The invention relates to novel polyester based UV-filters as well as to topical compositions comprising such novel polyester based UV-filters. Furthermore, the invention relates to coatings comprising such novel polyester based UV-filters and polyurethanes obtained and/or obtainable using such novel polyester based UV-filters.

Sun care products have evolved considerably over the years. Earlier formulations were intended to protect the user from UV-B radiation (UVB) as was once thought that UV-B rays were the most important contributors to wrinkling, skin disease, and skin cancer. However, more recent studies have shown that UV-A radiation (UVA) is equally or even more important in the development of solar damage and skin diseases, such as lupus erythematosus and melanoma and non-melanoma skin cancers. Thus, today's focus is toward eliminating as much of UVA (320-400 nm) and / or UVB (280-320 nm) light as possible.

Due to the increasing demand for high SPF sun care products with a UVA protection, there is an ongoing need for novel UV-filter substances which exhibit excellent UV-light absorption properties, contribute significantly to the Sun Protection Factor (SPF), reveal an excellent safety profile (such as e.g. a minimal skin penetration), are easily incorporated into topical cosmetic (e.g. having a good solubility in commonly used cosmetic solvents), exhibit a low viscosity to facilitate industrial handling while providing excellent sensorial properties in the final cosmetic formulation such as e.g. in regard of skin feel and texture.

During the last decades many publications have been made available to the public disclosing polymeric UV filters, which, by virtue of their chemical structure, exhibit an excellent safety profile due to a minimal skin penetration. However, up to today only one polymeric UV-filter has been made commercially available, i.e. PARSOL SLX by DSM Nutritional Products Ltd (I NCI: polysilicone-15), as polymeric UV filters are often highly viscous compounds exhibiting an insufficient solubility in cosmetic oils (such as e.g. Myritol, DUB DIS, Finsolv TN, Cetiol CC or mixtures thereof). Furthermore, the contribution to the SPF performance is often lower compared to the respective free chromophore (based on the chromophore content). Thus, there is an ongoing need of polymeric UV-filter substances which overcome the draw backs of the prior art.

Surprisingly, it has been found that specific polyester based UV filters exhibit an excellent solubility in cosmetic oils and a low viscosity which facilitates industrial handling. Furthermore, they are suitable to efficiently stabilize photo unstable UV-filters such as butyl methoxydibenzoylmethane.

Thus, in one aspect the invention relates to novel polyester based UV filters of formula (I)

Y ¹ is H-, HO-R ² -; or R—

R ¹ and R ² are, independently of each other, a divalent residue of a dicarboxylic acid (A), or a diester (B) or a diol (C) after removal of the terminal COOH or ester or OH groups; R ³ denotes to a linear or branched Ci_ ₆ alkyl group;

q represents an integer from 3 to 2Ό00; with the proviso that at least 5 wt.-% of the dicarboxylic acid (A) or the diester (B) or the diol (C), are a chromophore carrying diacid or diester or diol of formula (II)

Y- -R- -A- -R- -r (II) wherein

A denotes to an unsaturated or aromatic radical having at least 4 conjugated π-electrones with UVA, UVB, UVC or broadband activity; R ⁴ and R ⁵ , independently of each other, denote to a linear or branched C _1-6 alkylene diradical;

r and s are independently of each other 0 or 1 , preferably 0;

Y ³ denotes to a -OH, --COOH or -COOR ⁶ group and

R ⁶ denotes to a linear or branched Ci_ ₆ alkyl group

and

at least 20 wt.-% of the dicarboxylic acid (A) or the diester (B) or the diol (C) are dimeric fatty acid, dimeric fatty ester or dimeric fatty alcohol as well as mixtures thereof.

Dotted lines indicate in the present document the binding site to other substituents.

In all embodiments of the invention, preferably R ³ denotes to H, methyl or ethyl, most preferably to H or methyl.

In all embodiments q is preferably 3 to 100, more preferably 5 to 50.

The term "dimeric fatty acid" (also known as dimer fatty acids) is well known in the art and refers to the dimerisation product of mono- or polyunsaturated fatty acids. Preferred dimeric fatty acids are dimers of C ₁₀ to C ₃₀ , more preferably C ₁₂ to C ₂₄ , particularly C ₁₄ to C ₂ 2, and especially unsaturated C ₁₈ alkyl fatty acids. Suitable dimer fatty acids include the dimerisation products of oleic acid, linoleic acid, linolenic acid, palmitoleic acid, and elaidic acid.

In addition to the dimeric fatty acids, dimerisation usually results in varying amounts of oligomeric fatty acids (so-called "trimer") and residues of monomeric fatty acids (so-called "monomer"), or esters thereof, being present. The amount of monomer can, for example, be reduced by distillation. Suitable dimer fatty acids have a dimer acid content of greater than 60 wt.-%, preferably greater than 75 wt.-%, more preferably in the range from 90 to 99.5 wt.-%, particularly 92 to 99 wt.-%, and especially 95 to 98 wt.-% by weight. The trimer content is suitably less than 40 wt.-%, preferably in the range from 0.01 to 25 wt.-%, more preferably 0.05 to 15 wt.-%, particularly 0.1 to 5 wt.-%, and especially 1 to 4 wt.-% by weight. The monomer content is preferably less than 10 wt.-%, more preferably in the range from 0.01 to 5 wt.-%, particularly 0.01 to 1 wt.-%, and especially 0.05 to 0.4 wt.-%. All of the above wt.-% values are based on the total weight of trimer, dimer and monomer present. "Dimeric fatty esters" can be produced from dimeric fatty acids by esterification or by dimerisation of mono- or polyunsaturated fatty acid esters. Particularly suitable according to the present invention are dimer fatty acid methyl or ethyl esters.

"Dimeric fatty diols" (also known as dimerdiols) can be produced by conversion of the dimeric fatty acids into the respective diols, for example, by reduction of the carboxyl groups to hydroxyl groups, esterification of the carboxyl groups with low molecular weight diols and triols having a molecular weight of 90 to 150 g/mol such as 1 ,4-butanediol, 1 ,6-hexanediol, neopentyl glycol, diethylene glycol, glycerol and/or trimethylolpropane or by alkoxylation of the carboxyl groups, for example, by means of ethylene oxide and/or propylene oxide. Suitable dimeric fatty diols have a dimerdiol content of greater than 60%, preferably greater than 75 wt.-%, more preferably in the range from 90 to 99.5 wt.-%, particularly 93 to 99 wt.- %, and especially 94 to 98 wt.-%. The trimer content is suitably less than 40 wt.-%, preferably in the range from 0.01 to 25 wt.-%, more preferably 0.05 to 15 wt.-%, particularly 0.1 to 5wt.-%, and especially 0.5 to 3 wt.-%. The monomer content is preferably less than 10 wt.-%, more preferably in the range from 0.1 to 5 wt.-%, particularly 0.3 to 4 wt.-%, and especially 0.5 to 3 wt.-%. All of the above wt.-% values are based on the total weight of trimer, dimer and monomer present.

The preparation of "dimeric fatty acids", "dimeric fatty esters" and "dimeric fatty alcohols" is well known in the art and is e.g. disclosed in US 7,427,640 or US 6, 187,903 or in Fett/Lipid 101 (1999), Nr. 1 1 , S. 418-424 (Andreas Heidbreder et al.)

Dimeric fatty acids are e.g. available under the tradename Pripol™ from Croda such as e.g. Pripol™ 1013 (distilled dimer fatty acid), Pripol™ 1098 (high purity dimer fatty acid) or Pripol™ 1006 (hydrogenated dimer fatty acid) or under the tradename Jaric™ D51 , Jaric™ D 70 or Jaric™ D75 from Jarchem Industries Inc. An example of a dimeric fatty alcohol in particular suitable for the preparation of a polyester according to the invention is dimerdiol (CAS 147853-32-5, e.g. available from Croda as Pripol ^® 2033 or from Jarchem Industries Inc as Jardiol™ DD36). As alternative Priplast 3197 (Dimer acid-based polyester polyol) from Croda with very good defined structure (diol-acid-diol) and M _n =2000 can be used.

Examples of linear or branched Ci _-6 alkylene diradicals for R ⁴ and/ or R ⁵ are linear (unbranched) alkylene groups with 1 -6 carbon atoms or branched alkylene groups with 3-6 carbon atoms such as methylene, ethylene, propylene, butylene, pentylene or heptylene as well as isopropylene, 2-butylene, 3-butylene, 2-pentylene, 3-pentylene, 4-pentylene,

2- hexylene, 3-hexylene, 4-hexylene and or 5-hexylene.

Examples of linear or branched Ci _-6 alkyi groups for R ³ and/ or R ⁶ are linear (unbranched) alkyi groups with 1 -6 carbon atoms or branched alkyi groups with 3-6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl or heptyl as well as isopropyl, 2-butyl, 3-butyl, 2-pentyl, -

3- pentyl, 4-pentyl, 2-hexyl, 3-hexyl, 4-hexyl and or 5-hexyl.

Examples of groups A are any UV-light absorbing groups which, together with /or without the R ⁴ Y ³ and R ⁵ Y ³ moieties absorb light in the range of wavelengths 400 - 320 nm (UVA) and/ or 320 - 290 (UVB) and which together with /or without the R ⁴ Y ³ and R ⁵ Y ³ moieties are or can be used as chemical UV filters. These groups are in particular residues of compounds belonging to the groups of p-aminobenzoates, salicylates, cinnamates, benzophenones, anthranilates, dibenzoylmethanes, camphor derivatives (such as of benzylidene camphor type), β,β-diphenylacrylate derivatives, phenyl-benzimidazoles, phenyl-benzoxazoles, phenyl-benzothiazoles, phenyl-benzotriazoles, triazine derivatives, indanone and indalydene derivatives, imidazolines, methylenebis(hydroxyphenylbenzotriazole) derivatives, 4,4-diarylbutadienes, a-alkyl styrenes, enamines, pyridines, pyrimidines, benzalmalonates, merocyanines and others representing state of the art and known to those skilled in the art.

In all embodiments of the present invention it is preferred that only one compound of formula (I I), i.e. only one type of chromophore A is present in the polyester based UV filters of formula (I).

Particular suitable chromophore carrying diacids or diesters or diols of formula (I I) according to the present invention are selected from the group of

(I II) (IV) (V) wherein R ⁴ , R ⁵ and R ⁶ are as defined above;

R ⁷ represents H, linear or branched Ci _-6 alkyi, C _5- 6 cycloalkyl or aryl, preferably H or methyl;

R ⁸ represents H, linear or branched Ci _-8 alkyi, linear or branched Ci _-8 alkoxy or aryloxy, preferably linear Ci _-8 alkoxy such as most preferably methoxy;

R ⁹ represent H, linear or branched Ci _-6 alkyi, linear or branched Ci _-8 alkoxy or aryloxy, preferably H or methyl or linear Ci _-8 alkoxy such as most preferably H;

or

R ⁸ and R ⁹ together or R ⁸ and R ¹⁰ together form a group -X-(CH ₂ ) -X - wherein X represent N-R ⁷ , O or CH ₂ ;

R ¹⁰ and R ¹¹ represent independently from each other H, linear or branched Ci _-6 alkyi, linear or branched Ci _-8 alkoxy or aryloxy, preferably H or linear Ci _-8 alkoxy such as most preferably H;

R ¹² and R ¹³ represent independently from each other H, linear or branched C _1-8 alkyi, C _5-8 cycloalkyl or aryl, preferably branched Ci _-8 alkyi, most preferably a and/or β-branched alkyi, in particular isopropyl;

or

R ¹² and R ¹³ together with the nitrogen atom linking them form -(CH ₂ ) _m - ring which is optionally interrupted with -O- or by -NR ⁷ -, and/or substituted or unsubstituted with Ci _-6 alkyi;

L represents a -(CH ₂ ) _r - unit which is optionally interrupted with -O- or -NR ⁷ - and/or substituted or unsubstituted with Ci _-6 alkyi; n represents an integer from 0 to 5, preferably 0-2, most preferably 1.

m represents an integer from 2 to 7, preferably 4 to 6.

p represents an integer from 1 to 6, preferably 1 or 2

r represents an integer from 1 to 7, preferably 2 or 3.

Examples of linear or branched C _x-y alkyi for R ⁷ , R ⁸ ' R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are linear (unbranched) alkyi radicals with x to y carbon atoms or branched alkyi radicals with 3-y carbon atoms such as e.g. methyl, ethyl, 1 -methylethyl, 1 , 1-dimethylethyl, n-propyl, 1- methylpropyl, 2-methylpropyl, n-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, n-pentyl, 1 , 1 -dimethylpropyl, 1 ,2-dimethylpropyl, 2,2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, 1 - methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 , 1 -dimethylbutyl, 1 ,2- dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl or 2- ethylhexyl such as in particular methyl or ethyl.

Examples of C _x-y cycloalkyl are cycloalkyl radicals with x to y carbon atom such as e.g. cyclopentyl or cyclohexyl.

Examples of aryl are phenyl or naphthyl such as in particular phenyl.

Suitable Ci _-8 alkoxy are alkoxy radicals with 1 -8 carbon atoms such as methoxy, ethoxy, isopropoxy, n-propoxy, 1 -methylpropoxy, n-butoxy, n-pentoxy, 2-methylpropoxy, 3-methylbutoxy, 1 , 1 -dimethylpropoxy, 2,2-dimethylpropoxy, hexoxy, 1 -methyl-1 - ethylpropoxy, heptoxy, octoxy, 2-ethylhexoxy and phenyloxy. Particularly preferred alkoxy radicals are those having from 1 to 6 carbon atoms, very particularly preferably those having from 1 to 4 carbon atoms, such as methoxy, ethoxy, isopropoxy, n-propoxy, 1 - methylpropoxy and n-butoxy, in particular methoxy.

Suitable aryloxy are in particular phenyloxy radicals, more in particular methoxyphenyl or ethoxyphenyl radicals.

In all embodiments of the invention advantageously the compound of formula (II) is

Dimethyl(p-methoxybenzylidene)malonate Diethyl(p-methoxybenzylidene)malonate CAS:7443-25-6 CAS:678-23-6

In all embodiments of the present invention advantageously the compound of formula (II I) is

2-(3-Diisopropylamino-allylidene)-malonic acid 2-(3-Dimethylamino-allylidene)-malonic acid dimethyl ester; CAS:420826-15-9 dimethyl ester CAS: 26932-73-0

Most preferred compounds of formula (II) and (III) are in all embodiments of the present invention dimethyl (p-methoxybenzylidene) malonate which is e.g. commercially available as Hostavin PR-24 at Clariant and 2-(3-Diisopropylamino-allylidene)-malonic acid dimethyl ester (E or Z isomer or mixture thereof).

Next to compounds of formula (II) wherein Y ³ is --COOH or --COOR ⁶ and dimeric fatty acids or dimer fatty esters, further suitable dicarboxylic acid (A) or diester (B) are linear or branched, saturated or unsaturated Ci _-3 o dicarboxylic acids, preferably malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, caproic acid, undecane dicarboxylic acid, dodecane dicarboxylic acid, maleic acid, glutaconic acid, traumatic acid and higher homologs thereof as well as the respective diesters thereof. It is also possible, that R ¹ and R ² are divalent dicarboxylic acid residues derived from an anhydride instead of the corresponding diacid.

Next to compounds of formula (II) wherein Y ³ denotes to -OH and dimeric fatty alcohol further suitable diols (C) are aliphatic, linear or branched C ₂ -C ₃ 6 diols (optionally interrupted by oxygen atoms) or cycloaliphatic C5-C1 ₀ diols or residues of (poly)esters, (poly)amides, (poly)ester-amines (poly)urethanes or (poly)acrylics. In particular suitable further diols (C) are diethyleneglycol, glycerol, propyleneglycol, ethylene glycol, 1 ,2-propanediol, 1 ,3-butylene glycol, 1 ,4-butanediol, neopentyl glycol, 2-methyl-1 ,3-propanediol, diethylene glycol, tetraethylene glycol, 1 ,5-pentanediol, dipropylene glycol, cyclohexan-1 ,4-dimethanol or 1 ,6-hexanediol such as more in particular diethyleneglycol or propyleneglycol or 1 ,6-hexanediol as well as mixtures thereof. Further particular advantageous diols (C) according to the present invention are linear C ₂ -Ci ₀ alkyldiols such as 1 ,4-butanediol, 1 ,5-pentanediol or 1 ,6-hexanediol.

In all embodiments of the invention preferably at least 10 wt.-%, more preferably at least 20 wt.-%, most preferably from 20-55 wt.-% of the dicarboxylic acid (A), the diester (B) or the diol (C) are a compound of formula (II). It is furthermore advantageous if in addition at least 25 wt.-%, such as more preferably at least 30 wt.-%, even more preferably 35 wt.-% and most preferably at least 50 wt.-% of the dicarboxylic acid (A), the diester (B) or the diol (C) are dimeric fatty acid, dimeric fatty ester or dimeric fatty alcohol. It is furthermore advantageous if the ratio (w/w) of the dimeric fatty acid or dimeric fatty ester or dimeric fatty alcohol to the compound of formula (II) is selected in the range of 4:1 to 0.4:1.

In a particular embodiment, the invention relates to a polyester based UV-filter according to formula (I) wherein R ¹ and R ² are, independently of each other, a divalent residue of a dicarboxylic acid (A), a diester (B) or a diol (C) after removal of the terminal -COOH or ester or -OH groups, characterized in that the dicarboxylic acid (A) or the diester (B) or the diol (C) are selected, independently of each other, from the group consisting of

(a) a compound of formula (II) with all the definitions and preferences as given above, and

(b) dimeric fatty acid or dimeric fatty ester or dimeric fatty alcohol with all the definitions and preferences as given above, and optionally

(c) at least one C ₂ -C ₁₀ diol.

Preferably the C ₂ -C ₁₀ diol is selected from the group consisting of diethyleneglycol or propyleneglycol or hexanediol. Most preferably the at least one C ₂ -C ₁₀ diol is 1 ,6-hexandiol.

In one advantageous embodiments of the invention (a) is a chromophore carrying diacid or diester of formula (II) wherein Y ³ is -COOH or— COOR ⁶ , (b) is a dimeric fatty alcohol, and no additional diol (c) is present (i.e. (a) and (b) sum up to 100 wt.-%). Even more preferably, (a) is dimethyl (p-methoxybenzylidene) malonate and (b) is dimerdiol. It is furthermore advantageous if the ratio (w/w) of dimerdiol to the chromophore carrying diacid or a diester such as in particular of dimerdiol to dimethyl (p-methoxybenzylidene) malonate is selected in the range of 4:1 to 1 :1 , more preferably in the range of 4:1 to 2:1.

In another advantageous embodiment invention (a) is a chromophore carrying diacid or diester of formula (II) wherein Y ³ is -COOH or -COOR ⁶ , (b) is a dimeric fatty alcohol and the at least one diol (c) is 1 ,6-hexandiol. It is furthermore preferred if the ratio of the dimeric fatty alcohol to 1 ,6-hexandiol is selected in the range of 5:1 to 1 :1 and the ratio of dimeric fatty alcohol to chromophore carrying diacid or diester is selected in the range of 0.4:1 to 1.5:1 . Even more preferably the chromophore carrying diacid or diester (a) is selected from the group consisting of dimethyl (p-methoxybenzylidene) malonate or 2-(3-diisopropylamino-allylidene)-malonic acid dimethyl ester or 2-(3-dimethylpropylamino- allylidene)-malonic acid dimethyl ester and the dimeric fatty alcohol (b) is dimerdiol.

In a particular aspect of the invention the invention relates to novel polyester based UV filters obtainable by copolymerisation of

(i) at least 20 wt.-%, preferably at least 25 wt.-% of a dimeric fatty alcohol

(ii) at least 5 wt.-%, preferably from 20 to 55 wt.-% of a chromophore carrying diacid or a diester of formula (II) wherein Y ³ is -COOH or -COOR ⁶ and optionally

wherein the sum of the building blocks (i) to (iii) is 100 wt.-%.

Preferably the C2-C10 diol is selected from the group consisting of diethyleneglycol, glycerol, propyleneglycol, ethylene glycol, 1 ,2-propanediol, 1 ,3-butylene glycol, 1 ,4-butanediol, neopentyl glycol, 2-methyl-1 ,3-propanediol, diethylene glycol, tetraethylene glycol, 1 ,5-pentanediol, dipropylene glycol, cyclohexan-1 ,4-dimethanol or 1 ,6-hexanediol as well as mixtures thereof, more preferably from the group consisting of hexanediol, propyleneglycol or diethyleneglycol as well as mixtures thereof.

Preferably, the dimeric fatty alcohol (i) is dimerdiol and the chromophore carrying diacid or a diester of formula (II) (ii) is selected from the group consisting of diethyl (p-methoxybenzylidene) malonate, dimethyl (p-methoxybenzylidene) malonate, 2-(3- diisopropylamino-allylidene)-malonic acid dimethyl ester or 2-(3-dimethylpropylamino- allylidene)-malonic acid dimethyl ester and the C2-C10 diol (iii) is selected from the group consisting of hexanediol, propyleneglycol or diethyleneglycol as well as mixtures thereof.

In a particular embodiment the ratio (w/w) of the diols (i) and optionally (iii) to the chromophore carrying diacid or a diester is selected in the range of 5:1 to 1 :1.7, preferably in the range of 4:1 to 1 :1 such as e.g. 3.5:1.5 to 1 .5:1.

If no diol (iii) is present it is advantageous if the ratio (w/w) of the dimeric fatty alcohol and the chromophore carrying diacid or a diester such as in particular dimerdiol and dimethyl (p-methoxybenzylidene) malonate is selected in the range 4:1 to 1 :1 such as in the range of 3.7:1 to 1 .5:1 as this leads to particular well soluble polyester based UV filters in a wide range of cosmetic solvents such as e.g. Myritol, DUB DIS, Finsolv TN, Cetiol CC or mixtures thereof. Furthermore, these polyesters are colorless to slightly yellow liquids which ease industrial handling and cosmetic acceptance.

If a diol (iii) is present it is advantageous if the ratio (w/w) of dimeric fatty alcohol (i) to the diol (iii) is selected in the range of 5: 1 to 1 : 1 . Particular good solubility's are obtained if dimerdiol is used in combination with 1 ,6-hexanediol as co-building block and the ratio of the dimerdiol to 1 ,6-hexanediol is selected in the range of 5: 1 to 1 : 1 .

Polyester based UV filters obtained by copolymerisation of 55-80 wt.-% of dimerdiol and 20 - 45 wt.-% of dimethyl (p-methoxybenzylidene) malonate wherein the sum of dimerdiol and of dimethyl (p-methoxybenzylidene) malonate is 100 wt.-% are particularly preferred as such polymers most effectively stabilise Parsol 1789 (I NCI avobenzone) based on the chromophore content.

If the polyester based UV filter according to the invention is obtainable by copolymerisation of dimerdiol, dimethyl (p-methoxybenzylidene) malonate and hexanediol it is particularly advantageous if the ratio (w/w) of the dimerdiol to hexanediol is selected in the range of 1 .5:1 to 1 : 1 and the ratio (w/w) of the sum of dimerdiol and 1 ,6-hexanediol to dimethyl (p- methoxybenzylidene) malonate is selected in the range of about 0.8: 1 to 1 .5: 1

The use of C ₂ -Ci ₀ diols, preferably ethylene glycol, 1 ,2-propanediol, 1 ,3-butylene glycol, 1 ,4-butanediol, 1 ,6-hexanediol, neopentyl glycol, 2-methyl-1 ,3-propanediol, diethylene glycol, tetraethylene glycol, 1 ,5-pentanediol, dipropylene glycol, cyclohexan-1 ,4-dimethanol as well as mixtures thereof, preferably 1 ,6-hexandiol as co-building block is in particular advantageous if high chromophore loadings are desired such as chromophore loadings of ≥50 wt.-% (e.g. the ratio (w/w) of dimerdiol and 1 ,6-hexanediol to dimethyl (p- methoxybenzylidene) malonate is < 1 ).

The polyester based UV-filters according to the present invention are suitable to enhance the photostability of photo instable UV absorbers. Thus, the invention also relates to the use of a polyester based UV-filter according to the invention to enhance the photostability of photo-instable UV absorbers such as in particular butyl methoxydibenzoylmethane (PARSOL ^® 1789). The polyester based UV filters according to the invention are obtainable by copolymerization of at least one dicarboxylic acid (A) and/ or diester (B) and at least one diol (C) in a one pot reaction. Instead of the diester also the corresponding anhydride can be used. The copolymerisation of at least on diester (B) and at least one diol (C) can be performed using a transesterification catalyst. Suitable transesterification catalysts include titanium tetra butoxide, titanium tetra isopropoxide, zinc acetate and other suitable catalysts known to those skilled in the art. The copolymerization reaction is advantageously carried out at temperatures of 60-200 °C such as in particular for 120-150 °C such as at 140 °C under atmospheric pressure while water respectively alcohol(s) (if a diester is used as building block) formed is distilled off. Generally the reaction is terminated when the distillation of water/ alcohol ceases. If deemed necessary vacuum can be applied to enhance the distillation. Alternatively, the polyesters according to the present invention can be produced in analogy to EP 1 522 303 A1 example 1 by direct esterification at 240°C under vacuum conditions without catalyst. High amount of dimer fatty content can be achieved if first dimer fatty diol reacts with a dimer fatty acid at 240°C followed by addition of a chromophore carrying diacid or a diester thereof in the second step at 140°C. Exemplary dimer fatty acid suitable for the purpose of this invention is e.g. Pripol 1009.

The OH value of the polyesters according to the present invention is not critical and can easily be adjusted by the ratio of diol(s) to dicarboxylic acid(s) or diester(s) in the polymerisation process. In particular, the OH-value (measured as mg KOH/g) is selected in the range of 0-150, preferably 0-100.

Preferably in all embodiments of the invention the polyester based UV filters according to the invention have a number average molecular weight M _w in the range of about 500 to 100'OOOg mol ^"1 1 , more preferably in the range of about 1 Ό00 to 20Ό00 g mol ^"1 , more preferably of about 1 '500 to 15Ό00 g mol ^"1 . The weight average molecular weight Mw can be determined by Gel Permeation Chromatography (GPC) as described in the DIN 55672-1 using e.g. polystyrene standards.

The photostability of the polymer according to the present invention may be measured according to G. Berset et al. International Journal of Cosmetic Science 1996, 18(3), 167- 177. Furthermore, the polyester based UV filters according to the invention are useful as UV filter substances, i.e. for protecting ultraviolet-sensitive organic materials, in particular the skin and hair of humans and animals from the harmful effects of UV radiation. The polyester based UV filters according to the present invention are not only suitable for "immediate protection from acute sun damage" such as sun burn (sun erythema), but also protect against damages through sunlight-induced oxidative stress and/or immune suppression and/or their consequences, i.e. photo aging. Furthermore, the polyester based UV filters according to the present invention are also suitable to protect natural or artificial hair color. The polyester based UV filters according to the present invention also lead to a synergistic UV-light absorption if used in combination with at least one further UV-filter substance.

The polyester based UV filters according to the present invention are colorless or yellowish, liquid or viscous substances. They are exhibit a high photostability, a good solubility in organic solvents, especially cosmetic solvents such as in particular in Diisopropyl sebacate (DUB DIS), and a short and economical synthetic route.

The present invention also relates to compositions, preferably to topical compositions comprising a polyester based UV filter according to the present invention and a cosmetically acceptable carrier.

The amount of the polyester based UV filter in the compositions according to the invention is at least 0.01 wt.-%. More preferably an amount of 0.5 to 20 wt.-%, in particular 1 to 10 wt.-% such as e.g. from about 2 to 5 wt.-% based on the total weight of the composition is incorporated into the compositions.

In a particular embodiment, the compositions according to the invention further comprise an additional amount of an oil soluble, solid UV-filter substance. Suitable oil soluble, solid UV- filter substances are in particular butyl methoxydibenzoylmethane (BMDBM), bis- ethylhexyloxyphenol methoxyphenyl triazine (BEMT), benzophenone-3, drometrizole trisiloxane, ethylhexyl triazone, diethylhexyl butamido triazone, 4-methyl benzylidene camphor or 2-(4-Diethylamino-2-hydroxy-benzoyl)-benzoic acid hexylester as well as mixtures thereof, preferably butyl methoxydibenzoylmethane.

In a particular embodiment, the topical composition according to the invention further comprises butyl methoxydibenzoylmethane, which is effectively stabilized by the polyesters according to the present. Butyl methoxydibenzoylmethane is preferably used in an amount of at least 0.01 wt.-%. Particularly, the topical composition comprises butyl methoxydibenzoylmethane in an amount of 0.5 to 5 wt.-%, most in particular in an amount of 2 to 5 wt.-% based on the total weight of the composition.

In a further particular embodiment, the topical composition according to the invention further comprises bis-ethylhexyloxyphenol methoxyphenyl triazine in an amount of at least 0.01 wt.-%. Particularly, the topical composition comprises bis-ethylhexyloxyphenol methoxyphenyl triazine in an amount of 0.5 to 5 wt.-%, most in particular in an amount of 1 to 3 wt.-% based on the total weight of the composition.

It is also particularly advantageous if the topical composition according to the present invention comprises as solid UV absorbers BMDBM and bis-ethylhexyloxyphenol methoxyphenyl triazine in the amounts given above. Particularly BMDBM is incorporated in an amount of 2 to 5 wt.-% and bis-ethylhexyloxyphenol methoxyphenyl triazine in an amount of 1 to 3 wt.-% based on the total weight of the composition.

Where convenient other conventional UV-filter substances may be added into the topical compositions of the invention. The combination of UV-filter substances may show a synergistic effect. These additional UV-filter substances are advantageously selected from among acrylates such as 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (octocrylene, PARSOL ^® 340), ethyl 2-cyano-3,3-diphenylacrylate and the like; camphor derivatives such as 4-methyl benzylidene camphor (PARSOL ^® 5000), 3-benzylidene camphor, camphor benzalkonium methosulfate, polyacrylamidomethyl benzylidene camphor, sulfo benzylidene camphor, sulphomethyl benzylidene camphor, therephthalidene dicamphor sulfonic acid and the like; cinnamate derivatives such as ethylhexyl methoxycinnamate (PARSOL ^® MCX), ethoxyethyl methoxycinnamate, diethanolamine methoxycinnamate (PARSOL ^® Hydro), isoamyl methoxycinnamate and the like as well as cinnamic acid derivatives bond to siloxanes; p-aminobenzoic acid derivatives, such as p-aminobenzoic acid, 2-ethylhexyl p- dimethylaminobenzoate, N-oxypropylenated ethyl p-aminobenzoate, glyceryl p- aminobenzoate; benzophenones such as benzophenone-3, benzophenone-4, 2, 2', 4,4'- tetrahydroxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and the like; esters of benzalmalonic acid such as di-(2-ethylhexyl) 4-methoxybenzalmalonate; esters of 2-(4-ethoxy-anilinomethylene)propandioic acid such as 2-(4-ethoxy anilinomethylene) propandioic acid diethyl ester as described in the European Patent Publication EP 0895 776; organosiloxane compounds containing benzmalonate groups as described in the European Patent Publications EP 0358584 B1 , EP 0538431 B1 and EP 0709080 A1 such as polysilicone-15 (PARSOL ^® SLX); drometrizole trisiloxane (Mexoryl ^® XL); imidazole derivatives such as e.g. 2-phenyl benzimidazole sulfonic acid and its salts (PARSOL ^® HS). Salts of 2-phenyl benzimidazole sulfonic acid are e.g. alkali salts such as sodium- or potassium salts, ammonium salts, morpholine salts, salts of primary, sec. and tert. amines like monoethanolamine salts, diethanolamine salts and the like; salicylate derivatives such as isopropylbenzyl salicylate, benzyl salicylate, butyl salicylate, ethylhexyl salicylate (PARSOL ^® EHS, Neo Heliopan ^® OS), isooctyl salicylate or homomenthyl salicylate (homosalate, PARSOL ^® HMS, Neo Heliopan ^® HMS) and the like; triazine derivatives such as ethylhexyl triazone (Uvinul ^® T-150), diethylhexyl butamido triazone ethylhexyl triazone (Uvinul ^® T-150), diethylhexyl butamido triazone (Uvasorb ^® HEB), 2,4,6-Tris-(biphenyl)1 ,3,5- triazine and the like, merocyanines as e.g. disclosed in DE10 2007 024 345 on page 4, paragraph 19 which are incorporated by reference herein, encapsulated UV-filters such as encapsulated ethylhexyl methoxycinnamate (Eusolex ^® UV-pearls) or microcapsules loaded with UV-filters as e.g. disclosed in EP 1471995 and the like; dibenzoylmethane derivatives such as 4-tert.-butyl-4'-methoxydibenzoyl-methane (PARSOL ^® 1789), dimethoxydibenzoylmethane, isopropyldibenzoylmethane and the like; benzotriazole derivatives such as 2,2'-methylene-bis-(6-(2H-benzotriazole-2-yl)-4-(1 , 1 ,3,3,- tetramethylbutyl)-phenol (Tinosorb ^® M) and the like; bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb ^® S) and the like; phenylene-1 ,4-bis-benzimidazolsulfonic acids or salts such as 2,2-(1 ,4-phenylene)bis-(1 H-benzimidazol-4,6-disulfonic acid) (Neo Heliopan ^® AP); amino substituted hydroxybenzophenones such as 2-(4-Diethylamino-2-hydroxy-benzoyl)- benzoic acid hexylester (Uvinul ^® A plus) or 1 , 1 '-(1 ,4-piperazinediyl)bis[1 -[2-[4- (diethylamino)-2-hydroxybenzoyl]phenyl]-methanone (CAS 919803-06-8); Ionic UV-A filters as described in the International Patent Publication WO2005080341 A1 ; pigments such as microparticulated ZnO or Ti0 ₂ and the like. The term "microparticulated" refers to a particle size from about 5 nm to about 200 nm, particularly from about 15 nm to about 100 nm. The pigments may also be coated by other metal oxides such as e.g. aluminum or zirconium oxides or by organic coatings such as e.g. polyols, methicone, aluminum stearate, alkyl silane. Such coatings are well known in the art. Furthermore, the pigments (ZnO, Ti0 ₂ ) can be used in the form of commercially available oily or aqueous pre-dispersions. These pre- dispersions may further contain a dispersing aid and/ or solubilisator. Particularly preferred additional UV-filter substances to be used in combination with a polyester based UV filter according to the present invention are the commercially available and widely used UV-filter substances octocrylene (PARSOL ^® 340), 4-methyl benzylidene camphor (PARSOL ^® 5000), ethylhexyl methoxycinnamate (PARSOL ^® MCX), ethylhexyl triazone (Uvinul ^® T-150), diethylhexyl butamido triazone (Uvasorb ^® HEB), 2,2'-methylene- bis-(6-(2H-benzotriazole-2-yl)-4-(1 , 1 ,3,3,-tetramethylbutyl)-phenol (Tinosorb ^® M), bis- ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb ^® S), 2,2-(1 ,4-phenylene)bis-(1 H- benzimidazol-4,6-disulfonic acid (NeoHeliopan ^® AP), 2-(4-Diethylamino-2-hydroxy-benzoyl)- benzoic acid hexylester (Uvinul ^® A plus), 1 , 1 '-(1 ,4-piperazinediyl)bis[1-[2-[4-(diethylamino)- 2-hydroxybenzoyl]phenyl]-methanone (CAS 919803-06-8), polysilicone-15 (PARSOL ^® SLX), 2-phenyl benzimidazole sulfonic acid (PARSOL ^® HS), ethylhexyl salicylate (PARSOL ^® EHS), homomenthyl salicylate (PARSOL ^® HMS), Benzophenone-3 (Uvinul ^® M 40), Benzophenone-4 (Uvinul ^® MS 40), microfine titanium dioxide such as in particular PARSOL ^® TX as well as mixtures thereof.

The additional UV-filter substances are generally present in the compositions according to the invention in proportions ranging from 0.1 to 30 wt.-%, preferably ranging from 0.2 to 15 wt.-%, most preferably ranging from 0.5 to 10 wt.-% with respect to the total weight of the composition.

As dibenzoylmethane derivatives in particular BMDBM have a limited photostability it may be desirable to photostabilize these UV-filter substances in the topical compositions according to the invention. Thus, the invention also relates to topical compositions according to the invention which next to a dibenzoylmethane derivative such as in particular BMDBM also contain an effective amount of a stabilizer. The term effective amount of a stabilizer refers to an amount suitable for the photostabilization of a dibenzoylmethane derivative. The amount may vary from stabilizer to stabilizer (e.g. based on the mode of action) and can easily been determined by a person skilled in the art with normal trials, or with the usual considerations regarding the formulation of cosmetic composition. Suitable amounts may range from 0.01 to 1 wt.-% as well as from 0.5 to 20 wt.-%, such as 1 to 10 wt.-% with respect to the total weight of the composition.

Suitable stabilizers include octocrylene, diethylhexyl-2,6-naphthalate, polyester-8, diethylhexyl syringylidenemalonat, butyloctyl salicylate, polysilicone-15, tris(tetramethylhydroxypiperidinol)citrate, benzotriazolyl dodecyl p-cresol, benzophenone-3, 4-methylbenzylidene camphor, Methoxycrylene (Solastay S1 ) and/ or bis ethylhexyloxyphenol methoxyphenyl triazine. Particularly suitable as stabilizer is octocrylene.

Thus, in a further embodiment, the invention also relates to a topical composition comprising a polyester based UV filter according to the invention, BMDBM and octocrylene or Methoxycrylene, in particular octocrylene, preferably the polyester based UV filter is used in an amount of 0.5 to 20 wt.-%, BMDBM in an amount of 2 to 5 wt.-% and octocrylene in an amount of 2 to 10 wt.-%.

In another particular embodiment the topical compositions according to the present invention are free of p-methylbenzylidene camphor.

Preferably, the topical compositions according to the present invention furthermore contain one or more preservatives such as e.g. methylparabene, ethylparabene, propylparabene or butylparabene, isobutylparabene, benzoic acid and its salts (e.g. sodium benzoate), Sorbic acid and its salts (e.g. potassium sorbate, dehydracetic acid and its salts, bronopol, triclosan, imidazolidinyl urea, phenoxyethanol, benzyl alcohol, methylchloroisothiazolinone, methylisothiazolinone, chlorphenesin, ethylhexylglycerin, iodopropinylbutylcarbamate or pentylene glycol as well as mixtures thereof and without being limited thereto. A total content of about 0.01 to 2 wt.-% such as in particular 0.05 to 1 wt.-% of preservatives with respect to the total weight of the composition is preferred.

The topical compositions according to the present invention may in particular contain further ingredients such as moisturizers; anti-oxidants; insect repellents; ingredients for skin lightening, tanning prevention and/ or treatment of hyperpigmentation; tanning agents, ingredients for preventing or reducing wrinkles, lines, atrophy and/or inflammation; as well as topical anesthetics.

Particularly suitable moisturizers for the incorporation into the topical compositions according to the invention are glycerin, lactic acid and/ or lactates, in particular sodium lactate, butylene glycol, propylene glycol, biosaccaride gum-1 , glycine soja, ethylhexyloxyglycerin, pyrrolidoncarboxy acid, hydroxyethylurea and urea. It is further advantageous to use polymeric moisturizer such as water soluble or water gelifiable polysaccharides. In particular advantageous are e.g. hyaluronic acid, chitosan and/ or a polysaccharid rich in fucose [CAS No 178463-23-5, commercially available as Fucogel®1000 by SOLABIA S.A.]. The moisturizers can also be used as anti-ageing ingredients such as e.g. for the treatment of photo-aged skin.

The topical compositions according to the invention preferably contain at least one moisturizer in an amount (in total) of 0.1 to 20 wt.-%, preferably 0.5 to 10 wt.-% based on the total weight of the composition.

Particularly suited antioxidants for the topical compositions according to the invention encompass vitamin E and its derivatives such as particularly tocopheryl acetate. Tocopheryl acetate may be present in the topical compositions in an amount from about 0.05 wt.-% to about 25 wt.-%, in particular 0.05 wt.-% to 5 wt.-%. Another vitamin E derivative of interest is tocopheryl linoleate. Tocopheryl linoleate may be present in the topical composition in an amount from about 0.05 wt.-% to about 25 wt.-% in particular 0.05 wt.-% to 5 wt.-%.

Another suitable antioxidant is vitamin A and/or its derivatives. In particular retinoid derivatives such as retinyl palmitate or retinyl propionate is used in the topical compositions according to the invention in an amount of 0.01 - 5 wt.-%, in particular 0.01 - 0.3 wt.-%. The vitamin A and/ or its derivatives can also be used in an encapsulated form.

Another suitable antioxidant is Vitamin C (ascorbic acid) and/or its derivatives. In particular ascorbyl phosphate such as Stay C (sodium ascorbyl monophosphate) is used in the topical compositions according to the invention in an amount of 0.1 -5 wt.-% in particular 0.1 -2 wt.-%.

Suitable insect repellents include N,N-Diethyl-3-methylbenzamid (Meta-delphene, "DEET"), dimethylphtalat (Palatinol M, DMP), 1 -Piperidincarbonsaure-2-(2-hydroxyethyl)-1- methylpropylester as well as particularly 3-(N-n-butyl-N-acetyl-amino)-propionic acid (available as Insect Repellent ^® 3535 at Merck) as well as mixtures thereof.

Suitable skin lightening (depigmentation) agents to be used in the topical compositions according to the invention encompass alpha-arbutin, resveratrol, hydroquinone, azelaic acid, kojic acid as well as ascorbyl phosphates such as Magnesium-/, -ascorbyl-2- phosphate (MAP) or sodium ascorbyl monophosphate. Suitable tanning agents are dihydroxyacetone, erythrulose and/ or melanine derivates in an amount of 1 to 10 wt.-% based on the total weight of the composition according to the invention.

Further examples of cosmetically active ingredients suitable to be used in the topical composition according to the invention comprise peptides (e.g., Matrixyl™ [pentapeptide derivative]), oligopeptides, wax-based synthetic peptides (e.g., octyl palmitate and tribehenin and sorbitan isostearate and palmitoyl-oligopeptide), glycerol, alpha-glycosylrutin, natural or synthetic flavanoids or isoflavanoids, creatine, creatinine, guanidine (e.g. amino guanidine); vitamins and derivatives thereof such as vitamin C (ascorbic acid), vitamin A (e.g., retinoid derivatives such as retinyl palmitate or retinyl propionate), vitamin E (e.g., tocopherol acetate), vitamin B ₃ (e.g. niacinamide) and vitamin B ₅ (e.g. panthenol), vitamin B ₆ and vitamin B ₁₂ , biotin, folic acid; anti-acne actives or medicaments (e.g. resorcinol, salicylic acid, and the like); antioxidants (e.g. phytosterols, lipoic acid); flavonoids (e.g. isoflavones, phytoestrogens); skin soothing and healing agents such as aloe vera extract, allantoin and the like; agents suitable for aesthetic purposes such as essential oils, fragrances, skin sensates, opacifiers, aromatic compounds (e.g., clove oil, menthol, camphor, eucalyptus oil, and eugenol), desquamatory actives, hydroxy acids such as AHA acids, poly unsaturated fatty acids, radical scavengers, farnesol, antifungal actives in particular bisabolol, alkyldiols such as 1 ,2-pentanediol, hexanediol or 1 ,2-octanediol, phytol, polyols such as phytantriol, ceramides and pseudoceramides, amino acids, protein hydrolysates, polyunsaturated fatty acids, plant extracts like kinetin, DNA or RNA and their fragmentation products, carbohydrates, conjugated fatty acids, carnitin, carnosine, biochinonen, phytofluen, phytoen, and their corresponding derivatives and co-enzyme Q10 (ubiquinone) without being limited thereto.

The additional cosmetically active ingredient is typically included in an amount of at least 0.001 wt. % based on the total weight of the topical composition. Generally, an amount of about 0.001 wt. % to about 30 wt. %, preferably from about 0.001 wt. % to about 10 wt. % of an additional cosmetically active agent is used.

Particularly preferred examples of ingredients to be used in the compositions according to the invention are vitamin C (ascorbic acid) and/or its derivatives (e.g. ascorbyl phosphate such as Stay C (sodium ascorbyl monophosphate) from DSM Nutritional Products Ltd.), vitamin A and/or its derivatives (e.g., retinoid derivatives such as retinyl palmitate or retinyl propionate), vitamin E and/or its derivatives (e.g., tocopherol acetate), vitamin B ₆ , vitamin B biotin and/ or co-enzyme Q10.

The topical cosmetic compositions of the invention can also contain usual cosmetic or pharmaceutical adjuvants and additives, such as preservatives, film forming agents, antioxidants, fatty substances/ oils and/ or waxes, water, organic solvents, silicones, thickeners, softeners, emulsifiers, antifoaming agents, aesthetic components such as fragrances, surfactants, fillers, sequestering agents, anionic, cationic, nonionic or amphoteric polymers or mixtures thereof, propellants, acidifying or basifying agents, dyes, colorings/colorants, abrasives, absorbents, essential oils, skin sensates, astringents, perfumes or any other ingredients usually formulated into cosmetic compositions such as alcohols, polyols or electrolytes. Such cosmetic ingredients commonly used in the skin care industry, which are suitable for use in the compositions of the present invention are e.g. described in the CTFA Cosmetic Ingredient Handbook, Second Edition (1992) without being limited thereto.

The necessary amounts of the cosmetic and pharmaceutical adjuvants and additives can - based on the desired product form- easily be chosen by a skilled person in this field and will be illustrated in the examples, without being limited hereto.

The usual cosmetic adjuvants and additives such as e.g. emulsifiers, thickeners, surface active ingredients and film formers can show synergistic effects which can be determined by the expert in the field with normal trials, or with the usual considerations regarding the formulation of cosmetic composition.

The fatty substances can be an oil or a wax, or mixtures thereof. By the term "oil" is intended a compound which is liquid at ambient temperature. By the term "wax" is intended a compound which is solid or substantially solid at ambient temperature and for which the melting point is generally greater than 35° C.

Exemplary oils are mineral oils (liquid paraffin); vegetable oils (sweet almond, macadamia, blackcurrant seed or jojoba oil); synthetic oils, such as perhydrosqualene, fatty alcohols, acids or esters (such as the C12-15 alkyl benzoate marketed under the trademark "Finsolv TN" by Finetex, octyl palmitate, isopropyl lanolate or triglycerides, including those of capric/caprylic acids), or oxyethylenated or oxypropylenated fatty esters and ethers; silicone oils (cyclomethicone, polydimethylsiloxanes or PDMS); fluorinated oils; polyalkylenes and their mixtures.

Preferably the oils used in the compositions according to the invention are selected from the list of polar oils such as the lecitines and fatty acid triglycerides, namely triglycerinester of saturated or unsaturated, branched or linear alkanoic acids with a chain length of 8 to 24, particularly 12 to 18C-atoms. The fatty acid triglycerides may preferably be selected from the group of synthetic, semi synthetic and natural oils such as e.g. cocoglyceride, olive oil, sunflower oil, soy bean oil, peanut oil, palm oil, sweet almond oil macadamia oil, coconut oil etc.

Further particularly suitable are natural waxes such as bees wax, shea butter, and/ or lanolin.

Further particularly suitable polar oils according to the present invention may be selected from the group of esters of saturated or unsaturated, branched or linear alkanoic acids with a chain length of 3 to 30 C-atoms and saturated or unsaturated, branched or linear alcohols with a chain length of 3 to 30C-atoms as well as from the group of esters from aromatic carbonic acids and saturated or unsaturated, branched or linear alcohols with a chain length of 3 to 30C-atoms. Such ester oils are particularly selected from the group of phenylethylbenzoate, octylpalmitate, octylcocoate, octylisostearate, octyldodeceylmyristate, octyldodecanol, cetearylisononanoate, isopropylmyristate, isopropylpalmitate, isopropylstearate, isopropyloleate, n-butylstearate, n-hexyllaurate, n-decyloleate, isooctylstearate, isononylstearate, isononylisononanoate, 2-ethylhexylpalmitate, 2- ethylhexyllaurate, 2-hexyldecylstearate, 2-octyldodecylpalmitate, stearylheptanoate, isopropyl lauroyl sarkosinate, oleyloleate, oleylerucate, erucyloleate, erucylerucate, tridecylstearate, tridecyltrimellitate as well as synthetic and semi synthetic and natural mixtures of such esters such as e.g. jojoba oil.

Further particularly suitable oils may be selected from the group of dialkyl ether and dialkylcarbonates such as particularly dicaprylylether (Cetiol OE) and/ or dicaprylylcarbonate, (e.g. available as Cetiol CC at Cognis).

Further particularly suitable oils may be selected from the group of isoeikosan, neopentylglykoldiheptanoate, propylenglykoldicaprylaet caprylate/dicaprate, caprylic/ capric/ diglyceryl succinate, butylene glyckol dicaprylate/dicaprate, C _12- 13-Alkyllactate, Di-C _12- 13- alkyltartrate, triisostearin, dipentaerythrityl hexacaprylate hexacaprate, propylenglykolmonoisostearate, tricaprylin and dimethylisosorbid.

It is particularly advantageous if the oil phase of the topical compositions according to the invention contains an amount of Ci ₂ -i5-alkylbenzoate or consists essentially thereof.

Further particularly suitable oily components are e.g. butyloctylsalicylate (e.g. Hallbrite BHB from CP Hall), hexadecylbenzoate and butyloctylbenzoate as well as mixtures thereof (e.g. Hallstar AB).

The topical compositions according to the present invention may also contain apolar oils such as e.g. branched or linear hydrocarbons and waxes, in particular mineral oil, vaseline (Petrolatum), paraffin oil, squalan and squalen, polyolefins, hydrogenated polyisobutenes, C-13-16 isoparaffin and isohexadecan. Within the group of polyolefins polydecenes are preferred.

Exemplary waxy compounds in particular suitable for the use in the compositions according to the invention are paraffin wax, carnauba wax, beeswax or hydrogenated castor oil.

Exemplary organic solvents in particular suitable for the use in the compositions according to the invention include the lower alcohols and polyols having at most 8 carbon atoms. In particular the compositions according to the invention comprise ethanol in an amount of 5 to 40 wt.-% based on the total weight of the composition.

The thickeners are advantageously selected, in particular, from among the cross linked polyacrylic acids or modified or unmodified guar gums and celluloses, such as hydroxypropylated guar gum, methylhydroxyethylcellulose and hydroxypropylmethylcellulose.

Suitable film forming agents include polymers in the basis of PVP such as in particular copolymers of polyvinylpyrrolidon e.g. PVP hexadecen copolymer and PVP eicosen copolymer which are available as Antaron V216 and Antaron V220 at GAF Chemicals corporations. Further suitable film forming agents include polymeric film formers such as sodiumpolystyrenesulfonate (e.g. Flexan 130 from National Starch and Chemical Corp.) and/ or polyisobuten (e.g. Rewopal PIB1000 from Rewo). Further suitable polymers are e.g. polyacrylamide (Seppigel 305), polyvinylalkohole, PVP, PVP/VA copolymers, polyglycols and acrylate/octylacralymid copolymers (e.g. Dermacryl 79). Further suitable is the use of hydrated castor oil dimerdilinoleat (CAS 646054-62-8, I NCI Hydrogenated Castor Oil Dimer Dilinoleate), or PPG-3 Benzylethermyristate (CAS 403517-45-3).

The topical compositions according to the invention may further comprise one or several compounds from the group of siloxanes elastomers listed in order to enhance the water resistance and/ or enhance the light protection factor such as in particular siloxanes elastomers in the form of spherical powders with the I NCI nomenclature Dimethicone/Vinyl Dimethicone Crosspolymer, such as e.g. DOW CORNING 9506 Powder (by Dow corning)

It is particularly advantageous if the siloxane elastomer is used in combination with hydrocarbon oils, synthetic oils, synthetic esters, synthetic ether or mixtures thereof.

Of course, one skilled in this art will take care to select the above mentioned optional additional compound or compounds and/or their amounts such that the advantageous properties intrinsically associated with the combination in accordance with the invention are not, or not substantially, detrimentally affected by the envisaged addition or additions.

The term "topical composition" as used herein refers in particular to a cosmetic composition that can be topically applied to mammalian keratinous tissue, particularly human skin and hair.

The term "cosmetic preparation" or "cosmetic composition" as used in the present application refers to cosmetic compositions as defined under the heading "Kosmetika" in Rompp Lexikon Chemie, 10th edition 1997, Georg Thieme Verlag Stuttgart, New York as well as to cosmetic compositions as disclosed in A. Domsch, "Cosmetic Preparations", Verlag fur chemische Industrie (ed. H. Ziolkowsky), 4 ^th edition, 1992.

Preferred topical compositions according to the invention are skin care preparations, hair care preparations, decorative preparations, and functional preparations.

Examples of skin care preparations are, in particular, light protective preparations, anti- ageing preparations, preparations for the treatment of photo-ageing, body oils, body lotions, body gels, treatment creams, skin protection ointments, skin powders, moisturizing gels, moisturizing sprays, face and/or body moisturizers, skin-tanning preparations (i.e. compositions for the artificial/sunless tanning and/or browning of human skin), for example self-tanning creams as well as skin lightening preparations.

Examples for care preparations are hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations such as e.g. pretreatment preparations, hair tonics, styling creams, gels such as styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair- straightening preparations, liquid hair-setting preparations, hair foams (hair mousses) and hairsprays.

Examples of decorative preparations are, in particular, lipsticks, eye shadows, mascaras, dry and moist make-up formulations, rouges and/or powders.

Examples of functional preparations are cosmetic or pharmaceutical compositions containing active ingredients such as hormone preparations, vitamin preparations, vegetable extract preparations, anti-ageing preparations, and/or antimicrobial (antibacterial or antifungal) preparations without being limited thereto.

In a particular embodiment the topical compositions according to the invention are light- protective preparations, such as sun protection milks, sun protection lotions, sun protection creams, sun protection oils, sun blocks or tropical's or day care creams with a SPF (sun protection factor). Of particular interest are sun protection creams, sun protection lotions, sun protection milks and sun protection preparations in the form of a spray or aerosol.

In another particular embodiment the topical compositions are hair-washing preparations in the form of shampoos or hair treatment preparations intended to be left in the hair (and not washed out) such as hair-setting preparations, hairsprays, gels, pomades, styling creams or hair foams (hair mousses), particularly hairsprays, gels or hair foams (hair mousses).

A shampoo may, for example, have the following composition: from 0.01 to 5 wt.-% of a polyester based UV filter according to the present invention, 12.0 wt.-% of sodium laureth-2- sulfate, 4.0 wt.-% of cocamidopropyl betaine, 3.0 wt.-% of sodium chloride, and water ad 100 wt.-%. The topical compositions according to the present invention may be in the form of a suspension or dispersion in solvents or fatty substances, or alternatively in the form of an emulsion or micro emulsion (in particular of O/W- or W/O-type, Si/W- or W/Si-type), PIT- emulsion, multiple emulsion (e. g. 0/W/O- or W/O/W-type), pickering emulsion, hydrogel, alcoholic gel, lipogel, one- or multiphase solution or vesicular dispersion or other usual forms, which can also be applied by pens, as masks or as sprays. Preferably, the topical compositions are in the form of an emulsion or dispersion.

In one particular embodiment, the topical compositions according to the invention are in the form of an O/W emulsion. If the topical composition according to the invention is an O/W emulsion, then it contains advantageously at least one O/W- or Si/W-emulsifier selected from the list of glycerylstearatcitrate, glycerylstearate (self emulsifying), stearic acid, salts of stearic acid, polyglyceryl-3-methylglycosedistearate, ceteareth-20, steareth-2, steareth-12, PEG-40 stearate, Further suitable emulsifiers are phosphate esters and the salts thereof such as cetyl phosphate (Amphisol ^® A), diethanolamine cetyl phosphate (Amphisol ^® DEA), potassium cetyl phosphate (Amphisol ^® K), sodiumcetearylsulfat, sodium glyceryl oleate phosphate, hydrogenated vegetable glycerides phosphate and mixtures thereof. Further suitable emulsifiers are sorbitan oleate, sorbitan sesquioleate, sorbitan isostearate, sorbitan trioleate, Lauryl Glucoside, Decyl Glucoside, Sodium Stearoyl Glutamate, Sucrose Polystearate and Hydrated Polyisobuten. Furthermore, one or more synthetic polymers may be used as an emulsifier. For example, PVP eicosene copolymer, acrylates/Cio- ₃ o alkyl acrylate crosspolymer, acrylates/steareth-20 methacrylate copolymer, PEG-22/dodecyl glycol copolymer, PEG-45/dodecyl glycol copolymer, and mixtures thereof. The at least one O/W emulsifier is preferably used in an amount of about 0.001 to 10 wt.-%, more preferably in an amount of 0.1 to 7 wt.-% with respect to the total weight of the composition. Additionally the topical composition contains advantageously at least one co-emulsifier selected from the list of alkyl alcohols such as Cetyl Alcohol (Lorol C16, Lanette 16) Cetearyl Alcohol (Lanette O), Stearyl Alcohol (Lanette 18), Behenyl Alcohol (Lanette 22), Glyceryl Monostearate, Glyceryl Myristate (Estol 3650), Hydrogenated Coco- Glycerides (Lipocire Na10) without being limited to this and mixtures thereof.

In another particular embodiment, the topical compositions according to the invention are W/O emulsions. If the topical composition according to the invention is a W/O emulsion, then it contains advantageously at least one W/O- or W/Si-emulsifier selected from the list of polyglyceryl-2-dipolyhydroxystearat, PEG-30 dipolyhydroxystearat, cetyl dimethicone copolyol, polyglyceryl-3 diisostearate polyester esters of oleic/isostearic acid, polyglyceryl- 6 hexaricinolate, polyglyceryl-4-oleate, polygylceryl-4 oleate/PEG-8 propylene glycol cocoate, magnesium stearate, sodium stearate, potassium laurate, potassium ricinoleate, sodium cocoate, sodium tallowate, potassium castorate, sodium oleate, and mixtures thereof. Further suitable W/Si-emulsifiers are Lauryl Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone and/or PEG-9 Polydimethylsiloxyethyl Dimethicone. The at least one W/O emulsifier is preferably used in an amount of about 0.001 to 10 wt.-%, more preferably in an amount of 0.2 to 7 wt.-% with respect to the total weight of the composition.

The topical compositions according to the invention particularly exhibit a pH in the range of 3-10, preferably in the range of pH of 5-8, most preferred in the range of pH 4-7 which can be adjusted with conventional acids, bases or buffering solutions.

Which amount of the topical composition has to be applied, depends on the concentration of the active ingredient(s) in the product and the desired cosmetic effect(s). A typical "leave- on" composition like a skin care emulsion or light-protective preparation, for example, is usually applied in an amount of about 0.5 to about 2mg per cm ² skin. The applied amount is normally not critical, and the desired effect(s) may be achieved by using more of the composition, repeating the application of the composition and/or applying a composition which contains more of the active ingredient(s).

By "'leave-on' composition" as used herein a topical composition is meant which after having applied to the skin, is not removed intentionally. It is preferably left on the skin for a period of at least about 15 minutes, more preferably at least about 30 minutes, even more preferably at least about 1 hour, most preferably for at least several hours, e. g. up to about 12 hours.

The topical compositions according to the invention are in particular used for the protection against skin ageing (in particular photo ageing) and as sunscreen.

Another aspect of the invention broadly provides a coating composition comprising the polyesters of the present invention and/or as described herein.

A further aspect of the invention provides a coating obtained or obtainable from a coating composition of the present invention. A yet other aspect of the invention broadly provides a substrate and/or article having coated thereon an (optionally cured) coating composition of the present invention.

A yet further aspect of the invention broadly provides for use of polyesters of the present invention and/or as described herein to prepare a coating composition.

A still further aspect of the invention broadly provides a method for preparing a coated substrate and/or article comprising the steps of applying a coating composition of the present invention to the substrate and/or article and optionally curing said composition in situ to form a cured coating thereon. The curing may be by any suitable means, such as thermally, by radiation and/or by use of a cross-linker.

Preferred coating compositions are solvent coating compositions or aqueous coating compositions, more preferably are aqueous coating compositions.

Optionally aqueous coating compositions may also comprise a co-solvent. A co-solvent, as is well known in the coating art, is an organic solvent employed in an aqueous composition to ameliorate the drying characteristics thereof, and in particular to lower its minimum film forming temperature. The co-solvent may be solvent incorporated or used during preparation of polymers of the invention or may have been added during formulation of the aqueous composition.

The coating composition of the invention is particularly useful as or for providing the principle component of coating formulations (i.e. composition intended for application to a substrate without further treatment or additions thereto) such as protective or decorative coating compositions (for example paint, lacquer or varnish) wherein an initially prepared composition optionally may be further diluted with water and/or organic solvents, and/or combined with further ingredients or may be in more concentrated form by optional evaporation of water and/or organic components of the liquid medium of an initially prepared composition.

The coating composition of the invention may be applied to a variety of substrates including wood, board, metals, stone, concrete, glass, cloth, leather, paper, plastics, foam and the like, by any conventional method including brushing, dipping, flow coating, spraying, and the like. The coating composition of the invention may also be used to coat the interior and/or exterior surfaces of three-dimensional articles. The carrier medium may be removed by natural drying or accelerated drying (by applying heat) to form a coating.

The coating composition of the invention may contain other conventional ingredients including pigments, dyes, emulsifiers, surfactants, plasticisers, thickeners, heat stabilisers, levelling agents, anti-cratering agents, fillers, sedimentation inhibitors, UV absorbers, antioxidants, dispersants, reactive diluents, waxes, neutralising agents, adhesion promoters, defoamers, co-solvents, wetting agents and the like introduced at any stage of the production process or subsequently. It is possible to include fire retardants (such as antimony oxide) to enhance the fire retardant properties.

Another aspect of the invention broadly provides an optional water borne polyurethane obtained and/or obtainable from a polyester of the invention and/or as described herein.

A further aspect of the invention broadly provides the use of a polyester of the invention and/or as described herein to prepare an optionally water borne polyurethane.

A yet other aspect of the invention broadly provides a method for preparing an optionally water borne polyurethane comprising the steps of reacting a polyester of the invention and/or as described herein with a moiety comprising one or more isocyanate groups to form a polyurethane.

The moiety comprising one or more isocyanate groups may be a polyisocyanate for example an aliphatic polyisocyanate, an aromatic polyisocyanate and/or mixtures thereof. The term aromatic polyisocyanate as used herein denotes compounds in which all the isocyanate groups are directly bonded to an aromatic group, irrespective of whether aliphatic groups are also present. Examples of suitable aromatic polyisocyanates include but are not limited to p-xylylene diisocyanate, 1 ,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-methylene bis(phenyl isocyanate), polymethylene polyphenyl polyisocyanates, 2,4'-methylene bis(phenyl isocyanate) and 1 ,5- naphthylene diisocyanate. Preferred aromatic isocyanates include 2,4'-methylene bis(phenyl isocyanate) and 4,4'-methylene bis(phenyl isocyanate). Aromatic polyisocyanates may provide chemical resistance and toughness and/or may yellow on exposure to UV light. The term aliphatic polyisocyanate as used herein denotes compounds in which all the isocyanate groups are directly bonded to aliphatic or cycloaliphatic groups, irrespective of whether aromatic groups are also present.

Examples include but are not limited to ethylene diisocyanate, para-tetra methylxylene diisocyanate (p-TMXDI), meta-tetra methylxylene diisocyanate (m-TMXDI), 1 ,6- hexamethylene diisocyanate, isophorone diisocyanate (IPDI), cyclohexane-1 ,4-diisocyanate and 4,4'-dicyclohexylmethane diisocyanate. Aliphatic polyisocyanates may improve hydrolytic stability, resist UV degradation and/or do not yellow. Preferred aliphatic iscocyanates include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and 1 ,6-hexamethylene diisocyanate.

Preferably at least 70 wt%, more preferably at least 85 wt% and most preferably at least 95 wt% of the polyisocyanate may have two isocyanate groups.

Aromatic or aliphatic polyisocyanates which have been modified by the introduction of, for example, urethane, allophanate, urea, biuret, uretonimine and urethdione or isocyanurate residues may also be used to prepare polyurethanes of the present invention.

Preferred polyesters of the invention and/or as described herein that are suitable for use in preparing polyurethane are those comprising one or more isocyanate-reactive components such as -OH, -CHR ¹ -COOH where R ¹ can be H, alkyl (more preferably Ci to C ₈ alkyl); -SH, - NH- and -NH ₂ .

The following examples are provided to further illustrate the compositions and effects of the present invention. These examples are illustrative only and are not intended to limit the scope of the invention in any way.

Example 1

Preparation of polyester based UV-filters

All components in the ratios (wt.-%) as indicated in table 1 and table 2 below were charged in a 1 liter flask. The respective mixture was heated to the temperature indicated in the tables (reaction temperature), while methanol (MeOH) was distilled off. When the MeOH distillation stopped, a vacuum of 50 mm Hg was applied. After 3 hours of vacuum at 140 °C the obtained polyester was discharged in a glass jar, cooled at room temperature and further tested for its solubility in different cosmetic oils as outlined below.

Solubility in cosmetic oils:

1 g of the respective Polyester based UV filter was added to 1 g of a cosmetic oil as given in table 1 & 2. Afterwards the resulting two phase mixture was stirred (magnetic stirrer) at room temperature (-21 °C) for 7 days. Solubility was rated to be not sufficient (nOk) in case if phase separation was still observable. On the other hand, a clear solution without phase separation was rated as good solubility (i.e. corresponding to a solubility of at least 50wt.-% (Ok). The results are outlined in table 1 & 2.

Table 1

Polyester No. Ref. Ref. Ref. 1 2 3 4

Cromophore carrying diester

DMMBM 60.1 56.0 51.1 53.8 55.4 50.7

DiAMAD 84.3

Diols

Cyclohexan-1 ,4-dimethanol 15.7

Diethylene glycol 29.3 19.6 16.5

Propylene glycol 2.4

Hexane diol 24.0 1.8 21.3 22.4

Dimerdiol 17.0 29.3 25.4 31.3 26.9

Other building blocks

Glycerol (Triol) 2.9

Stearic acid 10.6

Ratio Dimerdiol/ Chromophore - - 0.3:1 0.6:1 0.5:1 0.6:1 0.5:1

Ratio [Sum Diol]/ Chromophore - - 0.8:1 1 :1 0.9:1 1 :1 1 :1

Ratio Dimerdiol/ 1 ,6-Hexanediol - - 0.7:1 - 14:1 1 .5:1 1 .2:1 Catalyst TiPT TBT TBT TBT TiPT TBT TBT [wt.-%] 0.1 0.04 0.04 0.1 0.04 0.1 0.04

Reaction temperature [°C] 140 140 140 140 140 140 140

Product form C C C V V V L

Mw 4733 1707 n.d 3270 1290 8730 1 160

OH mgKOH/g n.d. 30.1 n.d 6 42.6 18 105

Cosmetic Oils Solubility

Myritol nOk nOk nOk nOk nOk nOk Ok

DUB DIS nOk nOk nOk Ok Ok Ok Ok

Finsolv nOk nOk nOk nOk nOk nOk Ok

Cetiol CC nOk nOk nOk nOk nOk nOk nOk

Table 2

Finsolv FN Ok Ok Ok Ok Ok Ok Ok Ok Ok Ok Ok

Cetiol CC Ok Ok Ok Ok Ok Ok Ok Ok Ok Ok Ok

DMMBM: 2-[4-methoxy-benzylidene -malonic acid dimethyl ester (Hosl avin P R-25 from

Clariant)

DiAMAD: 2-(3-Diisopropylamino-allylidene)-malonic acid dimethyl ester

DmAMAD: 2-(3-Dimethylpropylamino-allylidene)-malonic acid dimethyl ester

Dimerdiol: Pripol™ 2033 from Croda

TBT: Titanium tetra butoxide;

TiPT: Titanium tetra isopropoxide;

ZA: Zn acetate;

V = viscous;

C crystalline;

L = liquid.

n.a. not analyzed

Example 3: Stabilization of PARSOL ^® 1789

Sample preparation cream: 10 mg of a sunscreen formulation comprising PARSOL ^® 1789 and a polyester according to the present invention as outlined below were weight onto an even glass micro slide and spread homogenously (Rakel) onto an area of 10cm ² (applied amount: 1 mg/cm ² ) and left to dry for 30 min before exposure.

Sunscreen formulation

Phase Ingrediens INCI Name % w/ w

Butyl Methoxydibenzoylmethane

A Parsol 1789 4.00

(Avobenzone; USAN)

Polyester as indicated in the table below 4.00

DUB DIS Diisopropyl Sebacate 12.00

Finsolv ^® TN C12-15 Alkyl Benzoate 10.00

AMPHISOL ^® K Potassium Cetyl Phosphate 2.00

Estol 3650 Glyceryl Myristate 4.00

Lanette 16 Cetyl Alcohol 1.00

Phenoxyethanol & Methylparaben &

Phenonip Ethylparaben & Butylparaben & 1 .00

Propylparaben & Isobutylparaben

Dow Corning 200/100 cs Dimethicone 0.80 dl-alpha -Tocopheryl

Tocopheryl Acetate 0.50 Acetate

Butylated

BHT 0.05

Hydroxytoluene

B Edeta BD Disodium EDTA 0.10

Glycerin Glycerin 5.00 Keltrol Xanthan Gum 0.30

Water dem. Aqua 55.15 C Triethanolamine (T.E.A.) Triethanolamine 0.10

Sample preparation film: 20 mg of a solution comprising 10wt.-% of the respective Polyester based UV-filter in EtOH/ Finsolv TN (6:4) were applied onto roughened glass plates using a syringe (applied amount: 2mg/cm ² ) and left to dry for 30 min before exposure.

Irradiation:

The glass slides were irradiated using a Solar simulator until 25 MED are reached; the control slides (unirradiated samples) were kept in the dark for the same time. Afterwards each slide was transferred into a Polyethylene container, 30 ml of solvent (MethanohTHF (1 :1 )) was added and the container was sonicated for about 15 min. The resulting solutions were analyzed via HPLC analysis or UV Spectroscopy. (Each measurement was done three times. Each test was done in triplicate.

Calculation:

Mean of peak area of the irradiated samples x 100

Percentage of non-degraded UV filter =

Mean of peak area of the unirradiated samples Results: Table 3

⁺ Recovery of PARSOL ^® 1789 after irradiation

^* Calculated based on 1 wt.-% of Dimethyl (p-methoxybenzylidene) malonate

As can be retrieved from table 3, the polyesters according to the present invention are suitable to stabilize Parsol ^® 1789. Furthermore, the effectiveness on the stabilization of Parsol ^® 1789 based on the chromophore content is significantly higher at lower chromophore loadings in film as well as in cream.