Title of Invention

A COSMETIC COMPOSITION FOR PREVENTING TANNING AND FOR LIGHTENING SKIN AND HAIR

Abstract This invention relates to a cosmetic composition to prevent tanning skinned hair lightening containing micronized UV filters. The micronized UV filters used according to the invention cover a broad UV spectrum and therefore have excellent sunscreen properties.
Full Text Use of mixtures of micropigments for preventing tanning and for lightening skin and hair
The present invention relates to the use of mixtures of micronized organic UV filters for preventing tanning and for lightening human skin and hair and to their use in cosmetic and pharmaceutical formulations.
It is known that certain organic UV filters, for example sparingly soluble benzotriazole or triazine compounds, have excellent UV filter properties if they are in micronized form.
Particularly in Asiatic countries, there is great interest in light protection filters or mixtures of light protection filters which preserve the colour of the skin following solar irradiation and, moreover, are able to impart a lighter appearance to the skin.
The object of the present invention is therefore to find micronized organic UV filters which prevent tanning of the skin and at the same time are able to lighten the skin.
Surprisingly, we have now found that micronized organic UV filters or mixtures of at least two micronized UV filters can achieve this object.
The present invention therefore provides for the use of mixtures of micronized organic UV filters for preventing tanning and for lightening of human skin.
Suitable UV filters which can be used according to the invention are organic, sometimes sparingly soluble, compounds, for example triazine derivatives, in particular hydroxyphenyltriazine compounds or benzotriazole derivatives, amides containing a vinyl group, cinnamic acid derivatives, sulfonated benzimidazoles, Fischer base derivatives, diphenylmalonitriles, oxalylamides, camphor derivatives, diphenylacrylates, paraaminobenzoic acid (PABA) and derivatives thereof, salicylates, benzophenones and also other classes of substance known as UV filters.
Preferred triazine derivatives which can be used according to the invention correspond to the formula







R20 is hydrogen; M; Ci-Csalkyl; -NH-Ci-CsalkyI; preferably -NH-tert-alkyI; or a radical of
the formula -(CHgJm-O-Tg; Ti and T2, indepenently of one another, are hydrogen; or Ci-CsalkyI; and m is 1 to 4.
Of very particular interest are compounds of the formula (2a) and (2b) in which
Ri7 and Ris, independently of one another, are CrCisalkyl; or -CH2-CH(-OH)-CH2-0-Ti;
R,9 is Ct-CioalkyI;
and compounds of the formula (2c) and (2d) in which
Ri7 and Ris, independently of one another, are Ci-C,8alkyl or -CH2-CH(-OH)-CH2-0-Ti; and
Ti is hydrogen; or CrCsalkyl.
Of the utmost interest are triazine compounds of the formula (2a) - (2d) in which Ri7 and Rie have the same meanings.
Further interesting triazine compounds which can be used according to the invention correspond to the formula

in which

R22, R23 and R24, independently of one another, are hydrogen, -OH; Ci-Caoalkyl, C2-C3oalkenyl,
6










Rao is hydrogen; alkali metal; an ammonium group -N(R33)4,
R33 is hydrogen; Ci-Csallcyi; or a polyoxyethylene radical which has 1 to 10 ethylene
oxide units and the terminal OH group can be etherified with a Ci-Csalcohol;
R31 is hydrogen; -OH; or Ci-Cealkoxy;
R32 is hydrogen or -COOR30; and
n isOorl.
If R30 is alkali metal, this is in particular potassium or very particularly sodium. (R33)4 is in particular a mono-, di- or tri-Ci-C4alkylammonium salt, a mono-, di- or tri-C2-C4alkanol-ammonium salt or a C1-C3alkyl ester thereof.
If R33 is a C1-C5alkyI group, this is in particular a C1-C2alkyl group, in particular a methyl group, and if R33 is a polyoxyethylene radical, then the latter contains in particular 2 to 6 ethylene oxide units.
Preferred benzotriazole compounds which can be used according to the invention correspond to the formula



R33 is C1-C5alkyl, preferably methyl or ethyl, or unsubstituted phenyl or phenyl substituted by one, two or three of the radicals OH, Ci-CsalkyI, Ci-Csalkoxy or CO-OR33;
R34, R35> R36 and R37, independently of one another, are C1-C5alkyI, preferably methyl or ethyl; or hydrogen;
Y is -NH or -0-; and
m is as defined above.
Preferred compounds of the formula (29) are 4-methyl-3-penten-2-one, ethyl 3-methyl-amino-2-butenoate, 3-methylamino-1-phenyl-2-buten-1-one and 3-methylamino-1-phenyl-2-buten-1-one.
Preferred cinnamides which can be used according to the invention correspond to the formula
(30) R38O— R38 is hydrogen or C1-C5alkoxy, preferably methoxy or ethoxy;
R39 is hydrogen or C1-C5alkyi, preferably methyl or ethyl; and
R40 is -(CONH)ni-phenyl, in which m is as defined above, and the phenyl group is
unsubstituted or substituted by one, two or three of the radicals OH, C1-C5alkyl,
C1-C3alkoxy or CO-OR30.
R40 is preferably phenyl, 4-methoxyphenyi or the phenylaminocarbonyl group.
Further preferred cinnamic acid derivatives are 2-ethylhexyl 4-methoxycinnamate or isoamylate or inter alia the cinnamic acid derivatives disclosed in US-A-5 601 811 and WO 97/00851.
Preferred sulfonated benzimidazoles which can be used according to the invention correspond to the formula







salicylic acid derivatives, in particular 2-ethylhexyl salicylates; homosalates; and isopropyl salicylates;
- benzophenone derivatives, in particular benzophenone-2, -3, and -4;
- dibenzoylmethane derivatives, in particular 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-propane-1,3-dione or butylmethoxydibenzoylmethane;
- diphenylacrylates, in particular 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, ethyl 2-cyano-3,3"-diphenylacrylate and 3-(benzofuranyl) 2-cyanoacrylate;
- 3-imidazol-4-ylacrylic acid and 3-imidazol-4-yl acrylate;
- benzofuran derivatives, in particular the p-aminophenylbenzofuran derivatives published in EP-A-582,189, US-A-5,338,539 and US-A-5-518,713;
- camphor derivatives, in particular 3-(4"-methyl)benzylidenebornan-2-one, 3-benzyl-idenebornan-2-one, N-[2(and 4)-2-oxyborn-3-ylidenemethyl)benzyl]acrylamide polymer, 3-(4"-trimethylammonium)benzylidenebornan-2-one methylsulfate, 3,3"-(1,4-phenylenedimethine)-bis(7,7-dimethyl-2-oxobicyclo[2.2.1]heptane-1-methanesulfonic acid) and salts thereof, 3-(4"-sulfo)benzylidenebornan-2-one and salts thereof; and
- menthyl o-aminobenzoate.
The UV filters listed above can be used according to the invention as individual compounds or also, preferably, as mixtures.
Preference is given to using the following mixtures of organic UV filters:
mixtures of methylenebisbenzotriazolyltetramethylbutylphenol and octyltriazone;
mixtures of octyltriazone and methylenebisbenzotriazolyltetramethylbutylphenol;
mixtures of 2-[(2,4-methoxy)phenyl]-4,6-bis[(2-hydroxy-4-methoxy)phenyl]-
(1,3,5)triazine and methyienebisbenzotriazolyltetramethylbutylphenol;
mixtures of methylenebisbenzotriazolyltetramethylbutylphenol and
dioctylbutamidotriazone;
mixtures of methylenebisbenzotriazolyltetramethylbutylphenol and octyl-2,2"-
methylenebis[6-(2H-benzotriazol-2-yl)-4-methylphenol,
mixtures of octyltriazone and trisresorcinyltriazine;
^7




mixtures of methylenebisbenzotriazolyltetramethylbutylphenol, dioctylbutamidotriazone and the compound of the formula (37).
In the radicals defined above, Ci-Ci8alkyl are straight-chain or branched all C1C18Alkoxy radicals are straight-chain or branched alkyl radicals, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy or octadecyloxy.
C2-C18Aikenyl is, for example, aliyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.
The mixtures of micronized organic UV filters which can be used according to the invention can be prepared in different ways.
Firstly, at least two of the abovementioned organic UV filters can be mixed as individual substances in the preparation process of the microparticles (micronization).
Another preparation option involves thoroughly mixing the already micronized individual substances of the UV filters together.
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A third preparation option involves melting together at least two of the abovementioned UV filters. Cooling the melt produces a homogeneous composite, which is micronized in the usual manner.
The homogeneous composites of at least two organic UV filters are also provided by the invention.
The invention further provides composites obtainable by fusing one or more inorganic micropigments into one or more organic UV filters.
Examples of micropigments are, for example, TiO2, ZnO, iron oxides or other inorganic oxides, mica or other suitable inorganic minerals, and also Ti, alkaline earth metal or zinc salts of organic acids.
In so doing, the undesired photocatalytic properties of some of these inorganic micropigments (TiO2, ZnO) can be simultaneously suppressed, and their positive properties can also be fully utilized.
The abovementioned inorganic UV filters are advantageously fused into methylenebisbenzotriazolyltetramethylbutylphenol. The resulting composite is then micronized in the usual manner.
The invention further provides composites obtainable by melting at least two electrically neutral organic UV filters with cationically or anionically charged compounds.
For this, cationically or anionically charged compounds are melted with the corresponding organic, electrically neutral UV filters and then cooled. This process permits, in the subsequent micronization step, the preparation of organic UV filter pigments having a permanent finishing of a positive or negative charge. Such a finishing effectively prevents aggregation of the micronized particles in the sunscreen preparations which can occur in cases where the particle diameter is
Cationically or anionically charged compounds which can be used are UV filters and also other compounds which have one or more cationic or anionic groups, for example
- N,N,N-trimethyl-4-(2-oxoborn-3-ylidenemethyl)aniline methylsulfate;
- camphorbenzalkonium methosulfate;
- fatty amines;
- betaines, for example cocamidopropylbetaine;
- quats, for example ricinoleamidopropyltrimonium methosulfate, Quarternium 18 , or cetyltrimethylammonlum bromide;
- behenic acid and other organic acids, for example isostearic acid, citricmonoglyceride or sodium methyl cocoyi taurate;
- phospholipids, for example phosphatidylcholine, phosphatidylserine or alkylamine oxide;
- ceramides and pseudoceramides and phytosterols.
The last-named compounds impart an oleophobic finishing to the micronized UV filters.
The proportion of cationic or anionic compounds in the composite is between 0.001 and 5% by weight, preferably 0.01 to 3% by weight, based on the weight of the UV filter(s).
The invention further provides composites obtainable by melting at least one sparingly soluble or insoluble organic UV filter with antioxidants.
For this, the sparingly soluble or insoluble organic UV filter(s) is/are melted together with antioxidants, cooled and then micronized in the usual manner.
Suitable antioxidants which can be used according to the invention are all organic substances having scavenger properties which can be melted together with organic UV filters. This gives novel types of micropigments which simultaneously prevent tanning of the skin and offer antioxidative action on its surface. This property is desired for cosmetic sun protection since, under the influence of UV and light, harmful free radicals can be formed both in formulations and on the skin. These can, for example, lead to so-called Mallorca acne or to premature skin ageing. By finishing the micronized UV filters with antioxidants, not only is protection against UV damage and prevention of tanning achieved, but also protection against photochemical degradation of constituents in the sunscreen formulation.
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The proportion of antioxidants in the composite is generally between 0.001 and 30% by weight, preferably 0.01 to 3% by weight, based on the weight of the UV filter(s).
A content of antioxidants is particularly advantageous in micropigments which, in addition to organic UV filters, comprise the abovementioned photocatalytically active inorganic micropigments, for example titanium dioxide, zinc oxide (including coated) or other suitable inorganic oxides, for example iron oxide.
Examples of antioxidants which may be listed are the following compounds: - tocopherols, for example a-tocopherol (CAS 59-02-9), tocopheryl acetate, vitamin E succinate.



-vanillin;
- ubiquinone;
- ferulic acid and derivatives;
- rutic acid and derivatives;

- urocanic acid and derivatives; and
- propolis.
Preference is given to using the following mixtures of antioxidants and organic UV filters: mixtures of methylenebisbenzotriazolyltetramethylbutylphenol, octyltriazone, titanium dioxide and tocopherol,
mixtures of 2,2"-methylenebis[6-(2H-benzotriazol-2-yl)-4-methylphenol, octyltriazone, trisresorcinyltriazine and vitamin E


The invention further provides composites obtainable by fusing meltable cosmetic, vegetable and pharmaceutical active ingredients into organic UV filters.
In general, micronized UV filters can be used as carriers of highly active substances, in particular cosmetic and/or pharmaceutical active substances. The advantage of such composites lies in the fact that it is possible for them to release the active substance(s) from the solid (slow release). A slow release also guarantees the uniform effectiveness of highly active active ingredients, for example antiinflammatories, care active ingredients or trace elements, for example Zn2+ or Mg2+ over the entire useful life of the UV pigments.
Examples of active Ingredients which can be used and which may be mentioned are:
- active ingredients for antimicrobial finishing and simultaneous antiinflammatory action,
for example triclosan or diclosan;
- antiinflammatory active ingredients, for example farnesol, panthenol or avocado oil;
- active ingredients having a deodorant or antiperspirant action, for example Zn
ricinoleates and alkyl citrates,
- undecylenic acid and derivatives thereof (e.g. diethanolamides)
- zinc undecylate;
- pyrithiones, for example sodium pyrithione;

- fused-in fragrances or fragrance mixtures, for example menthol, geraniol etc., which
impart a permanent odour which is uniform in intensity to these micropigments and the
formulations which comprise them.
To prepare the micronized organic UV filters or the micropigment mixtures, it is possible to use all known processes which are suitable for the preparation of microparticles, for example:
- wet grinding with a hard grinding medium, for example zirconium silicate and a protective surfactant or a protective polymer in water or a suitable organic solvent;
- spray drying from a suitable solvent, for example aqueous or organic suspensions containing solvent, or true solutions in water, ethanol, dichloroethane, toluene, N-methylpyrrolidone etc.;
- by expansion of supercritical liquids (e.g. CO2) in accordance with the RESS process (Rapid Expansion of Supercritical Solutions) in which the UV filter(s) is/are dissolved or expansion of liquid carbon dioxide together with a solution of one or more UV filters in a suitable organic solvent;
- by reprecipitation from suitable solvents, including supercritical liquids (GASR process = Gas Anti-Solvent Recrystallization / PCA process = Precipitation with Compressed Antisolvents).
Grinding apparatuses which can be used for the preparation of the micronized organic UV absorbers according to the invention are, for example, a jet, ball, vibratory or hammer mill, preferably a high-speed stirred mill. Grinding preferably takes place using a grinding auxiliary, for example an alkylated vinylpyrrolidone polymer, a vinylpyrrolidone/vinyl acetate copolymer, an acyl glutamate, an alkyl polyglucoside, ceteareth-25 or, in particular, a phospholipid.
The resulting micropigments or mixtures of micropigments usually have an average particle size of from 0.02 to 2 nm, preferably 0.05 to 1.5 nm, and very particularly from 0.1 to 1.0 nm.

Because of their lipophilicity, they can, alone or together with other soluble organic UV absorbers, be readily incorporated into oil- and fat-containing cosmetic formulations, for example oils, O/W or W/0 emulsions, wax pencils or gels, by known methods.
Surprisingly, formulations are obtained which have equal or improved protective action using less or even no soluble UV absorbers.
The invention further provides a cosmetic formulation comprising a mixture of micropigments, if desired one or more antioxidants and/or inorganic pigments and/or a cationic or anionic compound, and cosmetically compatible carriers or auxiliaries.
Cosmetic formulations according to the invention include various cosmetic compositions. In particular, the following compositions are, for example, suitable:
skincare compositions, for example skin washes and cleansers in the form of bar or
liquid soaps, syndets or washing pastes,
bath preparations, for example liquid (foam baths, milks, shower preparations) or solid
bath preparations, for example bath tablets or bath salts;
skincare compositions, for example skin emulsions, multiple emulsions or skin oils;
decorative bodycare compositions, for example face make-up in the form of day
creams or powder creams, face powder (loose or pressed), blusher or cream make-up,
eyecare compositions, for example eyeshadow preparations, mascara, eyeliner, eye
creams or eye-fix creams; lipcare compositions, for example lipstick, lip gloss, lip liner
pencil, nailcare compositions, such as nail varnish, nail varnish remover, nail hardeners
or cuticle removers;
personal hygiene care compositions, for example personal hygiene washing lotions or
personal hygiene sprays;
footcare compositions, for example foot baths, foot powders, foot creams or foot
balsams, special deodorants and antiperspirants or products for removing calluses;
light protection compositions, such as sun milks, lotions, creams and oils, sun blocks or
tropicals, pretanning preparations or aftersun preparations;
skin tanning compositions, for example self-tanning creams;
depigmentation products, for example preparations for skin bleaching or compositions
for skin lightening;
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insect-repelling compositions ("repellents"), for example insect oils, lotions, sprays or sticks;
deodorants, such as deodorant sprays, pump sprays and deodorant gels, sticks or roller balls;
antiperspirants, for example antiperspirant sticks, creams or roller balls; compositions for cleansing and caring for blemished skin, for example syndets (solid or liquid), peeling or exfoliation preparations or peeling masks; depilatories in chemical form, for example depilatory powders, liquid depilatories, cream or paste depilatories, depilatories in gel form or aerosol foams; shaving compositions, for example shaving soap, foaming shaving creams, nonfoaming shaving creams, foams, gels, preshave preparations for dry shaving, aftershaves or aftershave lotions;
fragrances, for example fragrance water (eau de Cologne, eau de toilette, eau de parfum, parfum de toilette, parfum), perfume oils or perfume creams; compositions for dental, denture and mouth care, for example toothpastes, gel toothpastes, tooth powders, mouthwash concentrates, antiplaque mouthrinses, denture cleaners or denture adhesives;
cosmetic compositions for treating hair, for example hair cleansers in the form of shampoos, hair conditioners, haircare compositions, for example pretreatment compositions, hair tonic, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, compositions for shaping hair, for example waving agents for the preparation of permanent waves (hotwave, mildwave, coldwave), hair-smoothing preparations, liquid hair-setting compositions, hair mousses, hair sprays, bleaching agents, for example hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semipermanent or permanent hair colorants, preparations containing self-oxidizing dyes, or natural hair colorants, such as henna or camomile.
These listed end formulations can be in the form of various application forms, for example
- in the form of liquid preparations as a W/0, 0/W, 0/W/O, W/O/W, PIT and all other types of microemulsions,
- in the form of a gel,
- in the form of an oil, a cream, milk or lotion,
- in the form of a powder, a lacquer, a tablet or make-up,
27







methoxycinnamate (2-isoamyl 4-ethoxycinnamate), 2,5-cliisopropyl methylcinnamate or a cinnamic acid amido derivative.
Examples of compounds of camphor derivatives: 4-methylbenzyiidenecamphor[3-(4"-methyl)benzylidenebornan-2-one], 3-benzylidenecamphor (3-benzylidenebornan-2-one), polyacrylamidomethylbenzylidenecamphor {N-[2(and 4)-2-oxyborn-3-ylidene-methyl)benzyl]acrylamide polymer}, trimoniumbenzylidenecamphor sulfate [3-(4"-trimethylammonium)benzylidenebornan-2-one meth ylsulfate], terephthalylidene-dicamphorsulfonic acid {3,3"-(1,4-phenylenedimethine)bis(7,7-dimethyl-2-oxobicyclo[2.2.1]heptane-1-methanesulfonic acid} or salts thereof, or benzylidene-camphorsulfonic acid [3-(4"-sulpho)benzylidenebornan-2-one] or salts thereof.
Examples of compounds of trianilino-s-triazine derivatives:
octyitriazine[2,4,6-trianilino(p-carbo-2"-ethyl-1"-oxy)-1,3,5-triazine, and the trianilino-s-triazine derivatives described in US-A-5,332,568, US-A-5,252,323, WO 93/17002 and WO 97/03642 and EP-A-0,517,104.
Examples of compounds of benzotriazoles: 2-(2-hydroxy-5-methylphenyl)benzotriazole.
The examples below serve to illustrate the invention v/ithout limiting it thereto. The cosmetic active substances are primarily given with their INCI name (INCI = International Nomenclature of Cosmetic ingredients).

Example 1:
50 parts of Methylene Bis-benzotriazolyl Tetramethylbutylphenol and 50 parts of Octyl Triazone are ground together using a grinding medium of zirconium silicate sand, a protective surfactant (Alkyl Polyglucoside) and water in a bead mill to give a mixed micropigment having a d50 of 190 nm. After the grinding medium has been separated off, the suspension of the mixed micropigment can be used to prepare sunscreen formulations.
Example 2:
32 parts of Octyl Triazone, 1 part of cetyltrimethylammonium bromide and 66 parts of Methylene Bis-benzotriazolyl Tetramethylbutylphenol are homogeneously melted together. The mixture is rapidly cooled to room temperature, and the solidified melt is comminuted mechanically (beater mill). This resulting powder is slurried in water, Decyl Glycoside is added, and the mixture is micronized together with a grinding auxiliary ("heavy sand") to a particle size diameter d50 of 200 nm. After the grinding auxiliary has been removed, an aqueous suspension of the micronized UV absorber composite is obtained. This suspension is rendered slightly acidic with citric acid and can be used for the preparation of cosmetic and pharmaceutical formulations.
Example 3:
25 parts of 2-[(2,4-methoxy)phenyl]-4,6-bis[(2-hydroxy-4-methoxy)phenyi]-(1,3,5)-triazine, 74 parts of Methylene Bis-benzotriazolyl Tetramethylbutylphenol and 1 part of Tetrakis[methylene-3(3",5"-di-t-butyl-4"-hydroxyphenyl)propionate]methane are homogeneously fused together. The mixture is rapidly cooled to room temperature, and the solidified melt is comminuted mechanically (beater mill). This resulting powder is slurried in water, firstly Decyl Glycoside is added, then, after continued grinding, Ceteareth-25, and the mixture is micronized together with a grinding auxiliary ("heavy sand") to a particle size diameter dso of 190 nm. After the grinding auxiliary has been separated off, an aqueous suspension of the micronized UV absorber composite is obtained, which can be used for the preparation of cosmetic and pharmaceutical formulations.

25 parts of Dioctyl Butamido Triazone are dissolved in 75 parts of molten Methylene Bi; benzotriazolyl Tetramethylbutylphenol. The mixture is cooled rapidly, comminuted mechanically to give a fine powder and then ground with a grinding medium of zirconiur silicate sand, a protective surfactant (phospholipid) and water to give a micropigment having a dso of 300 nm. The micropigment suspension separated off from the grinding medium is used for the preparation of sunscreen formulations.
Example 5:
24 parts of Octyl Triazone, 5 parts of Titanium Dioxide and one part of Tocopherol are mixed into 70 parts of molten fvlethylene Bis-benzotriazolyl Tetramethylbutylphenol. The mixture is cooled rapidly, comminuted mechanically to give a fine powder and then grou with a grinding medium of zirconium silicate sand, a protective surfactant (Alkyl Polyglucoside) and water to give a micropigment. The micropigment suspension separai off from the grinding medium is used for the preparation of sunscreen formulations.
In Examples 6 to 11 below, suspensions of microcomposites having the following compositions are prepared analogously to Examples 1 and 2:
Example 6:
60 parts of 2,2"-methylenebis[6-(2H-benzotriazol-2-yl)-4-methylphenol,
20 parts of Octyl Triazone, 19 parts of Tris Resorcinyl Triazine and 1 part of vitamin E,
adjusted to pH 6.5 with citric acid.



































Example 43: Q/W Emulsion
o/ /o
Glycerin Stearate/Polyethylene glycol(MWIOO) stearate 3.0
Cetyl/Stearyl Alcohol 20EO (Eumulgin B 2) 1.0
Cetyl/Stearyl Alcohol (Lanette O) 2.0
Caprylic/Capric triglyceride (l\/1yritol 318) 4.0
Dicaprylyl ether 6.0
Mineral oil and Quaternium-18 Hectorite 3.0
Glycerin stearate, Cetyl/stearyl Alcohol, Cetyl palmitate, coco 2.0
glycerides (Cutina CBS)
4-Methylbenzylidene Camphor 1.0
Octyl Triazone 2.0
Deionized Water ad 100.0
Glycerin, 85% 3.0
Preservative as required
Magnesium aluminium silicate (Vegum Ultra) 0,3
NaOH as required
Micropigment from Example 2 (50% Suspension) 10.0
Example 44:
Into the suncare product "Sensitive Skin" (children) from Lancaster (Monaco), characterized by the following ingredients: Ti02, ZnO and Aqua, Didecene, Glycerine, Cyclomethicone, Shea Butter, Sweet Almond Oil, Polyglycerin-4, Urea, Aluminium Starch, Octenyl succinate, Alumina, Parfum, MgS04, Silica, NaCI, Tocopheryl acetate, Caffeine, PVP/Eicosene Copolymer, Shellac, Simethicone, Phenoxyethanol, NaLactate, Methylsilanol, Menthyl Lactate, Allantoin, Bisabolol, Glycine, Panthenol, Propylene Glycol, Stoneroot Extract, Lecithin, Algae Extract, Methyldibromo Glutaronitrile, PVP, Citric Acid, Copper Gluconate, Ascorbic Acid, Ascorbyl Palmitate, PEG-8, Tocopherol, Acerola, Aloe Barbadensis Gel, Melanin, Alcohol denat. Dimethicone, Guar Hydroxypropyltrimonium Chloride, Dextrin, Glycoproteins Iron oxides, were subsequently mixed 4% of micronized 2,2"-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (d50 = 200 nm). The original SPF of 15 increased as a result to 25 and, following storage for a few days, increased again to an SPF of 31.
Example 45:
Into the sun milk "Active Sun Care Sensitive Skin" from Marbert Cosmetics, Dusseldorf, characterized by the following ingredients: TiO2, Benzophenone-3, Isoamyl p-Methoxycinnamate, and Aqua, C12-15 Alkyl benzoate, Caprylic/Capric Triglyceride, Cyclomethicone, Glycerine, Glyceryl Stearate, Cetearyl Alcohol, Tocopheryl acetate. Stearic Acid, Palmitic Acid, Parfum, NaCocoyI Lactylate, Xanthan Gum, Bisabolol, DMDM

Hydantoin, PVM/MA Decadiene Crosspolymer, Polyhydroxystearic acid, Alumina, NaOH, Glucose, lodopropynyl Butylcarbamate, Carrageenan, Silica and Glucuronic acid, were subsequently mixed 4% of micronized 2,2"-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (d50 = 200 nm). The original SPF of 6 increased as a result to 13 and, after storage for a few days, increased again to an SPF of 16.
Example 46:
Into the sunscreen emulsion "Delial Sonnenmilch 10" from Sara Lee, Dusseldorf, characterized by the following ingredients: Octyl Methoxycinnamate, NaPhenyl-benzimidazole Sulfonate, Butyl Methoxy Dibenzoylmethane and Aqua, Paraffinum liquidum, Alcohol denat., Isopropyl Palmitate, Glycerine, Cetearyl Alcohol, Glyceryl Stearate SE, Tocopheryl acetate, Phytantriol, Ascorbyl Palmitate, PEG-40 Castor Oil, NaCetearyl Sulfate, Dimethicone, Na-Carbomer, Na2-EDTA and Parfum, were subsequently mixed 4% of micronized 2,2"-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (d50 = 200 nm). The original SPF of 10 increased as a result to 18 and, after storage for a few days. Increased again to an SPF of 28.
Example 47:
Into the sun protection formulation "Ambre Solaire" SPF 12 from Laboratoires Gamier, Paris/Karlsruhe, characterized by the following ingredients: T102, Octocrylene, Butyl Methoxy Dibenzoylmethane, Terephthalylidene dicamphor sulfonic acid and Aqua, Cyclopentasiloxane, Glycerine, Propylene glycol, Isohexadecane, Stearic acid, Octyl palmitate, Stearyl heptanoate, PVP/Eicosene Copolymer, K-Cetyl Phosphate, Buxus chinensis, Tocopheryl acetate, Hydroxypropyl Methylcellulose, Phenoxyethanol, Stearyl caprylate, PEG-100 Stearate, Ethylparaben, Triethanolamine, Dimethiconol, Dimethicone, Propylparaben, Acrylates/Cio-3o-Alkyl acrylate crosspolymer, Na2-EDTA, Butyrospermum parkii, Cetyl Alcohol, Methylparaben, Butylparaben, BHT, Aluminium hydroxide. Glyceryl Stearate were subsequently mixed 4% of micronized 2,2"-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (d50 = 200 nm). The original SPF of 12 increased as a result to 18 and, after storage for a few days, increased again to an SPF of 28.
Example 48:
Into the sunscreen formulation "Ambre Solaire" SPF 6 from Laboratoires Gamier,
Paris/Karlsruhe, characterized by the following ingredients: TiOs, Octocrylene, Butyl

Methoxy Dibenzoylmethane, Terephthalylidene dicamphor sulfonic acid and Aqua, Cyclomethicone, Glycerine, Propylene glycol, Isohexadecane, Stearic acid, Octyl palmitate, Stearyl heptanoate, PVP/Eicosene Copolymer, K-Cetyl Phosphate, Buxus chinensis, Tocopheryl acetate, Hydroxypropyl Methylcellulose, Phenoxyethanol, Stearyl caprylate, PEG-100 Stearate, Ethylparaben, Triethanolamine, Dimethiconol, Dimethicone, Propylparaben, Acrylates/C10-30-Alkyl acrylate crosspolymer, Na2-EDTA, Butyrospermum parkii, Cetyl alcohol, Methylparaben, Butylparaben, BHT, Aluminium hydroxide. Glyceryl stearate and Parfum, were subsequently mixed 4% of micronized 2,2"-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (d50 = 200 nm). The original SPF of 6 increased as a result to 16 and, after storage for a few days, increased again to an SPF of 21.
Example 49: Prevention of the increase in skin tanning by a micronized UV absorber Methylene Bis-benzotriazolvl Tetramethylbutylphenol
Method:
20 yolunteers of direct Asian origin (father and mother) who have not been directly exposed
to the sun for the past 3 months, to whom an explanation of the study has been given, from
whom a declaration of consent has been obtained and who have satisfied the inclusion
conditions, are treated twice daily on the test sites on the upper thigh for three weeks with a
cream containing 2,2"-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-
phenol or with a placebo cream.
The volunteers are irradiated on the test sites on the upper thigh 3x weekly with 0.2 to 05
MED UVAB.
The first application of the preparations takes place after the first irradiation. Evaluation and
irradiation are carried out after each application of the test products. Comparable untreated
irradiated, or untreated nonirradiated areas serve as reference.
The colour values of the test fields are documented in each case using a Minolta CM-5G8i
camera as L*a*b* values in accordance with DIN 5033, ISO 7724/1, JIS Z8722.
The colour and lightness changes are determined for each subject and ascertained as the
difference between the respective skin colour of the untreated, nonirradiated reference area
and the test areas. These values are averaged over all subjects and given as L*, a* and b*
values.

Test preparations:
(A): Composition comprising 6% of 2,2"-Methylenebis(6-(2H-benzotriazoi-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol), Water, Octyl stearate, Coco glycerides, Propylene glycol, Methoxy-PEG-22/Dodecyl glycol copolymer, PEG-22/Dodecyl glycol copolymer, Hydroxyoctacosanyl hydroxystearate, Mineral oil, Phenoxyethanol & Parabens, Magnesium sulfate heptahydrate, Dimethlcone, Allantoin.
(B): Composition comprising 3% of 2,2"-Methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol), Water, Octyl stearate. Coco glycerides, Propylene glycol, Methoxy-PEG-22/Dodecyl glycol copolymer, PEG-22/Dodecyl glycol copolymer, Hydroxyoctacosanyl hydroxystearate. Mineral oil, Phenoxyethanol & Parabens, Magnesium sulfate heptahydrate, Dimethicone, Allantoin.
(C): Placebo comprising Water, Octyl stearate, Coco glycerides. Propylene glycol, Methoxy-PEG-22/Dodecyl glycol copolymer, PEG-22/Dodecyl glycol copolymer, Hydroxyoctacosanyl hydroxystearate, Mineral oil, Phenoxyethanol & Parabens, Magnesium sulfate heptahydrate, Dimethicone, Allantoin.
L*a*b* values compared with nonirradiated skin following repeated UVAB irradiation (3 X weekly) and in the case of the application of compositions (A) and (B).
Preparation Lightness L* Red component a* Yellow component b"
Number of irradiations 3 6 9369369
Placebo -5.32 -12.01 -14.01 4.90 2.33 0.52 3.09 6.82 7.93
(B) -1.05 -5.23 -7.13 0.45 0.77 -0.03 1.11 2.63 3.49
(A) 2.18 8.26 11.40 0.24 0.45 0.39 -0.38 -0.69 -0.21
Irradiated untreated -5.19 -12.38 -14.55 5.13 1.77 -0.19 2.64 6.39 7.44
Discussion of the results:
Lightness
While the placebo-treated and the untreated irradiated areas decrease in lightness to
roughly the same extent, i.e. become darker, this effect is considerably less in the case of

the application of the composition (B) over the time. In the case of the application of composition (A), lightening of the skin Is found.
Reddening
The red component of the irradiated skin is most intense after 3 irradiations and drops back to the normal value by the end of the irradiations. The Increase in the red component corresponds to the development of a UV-induced erythema, which arises only to a low degree in the case of the application of compositions (A) or (B).
Yellow component
The yellow component increases both In the case of the application of placebo and in the untreated irradiated control area. The increase is much less In the case of the application of composition (B) and is prevented in the case of the application of composition (A).


WE CLAIM:
1. A cosmetic formulation for preventing tanning and for lightening human skin and hair comprising micronized organic UV filters having an average particle size of from 0.002 to 2 μm selected from triazine or benzotriazole derivatives amides containing a vinyl group, cinnamic acid derivatives, sulfonated benzimidazoles, Fischer base derivatives, diphenylmalonitriles, oxalylamides, camphor derivatives, dibenzylacrylates, paraaminobenzoic acid (PABA) and derivatives thereof, salicylates and benzophenones, and, if desired one or more antioxidants and/or inorganic pigments and/or a cationic or anionic compound, and cosmetically compatible carriers or auxiliaries for preventing tanning and for lightening human skin and hair.
2. The composition according to claim 1, wherein the organic UV filters are chosen from triazine derivatives of the formula

in which
Ri, R2 and R3, independently of one another, are hydrogen; OH; C1-C18alkoxy;
-NH2; -NH-R4; -N(R4)2; -OR4,
R4 is C1-C5alkyl; phenyl; phenoxy; anilino; pyrrolo, wherein phenyl, phenoxy,
anilino or pyrrolo may be unsubstituted or substituted by one, two or three OH
groups, carboxyl, -CO-NH2, C1-C5alkyl or C1C5alkoxy; a methylidenecamphor
group; a group of the formula -(CH=CH)mC(=0)-0R4; a group of the formula
-56-
















in which
R50, R51, R52, R53, R54, independently of one another, are hydrogen, Ci-Cgalkyl or Cj-Ciocycloalkyl;
R55 is hydrogen; Ci-Cgalkyl; C5-C10cycloalkyI; hydroxyl; C1C8-alkoxy; COOR56; or CONR57R58;
R56, R57 and R58, independently of one another, are hydrogen or C1-C6alkyl; X and Y, independently of one another, are hydrogen, -CN; CO2R59; CONR59R60; or COR59; where the radicals X and Y may additionally be a Cp Cgalkyl radical, or a heteroaryl radical having 5 to 6 ring atoms, where, in addition, X and Y or
R50 together with one of the radicals X and Y can represent the radical to complete a 5- to 7-membered ring which may contain up to 3 heteroatoms, where the ring atoms may be substituted by exocyclically double-bonded oxygen and/or C1-C8alkyl and/or C5-C10cycloalkyl radicals, and/or may contain C=C double bonds;
Z is hydrogen; ammonium; alkali metal ion; or the cation of an organic nitrogen base used to neutralize the free acid group;
R59 and R60 independently of one another, are hydrogen, C1-C8alkyl or C5-Ciocycloalkyl; and n and m, independently of one another, are 0 or 1.
-64-

A process for the preparation of composite of the organic UV filters as claimed in any one of claims 2 to 6, which comprises thoroughly mixing the UV filters in micronized form to produce a composite.
A process for the preparation of composites of the organic UV filters claimed in any one of claims 2 to 6, which comprises micronizing the organic UV filters mixing and compacting at least two individual UV filters.
A process for the preparation of mixtures of the organic UV filters claimed in any one of claims 2 to 6, which comprises melting together at least two individual substances, cooling the melt, and then subjecting the resulting composite to a micronization process.
The cosmetic formulation according to claim 1, which additionally comprises an oil soluble, nonmicronized UV filter.

Documents:

536-mas-2000 abstract-duplicate.pdf

536-mas-2000 abstract.pdf

536-mas-2000 claims-duplicate.pdf

536-mas-2000 claims.pdf

536-mas-2000 correspondence-others.pdf

536-mas-2000 correspondence-po.pdf

536-mas-2000 description (complete)-duplicate.pdf

536-mas-2000 description (complete).pdf

536-mas-2000 form-1.pdf

536-mas-2000 form-19.pdf

536-mas-2000 form-26.pdf

536-mas-2000 form-3.pdf

536-mas-2000 form-4.pdf

536-mas-2000 form-5.pdf

536-mas-2000 others.pdf

536-mas-2000 petition.pdf


Patent Number 216202
Indian Patent Application Number 536/MAS/2000
PG Journal Number 13/2008
Publication Date 31-Mar-2008
Grant Date 10-Mar-2008
Date of Filing 11-Jul-2000
Name of Patentee CIBA SPECIALTY CHEMICALS HOLDING INC
Applicant Address KLYBECKSTRASSE 141, 4051 BASEL,
Inventors:
# Inventor's Name Inventor's Address
1 DR PETER FANKHAUSER HAUPSTRASSE 65, 4107 ETTINGEN,
2 DR HELMUT LUTHER TULLINGERWEG 3A, 79639 GRENZACH-SHYLEN,
3 DR WERNER BASCHONG MAIENGASSE 27, 4056 BASEL,
PCT International Classification Number A61K 7/40
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 1281/99 1999-07-12 Switzerland