Title of Invention

A COSMETIC COMPOSITION COMPRISING BENZOTRIAZOLE DERIVATIVES FOR PHOTOSTABILIZATION

Abstract Use of benzotriazole derivatives of formula R1 is C1-C30alkyl; C1-C5alkoxy; C1-C5alkoxycarbonyl;C5-C7Cycloalkyl; C6-C10aryl; aralkyi; R3 is hydrogen; C1-C5alkyl; C1-C5alkoxy; halogen, preferably CI; or hydroxy; R4 and R5 are each independently of the other hydrogen; or 1-C5alkyl; m is 1 or 2; n is 0 or 1; if m = 1, R2 is hydrogen; unsubstituted or phenyl-substituted C1-C12alkyl; or C6-C10aryl; if m = 2, R2 is the direct bond; or -(CH2)p-; and p is 1 to 3; for enhancing the photostability of cosmetic or dermatologic compositons comprising at least one further organic UV absorber.
Full Text USE OF BENZOTRIAZOLE DERIVATIVES FOR PHOTOSTABILISATION Use of benzotriazole derivatives
The present invention relates to the use of specific benzotriazole derivatives for enhancing the photostability of sunscreen compositions.
There is a growing need for effective topical sun protection preparations in order to prevent the damaging effects of UV light on human skin, for example sunburn, photo-allergic reactions, premature ageing of the skin and skin cancer. Most sun protection preparations now provide good protection against ultraviolet radiation in the wavelength range from 290 to 320 nm (UV-B range).
Numerous studies in recent years have shown that ultraviolet radiation in the wavelength range from 320 to 400 nm (UV-A range) makes a significant contribution to the skin damage caused by sunlight. Therefore an increasing requirement for adequate protection against UVA radiation exists. In addition, the availability of sun protection preparations having a high sun protection factor (hereinafter also referred to as SPF) has led to concerns that users are able to stay in the sun for longer and, as a result, are exposed to an increased amount of UVA radiation.
A UV filter should ideally convert absorbed UV radiation quickly and efficiently into harmless thermal energy without degradation of its protective action and any negative effects in the sunscreen preparations.
Although there is a large choice of suitable UVB filters good UVA absorbers are rare because they are mostly of low activity or of inadequate photostability. In particular, dibenzoyl-methane derivatives, for example 4-tert-butyl-4*-methoxydibenzoylmethane, the most common UVA filter, which is availabel under the trade name Parsol 1789 are degraded relatively quickly under the action of sunlight and, as a result, lose their protective action (R. M. Sayre et ai, Allured's Cosmetics & Toiletries, 114 (5): 85-91, 1999). In addition, it is known that the photostable UVB filters cinnamic acid esters, such as octyl methoxycinnamate which is available under the tradename Parsol MCX are frequently used in combination with dibenzoylme-thane derivatives. They may, however, form cycloaddition products with the dibenzoylme-thane derivative in a photoreaction processand consequently become destabilised.

As a result the photostability of the combination of these UV filters is decreased significantly.
Surprisingly it was found that specific benzotirazole derivatives may enhance the photostability of UV absorber systems comprising further organic UV absorbers like cinnamic acid esters or dibenzolymethan derivatives or combinations thereof.
Therefore, the present invention relates to the use of benzotriazole derivatives of formula

R3 is hydrogen; C1-C5alkyI; C1-C5alkoxy; halogen, preferably CI; or hydroxy;
R4 and R5 are each independently of the other hydrogen; or C1-C5alkyI;
m is 1 or 2;
n is 0 or 1;
if m = 1,
R2 is hydrogen; unsubstituted or phenyl-substituted C1-C12alkyl; or C6-C10aryl;
if m = 2,
R2 is the direct bond; or -(CH2)p-; and
p is 1 to 3;
for enhancing the photostability of cosmetic or dermatological compositons comprising at
least one further organic UV absorber.
C-1C30alkyl are straight-chain or branched alkyl radicals like methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.butyl, tert.butyl, amyl, isoamyl ortert.amyl, hexyl, 2-ethylhexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl. tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl or eicosyl.

C5-C7cycloalkyI is for example cyclopentyl, cycoheptyl or preferably cyclohexyl. C1-C5alkoxy is for example methoxy, ethoxy, propoxy, butyloxy or pentyloxy. C6-C10aryl is for example naphthyl or preferably phenyl. Preferably benzotrizoles of formula

These preferred values for the carbon atom content for R1 determine likewise the preferred and most preferred values for E1 and E2 whose sum in carbon atoms is one less than the total for T2.
The benzotriazoles used in the present invention are normally liquid or non-crystalline mixtures of benzotriazoles.


In a preferred embodiment, the benzotriazole derivative of formula (1) is present in a cosmetic or dermatological composition which compries at least one further UV absorber in an amount sufficient to photo-stabilize the corresponding UV absorber. "Photo-stabilizing" mrans that the benzotriazole derivative is present in an amount to reduce or eliminate the loss of UV-A absorbency of the cosmetic or dermatological composition which compries at least one further UV absorber following exposure to UV radiation.
In a more preferred embodiment the benzotriazole derivative of formula (1) is present in an amount sufficient to reduce the loss of UV-A absorbency of the composition by about fifty percent following exposure to 33 J/cm2 of full spectrum UV radiation.
In a most preferred embodiment the benzotriazole derivative of formula (1) is present in an amount from about 0.1 % to about 20%, by weight, of the composition.
Preferebly, the method of the present invention relates to cosmetic or dermatiological compositions, which comprise organic UV absorbers, which are selected from cinnamic acid derivatives and dibenzoylmethane derivatives.
Preferably, the cinnamic acid derivatives are selected from isopentyl p-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate and ethylhexyl methoxycinnamate.


A further object of the present invention refers to a cosmetic or dermatological composition according to claim 1 comprising
(a) 0.1 to 5 % b.w. of a dibenzoylmethane derivative;
(b) 0.1 to 10 % b.w. of a cinnamic acid derivative;
(c) a benzotriazole derivative in an amount which is sufficient to stabilize components (a)
and (b);
(d) optionally further UV absorbers; and
a cosmetically acceptable carrier.
Useful UV filters according to component (d) are listed in the Tables 1-3
The cosmetic or pharmaceutical preparations can be prepared by physically mixing the UV absorbers with the adjuvant using customary methods, for example by simply stirring together the individual components, especially by making use of the dissolution properties of the cosmetic UV absorbers.
The total amount of UV absorbers in the cosmetic or pharmaceutical preparations is from 0.05-40% by weight, based on the total weight of the composition.













Preferred cosmetic and/or dermatological compositions according to the present invention are:
1a. Cosmetic and/or dermatological compositions for the protection from UV radiation comprising a (a) a dibenzoylmethane derivative;(b) a cinnamic acid derivative; and (c) a benzotriazole derivative of formula (1) and powders having a core of at least one siloxane elastomer coated with trimethylsiloxylate and/or its derivatives as described in DE 101 57 489 from page 2, line 46 to page 4, line 6 and page 4, line 49 - 54.
lb. Cosmetic and/or dermatological compositions for the protection from UV radiation comprising (a) a dibenzoylmethane derivative;(b) a cinnamic acid derivative; and (c) a benzotriazole derivative of formula (1) and powders having a core of at least one

siloxane elastomer coated with trimethylsiloxylate and/or its derivatives and a further UV filter selected from the group of triazines, benzotriazoles, UV filters being liquid at room temperature, sulfonated, water soluble UV filters, oil soluble UV broadband filters and organic and/or anorganic pigments, which are preferably suface-coated as described in DE 101 57 489, § [051] -[0079].
Self-tanning composition comprising a cosmetic acceptable carrier:
(a) at least a self tanning agent; and
(a) a dibenzoylmethane derivative;
(c) a cinnamic acid derivative; and (d) a benzotriazole derivative of formula (1)
as described in EP-A-1,317,920.
Cosmetic and/or dermatological composition for topical use comprising in a cosmetic acceptable medium
(a) 0.1 - 15% b.w. of 1.4-di(3-methylidene-10-comphosulfonic) benzoic acid; as
described in EP-A-1,317,919; and
(b) a dibenzoylmethane derivative;(c) a cinnamic acid derivative; and (d) a benzotriazole
derivative of formula (1)
Cosmetic and/or dermatological composition for topical use, preferably for the photoprotection of the skin and/or hair comprising in a cosmetic acceptable medium
(a) at least an insoluble organic UV filter having a particle size from 10 nm to 5 i^m as
first filter as desribed, for example in EP-A-1,317,918 § [0025] - [0050]; and
(b) a dibenzoylmethane derivative;(c) a cinnamic acid derivative; and (d) a benzotriazole
derivative of formula (1);
Cosmetic and/or dermatological composition for the protection against UV radiation with UV filters selected from a combination of a dibenzoylmethane derivative; a cinnamic acid derivative; a benzotriazole derivative of formula (1); anorganic micro pigments; and at least one siloxane elastomer selected from the group existing of siloxane elastomers obtainable either by the reaction of vinyl-terminal polymethylsiloxane and methylhydrodimenthylsiloxane or by reaction of hydroxy-terminal dimethylpolysiloxane and trimethylsiloxy-terminal methylpolysioxane in form of spheric powder or in form of

gels as described in DE 101 55 865, § [0009] - [0013], [0020] - [0021] and [0045] - [0050].
Cosmetic and/or dermatological compositions for the protection against UV radiation comprising
(a) a dibenzoylmethane derivative;
(b) a cinnamic acid derivative;
(c) a benzotriazole derivative of formula (1); and
(d) at least one triazine- or benzotriazole derivative as described in WO 03/039507,
pages 5-16; and
optionally further cosmetic actives, adjuvants and additives as described in WO 03/039507, pages 17-26.
Cosmetic and/or dermatological compositions comprising
(a) a dibenzoylmethane derivative;
(b) a cinnamic acid derivative; and
(c) a benzotriazole derivative of formula (1); and

v./
R1and R2 independently from each other are branched or unbranched C6-C24alkyls; and

(e) a further UV filter selected from the group of triazines, benzotriazoles, liquid UV filters and organic and/or inorganic pigments as described in WO 03/039506, page 17. line 20 and page 18 - 20.
a. Cosmetic and/or dermatological composition comprising
(a) a dibenzoylmethane derivative;
(b) a cinnamic acid derivative;
(c) a benzotriazole derivative of formula (1); and
(d) 8-hexadecene-1.16-dicarboxylic acid;
as described in WO 03/039,502.
). Cosmetic and/or dermatological composition comprising
(a) a dibenzoylmethane derivative;
(b) a cinnamic acid derivative;
(c) a benzotriazole derivative of formula (1);

(d) 8-hexadecene-1.16-dicarboxylic acid; and
(e) a further UV-A filter and/or broadband filter selected from the group of pheny-lene-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonic-bissodium salt, 1,4-di(2-oxo10-sulfo-3-bornylidenemethyl)-benzene and the salts thereof and 2,4-bis-{4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine, wherein the filters may be present as single substances or in any combination of each substance.
Self-foaming, foaming, after-foaming or foamable cosmetic and/or dermatological compositions comprising
I. an emulsifier system as described for example in WO 03/039493, pages 6-19, consisting of
A. at least one emulsifier A selected from the group of totally partially or not neutralized, branched and/or unbranched, saturated and/or unsaturated C10-C40fatty acids; B at least one emulsifier B selected from the group of polyethoxylated C10-C40fatty
acid esters having an ethoxylation degree of 5 - 50; C at least one co-emulsifier C selected from the group of saturated and/or unsaturated branched and/or unbranched C10-C40fatty alcohols;

and II. until 30 % b.w., based on the overall weight of the composition,of a lipid phase comprising
(a) one or more lipids selected from silicon oils and silicon waxes; and
(b) one or more lipids selected from inpolar lipids having a polarity > 30 mM/m wherein the ratio (a): (b) is in the range of 1:3 - 3:1; and
(c) a dibenzoylmethane derivative;

(d) a cinnamic acid derivative; and
(e) a benzotriazole derivative of formula (1).
Cosmetic and/or dermatological compositions for the protection against UV radiation comprising
(a) a dibenzoylmethane derivative;
(b) a cinnamic acid derivative;
(c) a benzotriazole derivative of formula (1); and
(d) potassium-ethylenediaminetetramethlenephosphonate as described in
EP-A-1,310,239 § [0027] - [0028].
Cosmetic and/or dermatological compositions for the protection against UV radiation comprising
(a) a dibenzoylmethane derivative;
(b) a cinnamic acid derivative;
(c) a benzotriazole derivative of formula (1); and
(d) at least an acrylamide polymer, acrylamide copolymer, and derivatives thereof and/or an acrylamide polymer, acrylamide copolymer and derivatives thereof;
as described in EP-A-1,310,239.
Cosmetic and/or dermatological compositions for the protection from UV radiation comprising
(a) a dibenzoylmethane derivative;
(b) a cinnamic acid derivative;
(c) a benzotriazole derivative of formula (1); and
(d) imidosuccinic acid and/or derivatives thereof as described for example in EP.A-1,310,236 § [0028] - [0030].

dickering emulsions comprising fine disperse systems of W/0 or OAA/ type comprising
(1) an oil phase
(2) an aqueous phase,
(3) at least one type of a micronised particle, which

(a) have a mean particle size of (b) have hydrophilic and lipophilic properties which have also amphiphilic character and are dispersible in water and in oil as described in EP-A-1,310,235;
(4a) a dibenzoylmethane derivative; (4b)a cinnamic acid derivative; and (4c) a benzotriazole derivative of formula (1).
iJosmetic and/or dermatological compositions for the protection against UV radiation producing a permanent and non-covering colaration on the skin natural bronzing comprising in a cosmetical acceptable medium (a) at least a susceptible pigment obtained from the extraction with an organic or
hydroorganic solvent in a medium of myromydete culture of the type monascus; as
described in EP-A-1,302,199; 'b) a dibenzoylmethane derivative;
(c) a cinnamic acid derivative; and
;d) a benzotriazole derivative of formula (1).
Cosmetic and/or dermatological composition in form of an 0/W emulsion comprising
a) a dibenzoylmethane derivative;
b) a cinnamic acid derivative; and
c) a benzotriazole derivative of formula (1).
The basic compontents of the 0/W emulsion are disclosed in EP-A-1,291,012, § [0049] -[0277].
Cosmetic and/or dermatological composition in form of an W/0 emulsion comprising
a) a dibenzoylmethane derivative;
b) a cinnamic acid derivative; and
c) a benzotriazole derivative of formula (1).

The basic compontents of the W/0 emulsion are disclosed in EP-A-1,291,009, § [0047] -[0245].
Cosmetic and/or dermatological composition representing finedisperse systems of 0/W type comprising
(a) an oil phase,
(b) an aqueous phase,

(c) one or more stabilzers as disclosed in EP-A-1,291,007 § [0022] - [0080].
(d) at most 2.00 % b.w. of oner or more emulsifiers, and
(e) a dibenzoylmethane derivative;
(f) a cinnamic acid derivative; and
(g) a benzotriazole derivative of formula (1).
Further basic components of this cosmetic or dermatological composition are disclosed inEP-A-1,291,007.
Cosmetics sticks comprising
i) a lipid phase comprising at least an oil component and/or at least a wax component
as described in EPA-1,290,999 § [0031] - [0058] and i) a dibenzoylmethane derivative; ) a cinnamic acid derivative; and I) a benzotriazole derivative of formula (1).
Cosmetic and/or dermatological composition comprising in a cosmetic acceptable medium at least a cationic polymerisate as described in DE-A-101 29 527, a dibenzoylmethane derivative; a cinnamic acid derivative; and a benzotriazole derivative of formula (1), wherein the cationic polymerisate is obtainable by radical popolymerisation of


(c) 5 to 40 % b.w. of a monethylenic unsaturated monomer having at least an amino containing group wherein up to 40 % b.w., based on (a), (b), (c) and (d), of the monomer (a) may be substituted by a monomer of formula A, wherein R2 is C2-C22alkyl.
Cosmetic and/or dermatological composition for topical use, preferably for the photoprotection of the skin and/or hair comprising in a cosmetic acceptable medium
(a) at least one silicie derivative benzotriazole (first filter) as described in EP-A-
1,323,411 §[0021-0036]
(b) a dibenzoylmethane derivative;
(c) a cinnamic acid derivative; and
(d) a benzotriazole derivative of formula (1),
Cosmetic and/or dermatological composition comprising
(a) one or more lecithins for increasing the light protection factor and/or UVA protection as described in EP-A-1,166,759;
(b) a dibenzoylmethane derivative;
(c) a cinnamic acid derivative; and
(d) a benzotriazole derivative of formula (1),
Cosmetic and/or dermatological composition comprising
(a) triglyceride waxes as decribed in EP-A-1,000,611 to increase the UVA protection factor of cosmetic or dermatological compositions containing conventional UV-A- filters; and/or
(b) a dibenzoylmethane derivative;
(c) a cinnamic acid derivative; and (d) a benzotriazole derivative of formula (1),
Cosmetic and/or dermatological composition comprising
(a) ethylhexyl 2-cyano-3,3-diphenylacrylate (octocrylene) as described in EPA-1,034,778;
(b) a dibenzoylmethane derivative;
(c) a cinnamic acid derivative; and (
d) a benzotriazole derivative of formula (1),

for solubilizing and for increasing the light protection factor and/or the UV-A protection performance of the merocyanine derivative of formula (1).
24. Oil-free cosmetic or dermatological composition comprising
(a) a dibenzoylmethane derivative;
(b) a cinnamic acid derivative;
(c) a benzotriazole derivative of formula (1), and
(d) at least one UV filter liquid at room temperature as described in EP-A-1,074,241
25. Cosmetic light protection formulation comprising
(a) one or more amide oils as described in DE-A-19942714; and
(b) a dibenzoylmethane derivative;
(c) a cinnamic acid derivative; and
(d) a benzotriazole derivative of formula (1),
The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.
As water- and oil-containing emulsions (e.g. W/0, OA/V, OA/V/0 and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30 % by weight, preferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60 % by weight, especially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30 % by weight, especially from 1 to 30 % by weight und preferably from 4 to 20 % by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90 % by weight, especially from 30 to 90 % by weight, based on the total weight of the composition, of water, and from 0 to 88.9 % by weight, especially from 1 to 50 % by weight, of further cosmetically acceptable adjuvants.
The cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds as described below.

Fatty alcohols
Guerbet alcohols based on fatty alcohols having from 6 to 18, preferably from 8 to 10 carbon atoms including cetyl alcohol, stearyl alcohol, cetearyl alcohol, oleyl alcohol, octyldodecanol, benzoate of C12-C15 alcohols, acetylated lanolin alcohol, etc..
Esters of fatty acids
Esters of linear C6-C24 fatty acids with linear C3-C24 alcohols, esters of branched C6-C13car-boxylic acids with linear C6-C24 fatty alcohols, esters of linear C6-C24 fatty acids with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols, especially dioctyl malates, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, for example caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeo-stearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and technical-grade mixtures thereof (obtained, for example, in the pressure removal of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerisation of unsaturated fatty acids) with alcohols, for example, isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical-grade mixtures thereof (obtained, for example, in the high-pressure hydrogenation of technical-grade methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as monomer fractions in the dimerisation of unsaturated fatty alcohols).
Examples of such ester oils are isopropylmyristate, isopropylpalmitate, isopropylstearate, isopropyl isostearate, isopropyloleate, n-butylstearate, n-hexyllaurate, n-decyloleate, isooctyl-stearate, iso-nonylstearate, isononyl isononanoate, 2-ethylhexylpalmitate, 2-hexyilaurate, 2-hexyldecylstearate, 2-octyldodecylpalmitate, oleyloleate, oleylerucate, erucyloleate, erucyl-erucate, cetearyl octanoate, cetyl palmitate, cetyl stearate, cetyl oleate, cetyl behenate, cetyl acetate, myristyl myristate, myristyl behenate, myristyl oleate, myristyl stearate, myristyl pal-

mitate, myristyl lactate, propylene glycol dicaprylate/caprate, stearyl heptanoate, diisostearyl malate, octyl hydroxystearate, etc..
Other adjuvants
alpha glucosylrutin (CAS No. 130603-71-3), 2-butyloctyl o-hydroxybenzoate (CAS No. 190085-41-7), vitamin E (CAS No. 1406-18-4),, vitamin E acetate (CAS No. 58-95-7), diethylhexyl 2,6- naphthalate, di-n-butyl adipate, di(2-ethylhexyl)-adipate, di(2-ethylhexyl)-succinate and diisotridecyl acelaat, and also diol esters, such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol diisostearate, propylene glycol dipelargonate, butanediol diisostearate and neopentyl glycol dicaprylate. Esters of C6-C24 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, saturated and/or unsaturated, especially benzoic acid, esters of C2-Ci2dicarboxylic acids with linear or branched alcohols having from 1 to 22 carbon atoms or polyols having from 2 to 10 carbon atoms and from 2 to 6 hydroxy groups, or iminodisuccinic acid and imiondisuccinic acid salts [CAS 7408-20-0] or latex particles, aloe vera, chamomile, ginko biloba, ginseng, coenzyme Q10, laminaria ochroleuca extract, magnolia oborata extract, melalenca alternifolia leaf oil, rubus idaeus seed oil, vaccinium macrocarpon seed oil, pumpkin seed extract, pumpkin seed oil, grape seed extract, carnosine, alpha-arbutin, madecassoside, termino-laside, tetrahydrocurcuminoids (THC), mycosporines, mycosporine like amino acids from the red alga porphyra umbilicalis, mycosporine-like amino acids (as described in WO2002039974), cis-9-octadecenedioic acid, lipoic acid.laurimino dipropiomic acid tocopheryl phosphates (LDTP), microcrystalline cellulose (MCC), polycarbonates as described in WO 0341676, sterols (cholesterol, lanosterol, phytosterols), as described in WO0341675 and linear poly-alpha-glucans as described in US6616935
Natural or synthetic triglycerides including glyceryl esters and derivatives Di- or tri-glycerides, based on C6-C18 fatty acids, modified by reaction with other alcohols (caprylic/capric triglyceride, wheat germ glycerides, etc.). Fatty acid esters of polyglycerin (polyglyceryl-n such as polyglyceryl-4 caprate, polyglyceryl-2 isostearate, etc. or castor oil, hydrogenated vegetable oil, sweet almond oil, wheat germ oil, sesame oil, hydrogenated cottonseed oil, coconut oil, avocado oil, corn oil, hydrogenated castor oil, shea butter, cocoa butter, soybean oil, mink oil, sunflower oil, safflower oil, macadamia nut oil, olive oil, hydrogenated tallow, apricot kernel oil, hazelnut oil, borago oil, etc.

Waxes including esters of long-chain acids and alcohols as well as compounds having waxlike properties, e.g., carnauba wax, beeswax (white or yellow), lanolin wax, candellila wax, ozokerite, japan wax, paraffin wax, microcrystalline wax, ceresin, cetearyl esters wax, synthetic beeswax.etc. Also, hydrophilic waxes as Cetearyl Alcohol or partial glycerides.
Pearlescent waxes:
Ikylene glycol esters, especially ethylene glycol distearate; fatty acid alkanolamides, especially coco fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polyvalent, unsubstituted or hydroxy-substituted carboxylic acids with fatty alcohols having from 6 to 22 carbon atoms, especially long-chained esters of tartaric acid; fatty substances, for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially laurone and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having from 12 to 22 carbon atoms with fatty alcohols having from 12 to 22 carbon atoms and/or polyols having from 2 to 15 carbon atoms and from 2 to 10 hydroxy groups, and mixtures thereof.
Hydrocarbon oils:
Mineral oil (light or heavy), petrolatum (yellow or white), microcrystalline wax, paraffinic and isoparaffinic compounds, hydrogenated isoparaffinic molecules as polydecenes and polybu-tene, hydrogenated polyisobutene, squalane, isohexadecane, isododecane and others from plant and animal kingdom.
Silicones or siloxanes (orqanosubstituted polvsiloxanes)
Dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones, and also amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds, which at room temperature may be in either liquid or resinous form. Linear poly-siloxanes, dimethicone (Dow Corning 200 fluid, Rhodia Mirasil DM), dimethiconol, cyclic silicone fluids, cyclopentasiloxanes volatiles (Dow Corning 345 fluid), phenyltrimethicone (Dow Corning 556 fluid). Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units with hydrogenated silicates. A detailed survey by Todd et ai of suitable volatile silicones may in addition be found in Cosm. Toil. 91, 27 (1976).

Fluorinated or perfluorinated oils
Perfluorhexane, dimethylcyclohexane, ethylcyclopentane, polyperfluoromethylisopropyl
ether.
Emulsifiers
Any conventionally usable emulsifier can be used for the compositions. Emulsifier systems may comprise for example: carboxylic acids and their salts: alkaline soap of sodium, potassium and ammonium, metallic soap of calcium or magnesium, organic basis soap such as Laurie, palmitic, stearic and oleic acid etc... Alkyl phosphates or phosphoric acid esters, acid phosphate, diethanolamine phosphate, potassium cetyl phosphate. Ethoxylated carboxylic acids or polyethyleneglycol esters, PEG-n acylates. Linear fatty alcohols having from 8 to 22 carbon atoms, branched from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol propylene oxide with with fatty acids having from 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group. Fatty alcohol polyglycol-ether such as laureth-n, ceteareth-n, steareth-n, oleth-n. Fatty acid polyglycolether such as PEG-n stearate, PEG-n oleate, PEG-n cocoate. Monoglycerides and polyol esters. C12-C22 fatty acid mono- and di-esters of addition products of from 1 to 30 mol of ethylene oxide with polyols. Fatty acid and polyglycerol ester such as monostearate glycerol, diisostearoyi polyglyceryl-3-diisostearates, polyglyceryl-3-diisostearates, triglyceryl diisostearates, polyglyceryl-2-sesquiisostearates or polyglyceryl dimerates. Mixtures of compounds from a plurality of those substance classes are also suitable. Fatty acid polyglycolesters such as monostearate diethylene glycol, fatty acid and polyethylene glycol esters, fatty acid and saccharose esters such as sucro esters, glycerol and saccharose esters such as sucro glycerides. Sorbitol and sorbitan, sorbitan mono- and di-esters of saturated and unsaturated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition products. Polysorbate-n series, sorbitan esters such as sesquiisostearate, sorbitan, PEG-(6)-isostearate sorbitan, PEG-(10)-sorbitan laurate, PEG-17- dioleate sorbitan. Glucose derivatives, C8-C22 alkyl-mono and oligo-glycosides and ethoxylated analogues with glucose being preferred as the sugar component. OA/V emulsifiers such as methyl gluceth-20 sesquistearate, sorbitan stearate/sucrose cocoate, methyl glucose sesquistearate, cetearyl alcohol/cetearyl glucoside. W/0 emulsifiers such as methyl glucose dioleate/ methyl glucose isostearate. Sulfates and sulfonated derivatives, dialkylsulfosuccinates, dioctyl succinate, alkyl lauryl sulfonate, linear sulfonated parafins, sulfonated tetraproplyne sulfonate, sodium lauryl sulfates, amonium and ethanolamine lauryl sulfates, lauyl ether sulfates, sodium

laureth sulfates, sulfosuccinates, aceyl isothionates, alkanolamide sulfates, taurines, methyl taurines, imidazole sulfates. Amine derivatives, amine salts, ethoxylated amines, oxide amine with chains containing an heterocycle such as alkyl imidazolines, pyridine derivatives, isoquinoteines, cetyl pyridinium chlorure, cetyl pyridinium bromide, quaternary ammonium such as cetyltrimethylbroide amonium broide (CTBA), stearylalkonium. Amide derivatives, alkanolamides such as acylamide DEA, ethoxylated amides such as PEG-n acylamide, oxy-deamide. Polysiloxane/polyalkyl/polyether copolymers and derivatives, dimethicone, copo-lyols, silicone polyethylene oxide copolymer, silicone glycol copolymer. Propoxylated or POE-n ethers (Meroxapols), Polaxamers or poly(oxyethylene)m-block-poly(oxypropylene)n-block(oxyethylene). Zwitterionic surfactants that carry at least one quaternary ammonium group and at least one carboxylate and/or sulfonate group in the molecule. Zwitterionic surfactants that are especially suitable are betaines, such as N-alkyl-N,N-dimethylammonium glycinates, cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N.N-dimethyi-ammonium glycinates, cocoacyiaminopropyldimethylammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethylglycinate. N-alkylbetaine, N-alkylaminobetaines. Alkylimidazolines, alkylopeptides, lipoaminoacides, self emulsifying bases and the compounds as described in K.F.DePolo, A short textbook of cosmetology, Chapters, Table 8-7, p250-251.
Non ionic emulsifiers such as PEG-6 beeswax (and) PEG-6 stearate (and) polyglyceryl -2-isostearate [Apifac], glyceryl stearate ( and) PEG-100 stearate. [Arlacel 165], PEG-5 glyceryl stearate [arlatone 983 S], sorbitan oleate (and) polyglyceryl-3 ricinoleate.[Arlacel 1689], sorbitan stearate and sucrose cocoate [arlatone 2121], glyceryl stearate and laureth-23 [Cerasynth 945], cetearyl alcohol and ceteth-20 [Cetomacrogol Wax], cetearyl alcohol and colysorbate 60 and PEG-150 and stearate-20[Polawax GP 200, Polawax NF], cetearyl alcohol and cetearyl polyglucoside [Emulgade PL 1618], cetearyl alcohol and ceteareth-20 [Emulgade 1000NI, Cosmowax], cetearyl alcohol and PEG-40 castor oil [Emulgade F Special], cetearyl alcohol and PEG-40 castor oil and sodium cetearyl sulfate [Emulgade F], stearyl alcohol and steareth-7 and steareth-10 [Emulgator E 2155], cetearyl alcohol and szeareth-7 and steareth-10 [Emulsifying wax U.S.N.F], glyceryl stearate and PEG-75 stearate [Gelot 64], propylene glycol ceteth-3 acetate .[Hetester PCS], propylene glycol isoceth-3 acetate [Hetester PHA], cetearyl alcohol and ceteth-12 and oleth-12 [Lanbritol Wax N 21], PEG -6 stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and ceteth-20

nd steareth-20 [Tefose 2000], PEG-6 stearate and ceteth-20 and glyceryl stearate and teareth-20 [Tefose 2561], glyceryl stearate and ceteareth-20 [Teginacid H, C, X].
anionic emulsifiers such as PEG-2 stearate SE, glyceryl stearate SE [Monelgine, Cutina KD], ropylene glycol stearate [Tegin P], cetearyl Alcohol and Sodium cetearyl sulfate [Lanette N, Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate [Lanette W], trilaneth-4p
hopshate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl Sulfate [Teginacid Special]. Cationic acid bases such as cetearyl alcohol and petrimonium bromide.
the emulsifiers may be used in an amount of, for example, from 1 to 30 % by weight, especially from 4 to 20 % by weight and preferably from 5 to 10 % by weight, based on the total weight of the composition.
Vhen formulated in OA/V emulsions, the preferably amount of such emulsifier system could epresent 5% to 20% of the oil phase.
Adjuvants and additives
The cosmetic / pharmaceutical preparations, for example creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments, may in addition contain, as further adjuvants and additives, mild surfactants, su-per-fatting agents, consistency regulators, thickeners, polymers, stabilisers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, film formers, swelling agents, further UV light-protective factors, antioxidants, hydrotropic agents, preservatives, insect repellents, self-tanning agents, solubilisers, perfume oils, colourants, bacteria-inhibiting agents and the like.
super-fatting agents
Substances suitable for use as super-fatting agents are, for example, lanolin and lecithin and
also polyethoxylated or acrylated lanolin and lecithin derivatives, polyol fatty acid esters,
nonoglycerides and fatty acid alkanolamides, the latter simultaneously acting as foam
stabilisers.

Surfactants
Examples of suitable mild surfactants, that is to say surfactants especially well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or di-alkyi sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, a-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines and/or protein fatty acid condensation products, the latter preferably being based on wheat proteins.
Consistency regulators/thickeners and rheoloqy modifiers
Silicium dioxide, magnesium silicates, aluminium silicates, polysaccharides or derivatives thereof for example hyaluronic acid, xanthan gum, guar-guar, agar-agar, alginates, carra-ghenan, gellan, pectines, or modified cellulose such as hydroxycellulose, hydroxypropyl-methylcellulose. In addition polyacrylates or homopolymer of reticulated acrylic acids and polyacrylamides, carbomer (carbopol types 980, 981, 1382, ETD 2001, ETD2020, Ultrez 10) or Salcare range such as Salcare SC80(steareth-10 allyl ether/acrylates copolymer). Salcare SC81(acrylates copolymer), Salcare SC91 and Salcare AST(sodium acrylates copoly-mer/PPG-1 trideceth-6), sepigel 305(polyacrylamide/laureth-7), Simulgel NS and Simulgel EG (hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer), Stabilen 30 (acrylates / vinyl isodecanoate crosspolymer), Pemulen TR-1 (acrylates / CI 0-30 alkyl acrylate crosspolymer), Luvigel EM (sodium acrylates copolymer), Aculyn 28 (acrylates/beheneth-25 methacrylate copolymer), etc.
Polymers
Suitable cationic polymers are, for example, cationic cellulose derivatives, for example a qua-ternised hydroxymethyl cellulose obtainable under the name Polymer JR 400 from Amerchol, cationic starches, copolymers of diallylammonium salts and acrylamides, quarternised vinyl-pyrrolidone/vinyl imidazole polymers, for example Luviquat® (BASF), condensation products of polyglycols and amines, quaternised collagen polypeptides, for example lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®LyGrunau), quaternised wheat polypeptides, polyethyleneimine, cationic silicone polymers, for example amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretin/Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat 550 / Chemviron), poly-aminopolyamides, as described, for example, in FR-A-2 252 840, and the crosslinked water-soluble polymers thereof, cationic chitin derivatives, for example of quaternised chitosan,

optionally distributed as microcrystals; condensation products of dihaloalkyls, for example dibromobutane, with bisdialkylamines, for example bisdimethylamino-1,3-propane, cationic guar gum, for example Jaguar C-17, Jaguar C-16 from Celanese, quaternised ammonium salt polymers, for example Mirapol A-15, Mirapol AD-1, Mirapol AZ-1 from Miranol. As anionic, zwitterionic, amphoteric and non-ionic polymers there come into consideration, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and esters thereof, uncrosslinked polyacrylic acids and polyacrylic acids crosslinked with polyols, acrylamidopropyl-trimethylammonium chloride /acrylate copolymers, octyl acrylamide/methyl methacrylatetert-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactam terpolymers and also optionally derivatised cellulose ethers and silicones. Furthermore the polymers as described in EP 1093796 (pages 3-8, paragraphs 17-68) may be used.
Biogenic active ingredients
Biogenic active ingredients are to be understood as meaning, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.
Deodorising active ingredients
As deodorising active ingredients there come into consideration, for example, antiperspi-rants, for example aluminium chlorohydrates (see J. Soc. Cosm. Chem. 24, 281 (1973)). Under the trade mark Locron® of Hoechst AG, Frankfurt (FRG), there is available comer-cially, for example, an aluminium chlorohydrate corresponding to formula Al2(OH)5CI x 2.5 H2O, the use of which is especially preferred (see J. Pharm. Pharmacol. 26, 531 (1975)). Besides the chlorohydrates, it is also possible to use aluminium hydroxyacetates and acidic aluminium/zirconium salts. Esterase inhibitors may be added as further deodorising active ingredients. Such inhibitors are preferably trialkyi citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and especially thethyl citrate (Hydagen CAT, Hen-kel), which inhibit enzyme activity and hence reduce odour formation. Further substances that come into consideration as esterase inhibitors are sterol sulfates or phosphates, for example lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phos-

phate, dicarboxylic acids and esters thereof, for example glutaric acid, glutaric acid mono-ethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester and hydroxycarboxylic acids and esters thereof, for example citric acid, malic acid, tartaric acid or tartaric acid diethyl ester. Antibacterial active ingredients that influence the germ flora and kill or inhibit the growth of sweat-decomposing bacteria can likewise be present in the preparations (especially in stick preparations). Examples include chitosan, phenoxyethanol and chlorhexidine gluconate. 5-chloro-2-(2,4-dichlorophenoxy)-phenol (Triclosan, Irgasan, Ciba Specialty Chemicals Inc.) has also proved especially effective.
Anti-dandruff agents
As anti-dandruff agents there may be used, for example, climbazole, octopirox and zinc pyri-thione. Customary film formers include, for example, chitosan, microcrystalline chitosan, qua-ternised chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of quaternary cellulose derivatives containing a high proportion of acrylic acid, collagen, hyaluronic acid and salts thereof and similar compounds.
Antioxidants
In addition to the primary light-protective substances it is also possible to use secondary light-protective substances of the antioxidant kind that interrupt the photochemical reaction chain triggered when UV radiation penetrates the skin or hair. Typical examples of such antioxidants are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g. anserine), carotinoids, carotenes, lycopene and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglycose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyi, oleyl, linoleyl, cholesteryl and glyceryl esters thereof) and also salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodi-propionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and also sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine sulfoximine, buthionine suifones, penta-, hexa-, hepta-thionine sulfoximine), also (metal) chelating agents (e.g. hydroxy fatty acids, palmitic acid phytic acid, lactoferrin), hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts.

bilirubin, biliverdin, EDTA, EDDS, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol 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 also coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase, N-[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionyl]sulfanilic acid (and salts thereof, for example the disodium salts), zinc and derivatives thereof (e.g. ZnO, ZnSO4), selenium and derivatives thereof (e.g. selenium methionine), stilbene and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of those mentioned active ingredients. HALS (-'Hindered Amine Light Stabilizers") compounds may also be mentioned. Further synthetic and natural antioxidants are listed e.g. in patent WO 0025731: Structures 1-3 (page 2), structure 4 (page 6), structures 5-6 (page 7) and compounds 7-33 (page 8-14).
The amount of antioxidants present is usually from 0.001 to 30 % by weight, preferably from 0.01 to 3% by weight, based on the weight of the UV absorber of formula (1).
Hvdrotropic agents
To improve the flow behaviour it is also possible to employ hydrotropic agents, for example ethoxylated or non ethoxylated mono-alcohols, diols or polyols with a low number of carbon atoms or their ethers (e.g. ethanol, isopropanol, 1,2-dipropanediol, propyleneglycol, glyerin, ethylene glycol, ethylene glycol monoethylether. ethylene glycol monobutylether, propylene glycol monomethylether, propylene glycol monoethylether, propylene glycol monobutylether, diethylene glycol monomethylether; diethylene glycol monoethylether, diethylene glycol monobutylether and similar products). The polyols that come into consideration for that purpose have preferably from 2 to 15 carbon atoms and at least two hydroxy groups. The polyols may also contain further functional groups, especially amino groups, and/or may be modified with nitrogen. Typical examples are as follows: glycerol, alkylene glycols, for example ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol

and also polyethylene glycols having an average molecular weight of from 100 to 1000 Dalton; technical oligoglycerol mixtures having an intrinsic degree of condensation of from 1.5 to 10, for example technical diglycerol mixtures having a diglycerol content of from 40 to 50 % by weight; methylol compounds, such as, especially, trimethylolethane, trimethylol-propane, trimethylolbutane, pentaerythritol and dipentaerythritol; lower alkyl-glucosides, especially those having from 1 to 8 carbon atoms in the alkyl radical, for example methyl and butyl glucoside; sugar alcohols having from 5 to 12 carbon atoms, for example sorbitol or mannitol; sugars having from 5 to 12 carbon atoms, for example glucose or saccharose; amino sugars, for example glucamine; diaicohol amines, such as diethanolamine or 2-amino-1,3-propanediol.
Preservatives and Bacteria-inhibiting agents
Suitable preservatives include, for example,Methyl-,Ethyl-, Propyl-, Butyl- parabens, Benzal-konium chloride, 2-Bromo-2-nitro-propane-1,3-diol, Dehydroacetic acid, Diazolidinyl Urea, 2-Dichloro-benzyl alcohol, DMDM hydantoin. Formaldehyde solution, Methyldibromoglu-tanitrile, Phenoxyethanol, Sodium Hydroxymethylglycinate, Imidazolidinyl Urea, Triclosan and further substance classes listed in the following reference: K.F.DePolo - A short textbook of cosmetology. Chapter 7, Table 7-2, 7-3, 7-4 and 7-5, p210-219.
Typical examples of bacteria-inhibiting agents are preservatives that have a specific action against gram-positive bacteria, such as 2,4,4*-trichloro-2'-hydroxydiphenyl ether, chlorhexi-dine (1,6-di(4-chlorophenyl-biguanido)hexane) orTCC (3,4,4*-trichlorocarbanilide). A large number of aromatic substances and ethereal oils also have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. A natural deodorising agent of interest is the terpene alcohol farnesol (3,7,11-tri-methyl-2,6,10-dodecatrien-1-ol), which is present in lime blossom oil. Glycerol monolaurate has also proved to be a bacteriostatic agent. The amount of the additional bacteria-inhibiting agents present is usually from 0.1 to 2 % by weight, based on the solids content of the preparations.
Perfume oils
There may be mentioned as perfume oils mixtures of natural and/or synthetic aromatic substances. Natural aromatic substances are, for example, extracts from blossom (lilies, lavender, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli,

petitgrain), from fruit (aniseed, coriander, carraway, juniper), from fruit peel (bergamot, lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (tarragon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials also come into consideration, for example civet and castoreum. Typical synthetic aromatic substances are, for example, products of the ester, ether, aldehyde, ketone, alcohol or hydrocarbon type. Aromatic substance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citronellal, citronellyl oxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; the ketones include, for example, the ionones, isomethylionone and methyl cedryl ketone; the alcohols include, for example, anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol; and the hydrocarbons include mainly the terpenes and balsams. It is preferable, however, to use mixtures of various aromatic substances that together produce an attractive scent. Ethereal oils of relatively low volatility, which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, camomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavandin oil. Preference is given to the use of bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol, hexyl cinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, tangerine oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, muscatel sage oil, damascene, bourbon geranium oil, cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat alone or in admixture with one another.
Colourants
There may be used as colourants the substances that are suitable and permitted for cosmetic purposes, as compiled, for example, in the publication "Kosmetische Farbemittel" of the Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Wein-

heim, 1984, pages 81 to 106. The colourants are usually used in concentrations of from 0.001 to 0.1 % by weight, based on the total mixture.
Other adjuvants
It is furthermore possible for the cosmetic preparations to contain, as adjuvants, anti-foams, such as silicones, structurants, such as maleic acid, solubilisers, such as ethylene glycol, propylene glycol, glycerol or diethylene glycol, opacifiers, such as latex, styrene/PVP or sty-rene/acrylamide copolymers, complexing agents, such as EDTA, NTA, alaninediacetic acid or phosphonic acids, propellants, such as propane/butane mixtures, N2O, dimethyl ether, CO2, N2 or air, so-called coupler and developer components as oxidation dye precursors, reducing agents, such as thioglycolic acid and derivatives thereof, thiolactic acid, cysteamine, thiomalic acid or mercaptoethanesulfonic acid, or oxidising agents, such as hydrogen peroxide, potassium bromate or sodium bromate.
Suitable insect repellents are, for example, N,N-diethyl-m-toluamide, 1,2-pentanediol or insect repellent 3535; suitable self-tanning agents are, for example, dihydroxyacetone and/or erythrulose or dihydroxy acetone and/or dihydroxy acetone precursors as described in WO 01/85124 and/or erythrulose.
Polymeric beads or hollow spheres as SPF enhancers
The combination of the UV-absorbers and UV-absorber combinations, listed above, with SPF enhancers, such as non-active ingredients like Styrene/acrylates copolymer, silica beads, spheroidal magnesium silicate, crosslinked Polymethylmethacrylates (PMMA ; Micopearl M305 Seppic), can maximize better the UV protection of the sun products. Holosphere additives (Sunspheres® ISP, Silica Shells Kobo.) deflect radiation and the effective path length of the photon is therefore increased.( EP0893119). Some beads, as mentioned previously, provide a soft feel during spreading. Moreover, the optical activity of such beads, e.g.Micropearl M305, cans modulate skin shine by eliminating reflection phenomena and indirectly may scatter the UV light.
Cosmetic or pharmaceutical preparations
Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic
preparations. There come into consideration, for example, especially the following
preparations:

skin-care preparations, e.g. skin-washing and cleansing preparations in the form of tablet-form or liquid soaps, soapless detergents or washing pastes, bath preparations, e.g. liquid (foam baths, milks, shower preparations) or solid bath preparations, e.g. bath cubes and bath salts;
skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils; cosmetic personal care preparations, e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix creams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-care preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers;
foot-care preparations, e.g. foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callus-removing preparations; light-protective preparations, such as sun milks, lotions, creams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations; skin-tanning preparations, e.g. self-tanning creams;
depigmenting preparations, e.g. preparations for bleaching the skin or skin-lightening preparations;
insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks; deodorants, such as deodorant sprays, pump-action sprays, deodorant gels, sticks or roll-ons;
antiperspirants, e.g. antiperspirant sticks, creams or roll-ons;
preparations for cleansing and caring for blemished skin, e.g. synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks;
hair-removal preparations in chemical form (depilation), e.g. hair-removing powders, liquid hair-removing preparations, cream- or paste-form hair-removing preparations, hair-removing preparations in gel form or aerosol foams;
shaving preparations, e.g. shaving soap, foaming shaving creams, non-foaming shaving creams, foams and gels, preshave preparations for dry shaving, aftershaves or aftershave lotions;
fragrance preparations, e.g. fragrances (eau de Cologne, eau de toilette, eau de parfum, parfum de toilette, perfume), perfume oils or perfume creams;

cosmetic hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair-setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colourants, preparations containing self-oxidising dyes, or natural hair colourants, such as henna or camomile.
Presentation forms
The final formulations listed may exist in a wide variety of presentation forms, for example:
in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all
kinds 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,
in the form of a stick,
in the form of a spray (spray with propellent gas or pump-action spray) or an aerosol,
in the form of a foam, or
in the form of a paste.
Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of particular interest are sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray.
Of special importance as cosmetic preparations for the hair are the above-mentioned preparations for hair treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-

straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos.
A shampoo has, for example, the following composition: from 0.01 to 5 % by weight of a UV absorber according to the invention, 12.0 % by weight of sodium laureth-2-sulfate, 4.0 % by weight of cocamidopropyl betaine, 3.0 % by weight of sodium chloride, and water ad 100%.
For example, especially the following hair-cosmetic formulations may be used:
i) spontaneously emulsifying stock formulation, consisting of the UV absorber according to the invention, PEG-6-CioOxoalcohol and sorbitan sesquioleate, to which water and any desired quaternary ammonium compound, for example 4 % minkamidopropyl dimethyl-2-hydroxyethylammonium chloride or Quaternium 80 is added;
spontaneously emulsifying stock formulation consisting of the UV absorber according to the invention, tributyl citrate and PEG-20-sorbitan monooleate, to which water and any desired quaternary ammonium compound, for example 4 % minkamidopropyl dimethyl-2-hydroxyethylammonium chloride or Quaternium 80 is added;
quat-doped solutions of the UV absorber according to the invention in butyl triglycol and tributyl citrate;
mixtures or solutions of the UV absorber according to the invention with n-alkylpyrroiidone.
Other typical ingredients in such formulations are preservatives, bactericides and bacteriostatic agents, perfumes, dyes, pigments, thickening agents, moisturizing agents, humectants, fats, oils, waxes or other typical ingredients of cosmetic and personal care formulations such as alcohols, poly-alcohols, polymers, electrolytes, organic solvents, silicon derivatives, emollients, emulsifiers or emulsifying surfactants, surfactants, dispersing agents, antioxi-jants, anti-irritants and anti-inflammatory agents etc.

The cosmetic preparation according to the invention is distinguished by excellent protection of human skin against the damaging effect of sunlight.

Example 1: Preparation of the samples for the determination of the photostabilitv

Manufacturing instruction:
Heat part A and B to approximately 80°C. Add part A to part B under stirring and homogenize with an Ultra Turrax for a minute. Let cool down to 30°C and add part C. At room temperature adjust the pH between 6.50 and 7.00 with part D.


Compositions A and B are applied on rough quarz-plates (2µl/cm2).
Irradiation is carried out with an Altas CPS+ sunlight simulator. The times of irradiation are: Oh (no irradiation),
- 1h(5MED),
- 2h (10 MED) and
- 4h (20 MED).
For sufficient statistics 8 plates per time (x MED) are prepared.
After irradiation the samples can be recovered completely with a defined amount (5 ml) of a
solvent (tetrahydrofurane).
HPLC:
The recovery of the UV-absorber is analyzed via HPLC:
column: Hypersil ODS 5µm, 250mm x 4mm

Solvent A: Water + 2g/l TBAHS
Solvent B: Acetonitrile / THF 9:1 + 2g/l TBAHS
temperature: 35°C
wavelength: 354nm (for Detection of the compound of formula (101))
The results: are listed in Table 2:

The results in Table 2 clearly demonstrate the stabilizing effect of the composition A which comprises the compound of formula (103).

Claims
1. Use of benzotriazole derivatives of formula

R3 is hydrogen; C1-C5alkyI; C1-C5alkoxy; halogen, preferably CI; or hydroxy;
R4 and R5 are each independently of the other hydrogen; or C1-C5alkyI;
m is 1 or 2;
n is 0 or 1;
if m = 1,
R2 is hydrogen; unsubstituted or phenyl-substituted C1-C12alkyl; or C6-C10aryl;
if m = 2,
R2 is the direct bond; or -(CH2)p-; and
p is 1 to 3;
for enhancing the photostability of cosmetic or dermatologic compositons comprising at least
one further organic UV absorber.
2. Use according to claim 1, wherein benzotrizoles of formula

3. Use according to claim 1 or 2, wherein benzotrizoles of formula


R1 is a random statistical mixture of at least three isomeric branched secondary alkyl groups

E1 is a straight-chain C1-C14alkyl;
E2 is a straight-chain C4-C15alkyl; wherein the total number of carbon atoms in E1 plus E2 is
from 7 to 29; and R2 is C1-C5alkyl.
4. Use according to any of claims 1 to 3, wherein R1 is C8-C16alkyl
5. Use according to any of claims 1 to 4, wherein the benzotriazole of formula

is used.
6. Use according to any of claims 1 to 5, wherein the benzotrizole derivative is used in
amounts from 0.1 to 20 % b.w in the cosmetic or dermatological sun screen formulations.
7. Use according to any of claims 1 to 6, wherein the cometic or dermatological formulation
comprises further organic UV absorbers selected from cinnamic acid derivatives and
dibenzoylmethane derivatives.
8. Use according to claim 7 wherein the cinnamic acid derivatives are selected from isopentyl
p-methoxycinnamate, 2- ethylhexyl 4-methoxycinnamate and ethylhexyl methoxycinnamate.

9. Use according to claim 5 wherein the dibenzoylmethane derivative corresponds to formula

10. Cosmetic or dermatological composition according to claim 1 comprising
(a) 0.1 to 5 .w. of a dibenzoylmethane derivative;
(b) 0.1 to 10 %w. of a cinnamic acid derivative;
(c) a benzotriazole derivative in an amount which is sufficient to stabilize components (a)
and(b);
(d) optionally further UV absorbers; and
a cosmetically acceptable carrier.

Documents:

4802-CHENP-2007 CORRESPONDENCE OTHERS 05-2-2014.pdf

4802-CHENP-2007 CORRESPONDENCE OTHERS 22-04-2013.pdf

4802-CHENP-2007 FORM-3 22-04-2013.pdf

4802-CHENP-2007 AMENDED CLAIMS 09-09-2014.pdf

4802-CHENP-2007 AMENDED PAGES OF SPECIFICATION 09-09-2014.pdf

4802-CHENP-2007 CORRESPONDENCE OTHERS 22-11-2013.pdf

4802-CHENP-2007 EXAMINATION REPORT REPLY RECIEVED 09-09-2014.pdf

4802-CHENP-2007 FORM-1 09-09-2014.pdf

4802-CHENP-2007 FORM-3 22-11-2013.pdf

4802-CHENP-2007 POWER OF ATTORNEY 09-09-2014.pdf

4802-chenp-2007-abstract.pdf

4802-chenp-2007-claims.pdf

4802-chenp-2007-correspondnece-others.pdf

4802-chenp-2007-description(complete).pdf

4802-chenp-2007-drawings.pdf

4802-chenp-2007-form 1.pdf

4802-chenp-2007-form 26.pdf

4802-chenp-2007-form 3.pdf

4802-chenp-2007-form 5.pdf

4802-chenp-2007-pct.pdf

Form 3.pdf

Petition for Annexure.pdf

Petition for POR.pdf


Patent Number 263577
Indian Patent Application Number 4802/CHENP/2007
PG Journal Number 45/2014
Publication Date 07-Nov-2014
Grant Date 03-Nov-2014
Date of Filing 29-Oct-2007
Name of Patentee CIBA HOLDING INC
Applicant Address Klybeckstrasse 141, CH-4057 Basel
Inventors:
# Inventor's Name Inventor's Address
1 EHLIS, Thomas Harriet-straub-strasse 23, 79100 Freiburg
2 KÖNIG, Peter Badstubenweg 8, 79540 Lörrach
3 MÜLLER, Stefan Dorfstrasse 46, 79576 Weil Am Rhein
4 GIESINGER, Jochen Bandweg 3, 79639 Grenzach-wyhlen
5 HERZOG, Bernd Hornrain 21, 79639 Grenzach-wyhlen
6 KREYER, Gilbert Rue Des Maraichers 1, F-68300 Saint-louis
7 QUASS, Katja Emil-fritschi-weg 16, 79618 Rheinfelden
PCT International Classification Number A61K 8/49
PCT International Application Number PCT/EP2006/061686
PCT International Filing date 2006-04-20
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 05103494.0 2005-04-28 EUROPEAN UNION