Title of Invention

"A METHOD FOR PROTECTING BODY-CARE PRODUCTS AND HOUSEHOLD PRODUCTS"

Abstract Desribed is the use of specific merocyanine derivatives for protecting body-care and household products from histolytic and oxidative degradation. These compounds perform outstanding UV absorber properties.
Full Text stabilization of body-care and household products against degradation by UV radiation using merocvanine derivatives Stabilization of body-care and household products
The present invention relates to the use of selected light stabilizers for protecting body-care and household products from hemolytic and oxidative degradation.
The product trend of recent years towards increasing! Use of natural substances based on oil and fat in cosmetic formulations and household products also increases the problem of the oxidative degradation of fats and oils, resulting in rancidity. Natural oils or unsaturated fatty acids are hardly ever absent from emulsions. Oxidative changes may sometimes produce reactive metabolites, for example ketones, aldehydes, acids, epoxides and lip peroxides.
As a result there is on the one hand an undesirable change in the smell of the products and on the other hand substances may be obtained which may alter the skin tolerance. The uncontrolled formation of free radicals on the skin contributes primarily to the initiation and progression of a multitude of pathophysical modulations, for example inflammation, canceroge-nesis and the like.
However, oxidative degradation processes are not only found in the case of natural substances based on oil and fat. They are also found in a number of other cosmetic ingredients, such as fragrances and odoriferous substances, vitamins, colourants and the like.
To prevent oxidative degradation processes (photooxidation, autooxidation), so-called antioxidants (AO) are therefore used in cosmetic and food products. These antioxidants may be classified into compounds which prevent oxidation (complex fonners, reducing agents and the like) and into compounds which interrupt the free radical chain reactions, for example butylated hydroxytoluene (BHT), butylated hydroxyanisol (BHA), gallates, such as propyl-gallate (PG), or t-butylhydroquinone (TBHQ). However, the latter compounds often do not meet the requirements with respect to pH stability as well as to light and temperature stability.
As a consequence the actives in such containers unadvantageously change their properties due to autoxidative processes. This results for example in a reduction of viscosity and changes in color or smell.

Furthermore, the growing product trend in the recent years has also resulted in an increased use of transparent (glass, PET etc.) containers for cosmetic formulations and household products. Although both glass and ordinary plastics have a certain inherent absorption in the UV-B-range the absorption in the UV-A range is very low.
Various stabilization techniques for clear package products by UV absorption are commonly used and well known. For example broad-band UV light stabilizers of the benzotriazole class enhance product stability and shelf live due to their very good UV-A and UV-B absorption properties compared to other absorbers such as benzophenones which mainly absorb UV-B. The most effective today known stabilizers for preventing or delaying light induced fading of transparent packaged products are e.g. benzotriazole derivativess known under the trade names Ciba TINOGARD HS or Ciba TINOGARD TL
Surprisingly, it has been found that specific light stabilizers based on merocyanine derivatives perform outstanding UV absorber properties and are therefore suitable for product protection.
Therefore, the present invention relates to the use of merocyanine derivatives of formula



alkenyl; C7-C2oaralkyl; Ci-C2oheteroalkyl; C3-Ci2cycloheteroalkyl; Cs-Cuheteroaraikyl;
C6-C2oaryl; or C4-Cgheteroaryl; or Li and L2, Li and L3, L2 and L3, Li and R4, L2 and R4, Li and Ri, L2 and Ri, L3 and Ri, L3 and
R5, R3 and R4, Ri and R2, R7 and Rs, R5 and Re may be linked together to form 1. 2, 3 or
4 carbocyclic or N, O and/or S-heterocyclic rings, which may be further fused with other
aromatic rings and each N in a N-heterocycllc ring may be unsubstituted or substituted
by R10;
and each alkyl, alkenyl, alkenyl, cyclo alkyi or cycloalkylene group may be unsubstituted
or substituted by one or more Rn;
and each aryl, heteroaryl, aralkyl. arylene. heteroarylene or aralkylene may be
unsubstituted or substituted by one or more R12; R10 is R13; COR13; COOR13; or CONR13R14; R11 is halogen, OH; NR15R16; O-R15; S-R15; O-CO-R15; CO-Ris; 0x0; thong; CN; COOR15;
CONR15R16; SO2NR15R16; SO2R15; SO3R15; SiRisRieRni OSiRi5Ri6Ri7; POR15R16; or a
radical -X-Sil; R12 is Ci-Ci2alkylthio; C3-Ci2cycloalkylthio; CrCi2alkenylthio; C3-Ci2cycloalkenylthio;
CrCi2alkoxy; C3-Ci2cycloalkoxy; CrCi2alkenyloxy; or C3-Ci2cycloalkenyloxy which may
be unsubstituted or substituted by one or more R^; halogen; CN; SH; OH; CHO; Ris;
ORis; SR18; C(Ri8)=CRigR2o; O-CO-R19; NR18R19; CONR18R19; SO2NR18R19; SO2R18;
COOR18. OCOOR18; NRifiCORig; NR19COOR20; SiR15Ri6Ri7; OSiRi5Ri6Ri7;
P(=0)RigR2o; or a radical -X-Sil; Ri3, Ri4. Ri5, R16. Ri7, R18. Ri9 and R20 independently of each other are hydrogen;
Ci-C22alkyl; C3-Ci2cycloalkyl; C2-Ci2alkenyl; C3-Ci2cycloalkenyl; Ce-Cuaryl;
C4-Ci2heteroaryl; CrCisaraJkyl; or Cs-CieheteroaralkyI; or Ri3 and Run, R15 and R16, Rye and R17 and/or R18 and R19 may be linked together to form
unsubstituted or Gi-C4alkyl-substituted pyrrolidine, piperidine, piperazine or morpholinyl; X is a linker; and
Si! is a silane-, oligosiloxane orpolysiloxane moiety; t is a number from 0 to 12; u is a number from 1 to 12; V is a number from 0 to 12;

ifn=1
Ri and R2 independently of each other hydrogen; Ci-C22alkyl; hydroxy-Ci-C22alkyl; C2-C22al-kenyl; C2-C22 alkinyl; C3-Ci2cycloalkyl; C3-Ci2cycloalkenyl; CT-CzoaralkyI; Ci-C2ohetero-alkyl; C3-Ci2cycloheteroalkyl; C6-C2oaryl; Cg-Cnheteroaralkyl; CA-Cgheteroaryl; oral radi-
A

R21. R22, R23 independently form each other are Ci-C22alkyl; or Ci-C22alkoxy;
a is the bond to the linker X;
R3 is CN; NRsRe; -COR5; -COOR5; -SO2R5; -CONRsRe; C6"C2oaryl; or C4-C9heteroaryl;
p is a number from 0 to 100
q is a number from 1 to 20;
s is a number from 0 to 4;
if n = 2
Ri and R2 are each a bivalent radical selected from CrCsalkylene which may be interrupted
by one or more oxygen atoms; or Ri and R2 together with the nitrogen atoms form a six-membered heterocyclic ring; and
simultaneously R3 is defined as for n = 1; or R3 is a bivalent radical of formula -C0-Vi-CrCi2alkylene-Wi-*, wherein the asteroid indicates the bond to the second R3 Vi is -0-; or -NR7-; or the direct bond; Wi is the linkage to the second R3, wherein Wi is the direct bond; or selected from Cr
Ci2alkylene; or thienylene; and Ri and R2 simultaneously are defined as for n = 1; ifn = 3
one of Ri, R2 or R3 is a trivalent radical; ifn = 4





R21, R22 and R23, independently from each other are Ci-C22alkyl or CrC22alkoxy; A is a bond to the linker X; s is a number from 4 to 250; t is a number from 5 to 250; and q is a number from 1 to 30;
Halogen is chloro, bromo, fluoro or iodo, preferably a fluoro, more preferably fluoro alkyl like trifluoromethyl, a,a,a-trifluorethyl or perfluorinated alkyl groups like heptafluorpropyl.
Alkyl, cycloalkyl, alkenyl, alkylldene or cycloalkenyl residues can be straight-chain or branched, or also monocyclic or polycydic.
Alkenyl is for example straight-chain C2-Ci2alkenyl or preferably branched C3-Ci2alkenyl.
Ci-C22alkyl is for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-octyl, 1,1,3,3-tetra-methylbutyl, 2-ethylhexyl, nonyl, decyl, n-octadecyl, eicosyl, oderdodecyl.
C3-Ci2cycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trimethylcyclohexyl, menthyl, they, bony, 1-adamantyl or2-adamantyL
C2-Ci2alkenyl or C3-Ci2cycloalkenyl refers to unsaturated hydrocarbon residues containing one or multiple double bonds such vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadiene-2-yl, 2-cyclobutene-1-yl, 2-pentene-l-yl, 3-pentene-2-yl, 2-methyM-butene-3-yl, 2-methyl"3-butene-2-yl, 3-methyl-2-butene-1-yl, 1,4-pentadiene-3-yl, 2-cyclopentene-1-yl, 2-cyclohexene-1-yl. 3-cyclohexene-1-yl, 2,4-cyclohexadiene-1-yl, 1-p-menthene-8-yl, 4(10)-thujene-10-yl, 2-norbornene-1-yl, 2,5-norbornadiene-1-yl, 7,7-dimethyl-2,4-norcaradiene-3-yl or different isomers selected from hexenyl, octenyl. nonenyl, decenyl or dodecenyl.
Cz-CieAraikyl is for example benzyl, 2-ben2yl-2-propyl, p-phenyl-ethyl, 9-fluorenyl, aca-di-methylbenzyl, co-phenyl-butyl, co-phenyl-octyi, co-phenyl-dodecyl or 3-methyl'5-(1M',3,3-tetramethyl-butyO-benzyl.

The moiety may be unsubstituted or substituted on the alkyl- as well at the aryl-moiety of the aralkyl-group, but preferably is substituted on the aryl-moiety..
(Ci-C6)-Alkylating is for example methylene, ethyl-1-ene or propyl-2-ene.
C6-Ci4aryl is for example phenyl, naphthyl, biphenylyl, 2-fluorenyl, phenanthryl, anthracenyl orterphenylyl.
C4-Ci2heteroaryl is for example an unsaturated or aromatic radical with 4n+2 conjugated Ti-electrons, such as 2-thienyl, 2-furyl, 2-pyridyl, 2-thiazolyl, 2-oxazolyl. 2-imidazolyl, isothiazolyl, triazolyl or any other ring system consisting of thiophene-, furan-, pyridine, thiazol, oxazol, imidazol, isothiazol, triazol, pyridine- and phenyl rings, which are unsubstituted or substituted by 1 to 6 ethyl, methyl, ethylene and/or methylene groups, such as benzotriazolyl.
Cs-CieheteroaralkyI is for example a alkyl moiety which is substituted by a C4-C8heteroaryl group.
Preferably compounds of formula (1) are used, wherein
Li, L2 or L3, independently from each other are hydrogen; hydroxy; alkyI, which may be interrupted by one or more oxgen; COOR9; phenyl, which may be substituted by one or more halogen, alkyl alkoxy, trifluoroalkyi, C2-C5alkenyl; C4-C9heteroaryl; and
R9 is defined as in claim 1; and
n is 1; and more preferably compounds of formula (1), wherein
Li, L2 and L3, independently from each other are hydrogen, methyl, phenyl; or -COOR9; wherein
Rug is alkyI; and
n is 1.
Furthermore, compounds of formula (1) are used, wherein







Furthermore, compounds of formula (1) are preferred, wherein the stabilizers correspond to formula

Ri, R2. R3, R4, Li, L2, L3, Wi and W2 are defined as in formula (1).
Preferably compounds of formula (2a) are used, wherein
R3 is a radical of formula "C0-Vi-Ci-Ci2alkylene-**, wherein
Vi is-0;or-NH-;
Wi is the direct bond; CrC4alkylene; or thienylene;
Ri and R2, independently from each other are Ci-Ci2alkyl;
Li, L2 and L3 independently form each other are hydrogen; or alkyl; or
L3 and R2 together form a heterocyclic ring;
R4 is CN; COR7; COOR7; CONR7R8; SO2R7; and
R7 is Ci-C22alkyl; or phenyl.
Preferred compounds of formula (2b) are those, wherein
Ri is CrCsalkylene;
Li, L2 and L3 independently form each other are hydrogen; or alkyI; or
Li and L3 together form a carbocyclic ring;
R2 is hydrogen; or alkyI;
Wi is alkylene; or the direct bond;
R3 and R4 independently from each other are CN; COR7; COOR7; CONR7R8; SO2R7; and
R7and Rs, independently from each other are Ci-C22alkyl; or phenyl.
Furthermore, the use of compounds of formula











































ifn = 2
Ri and R2 are each a bivalent radical selected from CrCsalkylene which may be interrupted
by one or more oxygen atoms; or Ri and R2 together with the nitrogen atoms form a six-membered heterocyclic ring; and
simultaneously R3 is defined as for n = 1; or R3 is a bivalent radical of formula -C0-Vi-CrCi2alkylene-Wr*, wherein the aster indicates the bond to the second R3 Vi is -0-; or -NR7-; or the direct bond; Wi is the linkage to the second R3, wherein Wi is the direct bond; or selected from Ci-
Ci2alkylene; or hexylene; and Ri and R2 simultaneously are defined as for n = 1; ifn = 3
one of Ri, R2 or R3 is a trivalent radical; if n = 4



the asterices indicate the bond to the second, third and fourth R1/R2;
R24 is Ci-C22alkyl; or Ci-C22alkoxy;
wherein at least one of the radicals Ri, R2, R3 or R4 is a silicon organic compound,
are novel and represent a further object of the present invention.
The light stabilizers of formula (1) as well as mixtures of these compounds with other UV absorbers as listed in Tables 1-3, phenolic or non-phenolic antioxidants or with complex formers are particularly suitable for protecting body-care and household products against hemolytic degradation.
Examples of organic UV filters that can be used in admixture with the compounds of formula (1) are listed in the following Table:















The compounds of formula (1) may also be used in admixture with hindered amine light stabilizers as disclosed in WO 03/103622, e,g, hindered nitrify, hydroxylamine and hydroxylamine salt compounds.
Personal Care Uses
The merocyanines of formula (1) may be used as single component or in mixture with other stabilizers in particular for skin-care products, bath and shower additives, preparations con tainting fragrances and odoriferous substances, hair-care products, dentifrices, deodorizing and antiperspirant preparations, decorative preparations, light protection formulations and preparations containing active ingredients.
Skin-care products are, in particular, body oils, body lotions, body gels, treatment creams, skin protection ointments, shaving preparations, such as shaving foams or gels, skin powders, such as baby powder, moisturizing gels, moisturizing sprays, revitalizing body sprays, cellulite gels and peeling preparations.

Suitable bath and shower additives are shower gels, bath-salts, bubble baths and soap

c.

Preparations containing fragrances and odoriferous substances are in particular scents, perfumes, toilet waters and shaving lotions (aftershave preparations).
Suitable hair-care products are, for example, shampoos for humans and animals, in particular dogs, hair conditioners, products for styling and treating hair, perming agents, hair sprays and lacquers, hair gels, hair fixatives and hair dyeing or bleaching agents.
Suitable dentifrices are in particular tooth creams, toothpastes, mouth-washes, mouth rinses anti-plaque preparations and cleaning agents for dentures.
Suitable decorative preparations are in particular lipsticks, nail varnishes, eye shadows, mascaras, dry and moist make-up, rouge, powders, depilatory agents and suntan lotions
Suitable cosmetic formulations containing active ingredients are in particular hormone preparations, vitamin preparations, vegetable extract preparations and antibacterial preparations.

The mentioned body-care products may be in the form of creams, ointments, pastes, foams, gels, lotions, powders, make-ups, sprays, sticks or aerosols.
They preferably contain the light stabilizers of formulae (1) and, optionally, other UV absorbers, satirically hindered amines, completing agents and phenolic or non-phenolic antioxidants.
The present invention therefore also relates to a body-care product comprising at least one compound of formula (1).
The compounds o formula (1) are present in the body care and household products in a concentration of about 5 to about 10000 ppm, based on the total formulation, preferably from about 10 to about 5000 ppm, and most preferably from about 100 to about 1000 ppm.
The cosmetic compositions according to the present invention may also contain one or one more additional compounds as described below.
Fatty alcohols
Gerber alcohols based on fatty alcohols having from 6 to 18, preferably from 8 to 10 carbon atoms including acetyl alcohol, stearyl alcohol, cetearyl alcohol, solely alcohol, octyldodecanol, benzoate of CI2-C15 alcohols, acetylated lanolin alcohol, etc..
Esters of fattv acids
Esters of linear C6-C24 fatty acids with linear C3-C24 alcohols, esters of branched Ce-Ciscarboxylic acids with linear C6-C24 fatty alcohols, esters of linear C6-C24fatty acids with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols, especially di octyl maltase, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or timer trioi) and/or Guerbet alcohols, for example caproic acid, caprylic acid, 2-ethylhexanoic acid, caprice acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic ,-., isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic 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 Roe lens ox synthesis or in the dimerisation of unsaturated fatty acids) with alcohols, for example, isopropyl alcohol, caproic alcohol, carpel alcohol, 2-ethylhexyl alcohol, caprice alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, sisterly alcohol, volley alcohol, elaidyl alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, mercy alcohol and brassily 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 ox synthesis 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, iso-octylstearate. iso-nonylstearate, isononyl isononanoate, 2-ethylhexylpalmitate. 2-hexyl-laurate, 2-hexyldecylstearate, 2-octyldodecylpalmitate, oleyloleate, oleylerucate, erucylo-leate, erucylerucate, cetearyl octanoate, cetyl palmitate, cetyl stearate, cetyl oleate, cetyl behenate, cetyl acetate, myristyl myristate, myristyl behenate, myristyl oleate, myristyl stearate, myristyl palmitate, myristyl lactate, propylene glycol dicaprylate/caprate, stearyl heptanoate, diisostearyl malate, octyl hydroxystearate, etc..
Natural or synthetic diglycerides including glycerol esters and derivatives Di- or tri-glycerides, based on C6-C18 fatty acids, modified by reaction with other alcohols (caprylic/caprice 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 wax-like properties, e.g., carnauba wax, beeswax (white or yellow), lanolin wax,
Pearle scent waxes
Alkylene 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, laid ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially larine and dietary ether; fatty acids, such as stearic acid, hydroxy stearic 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, paraffin and isoparaffinic compounds, hydrogenated isoparaffinic molecules as polydecenes and polybutene, hydrogenated polyisobutene, squalane, isohexadecane, isododecane and others from plant and animal kingdom.
Silicones or slogans (orqanosubstituted polvsiloxanes)
Dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones, and also amino-, fatty acid-, alcohol-, polyesters-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds, which at room temperature may be in either liquid or resinous form. Linear polvsiloxanes, dimethicone (Dow Corning 200 fluid, Rhoda 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 al. of suitable volatile silicones may in addition be found in Cosm. Toil. 91, 27 (1976).
Fluorinated or perfluorinated oils
Perfluorhexane, dimethylcyclohexane. ethyicyclopentane, polyperfluoromethylisoproHy^ ether.

Emulsifiers
Any conventionally usable emulsifier can be used for the compositions. Emulsifier systems may comprise for example: carbocyclic 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 alkyi-phenols having from 8 to 15 carbon atoms in the alkyl group. Fatty alcohol polyglycolether 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 poly-ols. Fatty acid and polyglycerol ester such as monostearate glycerol, diisostearoyi polygly-ceryl-3-diisostearates, polyglyceryl-3-diJsostearates, 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 di-ethylene 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 ethanol-amine lauryl sulfates, lauyl ether sulfates, sodium laureth sulfates, sulfosuccinates, aceyl isothionates, alkanolamide sulfates, taurines, methyl taurines, imidazole sulfates. Amine uc.; vatives, 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, oxydeamide. Polysiloxane/polyalkyl/polyether copolymers and derivatives, dimethicone, copolyols, 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,NDdimethylammonium glycinates, cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, cocoacylaminopropyldimethyl-ammonium glycinate and 2Dalkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxy-ethylcarboxymethylglycinate, N-alkylbetaine. N-alkylaminobetaines. Alkylimidazolines, alkylopeptides, lipoaminoacides, self emulsifying bases and the compounds as described in K.F.DePolo, A short textbook of cosmetology, Chapter 8, 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 and steareth-20 [Tefose 2000], PEG-6 stearate and ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561], glyceryl stearate and ceteareth-20 [Teginacid H, C, Xj.
Anionic emulsifiers such as PEG-2 stearate SE, glyceryl stearate SE [Monelgine, Cutina KD], propylene glycol stearate [Tegin P], cetearyl Alcohol and Sodium cetearyl sulfate [Lanette N

Cutina LE, Crodaco! GP], cetearyl alcohol and sodium lauryl sulfate [Lanette W], trilaneth-4 phopshate 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 cetrimonium 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.
When formulated in OA/V emulsions, the preferably amount of such emulsifier system could represent 5% to 20% of the oil phase.
Super-fattinq 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,
monoglycerides 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, alky! 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
silicon 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 hydroxycelluiose, hydroxypropyl-methylcellulose. In addition polyacrylates or homopolymer of reticulated acrylic acfds ^i... 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 alky! 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 quaternised hydroxymethyl cellulose obtainable under the name Polymer JR 400 from Amerchol, cationic starches, copolymers of diallylammonium salts and acrylamides, quaternised vinylpyrrolidone/vinyl imidazole polymers, for example Luviquata (BASF), condensation products of polyglycols and amines, quaternised collagen polypeptides, for example lauryldimonium hydroxypropyl hydrolyzed collagen (LamequataL/Grunau), quaternised wheat polypeptides, polyethyleneimine, cationic silicone polymers, for example amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylene-triamine (Cartaretin/Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat 550 / Chemviron), polyaminopolyamides, as described, for example, in FR A / 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, vinyl-pyrrolidone / 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-trimethyl-ammonium chloride /acrylate copolymers, octyl acrylamide/methyl methacrylatetert. butyl-aminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/dimethylaminoethyl methacry-^ late/vinyl caprolactam terpolymers and also optionally derivatised cellulose ethers and s/i: cones. Furthermore the polymers as described in EP 1093796 (pages 3-8, paragraphs 17-68) may be used.

Cationic surfactants
cetyl trimethyl ammonium bromide (CTAB), dimethicone copolyols, amidomethicones, acrylamidopropyltrimonium chloride/Acrylamide copolymer, guar hydroxypropyl trimonium chloride, hydroxycetyl hydroxyethyl dimonium chloride quaternium compounds as listed in International Cosmetic Ingredient Dictionary and Handbook, 7^^ Edition 1997, for example Quaternium-80, polyquaternium compounds, as listed in International Cosmetic Ingredieni Dictionary and Handbook, 7^^ Edition 1997, for example polyquaternium- 5, polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-11, polyquaternium-17, poly-quaternium-18, polyquaternium-24 or polyquatemium-27, polyquaternium-28, polyqua-ternium-32, polyquaternium-37.
Biooenic 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 are for example, antiperspirants, for example aluminium chlorohydrates (see J. Soc. Cosm. Chem. 24, 281 (1973)). Under the trade mark Locrona of Hoechst AG, Frankfurt (FRG), there is available commercially, for example, an aluminium chlorohydrate corresponding to formula AI2(OH)5CI x 2.5 H20, 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 triethyl citrate (Hydagen CAT, Henkel), 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 phosphate, dicarboxyiic acids and esters thereof, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl es^'-adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malomc 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 pyrithione. Customary film formers include, for example, chitosan, microcrystalline chitosan, quaternised 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.
Hvdrotropic agents
For improvemrnt of 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 for that purpose comprise preferably 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 oligo-glycerol 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; me-thylol compounds, such as, especially, trimethylolethane. trimethylolpropane, trimethyl-olbutane, pentaerythritol and dipentaerythritol; lower alkyl-glucosides. especially those having from 1 to 8 carbon atoms in the alkyl radical, for example methyl and butyl giDc-ci ir 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; dialcohol amines, such as diethanolamine or 2-amino-1,3-propanediol

Preservatives
Suitable preservatives include, for example methyl-, ethyl-, propyl-, butyl- parabens, benz-alkonium chloride, 2-bromo-2-nitro-propane-1,3-diol, dehydroaceticacid, diazolidinyl urea, 2-dichloro-benzyl alcohol, dmdm hydantoin, formaldehyde solution, methyldibromoglutanitrile, phenoxyethanol. sodium hydroxymethylglycinate, imidazolidinyl urea, triclosan and further substance classes listed in the following reference: K.F.Depolo - A Short Textboot Bacteria-inhibiting agents
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, chlor-hexidine (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-trimethyl-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
Mixtures of natural and/or synthetic aromatic substances. Natural aromatic substances are, for example, extracts from blossom (lilies, lavender, roses, jasmine, neroii, 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, ce-darwood, rosewood), from herbs and grasses (tarragon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (gal-banum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials also come into consideration, for example civet and castoreum. Typical synthetic aromatic substance^ ' 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, phenoxy-ethyl 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, liiial and bourgeonai; 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 terpinoi; 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, liiial, 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, ally! 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.
Other adiuvants
It is furthermore possible for the cosmetic preparations to contain, as adjuvants, anti-foams, such as silicones, structurants, such as maleic acid, solubiiisers, such as ethylene glycol, propylene glycol, glycerol or diethylene glycol, opacifiers, such as latex, styrene/PVP or styrene/acrylamide copolymers, propellants, such as propane/butane mixtures, N20, dimethyl ether, C02, 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.

ml rv
Suitable insect repeHents are. for example, N,N-diethyl-m-toluamide, 1,2-pentanedi 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.

The present stabilizer systems are particularly suitable for stabilizing body care products, in particular:
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; body oils, body
lotions, body gels; skin protection ointments;
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 and odoriferous substances containing preparations (scents, 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;
dentifrices, in particular tooth creams, toothpastes, mouth-washes, mouth rinses, anti-plaque preparations and cleaning agents for dentures;
decorative preparations, in particular lipsticks, nail varnishes, eye shadows, mascaras, dry and moist make-up, rouge, powders, depilatory agents and suntan lotions cosmetic formulations containing active ingredients, in particular hormone preparations vitamin preparations, vegetable extract preparations and antibacterial preparations.
Suitable cosmetic formulations containing active ingredients are in particular hormone preparations, vitamin preparations, vegetable extract preparations and antibacterial preparations.
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/0, 0/W, 0/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 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: 0.01 to 5 % by weight of the compound of formula (1), 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:
a1) spontaneously emulsifying stock formulation, comprising the compound of formula (1) according to the invention, optionally another stabilizer, 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;
a2) spontaneously emulsifying stock formulation comprising the compound of formula (1) according to the invention, optionally another stabilizer, tributyl citrate and PEG-20-sorbitan monooleate, to which water and any desired quaternary ammonium compound for example 4 % minkamidopropyl dimethyl-2-hydroxyethylammonium chloride o[ Quaternium 80 is added;
b) quat-doped solutions comprising the compound of formula (1) according to the invention in butyl triglycol and tributyl citrate; and optionally another stabilizer;

c) mixtures or solutions comprising the compound of formula (1) according to the invention with alkylpyrrolidone; and optionally another stabilizer.
Examples of body care products of the present invention are listed in the Table below:

Body care product Jnaredients
moisturising cream vegetable oil, emulsifier, thickener, perfume, water, antioxidant, UV absorbers
shampoo surfactant, emulsifier, preservatives, perfume, antioxidant, UV absorbers
Toothpaste cleaning agent, thickener, sweetener, flavor, colorant, antioxidant, water, UV absorbers
lip-care stick vegetable oil, wax, Ti02, antioxidant, UV absorbers
Household products
The stabilizer systems of the present invention are also used in household cleaning and treatment agents, for example in laundry products and fabric softeners, liquid cleansing and scouring agents, glass detergents, neutral cleaners (all-purpose cleaners), acid household cleaners (bath), bathroom cleaners, WC cleaners, for instance in washing, rinsing and dishwashing agents, kitchen and oven cleaners, clear rinsing agents, dishwasher detergents, shoe polishes, polishing waxes, floor detergents and polishes, metal, glass and ceramic cleaners, textile-care products, rug cleaners and carpet shampoos, agents for removing rust, color and stains (stain remover salt), furniture and multipurpose polishes and leather and vinyl dressing agents (leather and vinyl sprays) and air fresheners.
Household cleaning agents are aqueous or alcoholic (ethanol or isopropyl alcohol) solutions of one or more of the following components:
anionic, nonionic, amphoteric and/or cationic surfactants
soaps, prepared by saponification of animal and vegetable greases
organic acids, like hydrochloric acid, phosphoric acid, or sulfuric acid,
for basic products inorganic (NaOH or KOH) or organic bases;
abrasives for improved cleaning of surfaces,
waxes and/or silicones for maintenance and protection of surfaces,
polyphosphates,
substances which eliminate hypochlorite or halogens;
peroxides comprising bleaching activators like TAED, for example sodium perborate or
H2O2;

enzymes;
in washing detergents discoloration inhibitors, soil-release compounds, grey scale
inhibitors, foam inhibitors, fluorescent whitening agents;
cleaning agents based on wax may comprise solvents selected from benzine, turpentine
and/or paraffines and emulsifiers based on wax;
filling agents like silicates, polyphosphates, Zeolithes for powdery cleaning agents;
pigments, lakes or soluble dyes;
perfumes; and
light stabilizers, antioxidants and chelating agents.
Colored cleaning agents and decorative cosmetic products can comprise the following dyes: inorganic pigments, for example iron oxide (Iron Oxide Red, Iron Oxide Yellow, Iron Oxide Black, etc.). Ultramarines, Chromium Oxide Green or Carbon Black; natural or synthetic orgnic pigments;
disperse dyes which may be solubilzed in solvents like direct hair dyes of the HC type, for example HC Red No. 3, HC Blue No. 2 and all other hair dyes listed in International Cosmetic Ingredient Dictionary and Handbook, 7th edition 19997) or the dispersion dyes listed in Color Index International or Society of Dyers and Colourists; color varnishes (insoluble salts of soluble dyes, like many Ca-, Ba- or Al-salts of anionic , dyes);
soluble anionic or cationic dyes, like acid dyes (anionic), basic dyes (cationic), direct dyes, reactive dyes or solvent dyes.
Generally, for the coloration of household- and body care products all substances are suitable which have an absorption in the visible light of electromagnetic radiation (wave length of ca. 4000 to 700 nm). The absorption is often caused by the following chromophores:
Azo- (mono-, di, tris-, or poly-)stilbene-, carotenoide-, diarylmethan-, triarylmethan-, xanthen-, acridin-, quinoline, methin- (also polymethin-), thiazol-, indamin-, indophenol-, azin-, oxazin, thiazin-, anthraquinone-, indigoid-, phtalocyanine- and further synthetic, natural and/or inorganic chromophores.
The present invention also relates to home care and fabric care products such as drain cleaners, disinfectant solutions, upholstery cleaners, automotive care products (e.g., to clean

and/or polish and protect paint, tires, chrome, vinyl, leather, fabric, rubber, plastic and fabric), degreasers, polishes (glass, wood, leather, plastic, marble, granite, and tile, etc.), and metal polishes and cleaners. Antioxidants are suitable to protect fragrances in above products as well as in dryer sheets. The present invention also relates to home care products such as candles, gel candles, air fresheners and fragrance oils (for the home).

The stabilizers of formula (1) according to the present invention are for example incorporated by dissolution in an oil phase or alcoholic or water phase, where required at elevated temperature.
The present body care products and household products have high stability towards color changes and chemical degradation of the ingredients present in these products. For example, present compositions that comprise a dye are found to have excellent color stability.
The following Examples illustrate the invention.






Efficacy comparison to state-of-the art stabilizers
Expample 1:
The following colored basic shampoo formulation is prepared:
Sodium Laureth Ether Sulfate 10%
Cocamidopropylbetaine 3%
Citric Acid to pH 5
FD&C Blue No. 1 0.002%
Stabilizer q.a.
The following stabilized und unstabilized samples of this formulation are prepared for light stability testing:
1. unstabilized basic shampoo formulation
2. basic shampoo formulation plus 0.05% of the compound of formula (AO 07)
3. basic shampoo formulation plus 0.05% of compound of formula (101)
4. basic shampoo formulation plus 0.05% of compound of formula (102)
5. basic shampoo formulation plus 0.05% of compound of formula (103)
6. basic shampoo formulation plus 0.05% of compound of formula (104),
7. basic shampoo formulation plus 0.05% of compound of formula (105)

The formulations were filled into 30 ml glass bottles and irradiated in an ATLAS Suntest XLS+ Xenon Lamp (light intensity 500W/m2, spectrum of light adjusted to indoor conditions, sample chamber temperature: 32°C).

Sample 3-7 comprising a stabilizer according to the present invention exhibits significantly better light stability compared to the state-of-the-art UV absorber of formula (AO 07).
Example 2:
The following colored basic shampoo formulation is prepared:
Sodium Laureth Ether Sulfate 10%
Cocamidopropylbetaine 3%
Citric Acid to pH 5
FD&C Blue No. 1 0.002%
Stabilizer q.a.
The following stabilized und unstabilized samples of this formulation are prepared for light stability testing:
1. unstabilized basic shampoo formulation
2. basic shampoo formulation plus 0.05% of the compound of formula (AO 07)
3. basic shampoo formulation plus 0.05% of the compound (AO 07) plus 0.003% or compound AO 02
4. basic shampoo formulation plus 0.05% of compound of formula (104).

The formulations were filled into 30 ml glass bottles and irradiated in an ATLAS Suntest XLS+ Xenon Lamp (light intensity 500W/m2, spectrum of light adjusted to indoor conditions, sample chamber temperature: 32°C).

Sample 4 comprises a stabilizer according to the present invention. It exhibits significantly better light stability compared to the state-of-the-art UV absorber of formula (AO 01), and performed even better than the highly effective stabilizer combination of sample 3.
Example 3:
The following stabilized and unstabilized samples were prepared for antioxidation testing:
1. pure linoleic acid
2. linoleic acid containing 0,05 % of compound of formula (104).
The samples were placed in a RACIMAT and heated to 80 °C. An airflow of 15 L/min was adjusted. The airstream bubbles through each heated sample and aftenA/ards through a water reservoir. Thus all volatile organic compounds formed by the oxidation process are carried Into the water resen/oir by the airstream. The conductivity of the water reservoir is monitored online during the measurement. Once oxidation starts volatile organic compounds like formic acid are transported into the water reservoir which results in a rapid (exponential) increase of conductivity. The time until oxidation starts is called "induction time".


Sample 2 comprising a stabilizer according to the present invention exhibits better oxidation stability compared to the unstabilized sample.

Preparation;
The components (A) are dispersed at room temperature.
(B) is mixed under heating until the paraben is completely dissolved and then (B) is added
with gentle stirring to (A).
(C) is blended until it is completely dissolved and is slowly added under stirring to the mixture
of (A) and (B).
The transparency of the gel can be increased by adding small amounts of triethanolamine (pH=5.6-5.75).


Preparation: Surfactant and water are blended until a homogeneous solution is obtained. The pH is adjusted to 6.0-6.5 with citric acid and the other components are added in the indicated sequence. The mixture is stirred until it is completely dissolved.

Preparation: The components are thoroughly mixed in the indicated sequence at SCC. A clear homogeneous solution is obtained.







Preparation: The components are stirred in the indicated sequence until a homogeneous mixture is obtained.







Claims:
1. Use of stabilizers of formula

aromatic rings and each N in a N-heterocyclic ring may be unsubstituted or substituted by Rio;
and each alkyl, alkenyl, alkynyl, cyclo alkyi or cycloalkylene group may be unsubstituted or substituted by one or more Rn;
and each aryl, heteroaryl, aralkyl, arylene, heteroarylene or aralkylene may be unsubstituted or substituted by one or more R12; Rio is R13; COR13; COOR13; or CONR13R14;

Rn is halogen. OH; NR15R16; O-Ris; S-R15; O-CO-R15; CO-Ris; 0x0; thiono; CN; COORis;
CONR15R16; SO2NR15R16; SO2R15; SO3R15; POR15R16; or a
radical -X-Sil; R12 is aikyithio; C3-C12cycloalkylthio; alkenyl thio; acycloalkenylthio;
CrC12alkoxy; C3-C12cycloalkoxy; Ci-C12alkenyloxy; or C3-C12cycloalkenyloxy which may
be unsubstituted or substituted by one or more Rn; halogen; CN; SH; OH; CHO; Ris;
Aria; Sirs; C(Ri8CRi9R2o; O-CO-R19; NRisRig; CONRisRisJ SO2NR18R19; SO2R18;
COOR18, OCOORis; NR18COR19; NR19COOR20; SiRisRieRiz; OSIRigRisRiz;
P(=0)Ri9R2o; or a radical -X-Sil; Ri3i Ru, Ri5» R16, Ri7> R181 Ri9 and R20 independently of each other are hydrogen;
CrC22alkyl; C3-C12Cycloalkyl; C2-C12alkenyl; C3-C12cycloalkenyl; C6-Ci4aryl;
C4-C12heteroaryl; aralkyl; or heteroaralkyI; or Ri3 and R14, R15 and R16, R16 and R17 and/or Rye and R19 may be linked together to form
unsubstituted or CrC4alkyl-substituted pyn'olidine, piperidine, piperazine or morpholine; X is a linker; and
Sil is a silane-, oligosiloxane or polysiloxane moiety; t is a number from 0 to 12; u is a number from 1 to 12; V is a number from 0 to 12; ion = 1 Ri and R2 independently of each other hydrogen; CrC22alkyl; hydroxy-CrC22alkyl; C2-C22al-
kenyl; C2-C22alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C2oaralkyl; CrC2ohetero-
alkyl; G3"C12cycloheteroalkyl; C6-C2oaryl; Cs-Cuheteroaralkyl; C4-C9heteroaryl; or a raids-
A


Ri and R2 are each a bivalent radical selected from alkylene which may be interrupted
by one or more oxygen atoms; or Ri and R2 together with the nitrogen atoms form a six-membered heterocyclic ring; and
simultaneously R3 is defined as for n = 1; or R3 is a bivalent radical of formula "C0-VrCrC12alkylene-Wr*, wherein the asteroid indicates the bond to the second R3 Vi is -0-; or -NR7-; or the direct bond; Wi is the linkage to the second R3, wherein Wi is the direct bond; or selected from Cr
C12alkylene; or thienylene; and Ri and R2 simultaneously are defined as for n = 1; ifn = 3
one of Ri, R2 or R3 is a trivalent radical; ifn = 4



R24 is Ci-C22alkyl; or Ci-C22alkoxy;
for protecting body-care and household products from histolytic and oxidative degradation.
2. Use according to claim 1, wherein
Li, L2 or L3, independently from each other are hydrogen; hydroxy; alkyl, which may be interrupted by one or more oxygen; COOR9; phenyl, which may be substituted by one or more halogen, alkyl, alkoxy, trifluoroalkyi, C2-C5alkenyl; C4-C9heteroaryl; and
R9 is defined as in claim 1; and
n is 1.
3. Use according to claim 1 or 2, wherein
Li, L2 and L3, independently from each other are hydrogen, methyl, phenyl; or -COOR9;
wherein R9 is alkyl; and
n is1.
4. Use according to claim 1 or 2, wherein








13. Use according to claim 12, wherein
in formula (2a)
R3 is a radical of formula "C0-VrCrC12alkylene-**, wherein
Vi is-0;or-NHs
Wi is the direct bond; CrC4alkylene; or phenylene;
Ri and R2, independently from each other are alkyi;
Li, L2 and L3 independently form each other are hydrogen; or alkyl; or
L3 and R2 together form a heterocyclic ring;
R4 is CN; COR7; COOR7; CONR7R8; SO2R7; and
R7 is Ci-C22alkyl; or phenyl.
14. Use according to claim 12, wherein
in formula (2b)
Ri is alkylene;
Li, L2 and L3 independently form each other are hydrogen; or alkyI; or
U and L3 together form a carbocyclic ring;
R2 is hydrogen; or alkyI;
W is alkylene; or the direct bond;
R3 and R4 independently from each other are CN; COR7; COOR7; CONR7R8; SO2R7; and
R7and Rs, independently from each other are Ci-C22alkyl; or phenyl.
15. Use according to claim 1, wherein the stabilizers correspond to the formula


16. Use according to claim 12, wherein
in formula (3a)
Li, L2 and L3 independently from each other are hydrogen; hydroxy; alkyl; or Li and L3
together form a carbocyclic ring; Ri and R2 independently from each other are hydrogen; or CrC12alkyl; R3 is *-C0-Vi-CrC12alkylene"**; Vi is-0;or-NH-;

R4 is CN; COR7; COOR7; CONRyRs; SO2R7; and
Ryan Rs, independently from each other are CrC22alkyl; or phenyl.
17. Use of the light stabilizer according to any one of claims 1 to 16 in body-care products for
the skin and its addenda.
18. Use according to claim 17, wherein the body-care products are selected from skin-care
products, bath and shower additives, preparations containing fragrances and odoriferous
substances, hair-care products, dentifrices, deodorizing and antiperspirant preparations,
decorative preparations, light protection formulations and preparations containing active
ingredients.

19. Use according to claim 17, wherein the body-care products are selected from body oils, body lotions, body gels, treatment creams, skin protection ointments, shaving preparations and skin powders.
20. Use according to claim 17, wherein the preparations contain fragrances and odoriferous substances which are selected from scents, perfumes, toilet waters and shaving lotions (aftershave preparations).
21. Use according to claim 17, wherein the body-care products are hair-care products and are selected from shampoos, hair conditioners, products for styling and treating hair, perming agents, hair sprays and lacquers, hair gels, hair fixatives and hair dyeing or bleaching agents.
22. Use according to claim 17, wherein the body-care products are decorative preparations and are selected from lipsticks, nail varnishes, eye shadows, mascaras, dry and moist make-up, rouge, powders, depilatory agents and suntan lotions.
23. Use according to claim 17, wherein the cosmetic preparations contain active ingredients and are selected from hormone preparations, vitamin preparations, vegetable extract preparations and antibacterial preparations.
24. Use of the light stabilizer according any one of claims 1 to 16 in household cleaning and treating agents.
25. Use according to claim 24 wherein the household cleaning and treating agents are selected from washing, rinsing and dishwashing agents, shoe polishes, polishing waxes, floor detergents and polishes, all purpose cleaners, bath and toilet cleaners, kitchen cleaners, car shampoos and waxes, neutral, acidic and alkaline cleaners, metal, glass and ceramic cleaners, textile care agents, agents for removing rust, color and stains (stain remover salt), bleaches, furniture and multipurpose polishes, surface protecting formulations, film forming formulations, air care formulations and candles.
26. A body-care product, which comprises at least one light stabilizer according to claim 1.

27. A household cleaning and treating agent, which comprises at least one light stabilizer according to claim 1.
28. Compounds of formula

R3 is CN; Norse; "COR5; -COOR5; -SO2R5; -Corners; Ce-Czoaryl; or CA-Cgheteroaryl; R4 is CN; -COR7; -COOR7; -CONRyRs; CrC22alkyl; C2-C22alkenyl; C2-C22alkinyl; C3-
C12cycloalkyl; C3-C12cycloalkenyl; C7-C2oaralkyl; CrC2oheteroalkyl; C3-C12cyclo-
Heteroalkyl; Cs-CuheteroaraJkyl; C6"C2oaryl; CrCialkylcarbonylaminO"C6-C20aryl; C4-
Cgheteroaryl; R5. Re, R7 and Re are independently of each other hydrogen; CrC22alkyl, C2-C22alkenyl,
C2-C22alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C2oaralkyl; COR9; -(COyCOO-Rg;
C1-C20 Heteroalkyl; Cs-CiacycloheteroalkyI; Cs-Cnheteroaralkyl; C6-C2oaryl; CrCsalkoxy-
C6-C2oaryl; "(CH2)rS03H; -(CHsHCOVORg; -(CHgVO-Ce-Cioaryl; -(CH2)vCOO-R9; C4"
Cgheteroaryl; -(CH2)u-SiRi5Ri6Ri7; or a radical -X-Sil; Rg is hydrogen; Ci-C22alkyl; C2-C22alkenyl; C2-C22alkinyl; C3-C12cycloalkyl; C3-C12cyclo-
alkenyl; C7-C2oaralkyl; CrC2oheteroalkyl; C3-C12cycloheteroalkyl; Cs-Cnheteroaralkyl;
C6-C2oaryl; or C4-C9heteroaryl; or Li and L3, are H or may be linked together to fonn 1, 2, 3 or 4 carboxylic or N, O and/or S-
heterocyclic rings, which may be further fused with other aromatic rings and each N in a
N-heterocyclic ring may be unsubstituted or substituted by R10;
and each alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylene group may be unsubstituted
or substituted by one or more R ;
and each aryl, heteroaryl, aralkyl. arylene, heteroarylene or aralkylene may be
unsubstituted or substituted by one or more R12; R10 is R13; COR13; COOR13; or CONR13R14; R11 is halogen, OH; NR15R16; O-Rise S-R15; CO-R15; 0x0; thiono; CN; COOR15; CONR15R16;
SO2NR15R16; SO2R15; SO3R15; POR15R16; or a radical -X-Sil; R12 is CrC12alkylthio; C3-C12cycloalkylthio; CrC12alkenylthio; C3-C12cycloalkenylthio;
CrC12alkoxy; C3-C12cycloalkoxy; Ci-C12alkenyloxy; or C3-C12cycloalkenyloxy which may
be unsubstituted or substituted by one or more R^; halogen; CN; SH; OH; CHO; Ris;

0Ri8; SR18; C(Ri8)=CRi9R2o; O-CO-R19; NRigRig; CONR18R19; SO2NR18R19; SO2R18;
COOR18, OCOOR18; NR18COR19; NR19COOR20; ; OSiRisRieRi?;
P(=0)Ri9R2o; or a radical -X-Sil; Ri3, Ri4, Ri5, R16, Ri7, R18. Ri9 and R20 independently of each other are hydrogen;
Ci-C22alkyl; C3-C12cycloalkyl; C2-C12alkenyl; C3-C12cyGloalkenyl; aryl;
C4-C12heteroaryl; aralkyI; or Cs-CieheteroaralkyI; or Ri3 and R14, R15 and Rye, Rye and R17 and/or R18 and R19 may be linked together to form
unsubstituted or CrC4alkyl-substituted pyrrolidine, piperidine, piperazine or morpholine; X is a linker; and
Sil is a silane-, oligosiloxane or polysiloxane moiety; t is a number from 0 to 12; u is a number from 1 to 12; V is a number from 0 to 12; if n = 1 Ri and R2 independently of each other hydrogen; CrC22alkyl; hydroxy-CrC22alkyl; C2-C22al-
kenyl; C2-C22alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C2oaralkyl; hereto-
alkyl; Cs-Ciacycloheteroaikyl; C6-C2oaryl; Cs-Cuheteroaralkyl; C4-C9heteroaryl; or a radii-
*

R21, R22, R23 independently form each other are Ci-C22alkyl; or Ci-C22alkoxy;
p is a number from 0 to 100
q is a number from 1 to 20;
s is a number from 0 to 4;
R3 is CN; Norse; -COR5; -COOR5; -SO2R5; -Corners; C6-C2oaryl; or C4-C9heteroaryl;
ifn = 2
Ri and R2 are each a bivalent radical selected from alkylene which may be interrupted
by one or more oxygen atoms; or Ri and R2 together with the nitrogen atoms form a six-membered heterocyclic ring; and
simultaneously R3 is defined as for n = 1; or R3 is a bivalent radical of formula -C0-VrC1-C12alkylene-Wi-*, wherein
the asterix indicates the bond to the second R3 Vi is -0-; or -NR7-; or the direct bond;

Wi is the linkage to the second R3, wherein Wi is the direct bond; or selected from Cr
C12alkylene; or phenylene; and Ri and R2 simultaneously are defined as for n = 1 ; ifn = 3
one of Ri, R2 or R3 is a trivalent radical; ifn = 4



the aster ices indicate the bond to the second, third and fourth R1/R2; R24 is C1-C22alkyl; or C1-C22all

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=QZ5jG0kH2ddzj77iy/WOVQ==&loc=egcICQiyoj82NGgGrC5ChA==


Patent Number 268796
Indian Patent Application Number 482/CHENP/2008
PG Journal Number 38/2015
Publication Date 18-Sep-2015
Grant Date 16-Sep-2015
Date of Filing 29-Jan-2008
Name of Patentee BASF SE
Applicant Address 67056, LUDWIGSHAFEN, GERMANY.
Inventors:
# Inventor's Name Inventor's Address
1 WAGNER, BARBARA IM VOGELSANG 10, 79539 LORRACH, GERMANY.
2 REICH, OLIVER SALINENWEG 22, D-79639 GRENZACH-WYHLEN, GERMANY.
PCT International Classification Number A61K 8/41
PCT International Application Number PCT/EP2006/064388
PCT International Filing date 2006-07-19
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 05107026.6 2005-07-29 EUROPEAN UNION
2 06100600.3 2006-01-19 EUROPEAN UNION