, esters, P-ketoesters, amines, P-ketoamines, amino acids, preferably a- or p-hydroxylated amino acids, and their derivatives, a- or p-hydroxy acids, \ethers and polyethers, imines, optionally hydroxylated amides, azo compounds, 00421 3925v4.doc thiols, ureas, thioether sulfoxides, thioether sulfones, optionally cyclic thioethers, di(thioethers), monoalcohols or polyols, dextrin and its derivatives, or thiazolidines. Process according to any one of Claims 26 to 34, characterized in that the metal alkoxide is chosen from tetra-n-propyl zirconate, tetraisopropyl zirconate, titanium tetraisopropoxide and aluminum tri-sec-butoxide.

36. Process according to any one of Claims 26 to 35, characterized in that the organic UV-A sunscreen agent is chosen from: dibenzoylmethane derivatives, camphor derivatives, benzimidazole derivatives, benzoxazole derivatives, benzophenone derivatives, silane or polyorganosiloxane derivatives comprising benzophenone group(s), anthranilates, and their mixtures.

37. Process according to any one of Claims 26 to 36, characterized in that the organic UV-A sunscreen agent is chosen from: 2-methyidibenzoylmethane, 20 4-methyld ibenzoyl methane, -4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 0 2,4-dimethyldibenzoyl methane, 000::: 2,5-dimethyld ibenzoyl methane, 4,4'-d iisopropyld ibenzoyl methane, 4,4'-dimethoxyd ibenzoyl methane, 4-te rt-butyl-4'-methoxyd ibenzoyl methane, 2-methyl-5-isopropyl-4'-methoxyd ibenzoyl methane 2-methyl-5-tert-butyl-4-methoxyd ibenzoyl methane, 2 ,4-di methyl-4'-methoxyd ibenzoyl methane, 2,6-dimethyl-4-te rt-b utyl-4'- rneth oxyd ibe nzoyl methane 004213925v4.doc 36

38. Process according to any one of Claims 26 to 37, characterized in that the organic UV-A sunscreen agent is 4-tert-butyl-4'- methoxydibenzoylmethane.

39. Process according to any one of Claims 26 to 38, characterized in that the functionalized organic or silicone polymer is a homopolymer or random, block and/or graft copolymer chosen from: alkyloxazoline homopolymers and copolymers; homopolymers and copolymers of (meth)acrylic acid, of crotonic acid, of maleic acid, of itaconic acid, of styrenesulfonic acid, of 2- (acrylamido)methylpropanesulfonic acid, of 2-sulfoethyl methacrylate, of vinylsulfonic acid and/or of vinylphosphonic acid; homopolymers of acrylic or methacrylic esters or amides and their copolymers with comonomers chosen from unsaturated carboxylic I acids, sulfonic acids, phosphonic acids, vinyl esters and ethers, 15 olefins, styrene, substituted styrenes, fluoro- and perfluoroolefins, perfluoroalkyl (meth)acrylates, fluorovinyl compounds and unsaturated organosilanes, organosiloxanes or organopolysiloxanes; vinyl alcohol homopolymers and copolymers; homopolymers of vinyl and/or allyl and/or methallyl esters or amides and their copolymers with comonomers chosen from unsaturated carboxylic acids, sulfonic acids, phosphonic acids, vinyl esters and ethers, olefins, styrene, substituted styrenes, fluoro- and perfluoroolefins, perfluoroalkyl (meth)acrylates, fluorovinyl compounds, and unsaturated organosilanes, organosiloxanes or S: 25 organopolysiloxanes; polyethers; polyesters; homopolymers and copolymers of olefins or of cycloolefins; polyamides and polyesteramides; polyurethanes and polyureas which can comprise polyether, polyester and/or polyorganosiloxane blocks; fluoropolymers; S natural polymers and modified natural polymers; 004213925v4.doc 37 polyorganosiloxanes; polyorganophosphazenes; polysilanes, polycarbosilanes or polysilazanes; and mixtures of these polymers.

40. Process according to any one of Claims 26 to 39, characterized in that the functionalized organic or silicone polymer is chosen from poly(2-ethyl-2- oxazoline), a terpolymer of vinyl acetate, of vinyl 4-tert-butylbenzoate and of crotonic acid (62/25/10), polydimethylsiloxane-diols, poly(ethylene glycol)s, poly(amyl [sic] alcohol) and poly(vinylpyrrolidone).

41. Process according to Claim 40, characterized in that the functionalized organic or silicone polymer is a polydimethylsiloxane-diol.

42. Process according to any one of Claims 26 to 41, characterized in that the solvent is a linear or branched lower alcohol.

43. Process according to Claim 42, characterized in that the alcohol is 15 ethanol.

44. Process according to any one of Claims 26 to 43, characterized in that the metal alkoxide is mixed with a solution of functionalized organic or silicone polymer before the addition of the screening agent.

45. Cosmetic and/or dermatological composition, characterized in that it S 20 comprises, in a cosmetically and/or dermatologically acceptable vehicle, an .effective amount of the material according to any one of Claims 1 to

46. Cosmetic and/or dermatological composition according to Claim characterized in that the material is in the form of particles obtained by drying and milling.

47. Cosmetic and/or dermatological composition according to Claim or 46, characterized in that the effective amount of the material according to any -Z one of Claims 1 to 25 lies within the range from 1% by weight to 99% by weight 004213925v4.doc 38 with respect to the total weight of the cosmetic and/or dermatological composition.

48. Cosmetic and/or dermatological composition according to any one of Claims 45 to 47, characterized in that the effective amount of the material according to any one of Claims 1 to 25 lies within the range from 5 to 60% by weight with respect to the total weight of the cosmetic and/or dermatological composition.

49. Cosmetic and/or dermatological composition according to any one of Claims 45 to 48, characterized in that the mean size of the particles obtained by drying and milling the material according to any one of Claims 1 to 25 lies within the range from 0.1 jim to 20 gim. Cosmetic and/or dermatological composition according to Claim 49, characterized in that the mean size of the particles obtained by drying and milling the material according to any one of the Claims 1 to 25 lies within the range from 0.1 gim to 10 m. 15 51. Cosmetic and/or dermatological composition according to any one of Claims 45 to 50, characterized in that an additive chosen from sunscreen agents other than organic UV-A sunscreen agents, agents for the artificial tanning and/or browning of the skin, pigments, fatty substances, organic solvents, thickeners, softeners or antioxidants is additionally added. 20 52. Material according to Claim 1, substantially as hereinbefore described with particular reference to any one of the examples.