WO2008119428A1 - Photostable compositions - Google Patents

Abstract

A formulation comprising at least one compound having at least one diethylhexyl radical and ethylhexyl methoxycinnamate, preferably in a ratio 5:1 to 1 :5.

Description

Photostable compositions

Background of the invention

Topical compositions are commonly used during outdoor work or leisure as a means for providing protection of exposed skin against acute and chronic adverse effects of solar radiation such as sunburn, cancer and photo-aging. Many effective sunscreen preparations are sold commercially or are described in cosmetic or pharmaceutical literature. In general sunscreen preparations are formulated as creams, lotions or oils containing as the active agent an ultra violet radiation absorbing chemical compound. The sunscreen functions by blocking passage of ultra violet radiation thereby preventing its penetration into the skin.

According to Zecchino et al. (US 5,008,100), sunscreen agents may be characterized in the order of decreasing effectiveness as either highly chromophoric (monomeric organic compounds and inorganic compounds such as titanium dioxide) and minimally chromophoric (polymeric organic solids).

Organic sunscreens are classified into UV-A filters, UV-B filters or broad spectrum filters (UV-A and UV-B functionality in a single molecule) depending on the type of radiation they absorb. UV-A sunscreens absorb radiation in the 320 to 400 nm regions of the ultra violet spectrum and UV- B sunscreens absorb radiation in the 290 to 320 nm regions of the ultra violet spectrum. Broad band sunscreens (UV-A and UV-B functionality) absorb radiation in the 290 to 400 nm region of the ultra violet spectrum and have two maximums, one in the UV-B region and the other in the UV- A region.

Representative references related to UV sunscreens are: US Patent No.

3,278,448, which discloses cinnamic acid derivatives such as 4-hydroxy, 3- 5-ditertbutyl-alphacarbethoxy-cinnamic acid ether ester in column 2, line 20; US Patent No. 3,538,226, which describes cinnamic acid alkyl ester derivatives at column 1 , lines 15-31 and column 2, lines 1-12 and column 3, lines 30-55 and 60; US Patent No. 5,175,340, which describes cinnamic acid alkyl esters having hydroxy radicals and alkoxy radicals on the phenyl ring, and US Patent No. 5,830,441 , which describes UV absorbents containing a cyano or cinnamyl moiety by the generic formula at col. 2, lines 1-21. Other references which disclose cinnamide compounds include U.S. Patent Nos. 5,601 ,811 , 4,335,054, 5,124,354, 5,294,643 and 5,514,711.

Unfortunately, some of the highly chromophoric monomeric organic compounds employed in sunscreen compositions are not photostable and the protection from sun damage is lost. In addition to lack of photostability of many organic sunscreens, they do not possess an antioxidant property which is essential for protecting skin or hair. Especially ethylhexyl methoxycinnamate (EHMC, octyl methoxycinnamate, OMC or oxtinoxate) is unstable in the presence of UV radiation mostly discussed because of photoinduced isomehsation and irreversible decomposition. This causes a loss of capacity for absorption and therefore a reduction of UV protection.

A proposed mechanism is as follows:

The ideal formulation comprising organic sunscreens should be nontoxic and non-irritating to the skin tissue and be capable of convenient application in a uniform continuous film. The product should be chemically and physically stable so as to provide an acceptable shelf life upon storage. It is particularly desirable that the preparation should retain its protective effect over a prolonged period after application. Thus, the active agent when present on the skin must be resistant to chemical and/or photo degradation. Techniques for stabilizing UV absorbent compositions are known. Representative disclosures in this area include U.S. Patent Nos. 5,567,418, 5,538,716, 5,951 ,968 and 5,670,140.

It is desirable to provide the antioxidant and photostable sunscreen functionality in a single molecule to enhance the effectiveness of the antioxidant properties as described in US 6,602,515. US 6,602,515 describes compounds with sunscreen activity, i.e. they are chromophoric within the ultra violet radiation range of from 290-400 nm and they also exhibit antioxidant properties. These compounds are represented by general formula I

In formula I, A is a moiety which provides chromophoric properties within the UV radiation range of 290-400 nm. This moiety comprises two monovalent groups having carbonyl (C=O) functionality. For formula I, each R⁶ is independently linear or branched d-Cs alkyl and R⁵ is hydrogen or linear or branched Ci_-S alkyl or linear or branched -0-Ci_-8 alkyl. The one or more compounds of formula I can preferably stabilize at least one additional sunscreening agent against photodegradation from exposure to sunlight. Preferred compounds are of formula Il below.

For formula II, - A -

R¹ is selected from the group consisting Of-C(O)CH₃, -CO₂R³, -C(O)NH₂ and -C(O)N(R⁴)₂; X is O or NH;

R² is linear or branched Ci to C₃₀ alkyl; R³ is linear or branched Ci to C₂o alkyl; each R⁴ is independently hydrogen or linear or branched Ci to C₈ alkyl;

R⁵ is linear or branched C₁-C₈ alkyl or hydrogen or linear or branched -0-C_1-8 alkyl, and R⁶ is linear or branched C₁-C₈ alkyl.

SUMMARY OF THE INVENTION

Unexpectedly, the present invention provides formulations which comprise at least one stabilising compound with at least one diethylhexyl radical, especially di(2-ethylhexyl) 2-(4-hydroxy-3,5-dimethoxybenzylidene)- malonate, and ethylhexyl methoxycinnamate, preferably in the ratio 5:1 to 1 :5 (stabilizeπEHMC), more preferably in the ratio 1 :1 to 1 :3.5. These formulations show a significant reduction of the decomposition of the sunscreen agent EHMC as to the formulations according to the prior art. In one preferred embodiment of the invention, the above described formulation is a sunscreen formulation.

In one preferred embodiment of the invention, the above described formulation is a personal care formulation.

In one preferred embodiment of the invention, the above described formulation is a pharmaceutical formulation.

Not being bound by any theory, it is believed that the following mechanism for the reduction of decomposition can be proposed:

Typical amounts of the stabilizing compounds within such compositions typically range from 0.1 to 10 wt%, preferably in the range from 0.5 to 5 wt%, especially preferred 0.5 wt%, 2 wt%, 3 wt% or 5 wt%, based on the total weight of the formulation. Typical amounts of EHMC range from 0.1 to 10 wt%, preferably from 1 to 7.5 wt%, especially preferred from 2 to 5 wt% based on the total weight of the formulation. Unexpectedly, the most preferred sunscreen compositions comprise 2, 3 or 5 wt% of di(2- ethylhexyl) 2-(4-hydroxy-3,5-dimethoxybenzylidene)-malonate and 5 wt% of EHMC. They individually provide a synergetic effect and extremely prevents photo degradation of EHMC.

Additionally, preferred combinations are disclosed in the claims.

These formulations as described above can contain one or more additional organic sunscreen agents for filtering UV-B or UV-A rays or they may additionally contain one or more metal oxide sunscreen agents such as titanium dioxide or zinc oxide.

In the light of the present application, the wording formulation is identically used as composition or as preparation.

These formulations may additionally contain a carrier and at least one component selected from the group consisting of dispersing agents, preservatives, anti-foams, perfumes, oils, waxes, propellants, dyes, pigment emulsifiers, surfactants, thickeners, humectants, exfoliants and emollients. These sunscreen formulations may be in the form of a cosmetic composition with a cosmetically acceptable carrier and one or more cosmetic adjuvants. The formulation can optionally have conventional antioxidants or other stabilizers which do not have UV absorbing characteristics. Other ingredients referred to above and discussed more particularly below are generally used in an amount from about 0.1 wt% to about 10 wt% of the sunscreen formulation. The balance comprises a cosmetically or pharmaceutically acceptable carrier.

Methods for improving the photostability of sunscreen formulations are also provided.

The formulations of this invention preferably offer protection from UV radiation with wavelengths of about 290 nm to 400 nm and preferably from wavelengths in the range of about 290-370 nm. Formulations of this invention also typically have a sunscreen protection factor (SPF) ranging from about 2 to 60, with a preferred SPF range of from about 10 to about 45. The target SPF range can be achieved with a combination of both inorganic and organic chromophoric compounds. SPF is determined by techniques well known in the art, on human skin as described in the Federal Register, August 25, 1978, Vol. 43, No. 166, pages 38259-38269 (Sunscreen Drug Products for over-the-counter Human Use, Food and Drug Administration). SPF values can also be approximated using in-vitro models as described, for example, in J. Soc. Cosmet. Chem. 44:127-133 (May/June 1989).

The formulations may contain dispersing agents, emulsifiers or thickening agents to assist in applying a uniform layer of the active compounds. Suitable dispersing agents for the sunscreen formulations include those useful for dispersing organic or inorganic sunscreen agents in either a water phase, oil phase, or part of an emulsion, including, for example, chitosan.

Emulsifiers may be used in the sunscreen formulations to disperse one or more of the compounds with at least one diethylhexyl radical or other component of the sunscreen formulation. Suitable emulsifiers include conventional agents such as, for example, glycerol stearate, stearyl alcohol, cetyl alcohol, dimethicone copolyol phosphate, hexadecyl-D- glucoside, octadecyl-D-glucoside, etc.

Thickening agents may be used to increase the viscosity of the sunscreen formulations. Suitable thickening agents include carbomers, acrylate-

/acrylonitrile copolymers, xanthan gum and combinations of these. The carbomer thickeners include the crosslinked CARBOPOL® acrylic polymers from B. F. Goodrich. The amount of thickener within the sunscreen formulation, on a solids basis without water, may range from about 0.001 to about 5%, preferably from 0.01 to about 1 % and optimally from about 0.1 to about 0.5% by weight.

Minor optional adjunct ingredients for the sunscreen formulations to be applied to skin or hair may include preservatives, waterproofing agents, fragrances, anti-foam agents, plant extracts (Aloe vera, witch hazel, cucumber, etc) opacifiers, skin conditioning agents and colorants, each in amounts effective to accomplish their respective functions.

The formulations may optionally contain an ingredient which enhances the waterproof properties such as, compounds that form a polymeric film, such as dimethicone copolyol phosphate, diisostearoyl trimethyolpropane siloxysilicate, chitosan, dimethicone, polyethylene, polyvinylpyrrolidone (PVP), polyvinylpyrrolidone/vinylacetate,

PVP/Eiconsene copolymer and adipic acids/diethylene glycol/glycerine crosspolymer etc. Waterproofing agents may be present at levels of from about 0.01 to about 10% by weight.

The formulations may also optionally contain one or more skin conditioning agents. These include humectants, exfoliants and emollients.

Humectants are polyhydric alcohols intended for moisturizing, reducing scaling and stimulating the removal of built scale from the skin. Typically polyhydric alcohols include polyalkylene glycols and more preferably alkylene polyols and their derivatives. Illustrative are propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol, sorbitol, 2- pyrrolidone-5-carboxylate, hydroxypropyl sorbitol, hexylene glycol, ethoxydiglycol 1 ,3-butylene glycol, 1 ,2,6-hexanetriol, glycerin, ethoxylated glycerin, propoxylated glycerin and mixtures thereof. Most preferably the humectant is glycerin. Amounts of humectant can range anywhere from 1 to 30%, preferably from 2 to 20% and optimally from about 5 to 10% by weight of the sunscreen composition.

The exfoliants suitable for use in the present may be selected from alpha- hydroxy carboxylic acids, beta hydroxycarboxylic acids and salts of these acids. Most preferred are glycolic, lactic and salicylic acids and their alkali, metal or ammonium salts.

Suitable emollients include those agents known for softening the skin or hair which may be selected from hydrocarbons, fatty acids, fatty alcohols and esters. Petrolatum is a common hydrocarbon type of emollient conditioning agent. Other hydrocarbons that may be employed include alkyl benzoate, mineral oil, polyolefins such as polydecene, and paraffins, such as isohexadecane. Fatty acids and alcohols typically have from about 10 to 30 carbon atoms. Illustrative are myristic, isostearic, hydroxystearic, oleic, linoleic, ricinoleic, behenic and eruicic acids and alcohols. Oily ester emollients may be those selected from one or more of the following, triglyceride esters, acetoglyceride esters, ethoxylated glycerides, alkyl esters of fatty acids, ether esters, polyhydric alcohol esters and wax esters. Additional emollients or hydrophobic agents include Ci₂ to Ci₅ alkyl benzoate, dioctyladipate, octyl stearate, octyldodecanol, hexyl laurate, octyldodecyl neopentanoate, cyclomethicone, dicapryl ether, dimethicone, phenyl trimethicone, isopropyl myristate, capriylic/capric glycerides, propylene glycol dicaprylate/dicaprate and decyl oleate.

The formulations may optionally contain one or more sunscreen agents as discussed above. In principle, all UV filters are suitable for a combination. Particular preference is given to those UV filters whose physiological safety has already been demonstrated. There are many tried and tested substances known from the specialist literature for both UVA and also UVB filters, e.g. Benzylidenecamphor derivatives, such as

- 3-(4'-methylbenzylidene)-dl-camphor (e.g. Eusolex® 6300),

- 3-benzylidenecamphor (e.g. Mexoryl® SD),

- polymers of N-{(2 and 4)-[(2-oxoborn-3-ylidene)- methyl]benzyl}acrylamide (e.g. Mexoryl® SW),

- N,N₁N-trimethyl-4-(2-oxobom-3-ylidenemethyl)-anilinium methylsulfate (e.g. Mexoryl® SK) or

- alpha-(2-oxoborn-3-ylidene)toluene-4-sulfonic acid (e.g. Mexoryl® SL),

benzoyl- or dibenzoylmethanes, such as

- 1 -(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1 ,3-dione (e.g. Eusolex® 9020) or

- 4-isopropyldibenzoylmethane (e.g. Eusolex® 8020),

benzophenones, such as

- 2-hydroxy-4-methoxybenzophenone (e.g. Eusolex® 4360) or

- 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (e.g. Uvinul® MS-40),

4,4,-diarylbutadienes as described in EP-A-O 916 335,

methoxycinnamic esters, such as

- isopentyl 4-methoxycinnamate, e.g. as a mixture of the isomers (e.g. Neo Heliopan® 1000),

salicylate derivatives, such as

- 2-ethylhexyl salicylate (e.g. Eusolex® OS),

- 4-isopropylbenzyl salicylate (e.g. Megasol®) or

- 3,3,5-trimethylcyclohexyl salicylate (e.g. Eusolex® HMS), 4-aminobenzoic acid and derivatives, such as

- 4-aminobenzoic acid,

- 2-ethylhexyl 4-(dimethylamino)benzoate (e.g. Eusolex® 6007),

- ethoxylated ethyl 4-aminobenzoate (e.g. Uvinul® P25), diphenylacrylates, e.g. 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (Eusolex® OCR) and further substances, such as 2-phenylbenzimidazole-5-sulfonic acid, and its potassium, sodium and triethanolamine salts (e.g. Eusolex® 232), 3,3'-(1 ,4-phenylenedimethylene)-bis(7,7-dimethyl-2-oxobicyclo[2.2.1]hept- 1-ylmethanesulfonic acid and its salts (e.g. Mexoryl® SX), 2,4,6-trianilino-

(p-carbo-2'-ethylhexyl-1 '-oxy)-1 ,3,5-triazine (e.g. Uvinul® T 150) and 2-(4- Diethylamino-2-hydroxy-benzoyl)-benzoic acid hexyl ester (e.g. UvinulD A Plus, BASF).

The compounds given in the list are only to be regarded as examples. It is of course also possible to use other UV filters.

These organic UV filters are usually incorporated into cosmetic formulations in an amount of from 0.5 to 10% by weight, preferably 1 - 8% by weight.

Further suitable organic UV filters are, for example, 2-(2H-benzotriazol-2- yl)-4-methyl-6-(2-methyl-3-(1 ,3,3,3-tetramethyl-1-(trimethylsilyloxy)- disiloxanyl)propyl)phenol (e.g. Silatrizole®), bis(2-ethylhexyl) 4,4'-[(6-[4- ((1 ,1 -dimethyl-ethyl) — aminocarbonyl)phenylamino]-1 ,3,5-triazine-2,4-diyl)- diimino]-bis-benzoate (e.g. Uvasorb® HEB)₁ (trimethylsilyl)- [trimethylsilyl)oxy]-poly-[oxy-(dimethyl [and about 6% methyl[2-[p-[2,2-bis- (ethoxycarbonyl]vinyl]phenoxy]-1-methylenethyl] and about 1.5% methyl[3- [p-[2,2-bis(ethoxycar-bonyl)-vinyl)phenoxy)propenyl) and 0.1 to 0.4% (methyl-hydrogen]silylene]] (nD60) (CAS No. 207 574-74-1 ), 2,2'- methylenebis(6-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol) (CAS No. 103 597-45-1 ), 2,2'-(1 ,4-phenylene)bis(1 H-benzimidazol-4,6- disulfonic acid, monosodium salt) (CAS No. 180 898-37-7) and 2,4-bis{[4- (2-ethylhexyloxy)-2-hydroxyl]phenyl}-6-(4-methoxyphenyl)-1 ,3,5-triazine (CAS No. 103 597-45-, 187 393-00-6).

These organic UV filters are usually incorporated into cosmetic formulations in an amount of from 0.5 to 20% by weight, preferably 1 -

15% by weight. Conceivable as inorganic UV filters are those from the group of titanium dioxides, such as, for example, coated titanium dioxide (e.g. Eusolex® T- 2000, Eusolex® T-AQUA), zinc oxides (e.g. Sachtotec®), iron oxides and also cerium oxides. These inorganic UV filters are generally incorporated into cosmetic formulations in an amount of from 0.5 to 20% by weight, preferably 2 - 10 wt%.

Preferred compounds with UV-filtering properties in addition to ethylhexy methoxycinnamate (EHMC or octyl methoxycinnamate, commercial product (e.g. Eusolex® 2292)) are 3-(4'-methylbenzylidene)-dl-camphor, 1- (4-tert-butyl-phenyl)-3-(4-methoxy-phenyl)-propane-1 ,3-dione, 4-iso- propyldi-benzoylmethane, 2-hydroxy-4-methoxy-benzo-phenone, 3,3,5- trimethylcyclohexyl salicylate, 2-ethylhexyl 4-(dimethylamino)-benzoate, 2- ethylhexyl 2-cyano-3,3-diphenylacrylate, 2-phenyl-benzimidazole-5- sulfonic acid and its potassium, sodium and triethanolamine salts.

All of the UV filters specified herein including the compounds of formula I can also be used in encapsulated form. In particular, it is advantageous to use organic UV filters in encapsulated form. Specifically, the following advantages arise: . The hydrophilicity of the capsule wall can be set independently of the solubility of the UV filter. First, for example, it is possible to incorporate even hydrophobic UV filters into purely aqueous formulations. In addition, the oily impression which is often perceived as unpleasant upon application of the preparation comprising hydrophobic UV filters is prevented.

- Certain UV filters, in particular dibenzoylmethane derivatives, exhibit only reduced photostability in cosmetic formulations. By encapsulating these filters or compounds which impair the photostability of these filters, such as, for example, the above-mentioned cinnamic acid derivatives, it is possible to increase the photostability of the overall formulation.

- The literature discusses again and again the penetration of the skin by organic UV filters and the irritancy potential associated therewith upon direct application to the human skin. The encapsulation of the corresponding substances proposed here presents this effect. - Generally, by encapsulating individual UV filters or other ingredients, it is possible to avoid formulation problems which arise as a result of interaction of individual formulation constituents with one another, such as crystallization processes, precipitations and agglomeration, since the interaction is prevented.

It is therefore preferred according to the invention if one or more of the above-mentioned UV filters are present in encapsulated form. In this connection, it is advantageous if the capsules are so small that they can not be observed with the naked eye. To achieve the above-mentioned effects, it is also necessary for the capsules to be sufficiently stable and not to release the encapsulated active ingredient (UV filter) into the surroundings, or to release it only to a slight extent.

Suitable capsules can have walls made of inorganic or organic polymers. For example, US 6,242,099 B1 describes the preparation of suitable capsules with balls made of chitin, chitin derivatives or polyhydroxylated polyamines. Capsules which are to be used particularly preferably according to the invention have walls which can be obtained by a sol-gel process, as is described in the applications WO 00/09652, WO 00/72806 and WO 00/71084. Preference is given here in turn to capsules whose walls are made of silica gel (silica; undefined silicon oxide hydroxide). The preparation of corresponding capsules is known to the person skilled in the art, for example, from the cited patent applications, the contents of which also expressly belonging to the subject-matter of the present application.

Here, the capsules are present in formulations according to the invention preferably in amounts which ensure that the encapsulated UV filters are present in the formulation in the amounts given above.

The protecting action against oxidative stress or against the effect of free radicals can be further improved if the formulation comprises one or more antioxidants.

There are many tried and tested substances known from the specialist literature which can be used, e.g. amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-camosine, D- carnosine, L-carnosine and derivatives thereof (e.g. anserine), carotinoids, carotenes (e.g. ϋ-carotene, Ocarotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols

(e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, D-linoleyl, cholesteryl and glycerylesters thereof), and salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), and sulfoximine compounds (e.g. buthionine- sulfoximine, homocysteine-sulfoximine, buthionine-sulfone, penta-, hexa- and heptathionine-sulfoximine) in very low tolerated doses (e.g. pmol to μmol/kg), and also (metal) chelating agents, (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof, vitamin C and derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (e.g. vitamin A palmitate), and coniferyl benzoate of benzoin resin, rutin and salts of the sulfuric ester of rutin and derivatives thereof, α-glycosyl rutin, ferulic acid, furfurylidineglucitol, carosine, butylhydroxy-toluene, butylhydroxyanisol, nordihydroguaretic acid, trihydroxybutyrophenone, quercetin, uric acid and derivatives thereof, mannose and derivatives thereof, zinc and derivatives thereof (e.g. ZnO, ZnSO4), selenium and derivatives thereof (e.g. selenomethionine), stilbenes and derivatives thereof (e.g. stilbene oxide, trans- stilbene oxide).

Useful antoxidants are additionally compounds of formula B

in which

R¹ is selected from the group comprising -C(O)CH₃, -CO₂R³, -C(O)NH₂ and -C(O)N(R⁴)₂,

X is O or NH,

R² is linear or branched alkyl with 1 to 30 C-atoms, R³ is linear or branched alkyl with 1 to 20 C-atoms,

R⁴ is independently of each other H or linear or branched alkyl with 1 to 8

C-atoms,

R⁵ is linear or branched alkyl with 1 to 8 C-atoms or linear or branched alkoxy with 1 to 8 C-atoms and R⁶ js linear or branched alkyl with 1 to 8 C-atoms, especially derivatives of

2-(4-hydroxy-3,5-dimethoxybenzyl)-malonic acid, especially preferred di-(2- ethylhexyl) 2-(4-hydroxy-3,5-dimethoxybenzy)-malonate (e.g. RonaCare^®

AP).

Mixtures of antioxidants are likewise suitable for use in the cosmetic formulations according to the invention. Known and commercial mixtures are, for example, mixtures comprising, as active ingredients, lecithin, L-(+)- ascorbyl palmitate and citric acid (e.g. Oxynex® AP), natural tocopherols, L-(+)-ascorbyl palmitate, L-(+)-ascorbic acid and citric acid (e.g. Oxynex® K LIQUID), tocopherol extracts from natural sources, L-(+)-ascorbyl palmitate, L-(+)-ascorbic acid and citric acid (e.g. Oxynex® L LIQUID), DL- D-tocopherol, L-(+)-ascorbyl palmitate, citric acid and lecithin (e.g. Oxynex® LM) or butylhydroxytoluene (BHT), L-(+)-ascorbyl palmitate and citric acid (e.g. Oxynex® 2004).

The formulations according to the invention can comprise vitamins as further ingredients. Preferably, vitamins and vitamin derivatives chosen from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamine chloride hydrochloride (vitamin B1 ), riboflavin (vitamin B2) nicotinamide, vitamin C (ascorbic acid), vitamin D, ergocalciferol (vitamin D2), vitamin E, DL-tocopherol, tocopherol E acetate, tocopherol hydrogen-succinate, vitamin K1 , esculin (vitamin P active ingredient), thiamine (vitamin B1 ) nicotinic acid (niacin), pyridoxine, pyridoxal, pyridoaxmine, (vitamin B6), panthothenic acid, biotin, folic acid and cobalamine (vitamin B12) are present in the cosmetic formulations according to the invention, particularly preferably vitamin A palmitate, vitamin C, DL-tocopherol, tocopherol E acetate, nicotinic acid, panthothenic acid and biotin.

Examples of application forms of the cosmetic or pharmaceutical formulations according to the invention which may be mentioned are: solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, foams, surfactant-containing cleansing preparations, oils, aerosols and sprays. Examples of other application forms are sticks, shampoos and shower preparations. Any customary carriers, auxiliaries and optionally further active ingredients may be added to the formulation.

Preferred auxiliaries originate from the group of preservatives, antioxidants, stabilizers, solubility promoters, vitamins, colorants, odour improvers.

Ointments, pastes, creams and gels may comprise the customary carriers, e.g. animal and vegetable fats, waxes, paraffins, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silica, talc and zinc oxide or mixtures of these substances.

Powders and sprays may comprise the customary carriers, e.g. lactose, talc, silica, aluminium hydroxide, calcium silicate and polyamide powder or mixtures of these substances. Sprays can additionally comprise customary propellants, e.g. chlorofluorocarbons, propane/butane or dimethyl ether.

Solutions and emulsions can comprise the customary carriers, such as solvents, solubility promoters and emulsifiers, e.g. water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1 ,3-butylglycol, oils, in particular cotton seed oil, peanut oil, wheatgerm oil, olive oil, castor oil and sesame oil, glycerol fatty acid ester, polyethylene glycols and fatty acid esters of sorbitan or mixtures of these substances. Suspensions can comprise the customary carriers such as liquid diluents, e.g. water, ethanol or propylene glycol, suspending agents, e.g. ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminium metahydroxide, bentonite, agar agar and tragacanth or mixtures of these substances.

Soaps can comprise the customary carriers, such as alkali metal salts of fatty acids, salts of fatty acid mono esters, fatty acid protein hydrolysates, isethionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugars or mixtures of these substances.

Surfactant-containing cleansing products can comprise the customary carrier substances, such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic monoesters, fatty acid protein hydrolysates, isethionates, imidazolinium derivatives, methyl taurates, sarcosinates, fatty acid amide ether sulfates, alkylamidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated glycerol fatty acid esters or mixtures of these substances.

Face and body oils can comprise the customary carrier substances such as synthetic oils, such as fatty acid esters, fatty alcohols, silicone oils, natural oils, such as vegetable oils and oily plant extracts, paraffin oils, lanolin oils or mixtures of these substances.

Further typically cosmetic application forms are also lipsticks, lipcare sticks, mascara, eyeliner, eyeshadow, blusher, powder make-up, emulsion make-up and wax make-up, and sunscreen, presun and aftersun preparations.

All compounds or components which can be used in the cosmetic formulations are either known and available commercially or can be synthesized by known processes. As dispersant or solubilizer it is possible to use an oil, wax or other fatty substance, a lower monoalcohol or a lower polyol or mixtures thereof. Preferred monoalcohols or polyols include ethanol, isopropanol, propylene glycol, glycerol and sorbitol.

A preferred embodiment of the invention is an emulsion in the form of a protective cream or milk and which comprise, for example, fatty alcohols, fatty acids, fatty acid esters, in particular triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of water.

Further preferred embodiments are oily lotions based on natural or synthetic oils and waxes, lanolin, fatty acid esters, in particular triglycerides of fatty acids, or oily-alcoholic lotions based on a lower alcohol, such as ethanol, or a glycerol, such as propylene glycol, and/or a polyol, such as glycerol, and oils, waxes and fatty acid esters, such as triglycerides of fatty acids.

The cosmetic preparation according to the invention can also be in the form of an alcoholic gel which comprises one or more lower alcohols or polyols, such as ethanol, propylene glycol or glycerol, and a thickener, such as siliceous earth. The oily-alcoholic gels also comprise natural or synthetic oil or wax.

Preferred compositions of our invention are hydrogels. The hydrophilicity of the capsule wall can be set independently of the solubility of the UV filter. For example, it is possible to incorporate even hydrophobic UV filters into purely aqueous formulations. Due to this possibility to include high amounts of hydrophobic UV filters in encapsulated or immobilized form, as described above, those hydrogels of our inventions can posses high SPF values, in a range normally only acheived with oily formulations.

The solid sticks consist of natural or synthetic waxes and oils, fatty alcohols, fatty acids, fatty acid esters, lanolin and other fatty substances. AII compounds or components which can be used in the cosmetic or pharmaceutical formulations are either known and available commercially or can be synthesized by known processes.

The composition according to the invention is particularly suitable for protecting human skin against the harmful influences of the UV constituents in sunlight, in addition they also offer protection against ageing processes of the skin and against oxidative stress, i.e. against damage caused by free radicals, as are produced, for example, by solar irradiation, heat or other influences.

Therefore the use of a composition according to our invention for the manufacture of a medicament suitable for the prophylaxis of damages of the skin caused by sunray, especially for the prophylaxis of sunburn and sun-caused erythrema is another embodiment of our invention. A further embodiment is the cosmetic prophylaxis of damages of the skin caused by sunray, especially for the prophylaxis of sunburn and sun-caused erythrema.

The formulation may comprise adjuvants which are customarily used in this type of composition, such as, for example, thickeners, softeners, moisturizers, surface-active agents, emulsifiers, preservatives, perfumes, waxes, lanolin, propellants, dyes and/or pigments which colour the composition itself or the skin, and other ingredients customarily used in cosmetics.

The composition may be a foamable composition able to be foamed up with or without a propellant. According to our invention it is especially preferred if the foam is produced without the use of an organic propellant. Sprays using organic propellents may not be stored in direct sun or at higher temperatures; conditions that for example can often be found on the beach during summer. An advantage of preferred compositions according to our invention is that the may be stored and used even under these conditions. Preferred compositions are included in a foam dispenser, preferably in a foam dispenser that requires no organic propellant as described above.

As foam builders / stabilisers in general all substances able to build or stabilise a foam may be used. Those substances in general are known to those skilled in the art. Preferred foam builders / stabilisers are those which are skin tolerant or even more preferably give a benefit to the skin.

The foam builders / stabilisers are usually present in an amount of about 0.01 to 20 % by weight, preferably in an amount of 0.1 to 5 % by weight and even more preferred in an amount of 0.1 to 3 % by weight.

Preferred foam builders / stabilisers are cetyl phosphate, DEA cetyl phosphate, TEA myristate, TEA stearate, magnesium stearate, sodium stearate, potassium laurate, potassium ricinoleate, sodium cocoate, sodium tallowate, potassium castorate, sodium oleate and mixtures thereof.

Other preferred foam stabilisers are so called foam boosters. Foam boosters are substances which increase the surface viscosity of the liquid which surrounds the individual bubbles in a foam. These agents are commonly used in shaving soaps, shampoos, bubble baths, liquid soaps, mousses, or aerosol-dispensed foams. Also Film Formers or Viscosity- Increasing Agents maybe used as foam boosters. The listing below gives examples for foam boosters which can also be classified as surfactants (INCI names):

Acetamide MEA, Almondamide DEA, Almondamidopropylamine Oxide, Almondamidopropyl Betaine, Apricotamide DEA, Apricotamidopropyl Betaine, Avocadamide DEA, Avocadamidopropyl Betaine, Babassuamide DEA, Babassuamidopropylamine Oxide, Babassuamidopropyl Betaine, Behenamide DEA, Behenamide MEA, Behenamidopropyl Betaine, Behenamine Oxide, Behenyl Betaine, Canolamidopropyl Betaine, Capramide DEA, Carnitine, Cetearyl Alcohol, Cetyl Alcohol, Cetyl Betaine, Cocamide DEA, Cocamide MEA, Cocamide MIPA, Cocamidoethyl Betaine, Cocamidopropylamine Oxide, Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Cocamine Oxide, Cocoamphodi- propionic Acid, Cocobetainamido Amphopropionate, Coco-Betaine, Coco- Hydroxysultaine, Coco-Morpholine Oxide, Coconut Alcohol, Coco/Oleamidopropyl Betaine, Coco-Sultaine, Cocoyl Sarcosinamide DEA, DEA-Cocoamphodipropionate, DEA-Lauraminopropionate, Decyl Alcohol, Decylamine Oxide, Decyl Betaine, Diethanolaminooleamide DEA,

Dihydroxyethyl C8-10 Alkoxypropylamine Oxide, Dihydroxyethyl C9-11 Alkoxypropylamine Oxide, Dihydroxyethyl C12-15 Alkoxypropylaminde Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide, Dimethicone Propyl PG-Betaine, Disodium Caproamphodiacetate,

Disodium Caproamphodipropiante, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cetearyl SulfosuccinateDisodium Cocamido MIPA-Sulfosuccinate, Disodium Cocamido PEG-3 Sulfosuccinate, Disodium Cocaminopropyl Iminodiacetate, DisodiumCocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium C12-15 Pareth Sulfosuccinate, Disodium Deceth-5 Sulfosuccinate, Disodium Deceth-6 Sulfosuccinate, Disodium Hydrogenated Cottonseed Glyceride Sulfosuccinate, Disodium lsodecyl Sulfosuccinate, Disodium lsostearamido MEA-Sulfosuccinate, Disodium lsostearamido MIPA-Sulfosuccinate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium lsostearyl Sulfosuccinate, Disodium Laneth-5 Sulfosuccinate, Disodium Lauramido MEA-Sulfosuccinate, Disodium Lauramido PEG-2 Sulfosuccinate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Laureth

Sulfosuccinate, Disodium Laureth-6 Sulfosuccinate, Disodium Laureth-9 Sulfosuccinate, Disodium Laureth-12 Sulfosuccinate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropiante, Disodium Lauryl Sulfosuccinate, Disodium Myristamido MEA-Sulfosuccinate, Disodium Nonoxynol-10 Sulfosuccinate, Disodium Oleamido MEA-Sulfosuccinate, Disodium Oleamido MIPA-Sulfosuccinate, Disodium Oleamido PEG-2 Sulfosuccinate, Disodium Oleoamphodipropionate, Disodium Oleth-3 Sulfosuccinate, Disodium Oleyl Sulfosuccinate, Disodium Palmitamido PEG-2 Sulfosuccinate, Disodium Palmitoleamido PEG-2 Sulfosuccinate, Disodium PEG-4 Cocamido MIPA-Sulfosuccinate, Disodium PPG-2- lsodeceth-7 Carboxyamphodiacetate, Disodium Ricinoleamido MEA- Sulfosuccinate, Disodium Stearamido MEA-Sulfosuccinate, Disodium Stearoamphodiacetate, Disodium Stearyl Sulfosuccinamate, Disodium Stearyl Sulfosuccinate, Disodium Tallamido MEA-Sulfosuccinate, Disodium Tallowamido MEA-Sulfosuccinate, Disodium Tallowamphodiacetate, Disodium Tallow Sulfosuccinamate, Disodium

Tridecylsulfosuccinate, Disodium Undecylenamido MEA-Sulfosuccinate, Disodium Undecylenamido PEG-2 Sulfosuccinate, Disodium Wheat Germamido MEA-Sulfosuccinate, Disodium Wheat Germamido PEG-2 Sulfosuccinate, Disodium Wheatgermamphodiacetate, Di-TEA-Oleamido PEG-2 Sulfosuccinate, Ditridecyl Sodium Sulfosuccinate, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow Alcohol, Hydrogenated Tallowamide DEA, Hydrogenated Tallowamine Oxide, Hydrogenated Tallow Betaine, Hydroxyethyl Carboxymethyl Cocamidopropylamine, Hydroxyethly Hydroxypropyl C12-15 Alkoxypropylamine Oxide, Hydroxystearamide MEA, lsostearamide DEA, lsostearamide MEA, lsostearamide MIPA, lsostearamidopropylamine Oxide, Isostearamido- propyl Betaine, lsostearamidopropyl Morpholine Oxide, Lactamide MEA, Lanolinamide DEA, Lauramide DEA, Lauramide MEA, Lauramide MIPA, Lauramide/Myristamide DEA, Lauramidopropylamine Oxide, Lauramido- propyl Betaine, Lauramine Oxide, Lauroampho-dipropionic Acid, Lauryl Alcohol, Lauryl Betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, Lecithinamide DEA, Linoleamide DEA, Linoleamide MEA, Linoleamide MIPA, Methyl Morpholine Oxide, Minkamide DEA, Minkamidopropylamine Oxide, Minkamidopropyl Betaine, Myristamide DEA, Myristamide MEA, Myristamide MIPA, Myristamidopropylamine Oxide, Myristamidopropyl

Betaine, Myristamine Oxide, Myristaminopropionic Acid, Myristyl Alcohol, Myristyl Betaine, Myristyl/Cetyl Amine Oxide, Oleamide DEA ,Oleamide MEA, Oleamide MIPA, Oleamidopropylamine Oxide, Oleamidopropyl Betaine, Oleamidopropyl Hydroxysultaine, Oleamine Oxide, Oleyl Betaine, Olivamide DEA, Olivamidopropylamine Oxide, Olivamidopropyl Betaine, Palmamide DEA, Palmamide MEA, Palmamide MIPA, Palmamidopropyl Betaine, Palmitamide DEA, Palmitamide MEA, Palmitamidopropylamine Oxide, Palmitamidopropyl Betaine, Palmitamine Oxide, Palm Kernel Alcohol, Palm Kernelamide DEA, Palm Kernelamide MEA, Palm Kernelamide MIPA, Palm Kemelamidopropyl Betaine, Peanutamide MEA, Peanutamide MIPA, PEG-3 Cocamide, PEG-2 Hydrogenated Tallow Amine, PEG-3 Lauramide, PEG-3 Lauramide Oxide, PEG-2 Oleamide, PEG-3 Oleamide, PEG-2 Oleamine, PEG-2 Soyamine, PEG-2 Stearamine, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Ricinoleamide DEA, Ricinoleamide MEA, Ricinoleamide MIPA, Ricinoleamidopropyl Betaine, Sesamide DEA, Sesamidopropylamine

Oxide, Sesamidopropyl Betaine, Sodium Caproamphoacetate, Sodium Caproamphohydroxy-propylsulfonate, Sodium Caproamphopropionate, Sodium Capryloampho-acetate, Sodium Capryloamphohydroxypropyl- sulfonate, Sodium Capryloamphoproprionate, Sodium Cocoamphoacetate, Sodium Cocoamphohydroxypropylsulfonate, Sodium Cocoampho- propionate, Sodium Comamphopropionate, Sodium Isostearoampho- acetate, Sodium Isostearoamphopropionate, Sodium Lauramidopropyl Hydroxyphostaine, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroamphoacetate, Sodium/MEA Laureth-2 Sulfosuccinate, Sodium Myristoamphoacetate, Sodium

Oleoamphoacetate, Sodium Oleoampho-hydroxy-propylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Tallamphopropionate, Sodium Tallowamphoacetate, Sodium Tallowate, Sodium Undecylenoampho- acetate, Sodium Undecylenoampho-propionate, Sodium Wheat Germamphoacetate, Soyamide DEA, Soyamidopropyl Betaine, Stearamide AMP, Stearamide DEA, Stearamide DEA-Distearate, Stearamide MEA, Stearamide MEA-Stearate, Stearamide MIPA, Stearamidopropylamine Oxide, Stearamidopropyl Betaine, Stearamine

Oxide, Stearyl Alcohol, Stearyl Betaine, Tallamide DEA, Tallowamide DEA, Tallowamide MEA, Tallowamidopropylamine Oxide, Tallowamidopropyl Betaine, Tallowamidopropyl Hydroxysultaine, Tallowamine Oxide, Tallow Betaine, TEA-Lauraminopropionate, TEA-Myristaminopropionate, Trideceth-2 Carboxamide MEA, Trisodium Lauroampho PG-Acetate Phosphate Chloride, Undecylenamide DEA, Undecylenamide MEA, Undecylenamidopropylamine Oxide, Undecylenamidopropyl Betaine, Wheat Germamide DEA, Wheat Germamidopropylamine Oxide, Wheat Germamidopropyl Betaine. In another embodiment at least one foam builder / stabiliser is selected from foaming surfactants, preferably from alkylglyosides, anionic protein derivatives or fatty acid sulfonates.

An especially preferred foam builder / stabilisers are anionic protein derivatives, such as lipoaminoacids described in WO 98/09611 , WO

99/27902 and WO 99/45899. Most preferred under these anionic protein derivatives are sodium lauroyl oat amino acids, for example known as Proteol™ Oat (Tradename of Seppic).

The cosmetic formulation can also be used to protect the hair against photochemical damage in order to prevent changes of colour shades, decoloration or damage of a mechanical nature. In this case, a suitable formulation is in the form of a shampoo or lotion for rinsing out, the formulation in question being applied before or after shampooing, before or after colouring or bleaching or before or after permanent waving. It is also possible to choose a formulation in the form of a lotion or gel for styling or treating the hair, in the form of a lotion or gel for brushing or blow-waving, in the form of a hair lacquer, permanent waving composition, colorant or bleach for the hair. The cosmetic formulation may comprise various adjuvants used in this type of composition, such as surface-active agents, thickeners, polymers, softeners, preservatives, foam stabilizers, electrolytes, organic solvents, silicone derivatives, antigrease agents, dyes and/or pigments which colour the composition itself or the hair, or other ingredients customarily used for hair care.

To protect the skin and/or natural or sensitized hair against solar rays, the cosmetic composition is applied to the skin or the hair. Sensitized hair is understood here as meaning hair which has been subjected to a chemical treatment, such as a permanent waving treatment, a colouring process or bleaching process.

Formulations of this invention as described in Formulations 1-17 can be prepared by conventional means. The abbreviation DESM means di-ethylhexy-3,5-dimethoxy-4- hydroxybenzylidene malonate or Diethylhexyl Syringlidenemalonate according to INCI.

Oxynex® ST Liquid means a composition of di-ethylhexyl-3,5-dimethoxy-4- hydroxybenzylidene malonate (90%) and medium chain triglycerides (10%) or Diethylhexyl Syringlidenemalonate (and) Caprylic/Capric Triglyceride according to INCI.

Formulation 1

Procedure:

Combine phase B ingredients. Stir and heat to 70-75⁰C. Combine Phase A ingredients. Heat while stirring to 70-75⁰C. Add Phase B to Phase A while stirring. Add preservative. Stir, allowing mixture to cool to room temperature. Formulation 2: Sunscreen Oil/Water Spray Lotion

Procedure

Combine A-1 ; stir and heat to 6O⁰C until all solids are dissolved. Disperse A-2 in A-1 with agitation. Combine B-1 ; stir and heat to 60⁰C. Disperse B-2 in B-1 with agitation. Add A to B while stirring vigorously. Gently homogenize allowing mixture to cool to 40°C. Add C to A/B: gently homogenize until mixture is uniform. Stir with anchor mixer allowing mixture to reach 25°C prior to packaging. Use a high shear pump spray device for dispensing (e.g., Eurogel pump by Seaquist Perfect) Formulation 3: Sunscreen Cream

Procedure

Add Phase A ingredients to main vessel under impeller agitation. Heat phase A to 75-80⁰C. Combine Phase B ingredients; heat and mix to 85⁰C. Slowly add Phase B to batch; mix for 15 minutes at 85°C. Remove from heat; switch to paddle mixing and cool to room temperature. Formulation 4: Water/Oil Broad Spectrum Sunscreen Lotion

Procedure

Combine A-1 ; stir and heat to 55-6O⁰C until all solids are dissolved. Disperse A-1 in A-1 by propeller agitation. Combine B; stir and heat to 50- 55°C. Slowly add B to A while stirring vigorously. Add C to A/B; gently homogenize until mixture is uniform. Stir with anchor mixer allowing mixture to cool to room temperature. Formulation 5: UVA/UVB Sun Protection Cream with Avobenzone

Procedure

Combine A-1 ; heat to 50EC while stirring until methylparaben is dissolved.

Disperse A-2 in A-1 with a sifter. Heat A to 65°C

Combine B; heat to 65-70⁰C while stirring until solids are dissolved.

Add B to A. Homogenize Add C at 55-60⁰C. Continue to homogenize allowing mixture to cool to 40-45⁰C

Add D; stir with propeller mixer until uniform.

Adjust pH with TEA to 6.5-7.0 Formulation 6: Oil/Water Sunscreen Lotion

Procedure

Prepare Phase B by dispersing Carbopol in water . Heat the dispersion to

70-75⁰C.

Combine Phase A ingredients. Stir and heat to 70-75⁰C.

Add Phase B to Phase A while stirring.

Add Phase C. Homogenize until mixture cools to 45-4O⁰C.

Add Phase D. Stir allowing mixture to cool to room temperature. Formulation 7: Oil/Water Sunscreen Lotion

Procedure

Preapare Phase B by dispersing Carbopol in water . Heat the dispersion to

70-75⁰C.

Combine Phase A ingredients. Stir and heat to 70-75⁰C.

Add Phase B to Phase A while stirring.

Add Phase C. Homogenize until mixture cools to 45-40⁰C.

Add Phase D. Stir allowing mixture to cool to room temperature. Formulation 8: Sunscreen Oil/Water Spray Lotion

Procedure

Combine A-1 ; stir and heat to 60 ⁰C until allsolids are dissolved. Disperse A-2 in A-1 with agitation. Combine B-1 ; stir and heat to 60 ⁰C. Disperse B- 2 in B-1 with agitation. Add A to B while stirring vigorously, gently homogenize allowing mixture to cool to 40 ⁰C. Add C to A/B: gently homogenize until mixture is uniform. Stir with anchor mixer allowing to reach 25 ⁰C prior to packaging. Use a high shear pump spray device for dispensing (e.g., Eurogel pump by Seaquist Perfect) Formulation 9: Sunscreen Cream

Procedure

Add Phase A ingredients to main vessel under impeller agitation. Heat phase A to 75-80⁰C. Combine Phase B ingredients; heat and mix to 85⁰C. Slowly add Phase B to batch; mix for 15 minutes at 85°C. Remove from heat; switch to paddle mixing and cool to room temperature. Formulation 10: Water/Oil Broad Spectrum Sunscreen Lotion

Procedure

Combine A-1 ; stir and heat to 55-60⁰C until all solids are dissolved. Disperse A-1 in A-1 by propeller agitation. Combine B; stir and heat to 50- 55°C. Slowly add B to A while stirring vigorously. Add C to A/B; gently homogenize until mixture is uniform. Stir with anchor mixer allowing mixture to cool to room temperature. Formulation 11 : w/o liquid foundation [wt%]

Procedure:

A: Homogenizing 1-9, then add to 10, 11 uniformly

B: Heat 12-19 to solve. During stirring, add B to A slowly. Formulation 12: w/o milky lotion

Procedure:

A: Heat at 75°C 1-7 while stirring.

B: Heat at 75°C 8-12 while stirring.

During stirring, B is added to A and mix 13 and 14, then cool down to

35°C.

Formulation 13: o/w liquid foundation [wt%]

Procedure:

A: heat at 75°C 1-10 while stirring.

B: heat at 75°C 11-16 while stirring.

During stirring, add B to A and Mix 17 to 20. Then cool down to 35⁰C. Formulation 14: cream foundation

Procedure:

A: Heat 6-14 to 95°C while stirring.

B: Mix 1-5 uniformly.

Add B to A and disperse. At 80⁰C pour into an aluminium pan and cool to room temperature.

Formulation 15: Pressed powder foundation

Procedure:

A: Pulverize 1-11.

B: Mix 12-16 uniformly.

Using mixer B is added to A and mixed uniformly. The bulk is weighed appropriately, pou into aluminium mold with pan and pressed.

Formulation 16: w/o sunscreen lotion (separate type)

Procedure:

A: Disperse 1-8 uniformly.

B: Mix 9, 10.

While stirring, add B to A and mix.

Formulation 17: lip balm

Procedure:

Heat 1-9 up to 95°C and melt. The bulk is then poured into aluminium mold and cooled. The stick is set into an applicator.

EXAMPLES

Example I: Determination of the in vitro photostability of EHMC

Table 1 :

INCl

% % % % % %

Phase A

Ethylhexyl 2,00 2,00 5,00 5,00 7,00 7,00

Methoxycinnamate,

BHT

Diethylhexyl 2,00 2,00 2,00

Syringylidenemalonate lsostearyl Phosphate 3,00 3,00 3,00 3,00 3,00 3,00

Cetearyl lsononanoate 7,00 7,00 6,00 6,00 6,00 5,00

Dicaprylyl Ether 7,00 7,00 6,00 6,00 6,00 5,00

Ethylhexyl Stearate 6,00 4,00 5,00 3,00 3,00 3,00

Carbomer 0,15 0,15 0,15 0,15 0,15 0,15

Propylparaben 0,05 0,05 0,05 0,05 0,05 0,05

Phase B

Ectoin 0,30 0,30 0,30 0,30 0,30 0,30

Allantoin 0,30 0,30 0,30 0,30 0,30 0,30

Glycerin 5,00 5,00 5,00 5,00 5,00 5,00

Tromethamine 0,43 0,43 0,43 0,43 0,43 0,43

Methylparaben 0,15 0,15 0,15 0,15 0,15 0,15

Aqua (Water) 68,62 68,62 68,62 68,62 68,62 68,62

100,00 100,00 100,00 100,00 100,00 100,00

Procedure:

Combine Phase A and heat up to 80⁰C until solid UV filter is dissolved.

Add Carbomer. Combine Phase B and heat separately to 80⁰C. Add

Phase B to Phase A while stirring and homogenize. Cool down while stirring.

Six o/w emulsions are tested in which the concentration of EHMC is in the range of 2.0 to 7 wt% as given in detail in Table 1. The control is the corresponding o/w emulsion without the stabilizing compound di-(2- ethylhexyl) 3,5-dimethoxy-benzylidene-malonate (= DESM).

Method:

Determination of the in vitro photostability of organic UV filters in personal care products by analyzing the photo degradation rate of each individual

UV filter caused by irreversible photoreactions. The term "photostability", as used, addresses irreversible photoreactions of UV filter molecules that lead to the formation of photo degradation products. By contrast it excludes reversible photoreactions such as photoisomerization. Therefore this method is considering both reaction types separately to finally calculate a UV filter's photostability only via its irreversible photo degradation pathways.

Various methodologies have been published on the issue of "photostability of UV filters" using different techniques [e.g. 1 , 2]. The term "(ir)reversible photoreaction" has been introduced by Beck et al. in 1985, and was further investigated by Schwack et al. [3, 4, 5].

It is the principle of this method to detect changes chromatographically (HPLC method) in individual UV filter concentrations before and after UV irradiation with solar simulated light. The option to measure photostability of a product via changes in its spectral absorption properties (photometer method) is insufficient since irreversible and reversible photoreactions cannot be differentiated. Difficulties may also arise by the overlap of UV spectra of parent isomers, photo isomers and photoproducts.

According to this method products are exposed to a single representative UV dose that has been shown to sufficiently differentiate between single photostability levels. Results allow comparing products for their relative photostability but do not allow drawing quantitative conclusions towards the real life UV protection performance (e.g. sun protection factor).

The term "UV dose", as used under this method, describes an absolute dose of total UV in kJ per m² (between 290 and 400 nm). The dose should better not be weighted for biological responses (e.g. erythematic response) since, for the same nominal UV dose, calibration difficulties in the short UVB region may lead to different actual UV doses applied. In addition the use of an absolute dose seems favourable since the wavelength response for photo degradation may differ from e.g. the erythematic response in humans. Within this method the UV dose is therefore calculated from the un-weighted UV irradiance with respect to the given specifications that sufficiently characterize both, the spectral distribution and irradiance of a solar simulator with a realistic UV light emission (reference spectrum [6]).

Application:

Substrate: Glass micro-slides (76 x 26 mm); frosted on one surface (Chance Propper Ltd. Spon Lane, England). Frosted side = application side.

Application rate: 2 mg/cm²

Balances: Sartorius A200S Inv. Nr. 312316 (weighing on glass holder to avoid electrostatic interference) Application: By positive displacement pipette (Transferpettor, Fa. Brand, vol. 10-40μL). Number of droplets on substrate before spreading: 20 to 20

Spreading: By naked finger (saturated with product). Spread sample over the whole plate within 30 s.

UV source for irradiation:

Suntest Atlas CPS+ with cooling tray and optical filters (Atlas UV filter "Spezialglas"). Equipped with UV radiometer (Radialux). An external revision of the applied UV-radiation at each stage is determined yearly. Radiometer is used for internal cross-calibration against external. UVA+B irradiance: 60 ± 10 Wm^"2 (DIN 67501 UVA+B irradiance = 60,7 Wm^'2) compared value Suntest CPS+: 51 ,78 Wm^"2 (at step 4). Ratio UVA to UVB: UVA=320-400nm, UVB=290-320nm, 18 ± 3 (DIN 67501 UVA to UVB ratio = 18,5), compared value Suntest CPS+: 19,3 (at step 4). UV dose : UV dose t1 = 25 kJm^"2 (pre-irradiation), UV dose t2 = 250 kJm^"2 (irradiation).

Analytical Preparation: lsopropanol (50 mL); plate elution with 40 mL in 100-glass cylinder (2.6cm0, cut off at e.g. 53mL mark, provided with a spout); ultrasound extraction; transfer to 50 mL volumetric brown glass flask through glass funnel with washings; membrane filtration [type] into HPLC sample vial (brown).

Analytical measurement: HPLC with appropriate parameters.

Test procedure: Number of samples (plates):

Following the method-principle to take photo isomerisation into account, three groups of samples should be prepared, each group consisting of up to four plates (groups "dark control", 11" and "t2").

The group "dark control" consists of the plates 1 , 2, 3, 4. These samples are kept in the dark. They serve as reference plates to ensure the correct product application rate. The measured UV filter concentrations should be equivalent to 95-100% of the nominal application rate (example: for an application rate of 2mg(product)cm^"2 and a UV filter content of 5%, the measured concentrations should be in the range of 95-100 μg(UV filter)cm^~2).

The group 11" consists of the plates a', b\ c', d'. These samples are used for the pre-irradiation step. "Pre-irradiation" means the application of a low UV dose (e.g. 25 kJm^'2) that generates sufficient photo isomer from a parent isomer. The difference of parent isomer concentrations between "dark control" and "t1 " plates can be used to calibrate the photo isomer concentration. Remark: This calibration method is used due to the practical difficulties associated with photo isomers, such as availability, purity, and light sensitivity.

The group "t2" consists of the plates a, b, c, d. These samples are used for the irradiation step. "Irradiation" means the application of a realistically high UV dose (e.g. 250 kJm^"2). Irreversible photo degradation (= photo- unstable) of a UV filter is measured as the difference of a the sum of parent- and photo-isomer-concentrations at "t2" versus 11". Remark: It is insufficient to compare sum integrals instead of sum concentration of both isomers since the ratio of their absorbance coefficients might be unknown.

Optionally for products not visibly generating photo isomers it is possible to calculate photostability by the comparison of 12" versus "dark control" samples.

Product application: The weight of the blank substrate can be noted before the product application to calculate later the dry amount of product. Then a pre- calculated volume of product is quickly applied to the substrate in small droplets by using a pipette or another application aid. The application amount is immediately weighed and noted ("wet weight"). Next the product is quickly spread over the complete substrate surface using the naked finger or another spreading aid.

The spreading should lead to a uniform film within 30 seconds. After spreading the sample is allowed to equilibrate for 30 min in the dark at room temperature to ensure self-levelling of the formula. Now the sample can be weighed again ("dry weight"). It is the aim to finally prepare up to 12 samples that differ in their dry product amounts by no more than plus- minus 5% of their mean.

UV source and irradiation:

The UV source should be controlled at least yearly for compliance with the given specifications by an independent expert (see chapter "materials and methods"). This compliance check is conducted with a spectroradiometer that is calibrated against an international calibration standard. Between two inspections the UV source emission is monitored with a lab-radiometer that should be cross calibrated against the external spectroradiometer at the time of the external inspection.

For the irradiation step it has to be ensured that all samples are exposed to the same irradiance. This can be achieved either by randomly distribute the plates on the tray or rotate them (e.g. with a disc player). During the irradiation process thermal effects are excluded by using a water-cooled tray.

According to the plate and positioning code up to eight plates of the groups "t1" and "t2" are placed inside the solar simulator. After pre-irradiation the plates of group"t1" are removed from the tray and stored in the dark. The irradiation is then continued to deliver the full irradiation dose. All groups of samples are then subjected to the analytical preparation step.

Analytical preparation:

The sample is placed into a suitable glass vessel. The vessel is filled with extraction solvent to completely cover the sample. Then the vessel is placed into an ultrasound bath for extraction (time of extraction depends on product, e.g. 10 min). After extraction the supernatant is transferred with washings through a glass funnel into a volumetric brown glass flask.

The flask is now filled up to the mark with solvent. A membrane filtration step follows to obtain a clear final sample solution that can be analysed by

HPLC.

DATA PROCESSING:

The HPLC analysis delivers data for each UV filter in up to 12 samples (4 samples "dark control"; 4 samples "pre-irradiated t1"; 4 samples "irradiated t2". The data are provided as concentrations [μgrnL^"1] and peak-integrals (for indirect photo isomer calibration).

References: [1] G. Berset, H. Gonzenbach, R. Christ, R. Martin, A. Deflandre, R.

Mascotto, JDR Jolly, W. Lowell, R. Pelzer, T. Stiehm, "Proposed protocol for determination of photostability, Part I: Cosmetic UV-Filters, Int. J.

Cosmet. Sci. 18(4), 1996, 167.

[2] A. Kammeyer, W. Westerhof, PA. Bolhuis, AJ. Ris, EA. Hische, ,,The spectral stability of several sunscreening agents on stratum corneum sheets, Int. J. Cosmet. Sci. 9, 1987, 125.

[3] I. Beck, A. Deflandre und G. Lang, ..Photostability assessment of sunscreens. Benzylidene camphor and dibenzoylmethane derivatives", J.

Photochem., 30, 1985, 215. [4] w. Schwack und T. Rudolph, ..Photochemistry of dibenzoylmethane

UVA filters", J. Photochem. Photobiol. B, 28, 1995, 229.

[5] T. Rudolph, "Photoreaktionen chemischer UV-Filter", 1. Auflage 1996,

Verlag Mainz, ISBN 3-89653-056-9.

[6] DIN67501 (1996). Method. brief description:

The determination of the in vitro photostability of EHMC takes place by analyzing the photo degradation rate of EHMC caused by irreversible photoreactions. The EHMC concentration is measured by high performance liquid chromatography before and after irradiation with solar stimulated UV light.

The term "UV dose" as used herein, describes an absolute dose of total UV in kJ per m² (between 290 and 400 nm). The UV dose is therefore calculated from the un-weighted UV irradiance with respect to the given specifications that sufficiently characterize both, the spectral distribution and irradiance of a solar simulator with a realistic UV light emission. Irradiation dose: 5 MED (250 kJ/m²). Application rate: 2 mg/cm²

Results:

It is therefore clearly shown and visualized in Figure 1 that DESM is a good stabilizer for UV induced degradation of EHMC. Figure 2 gives corresponding details of this results expressed in μmol/cm³. Depending on the ratio DESM/EHMC, a reduction of the irreversible photodegradation of EHMC up to 60% can be obtained e.g. from 13.1 to 5.2 only in case of a ratio 2:2 (OMC/DESM) as given in Fig 1.

Example Il : An additional experiment further prove the prevention of photo degradation and synergism of UV absorbance for EHMC with DESM

Experiment:

Irradiation takes place with a UV fluorescent lamp (TOSHIBA FL20BLB) with the conditions: wavelength: 315-400nm; illuminance: 500 mW (UVA), 2200 mW (UVB); measurement of illuminance by UV-RADIOMETER UVR+3036/S2:CLINICALSUPPLY; radiation time: 4 hours.

Formulation for Sample 1 : EHMC 5 wt%, Glyceryl tri(2-ethylhexanoate) 95 wt%.

Formulation for Sample 2: EHMC 5 wt%, DESM 1 wt%, Glyceryl tri(2- ethylhexanoate) 94 wt%.

Formulation for Sample 3: EHMC 5 wt%, DESM 2 wt%, Glyceryl tri(2- ethylhexanoate) 93 wt%. Formulation for Sample 4: EHMC 5 wt%, DESM 3 wt%, Glyceryl tri(2- ethylhexanoate) 92 wt%.

Formulation for Sample 5: EHMC 5 wt%, DESM 5 wt%, Glyceryl tri(2- ethylhexanoate) 90 wt%.

Preparation of the samples which are irradiated:

The formulation as described above is weighed approximately 0.5 g on a glass plate (10cm x 20 cm) and spread as a film using a scraper.

Procedure of photostability measurement:

The absorbance is measured with a UV-photometer (UV-2500PC, SHIMAZU, scan speed: medium, lit length: 2, sampling width: 0,2). The quantitative analysis of EHMC is measured by HPLC, column INERTSIL 4,6 x 250 mm, eluent: Methanol/water = 95/5, flow rate 1.0 ml/min. Results:

Formulation 1 : after UV-radiating, peak absorbance (293 nm) of EHMC decreased to 66% before radiating.

Formulation 2: after UV-radiating, peak absorbance (293 nm) of EHMC decreased to 83% before radiating.

Formulation 3: after UV-radiating, peak absorbance (293 nm) of EHMC decreased to 83% before radiating.

Formulation 4: after UV-radiating, peak absorbance (293 nm) of EHMC decreased to 86% before radiating.

Formulation 5: after UV-radiating, peak absorbance (293 nm) of EHMC decreased to 90% before radiating.

As a result, the increasing UV absorbance of formulations with combine EHMC with DESM depend on the concentration of DESM.

A synergistic effect of DESM with EHMC can be proven by a calculation. The combined UV absorbance of peak wavelength (293 nm) show 10% of synergetic effect onto the theoretical value. (Fig. 3)

Example III:

The photostability and the synergetic effect are experimented by using practical sunscreen milk formulae preferred with in vitro SPF.

Condition of in vitro SPF

Facility: SPF Analyzer System UV-1000S (Labsphere) Substrate: 3M™ Tape #1526 (5 cm x 8 cm) Quantity: 40 mg (1.0 mg/cm²)

Production milk is weighed on the substrate cramped with metal flame, then applied with fingertips uniformly.

Procedure:

A: 1 to 5 is mixed , then 6 is dispersed;

B: 7 to 11 is solved uniformly. During stirring B is added slowly to A.

The in vitro SPF of application 1 is higher than the comparison 1 and 2 because of the booster effect of DESM for EHMC. Additional to the booster effect, the decreasing SPF value of application 1 after UV irradiation compared to comparison 1 indicates a prevention of the degradation of EHMC by DESM after UV irradiation.

From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

Claims

WHAT IS CLAIMED IS

1. A formulation comprising at least one compound having at least one diethylhexyl radical and ethylhexyl methoxycinnamate.

2. A formulation according to claim 1 wherein the at least one compound having at least one diethylhexyl radical and ethylhexyl methoxycinnamate is comprised in a ratio 5:1 to 1:5.

3. A formulation according to claim 1 or 2 wherein the at least one compound having at least one diethylhexyl radical and ethylhexyl methoxycinnamate is comprised in a ratio 1 :1 to 1 :3.5.

4. A formulation according to one or more of claims 1 to 3 wherein the amount of ethylhexyl methoxycinnamate range from 0.1 to 10 wt% based on the total weight of the formulation.

5. A formulation according to claim 4 wherein the amount of ethylhexyl methoxycinnamate range from 1 to 7.5 wt% based on the total weight of the formulation.

6. A formulation according to one or more of claims 1 to 5 wherein the amount of the at least one compound having at least one diethylhexyl radical range from 0.1 to 10 wt% based on the total weight of the formulation.

7. A formulation according to one or more of claims 1 to 6 wherein the amount of the at least one compound having at least one diethylhexyl radical range from 0.5 to 5 wt% based on the total weight of the formulation.

8. A formulation according to one or more of claims 1 to 7 wherein the compound having at least one diethylhexyl radical is di(2-ethylhexyl)

2-(4-hydroxy-3,5-dimethoxybenzylidene)-malonate.

9. A formulation according to one or more of claims 1 to 8 wherein the amount of at least one compound having at least one diethylhexyl radical is 2, 3 or 5 wt% and the amount of ethylhexyl methoxycinnamate is 5 wt% based on the total weight of the formulation.

10. A formulation according to one or more of claims 1 to 9 comprising at least one additional organic sunscreen agent for filtering UV-B or UV- A rays.

11. A formulation according to claim 10 comprising a UV filter selected from the group of Benzylidenecamphor derivatives, such as

- 3-(4'-methylbenzylidene)-dl-camphor,

- 3-benzylidenecamphor, - polymers of N-{(2 and 4)-[(2-oxoborn-3-ylidene)- methyl]benzyl}acrylamide,

- N,N,N-trimethyl-4-(2-oxobom-3-ylidenemethyl)-anilinium methylsulfate, or

- alpha-(2-oxoborn-3-ylidene)toluene-4-sulfonic acid,

benzoyl- or dibenzoylmethanes, such as

- 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1 ,3-dione, or

- 4-isopropyldibenzoylmethane,

benzophenones, such as

- 2-hydroxy-4-methoxybenzophenone or

- 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt,

4,4,-diarylbutadienes,

methoxycinnamic esters, such as

- octyl methoxycinnamate,

- isopentyl 4-methoxycinnamate, e.g. as a mixture of the isomers, salicylate derivatives, such as

- 2-ethylhexyl salicylate,

- 4-isopropylbenzyl salicylate or

- 3,3,5-trimethylcyclohexyl salicylate,

4-aminobenzoic acid and derivatives, such as

- 4-aminobenzoic acid,

- 2-ethylhexyl 4-(dimethylamino)benzoate,

- ethoxylated ethyl 4-aminobenzoate,

diphenylacrylates, e.g. 2-ethylhexyl-2-cyano-3,3-diphenylacrylate

and substances, such as 2-phenylbenzimidazole-5-sulfonic acid, and its potassium, sodium and triethanolamine salts, 3,3'-(1 ,4- phenylenedimethylene)-bis(7,7-dimethyl-2-oxobicyclo[2.2.1]hept-1- ylmethanesulfonic acid and its salts, 2,4,6-trianilino-(p-carbo-2'- ethylhexyl-1'-oxy)-1 ,3,5-triazine and 2-(4-Diethylamino-2-hydroxy- benzoyl)-benzoic acid hexyl ester.

12. A formulation according to claim 10 comprising a UV filter selected from the group of

2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-(1 ,3,3,3-tetramethyl- 1 -(trimethylsilyloxy)-disiloxanyl)propyl)phenol, bis(2-ethylhexyl) 4,4'- [(6-[4-((1 , 1 -dimethyl-ethyl)— aminocarbonyl)phenylamino]-1 , 3,5- triazine-2,4-diyl)-diimino]-bis-benzoate, (trimethylsilyl)- [trimethylsilyl)oxy]-poly-[oxy-(dimethyl [and about 6% methyl[2-[p-[2,2- bis-(ethoxycarbonyl]vinyl]phenoxy]-1-methylenethyl] and about 1.5% methyl[3-[p-[2,2-bis(ethoxycar-bonyl)-vinyl)phenoxy)propenyl) and 0.1 to 0.4% (methyl-hydrogen]silylene]]_F 2,2'-methylenebis(6-(2H- benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol), 2,2'-(1 ,4- phenylene)bis(1 H-benzimidazol-4,6-disulfonic acid, monosodium salt) and 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxyl]phenyl}-6-(4- methoxyphenyl)-1 ,3,5-triazine.

13. A formulation according to one or more of claims 1 to 12 which comprises at least one inorganic metal oxide sunscreen agent.

14. A formulation according to claim 13 in which the inorganic metal oxide is from the group of titanium dioxides, zinc oxides, iron oxides and cerium oxides.

15. A formulation according to one or more of claims 1 to 14 comprising one or more antioxidants.

16. A formulation according to one or more of claims 1 to 15 comprising vitamins.

17. A formulation according to one or more of claims 1 to 16 wherein the formulation is a cosmetic composition with a cosmetically acceptable carrier.

18. A formulation according to claim 17 wherein the formulation comprises one or more cosmetic adjuvants.

19. A formulation according to one or more of claims 1 to 18 wherein the formulation is a sunscreen formulation.

20. A formulation according to one or more of claims 1 to 19 comprising preservatives, waterproofing agents, fragrances, anti-foam agents, plant extracts, opacifiers, skin conditioning agents or colorants.

21. A formulation according to one or more of claims 1 to 20 wherein the formulation is a personal care formulation.

22. Use of a formulation according to one or more of claims 1 to 21 for the cosmetic prophylaxis of damages of the skin caused by sunray.

23. Use according to claim 22 for the prophylaxis of sunburn and sun- caused erythrema.

24. Use of a formulation according to one or more of claims 1 to 21 to protect the hair against photochemical damage.

25. A formulation according to one or more of claims 1 to 21 wherein the formulation is a pharmaceutical formulation.

26. A formulation according to claim 25 for the prophylaxis of damages of the skin caused by sunray.