USOO6858216B2 (12) United States Patent (10) Patent No.: US 6,858,216 B2 Schulze Zur Wiesche et al. (45) Date of Patent: Feb. 22, 2005

(54) COSMETICAGENT CONTAINING DE 44 13 686 C2 10/1996 2-FURANONE DERVATIVES DE 19738 866 A1 3/1999 DE 19756 454 C1 6/1999 (75) Inventors: Erik Schulze zur Wiesche, Hamburg EP O O47 714 B1 10/1985 (DE); Detlef Hollenberg, Erkrath (DE); E. s 2. g A2 3. Britta Bossmann, Erkrath (DE) EP O 283 817 B1 12/1990 (73) ASSignee: Henkel Kommanditgesellschaft auf E. s R is: Aktien, Duesseldorf (DE) EP O 561 999 B1 1/1996 EP O 612 759 B1 10/1996 (*) Notice: Subject to any disclaimer, the term of this EP O 740 741 B2 11/1996 patent is extended or adjusted under 35 GB 2104 O91 A 3/1983 U.S.C. 154(b) by 0 days. GB 2 235 451 A 3/1991 JP 04-091084 3/1992 JP O7-1261.48 5/1995 (21) Appl. No.: 10/289,061 JP O7-242526 9/1995 (22) Filed: Nov. 6, 2002 JP 08-026942 1/1996 JP 11-292753 10/1999 (65) Prior Publication Data WO WO 92/13829 A1 8/1992 WO WO 94/0897O A1 4/1994 US 2003/0206933 A1 Nov. 6, 2003 OTHER PUBLICATIONS Related U.S. Application Data Database accession No. 131:303228 CA XP002185854 (JP (63) Continuation of application No. PCT/EP01/04822, filed on 11292753 Oct. 26, 1999). Apr. 28, 2001. Database accession No. 124:269960 CA XP002185855 (JP (30) Foreign Application Priority Data 08 026942 Jan. 30, 1996). May 6, 2000 (DE) ...... 1OO 22 O77 Database accession No. 124:66215 CA XP 002185856 (JP 07 242526 Sep. 19, 1995). (51) Int. Cl." ...... A61K 7/00; A61K 47/30 Database accession No. 123:122753 CA XP002185857 (JP (52) U.S. Cl...... 424/401; 424/400; 514/772.2 07 126148 May 16, 1996). (58) Field of Search ...... 424/400, 401; 514/772.2 Database accession No. 1992–147994 XP002185858 (JP 04 091084 Mar. 24, 1992). (56) References Cited International Cosmetic Ingredient Dictionary and Hand book, 7th Edition, 1997, (cover page and table of contents). U.S. PATENT DOCUMENTS A.K. Biswas et al., “Surface-Active Properties of Sodium 4,237,253 A 12/1980 Jacquet et al. Salts of Sulfated Fatty Acid Monoglycerides”,Journal of the 4,393,886 A 7/1983 Strasilla et al. American Oil Chemists Society, Vol. 37, pp. 171-175 4.420,622 A 12/1983 van de Moesdijk et al. (1960). 4,583.986 A 4/1986 Lapidus 4,672,078 A 6/1987 Sakai et al. F. U. Ahmed, “Efficient synthesis of Fatty Monoglyceride 4,804,486 A 2/1989 Day Sulfates from Fatty Acids and Fatty Acid Methyl Esters”, 4,814,101 A 3/1989 Schieferstein et al. Journal of the American Oil Chemists Society, vol. 67, pp. 4,865,774 A 9/1989 Fabry et al. 8-14 (1990). 4,931,218 A 6/1990 Schenker et al. Fallbe et al., Rompp-Lexikon Chemis, vol. 10, Georg thieme 5,151,304. A 9/1992 Lee 5,294,726 A 3/1994 Behler et al. Verlag Stuttgart, NYork, pp. 1764 (1997). 5,312.932 A 5/1994 Behler et al. Introduction to the Ingredient Declaration of Cosmetic Pro 5,322,957 A 6/1994 Fabry et al. ducs, published by the Industrieverband Korperpflege- und 5,484,531 A 1/1996 Kuehne et al. Waschmittel elV. (IKW) Frankfurt, 3rd Edition, p. 44. 5,534.267 A 7/1996 Neunhoeffer et al. 5,618,850 A * 4/1997 Coury et al...... 514/772.2 Schrader, Grundlagen und Rezepturen der Kosmetika, Vol. 5,773,595 A 6/1998 Weuthen et al. 2, Huthig Buch Vergla Heidelberg, (1989). 5,831,080 A 11/1998 Sepka et al. (List continued on next page.) FOREIGN PATENT DOCUMENTS CA 2066 226 3/1991 Primary Examiner. Shelley A. Dodson DE 28 17369 A1 10/1978 (74) Attorney, Agent, or Firm-Stephen D. Harper; Glenn DE 37 23 354 A1 1/1989 E. J. Murphy; Gregory M. Hill DE 37 25 O3O A1 2/1989 DE 3926 344 A1 2/1991 (57) ABSTRACT DE 39 29 973 A1 3/1991 DE 40 27 241 A1 7/1991 There is provided cosmetic agents containing 2-furanone DE 42 04 700 A1 8/1993 derivatives for the treatment of skin and hair. DE 195 03 456 C1 11/1995 DE 44 40 625 A1 5/1996 17 Claims, No Drawings US 6,858.216 B2 Page 2

OTHER PUBLICATIONS Charles Zviak, “Hair Coloring”, The Science of Hair Care, Chapter 7, vol. 7, Dermatology, Marcel Dekker Inc., pp. Kahlweit et al., “Phasenverhalten ternarer Systeme des Typs 248-250 (1986). HO-O1-nichtionisches Amphiphil', Angewandte Chemie Charles Zviak, “Oxidation Coloring”, The Science of Hair vol. 97, pp. 655–669 (1985). Care, Chapter 8, vol. 7, Dermatology, Marcel Dekker Inc., Forster et al., “Influence of Microemulsion Phases on the Preparation of Fine-Disperse Emulsions”, Advances in Col pp. 264-267 (1986). loid and Interface Sciences, vol. 58, pp. 119-149 (1995). * cited by examiner US 6,858.216 B2 1 2 COSMETICAGENT CONTAINING DESCRIPTION OF THE INVENTION 2-FURANONE DERVATIVES The invention firstly therefore provides a cosmetic agent CROSS REFERENCE TO RELATED containing customary cosmetic constituents, characterized APPLICATIONS 5 in that it contains, as active ingredient, a 2-furanone of the This application is a continuation under 35 U.S.C. S365 formula (I) and/or of the formula (II), (c) and S120 of International Application No. PCT/EP01/ formula (I) 04822 filed Apr. 28, 2001 and under S119 of German O O R6 Application No. 100 22 077.0 filed May 6, 2000. 1O R5 SUMMARY OF THE INVENTION 1. 4 The invention relates to cosmetic agents containing cer R R2 R3 R formula (II) tain derivatives of 2-furanone, and to the use of these agents O O R10 for the treatment of keratin fibers and skin. 15 BACKGROUND OF THE INVENTION Cosmetic agents for caring for and maintaining the natural R7 R8 functions of the skin and hair are becoming more and more important. This is due, inter alia, to the changed consumer in which the radicals R to R', independently of one habits and fashion trends. Thus, for example as a result of the another, represent: intensive utilization of tanning Studios, the Structure of skin hydrogen, -OH, a methyl, methoxy, aminomethyl or and hair is permanently damaged to a greater extent by UV hydroxymethyl radical light. This damage is evident on the Skin, like on the hair, for -C-C-Saturated or mono- or diunsaturated, branched example from a loSS in elasticity. or linear hydrocarbon radical, In addition, extensive physical activity outdoors leads to 25 frequent intensive cleaning of skin and hair. As a result, the -C-C-Saturated or mono- or diunsaturated, branched protective film of Sebum, which is produced continuously by or linear mono-, di- or trihydroxy hydrocarbon radical, the numerous Sebaceous glands, or else the Sebum produc -C-C-Saturated or mono- or diunsaturated, branched tion of the Sebaceous glands itself may be considerably or linear mono-, di- or triamino hydrocarbon radical, impaired. This results in greasy Skin and greasy hair. a group -OR'', where R' is a -C-C-saturated or Fashion trends with current colors for “make-up”, lip mono- or diunsaturated, branched or linear hydrocar Sticks for coloring the lipS and mascara, and also hair bon radical, -C-C-Saturated or mono- or diunsaturated, branched or linear mono-, di- or trihy colorants and waving agents contribute, in the case of droxy hydrocarbon radical, Stressed skin and predamaged hair, to further impairment of 35 the natural State of skin and hair. It is therefore not Surprising a group -NR'R'', where R and Ra, in each case that the number of consumers with Sensitive, less elastic, independently of one another, are hydrogen, a methyl, rough and irritable skin, and hair which is impaired with a -C-C-Saturated or mono- or diunsaturated, regard to combability, Shine, elasticity, brittleneSS and maxi branched or linear hydrocarbon radical, a -C-C- Saturated or mono- or diunsaturated, branched or linear mum breaking force is increasing considerably. 40 There has therefore been no lack of attempts to overcome mono-, di- or trihydroxy hydrocarbon radical, these inadequacies. In this regard, skincare emulsions have, a group -COOR'', where R'' is hydrogen, a methyl, a inter alia, been further optimized with regard to their irri -C-C-Saturated or mono- or diunsaturated, tancy potential through the choice of Suitable emulsifiers. branched or linear hydrocarbon radical, a -C-C- For the cleaning of Skin and hair, use is made of mild 45 Saturated mono- or diunsaturated, branched or linear Surfactants in order not to additionally burden Skin and hair. mono-, di- or trihydroxy hydrocarbon radical, a Refatting Substances have been used to try to avoid Stimu -C-C-Saturated or mono- or diunsaturated, lating Sebum production during cleaning. UV protectants branched or linear mono-, di- or triamino hydrocarbon and Vitamins, Such as, for example, Vitamin E, are said to radical, alleviate the disadvantageous effects of UV light. Protein 50 a group -CONR'R'', where R' and R'' are in each hydrolyzates are used for correcting the internal Structure of case hydrogen, methyl, a -C-C-Saturated or mono skin and hair. Plant and algae extracts can be used, for or diunsaturated, branched or linear hydrocarbon example, to influence the moisture level in Skin and hair. radical, a -C-C-Saturated mono- or diunsaturated, In addition, cosmetic active ingredients are being increas branched or linear mono-, di- or trihydroxy hydrocar ingly used in agents for cleaning and caring for Surfaces Such 55 bon radical, a -C-C-Saturated or mono- or as glass, porcelain, leather, textiles, floors of all types in the diunsaturated, branched or linear mono-, di- or triamino home and commercially in order not to additionally burden hydrocarbon radical, the Skin of the user of Such products. For example, hand a group -COR', where R' is a methyl, a -C-C- dishwashing detergents with care additives Such as proteins Saturated or mono- or diunsaturated, branched or linear or refatting Substances are commercially available. 60 hydrocarbon radical, a -C-C-Saturated or mono- or However, there is still a need for agents which are diunsaturated, branched or linear mono-, di- or trihy characterized by a reduction in the undesired damage to skin droxy hydrocarbon radical, a -C-C-Saturated or and hair. It has now been found that the use of derivatives mono- or diunsaturated, branched or linear mono-, di of 2-furanone as active ingredient in cosmetic agents leads or triamino hydrocarbon radical, to Surprisingly good properties of the treated Skin and of the 65 a group -OCOR'', where R7 is a methyl, a -C-Cio hair, in particular to improved combabilities, to improved Saturated or mono- or polyunsaturated, branched or Shine and to improved elasticity. linear hydrocarbon radical, a -C-Cio-Saturated or US 6,858.216 B2 3 4 mono- or polyunsaturated, branched or linear mono-, a group -COR', where R' is a methyl, a -C-C- di-, tri- or polyhydroxy hydrocarbon radical, a Saturated or mono- or diunsaturated, branched or linear -C-Cio-Saturated or mono- or polyunsaturated, hydrocarbon radical, a -C-C-Saturated or mono- or branched or linear mono-, di-, tri- or polyamino hydro diunsaturated, branched or linear mono-, di- or trihy carbon radical, droxy hydrocarbon radical, a -C-C-Saturated or with the proviso that for the case when R and Rare -OH mono- or diunsaturated, branched or linear mono-, di and at the same time R' or R" are hydrogen, the remaining or triamino hydrocarbon radical, group R or R' is not a dihydroxyethyl radical. a group -OCOR'', where R'' is a methyl, a -C-Cio 2-Furanones are known compounds and are described, for Saturated or mono- or polyunsaturated, branched or example, in "Romppy's Lexicon of Chemistry, Interactive linear hydrocarbon radical, a -C-Cio-Saturated or CD-Rom Version 2.0, using the keyword “dihydro-3- mono- or polyunsaturated, branched or linear mono-, hydroxy-4,4-dimethtyl-2(3H)-furanone", and in “Ullmann's di-, tri- or polyhydroxyalkyl radical, or a -C-C- Encyclopedia, sixth edition 1999, electronic release' in Saturated or mono- or polyunsaturated, branched or Sections 2.4, 2.7, 3.2, 3.4, 4.3, 6, 11 and 15 and the linear mono-, di-, tri- or polyamino hydrocarbon radi Specifications cited therein with regard to the preparation 15 cal. and use. Reference is expressly made to these chapters and In a further embodiment of the teaching according to the the literature cited therein. The compounds of the formulae invention, it has been found that in the compounds of the (I) and (II) are used as intermediates in the Synthesis of formula (I) or of the formula (II), the radicals R, R and R' natural Substances, and also in the preparation of medica preferably independently of one another represent: ments and Vitamins. The preparation of the active ingredi hydrogen, an -OH, a methyl, methoxy, aminomethyl, ents according to the formulae (I) and (II) can be carried out, hydroxymethyl radical, for example, by reacting primary alcohols with acrylic acids. In addition, compounds of the formula (I) are obtained by a-C-C-Saturated or mono- or diunsaturated, branched reactions Starting from hydroxypivaldehyde. Similarly, car or linear hydrocarbon radical, bonylations of alkynes lead to substituted 2-furanones of the 25 a-C-C-Saturated or mono- or diunsaturated, branched formula (I) or (II). Finally, the compounds of the formula (I) or linear mono-, di- or trihydroxy hydrocarbon radical or of the formula (II) can be obtained by intramolecular O esterification of the corresponding hydroxycarboxylic acids. a-C-C-Saturated or mono- or diunsaturated, branched For example, the following compounds are obtained by one or linear mono-, di- or triamino hydrocarbon radical. of the synthesis routes listed above: 2,5-dihydro-5-methoxy In addition, it may be preferred if in the novel active 2-furanone, tetrahydro-5-oxo-2-furanecarboxylic acid, ingredient according to formula (I) and/or formula (II), for dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone, or 3,4- the radicals R, R, R and R', independently of one dimethyl-5-pentylidenedihydro-2(5H)-furanone or another, represent: 4-hydroxy-2,5-dimethyl-3(2H)-furanone. The 2-furanones hydrogen, a -OH, a methyl, methoxy, aminomethyl, according to the invention of course include all possible 35 hydroxymethyl radical, Stereoisomers, and also mixtures thereof. The 2-furanones a-C-C-Saturated or mono- or diunsaturated, branched according to the invention do not permanently affect the or linear hydrocarbon radical, odor of the cosmetic agents Such that perfuming of the a -C-C-Saturated or mono- or diunsaturated, branched agents has to be carried out Separately. or linear mono-, di- or trihydroxy hydrocarbon radical Preferred compounds of the formula (I) and/or of the 40 O formula (II) may be compounds in which the substituents a -C-C-Saturated or mono- or diunsaturated, branched R, R and R", independently of one another, represent: or linear mono-, di- or triamino hydrocarbon radical. hydrogen, an -OH, a methyl, methoxy, aminomethyl, In a particularly preferred embodiment of the teaching hydroxymethyl radical, according to the invention, a compound of the formula (I) is a-C-C-Saturated or mono- or diunsaturated, branched 45 used. In this connection, it may be preferred that, in a or linear mono-, di- or trihydroxy hydrocarbon radical, compound of the formula (I), the radicals R and R, a-C-C-Saturated or mono- or diunsaturated, branched independently of one another, represent: or linear mono-, di- or triamino hydrocarbon radical, hydrogen, an -OH, a methyl, methoxy, aminomethyl, a group -OR'', where R' is a -C-C-saturated or 50 hydroxymethyl radical, mono- or diunsaturated, branched or linear hydrocar a-C-C-Saturated or mono- or diunsaturated, branched bon radical, -C-C-Saturated or mono- or or linear mono-, di- or trihydroxy hydrocarbon radical, diunsaturated, branched or linear mono-, di- or trihy a group -OR'', where R' is a -C-C-saturated or droxy hydrocarbon radical, mono- or diunsaturated, branched or linear hydrocar a group -NR'R'', where R'' and R', in each case 55 bon radical, -C-C-Saturated or mono- or independently of one another, are hydrogen, a methyl, diunsaturated, branched or linear mono-, di- or trihy a -C-C-Saturated or mono- or diunsaturated, droxy hydrocarbon radical, branched or linear hydrocarbon radical, a -C-C- a group -COOR", where R' is hydrogen, a methyl, a Saturated or mono- or diunsaturated, branched or linear -C-C-Saturated or mono- or diunsaturated, mono-, di- or trihydroxy hydrocarbon radical, 60 branched or linear hydrocarbon radical, a -C-C- a group -COOR", where R'' is hydrogen, a methyl, a Saturated mono- or diunsaturated, branched or linear -C-C-Saturated or mono- or diunsaturated, mono-, di- or trihydroxy hydrocarbon radical, branched or linear hydrocarbon radical, a -C-C- a group -COR'', where R'' is a methyl, a -C-C- Saturated or mono- or diunsaturated, branched or linear Saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxy hydrocarbon radical, a C-C- 65 hydrocarbon radical, a -C-C-Saturated or mono- or Saturated or mono- or diunsaturated, branched or linear diunsaturated, branched or linear mono-, di- or trihy mono-, di- or triamino hydrocarbon radical, droxy hydrocarbon radical, US 6,858.216 B2 S 6 a group -OCOR'', where R'' is a methyl, a -C-Cio Homopolymers of the general formula (III), Saturated or mono- or polyunsaturated, branched or linear hydrocarbon radical, a -C-Cio-Saturated or (III) mono- or polyunsaturated, branched or linear mono-, R18 di-, tri- or polyhydroxy hydrocarbon radical. In addition, in this particularly preferred embodiment of - CH-C- X the teaching according to the invention, it may be advanta geous if, in the compounds of the formula (I), the radicals R and R", independently of one another, represent: hydrogen, an -OH, a methyl, methoxy, aminomethyl, in which R=-H or -CH, R', R and R', indepen hydroxymethyl radical, dently of one another, are chosen from C-alkyl, -alkenyl a-C-C-Saturated or mono- or diunsaturated, branched or hydroxyalkyl groups, m=1, 2, 3 or 4, n is a natural number or linear mono-, di- or trihydroxy hydrocarbon radical, and X is a physiologically compatible organic or inorganic a group -OR'', where R' is a -C-C-saturated or anion, and also copolymers consisting essentially of the mono- or diunsaturated, branched or linear hydrocar monomer units listed in formula (III) and also nonionogenic bon radical, -C-C-Saturated or mono- or 15 monomer units are particularly preferred cationic polymers. diunsaturated, branched or linear mono-, di- or trihy Within the Scope of these polymers, preference is given droxy hydrocarbon radical, according to the invention to those for which at least one of a group -COOR'', where R'' is hydrogen, a methyl, a the following conditions applies: -C-C-Saturated or mono- or diunsaturated, R" is a methyl group branched or linear hydrocarbon radical, a -C-C- Saturated mono- or diunsaturated, branched or linear R'R'' and R are methyl groups mono-, di- or trihydroxy hydrocarbon radical, m has the value 2. a group -OCOR'', where R'' is a methyl, a -C-Cio Suitable as physiologically compatible counterion X are, Saturated or mono- or polyunsaturated, branched or for example, halide ions, Sulfate ions, phosphate ions, linear hydrocarbon radical, a -C-Cio-Saturated or 25 methoSulfate ions, and organic ions, Such as lactate, citrate, mono- or polyunsaturated, branched or linear mono-, tartrate and acetate ions. Preference is given to halide ions, di-, tri- and/or polyhydroxy hydrocarbon radical. in particular chloride. In this preferred embodiment, it may be further advanta A particularly Suitable homopolymer is the, if desired geous for the compounds according to formula (I) for the cro SS linked, poly radicals R and R, independently of one another, represent: (methacryloyloxyethyltrimethylammonium chloride) with hydrogen, an -OH, a methyl, methoxy, aminomethyl, the INCI name Polyduaternium-37. The crosslinking can if hydroxymethyl radical, desired take place using polyolefinically unsaturated a-C-C-Saturated or mono- or diunsaturated, branched compounds, for example di Vinyl be n Zene, or linear mono-, di- or trihydroxy hydrocarbon radical, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, a group -OR'', where R' is a -C-C-saturated or 35 polyallyl polyglyceryl ether, or allyl ethers of Sugars or Sugar mono- or diunsaturated, branched or linear hydrocar derivatives, Such as erythritol, pentaerythritol, arabitol, bon radical, -C-C-Saturated or mono- or mannitol, Sorbitol, Sucrose or glucose. Methylenebisacryla diunsaturated, branched or linear mono-, di- or trihy mide is a preferred crosslinking agent. droxy hydrocarbon radical. The homopolymer is preferably used in the form of a In a very particularly preferred embodiment of the teach 40 nonaqueous polymer dispersion which should have a poly ing according to the invention, the compound according to mer content not below 30% by weight. Such polymer the formula (I) used is dihydro-3-hydroxy-4,4-dimethyl-2 dispersions are available commercially under the names (3H)-furanone. Salcare(R) SC 95 (about 50% polymer content, further com The active ingredient according to the invention is used in ponents: Mineral Oil (INCI name) and tridecylpolyoxypro the cosmetic agents in amounts of from 0.001 to 10% by 45 pylene polyoxyethylene ether (INCI name: PPG-1 weight, based on the Overall agent, preferably in amounts of Trideceth-6)) and Salcare(R) SC 96 (about 50% polymer from 0.01 to 5% by weight and very particularly preferably content, further components: mixture of diesters of propy in amounts of from 0.05 to 3% by weight. lene glycol with a mixture of caprylic and capric acid (INCI In a preferred embodiment of the teaching according to name: Propylene Glycol Dicaprylate/Dicaprate) and tride the invention, the effect can be further increased with 50 cylpolyoxypropylene polyoxyethylene ether (INCI name: polymers. PolymerS is understood as meaning both natural PPG-1 Trideceth-6)). and Synthetic polymers, which may be anionic, cationic, Copolymers with monomer units according to formula amphoterically charged or nonionic. (III) contain, as nonionogenic monomer units, preferably Cationic polymers are understood as meaning polymers acrylamide, methacrylamide, acrylic C-alkyl esters and which have, in the main chain and/or Side chain, a group 55 methacrylic C-alkyl esters. Of these nonionogenic which may be “temporarily” or “permanently” cationic. monomers, the acrylamide is particularly preferred. AS According to the invention, “permanently cationic' is used described above in the case of the homopolymers, these to refer to those polymers which have a cationic group copolymers too may be crosslinked. A copolymer preferred irrespective of the pH of the agent. These are usually according to the invention is the crosslinked acrylamide polymers which contain a quaternary nitrogen atom, for 60 methacryloyloxyethyltrimethylammonium chloride copoly example in the form of an ammonium group. Preferred mer. Those copolymers in which the monomers are present cationic groups are quaternary ammonium groups. In in a weight ratio of about 20:80 are available commercially particular, those polymers in which the quaternary ammo as about 50% Strength nonaqueous polymer dispersion under nium group are bonded via a C-hydrocarbon group to a the name Salcare(R) SC 92. polymer main chain constructed from acrylic acid, meth 65 Further preferred cationic polymers are, for example, acrylic acid or derivatives thereof have proven particularly quaternized cellulose derivatives, as are available com Suitable. mercially under the names Celquate) and Polymer JRR). US 6,858.216 B2 7 8 The compounds CelquatCE) H 100, CelquatcE L 200 and Particularly Suitable chitosans have a degree of deacety Polymer JROR 400 are preferred quaternized cellulose lation of at least 80% and a molecular weight of 5:10 to derivatives, 5-10° (g/mol). cationic alkyl polyglycosides according to German patent For the preparation of preparations according to the DE 44 13 686, invention, the chitosan must be converted into the Salt form. cationized honey, for example the commercial product This can be carried out by dissolution in dilute aqueous Honeyguate 50, acids. Suitable acids are either mineral acids, Such as, for example, hydrochloric acid, Sulfuric acid and phosphoric cationic guar derivatives, Such as, in particular, the prod acid, or organic acids, e.g. low molecular weight carboxylic ucts Sold under the trade names CoSmedia(E) Guar and acids, polycarboxylic acids and hydroxycarboxylic acids. It JaguarE, is also possible to use higher molecular weight alkylsulfonic polysiloxanes with quaternary groups, Such as, for acids or alkylsulfuric acids or organophosphoric acids, pro example, the commercially available products Q2-7224 Vided these have the required physiological compatibility. (manufacturer: Dow Corning; a Stabilized Suitable acids for converting the chitosan into the salt form trimethylsilylamodimethicone), Dow Corning(R 929 are, for example, acetic acid, glycolic acid, tartaric acid, Emulsion (comprising a hydroxylamino-modified 15 malic acid, citric acid, lactic acid, 2-pyrrolidinone-5- Silicone, which is also referred to as Amodimethicone), carboxylic acid, benzoic acid or Salicyclic acid. Preference SM-2059 (manufacturer: General Electric), SLM is given to using low molecular weight hydroxycarboxylic 55067 (manufacturer: Wacker) and Abil(R)-Quat 3270 acids, Such as, for example, glycolic acid or lactic acid. and 3272 (manufacturer: Th. Goldschmidt; diguater The anionic polymers which can aid the action of the nary polydimethylsiloxanes, Quaternium-80), active ingredient according to the invention are an anionic polymeric dimethyldiallylammonium Salts and copoly polymers which have carboxylate and/or Sulfonate groups. mers thereof with esters and amides of acrylic acid and Examples of anionic monomers of which Such polymers can methacrylic acid. The products available commercially consist are acrylic acid, methacrylic acid, crotonic acid, under the names Merquat (R) 100 (poly male ic anhydride and 2-acrylamido-2- (dimethyldiallylammonium chloride)) and Mer 25 methylpropanesulfonic acid. Here, the acidic groups may be quat(R550 (dimethyldiallylammonium chloride completely or partially present as Sodium, potassium, acrylamide copolymer) are examples of Such cationic ammonium, mono- or triethanolammonium Salt. Preferred polymers, monomers are 2-acrylamido-2-methylpropanesulfonic acid copolymers of vinylpyrrollidone with quaternized deriva and acrylic acid. tives of the dialkylamino alkyl acrylate and Anionic polymers which have proven very particularly methacrylate, Such as, for example, Vinylpyrrollidone effective are those which contain, as the Sole monomer or dimethylaminoethyl methacrylate copolymers quater comonomer, 2-acrylamido-2-methylpropanesulfonic acid, nized with diethyl Sulfate. Such compounds are avail where the Sulfonic acid group can completely or partially be able commercially under the names Gafquate)734 and in the form of the Sodium, potassium, ammonium, mono- or Gafquat(R755, 35 triethanolammonium Salt. Particular preference is given to the homopolymer of vinylpyrrollidone-vinylimidazolium methochloride 2-acrylamido-2-methylpropanesulfonic acid, which is com copolymers, as are Supplied under the names Luvi mercially available, for example, under the name quat(R) FC 370, FC 550, FC 905 and HM 552. Rheothik(E) 11-80. quaternized polyvinyl alcohol, 40 Within this embodiment, it may be preferred to use and the polymers with quaternary nitrogen atoms in the copolymers of at least one anionic monomer and at least one polymer main chain known under the names nonionogenic monomer. With regard to the anionic Polygulaternium 2, monomers, reference is made to the Substances listed above. Polyguaternium 17, Preferred nonionogenic monomers are acrylamide, Polyguaternium 18 and 45 methacrylamide, acrylic esters, methacrylic esters, Polyguaternium 27. Vinylpyrrolidone, Vinyl ethers and vinyl esters. AS cationic polymers, it is likewise possible to use the Preferred anionic copolymers are acrylic acid-acrylamide polymers known under the names Polyduaternium-24 copolymers and, in particular, polyacrylamide copolymers (commercial product e.g. Quatrisoft(R) LM 200). According with Sulfonic acid group-containing monomers. A particu to the invention, it is likewise possible to use the copolymers 50 larly preferred anionic copolymer consists of 70 to 55 mol of vinylpyrrollidone, as are available as commercial products % of acrylamide and 30 to 45 mol % of 2-acrylamido-2- Copolymer 845 (manufacturer: ISP), Gaffix(R) VC 713 methylpropanesulfonic acid, where the Sulfonic acid group (manufacturer: ISP), Gafquat(R) ASCP 1011, Gafquat(RHS is completely or partially in the form of the Sodium, 110, Luviguat(E8155 and Luviguat(R) MS 370. potassium, ammonium, mono- or triethanolammonium Salt. Further cationic polymers according to the invention are 55 This copolymer can also be in crosslinked form, where the the So-called “temporarily cationic' polymers. These poly crosslinking agents used are preferably polyolefinically mers usually contain an amino group which, at certain pH unsaturated compounds Such as tetraallyloxyethane, values, is in the form of a quaternary ammonium group and allylsucrose, allylpentaerythritol and methylenebisacryla thus cationic. Preference is given, for example, to chitosan mide. Such a polymer is present in the commercial product and derivatives thereof, as are freely available commercially, 60 Sepigel(R305 from SEPPIC. Use of this compound, which as for example, under the trade names Hydagence CMF, Hyd well as comprising the polymer component comprises a agen(R) HCMF, Kytamer(R) PC and Chitolam(R) NB/101. hydrocarbon mixture (C-C-isoparaffin) and a noniono Chitosans are deacetylated chitins which are available com genic emulsifier (Laureth-7), has proven particularly advan mercially in varying degrees of deacetylation and varying tageous within the Scope of the teaching according to the degrees of degradation (molecular weights). Their prepara 65 invention. tion is described, for example in DE 44 40 625 A1 and DE The Sodium acryloyldimethyltaurate copolymerS Sold 19503 465 A1. under the name Simulgel(R600 as a compound with isohexa US 6,858.216 B2 9 10 decane and polySorbate-80 have also proven particularly The agents according to the invention can, in a third effective according to the invention. variant, also comprise nonionogenic polymers. Likewise preferred anionic homopolymers are Suitable nonionogenic polymers are, for example: uncroSSlinked and crosslinked polyacrylic acids. Here, allyl Vinylpyrrolidone/vinyl ester copolymers, as are Sold, for ethers of pentaerythritol, of Sucrose and of propylene may be preferred crosslinking agents. Such compounds are com example, under the trade name Luviskol(R) (BASF). mercially available, for example, under the trade name LuViskol(R) VA 64 and Luviskol(R) VA 73, each being CarbopolE). Vinylpyrrolidone/vinyl acetate copolymers, are like Copolymers of maleic anhydride and methyl vinyl ether, wise preferred nonionic polymers. in particular those with crosslinking, are likewise color Cellulose ethers, Such as hydroxypropylcellulose, retaining polymers. A maleic acid-methyl Vinyl ether 1O hydroxyethylcellulose and copolymer crosslinked with 1,9-decadiene is commercially methylhydroxypropylcellulose, as are Sold, for available under the name Stabileze(R). QM. example, under the trade names Culminal(F) and Further polymers which can lacuna used as a constituent Benecel(R) (AQUALON) for increasing the action of the active ingredient according Shellac to the invention are amphoteric polymers. The term ampho 15 Polyvinylpyrrolidones, as are Sold, for example, under the teric polymers covers both those polymers which have both free amino groups and also free -COOH or SOH groups name Luviskol(R) (BASF). in the molecule and are capable of forming internal Salts, and Siloxanes. These siloxanes may either be water-soluble or also Zwitterionic polymers which contain quaternary ammo water-insoluble. Both volatile and also nonvolatile nium groups and -COO or -SO groups in the Siloxanes are Suitable, nonvolatile Siloxanes being molecule, and those polymers which contain -COOH or understood as meaning those compounds whose boil SOH groupS and quaternary ammonium groupS. ing point at atmospheric pressure is above 200 C. One example of an amphopolymer which can be used Preferred siloxanes are polydialkylsiloxanes, Such as, according to the invention is the acrylic resin obtainable for example, poly dimethyl Silo Xane, under the name Amphomer(R), which represents a copolymer 25 polyalkylarylsiloxanes, Such as, for example, of tert-butylaminoethyl methacrylate, N-(1,1,3,3- polyphenylmethylsiloxane, ethoxylated polydialkylsi tetramethylbutyl)acrylamide and two or more monomers loxanes and polydialkylsiloxanes which contain amine from the group consisting of acrylic acid, methacrylic acid and/or hydroxy groups. and Simple esters thereof. Glycosidically substituted silicones according to EP Further amphoteric polymers which can be used accord O612759 B1. ing to the invention are the compounds given in British It is also possible according to the invention for the laid-open Specification 2104.091, European laid-open Speci preparations used to contain two or more, in particular two, fication 47 714, European laid-open specification 217 274, different polymers of equal charge and/or in each case one European laid-open specification 283 817 and German laid ionic and one amphoteric and/or nonionic polymer. open specification 28 17369. 35 According to the invention, the term polymer is likewise Amphoteric polymers which are preferably used are those understood as meaning Special preparations of polymers polymers which are composed essentially of Such as Spherical polymer powders. Various methods are (a) monomers with quaternary ammonium groups of the known for preparing Such microSpheres from various general formula (IV): monomers, e.g. by Special polymerization processes or by 40 dissolution of the polymer in a Solvent and Spraying into a R22 CH=CR2-CO-Z-(CH)-N(R'R'RAC) (IV) medium in which the Solvent can evaporate or diffuse out of the particles. One Such proceSS is known, for example, from in which R’ and R, independently of one another, are EP 466 986 B1. Suitable polymers are, for example, hydrogen or a methyl group, and R, R and R', polycarbonates, polyurethanes, polyacrylates, polyolefins, independently of one another, are alkyl groups having 45 polyesters or polyamides. Those Spherical polymer powders 1 to 4 carbon atoms, Z is an NH group or an oxygen whose primary particle diameter is less than 1 um are atom, n is an integer from 2 to 5 and A is the anion particularly Suitable. Those products based on a poly of an organic or inorganic acid and methacrylate copolymer are available commercially, for (b) monomeric carboxylic acids of the general formula (V): example, under the trade name Polytrap(R) Q5-6603 (Dow 50 Corning). Other polymer powders, e.g. those based on R7-CH=CR-COOH (V) polyamides (nylon 6, nylon 12), are available with a particle size of 2-10 um (90%) and a specific surface area of ca. 10 in which R7 and R, independently of one another, are m/g under the trade name Orgasol® 2002 DU Nat Cos hydrogen or methyl groups. (Atochem S. A., Paris). Further spherical polymer powders These compounds can be used in accordance with the 55 which are Suitable for the purpose according to the invention invention either directly or else in salt form, which is are, for example, the polymethacrylates (Micropearl M) obtained by neutralization of the polymers, for example with from SEPPIC or (Plastic Powder A) from NIKKOL, the an alkali metal hydroxide. With regard to the details of the styrene-divinylbenzene copolymers (Platic Powder FP) preparation of these polymers, reference is made expressly from NIKKOL, the polyethylene and polypropylene pow to the content of German laid-open specification 3929 973. 60 ders (ACCUREL EP 400) from AKZO, and also silicone Very particular preference is given to those polymers in polymers (Silicone Powder X2-1605) from Dow Corning which monomers of type (a) are used in which R, R and and also spherical cellulose powders. Rare methyl groups, Z is an NH group and A is a halide, The polymers are present in the agents used according to methoxysulfate or ethoxysulfate ion; acrylamidopropyl the invention preferably in amounts of 0.01 to 10% by trimethylammonium chloride is a particularly preferred 65 weight, based on the overall agent. Amounts of from 0.1 to monomer (a). The monomer (b) used for said polymers is 5% by weight, in particular from 0.1 to 3% by weight, are preferably acrylic acid. particularly preferred. US 6,858.216 B2 11 12 In a further embodiment of the agents according to the Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium invention, the effect can be further increased through the use Hydroxypropyl Hydrolyzed Keratin, Cocodimonium of protein hydrolyzates and derivatives thereof. Protein Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium hydrolyzates are product mixtures which are obtained by Hydroxypropyl Hydrolyzed Silk, Cocodimonium Hydrox acidically, basically or enzymatically catalyzed degradation ypropyl Hydrolyzed Soy Protein, Cocodimonium Hydrox of proteins. ypropyl Hydrolyzed Wheat Protein, Cocodimonium According to the invention, protein hydrolyZates used Hydroxypropyl Silk Amino Acids, Hydroxypropyl Arginine may either be of vegetable origin or of animal origin. Lauryl/Myristyl Ether HCl, Hydroxypropyltrimonium Animal protein hydrolyZates are, for example, elastin, Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein, collagen, keratin, Silk and milk protein protein hydroly Zates, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydrox which may also be in the form of salts. Such products are ypropyltrimonium Hydrolyzed Conchiolin Protein, Hydrox Sold, for example, under the trade names Dehylan E) ypropyltrimonium Hydrolyzed keratin, Hydroxypropyltri (Cognis), Promois(R (Interorgana), Collapuron(F) (Cognis), monium Hydrolyzed Rice Bran Protein, Nutrilance (Cognis), Gelita-Sol{R (Deutsche Gelatine Fab Hydroxypropyltrimonium Hydrolyzed Silk, Hydroxypropy riken Stoess & Co), Lexein(R) (Inolex) and Kerasol(R) 15 ltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydro (Croda). lyzed Vegetable Protein, Hydroxypropyltrimonium Hydro According to the invention, preference is given to the use lyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed of protein hydrolyZates of vegetable origin, e.g. Soybean, Wheat Protein/Siloxysilicate, Laurdimonium Hydroxypro almond, rice, pea, potato and wheat protein hydroly Zates. pyl Hydrolyzed Soy Protein, Laurdimonium Hydroxypropyl Such products are obtainable, for example, under the trade Hydrolyzed Wheat Protein, Laurdimonium Hydroxypropyl names Gluadin(R) (Cognis), DiaMindB (Diamalt), Lexein(R) Hydrolyzed Wheat Protein/Siloxysilicate, Lauryldimonium (Inolex) and Crotein(R) (Croda). Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Although the use of protein hydroly Zates as Such is Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium preferred, it is possible to use instead of them amino acid Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium mixtures which may have been obtained by another method, 25 Hydroxypropyl Hydrolyzed Silk, Lauryldimonium Hydrox or individual amino acids Such as, for example, arginine, ypropyl Hydrolyzed Soy Protein, Steardimonium Hydrox lysine, histidine or pyrroglutamic acid. Likewise possible is ypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl the use of derivatives of protein hydroly Zates, for example Hydrolyzed Collagen, Steardimonium Hydroxypropyl in the form of their fatty acid condensation products. Such Hydrolyzed Keratin, Steardimonium Hydroxypropyl Hydro products are Sold, for example, under the names Lamepon(E) lyzed Rice Protein, Steardimonium Hydroxypropyl Hydro (Cognis), Gluadine (Cognis), Lexein(E) (Inolex), Crolastin lyzed Silk, Steardimonium Hydroxypropyl Hydrolyzed Soy (Croda) or Crotein(R) (Croda). Protein, Steardimonium Hydroxypropyl Hydrolyzed Veg According to the invention, it is also possible to use etable Protein, Steardimonium Hydroxypropyl Hydrolyzed cationized protein hydroly Zates, where the parent protein Wheat Protein, Steartrimonium Hydroxyethyl Hydrolyzed hydrolyzate can originate from animal, for example from 35 Collage n, Quaternium-76 Hydrolyzed Collage n, collagen, milk or keratin, from plant, for example from Quaternium-79 Hydrolyzed Collagen, Quaternium-79 wheat, corn, rice, potatoes, Soybean or almonds, from Hydrolyzed Keratin, Quaternium-79 Hydrolyzed Milk marine life forms, for example from fish collagen or algae, Protein, Quaternium-79 Hydrolyzed Silk, Quaternium-79 or protein hydroly Zates obtained by biotechnological meth Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat ods. The protein hydrolyzates forming the basis of the 40 Protein. Very particular preference is given to the vegetable cationic derivatives according to the invention can be based cationic protein hydrolyzates and derivatives. obtained from the corresponding proteins by a chemical, in In the agents used according to the invention, the protein particular alkaline or acidic, hydrolysis, by an enzymatic hydrolyzates and derivatives thereof are present in amounts hydrolysis and/or a combination of the two types of hydroly of 0.01-10% by weight, based on the overall agent. Amounts Sis. Hydrolysis of proteins usually gives a protein hydrolyZ 45 of from 0.1 to 5% by weight, in particular 0.1 to 3% by ate with a molecular weight distribution of about 100 daltons weight, are very particularly preferred. up to Several thousand daltons. Preference is given to those In a further preferred embodiment, the agents according to cationic protein hydroly Zates whose parent protein content the invention comprise Surfactants. The term Surfactants is has a molecular weight of from 100 up to 25 000 daltons, understood as meaning Surface-active Substances which preferably 250 to 5000 daltons. In addition, cationic protein 50 carry an anionic or cationic charge in the molecule. It is also hydrolyzates are understood as meaning quaternized amino possible for both an anionic and also a cationic charge to be acids and mixtures thereof. Quaternization of the protein present in the molecule. These Zwitterionic or amphoteric hydrolyzates or of the amino acids is often carried out using Surface-active Substances can likewise be used according to quaternary ammonium Salts, Such as, for example, N,N- the invention. In addition, the Surface-active Substances may dimethyl-N-(n-alkyl)-N-(2-hydroxy-3-chloro-n-propyl) 55 also be nonionic. ammonium halides. In addition, the cationic protein hydro Suitable anionic Surfactants in preparations according to ly Zates can also be derivatized yet further. Typical examples the invention are all anionic Surface-active Substances Suit of the cationic protein hydroly Zates and derivatives accord able for use on the human body. These are characterized by ing to the invention which may be mentioned are the a Solubilizing anionic group, Such as, for example, a products given under the INCI names in the “International 60 carboxylate, Sulfate, Sulfonate or phosphate group, and a Cosmetic Ingredient Dictionary and Handbook”, (seventh lipophilic alkyl group having about 8 to 30 carbon atoms. In edition 1997, The Cosmetic, Toiletry and Fragrance Asso addition, glycol or polyglycol ether groups, ester, ether and ciation 1101 17th Street, N.W., Suite 300, Washington, D.C. amide groups, and also hydroxyl groups may be present in 20036-4702) and commercially available: Cocodimonium the molecule. Examples of Suitable anionic Surfactants are, Hydroxypropyl Hydrolyzed Collagen, Cocodimonium 65 in each case in the form of the Sodium, potassium and Hydroxypropyl Hydrolyzed Casein, Cocodimonium ammonium and also the mono-, di- and trialkanolammo Hydroxypropyl Hydrolyzed Collagen, Cocodimonium nium Salts having 2 to 4 carbon atoms in the alkanol group, US 6,858.216 B2 13 linear and branched fatty acids having 8 to 30 carbon atoms (Soaps), (VIII) ethercarboxylic acids of the formula R-O-(CHCH tiochetto COR36 O)-CH-COOH in which R is a linear alkyl group having 8 to 30 carbon atoms and X=0 or 1 to 16, 5 ioctl.ction acyl Sarcosides having 8 to 24 carbon atoms in the acyl CHO(CH2CH2O); SOX grOup, in which RCO is a linear or branched acyl radical acyl taurides having 8 to 24 carbon atoms in the acyl having 6 to 22 carbon atoms, X, y and Z are in total O grOup, 1O or numbers from 1 to 30, preferably 2 to 10, and X is acyl isethionates having 8 to 24 carbon atoms in the acyl an alkali metal or alkaline earth metal. Typical grOup, examples of monoglyceride (ether) Sulfates Suitable for SulfoSuccinic mono- and dialkyl esters having 8 to 24 the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid carbon atoms in the alkyl group and SulfoSuccinic 15 monoglyceride, palmitic acid monoglyceride, Stearic monoalkyl polyoxyethyl esters having 8 to 24 carbon acid monoglyceride, oleic acid monoglyceride and tal atoms in the alkyl group and 1 to 6 oxyethyl groups, low fatty acid monoglyceride, and also ethylene oxide linear alkaneSufonates having 8 to 24 carbon atoms, adducts thereof with Sulfur trioxide or chlorosulfonic linear alpha-olefinSulfonates having 8 to 24 carbon atoms, acid in the form of its Sodium Salts. Preference is given to using monoglyceride sulfates of the formula (VIII) in alpha-Sulfofatty acid methyl esters of fatty acids having 8 which RCO is a linear acyl radical having 8 to 18 to 30 carbon atoms, carbon atoms. Monoglyceride Sulfates and monoglyc alkyl Sulfates and alkyl polyglycol ether Sulfates of the eride ether Sulfates are described, for example, in formula R-O(CH2CH2O), OSOH in which R is a EP-B10561825, EP-B10561999, DE-A142 04700 preferably linear alkyl group having 8 to 30 carbon 25 or by A. K. Biswas et al. in J. Am. Oil Chem. Soc. 37, atoms and X=0 or 1 to 12, 171 (1960) and F. U. Ahmed in J. Am. Oil Chem. Soc. 67, 8 (1990). mixtures of Surface-active hydroxySulfonates according Preferred anionic Surfactants are alkyl Sulfates, alky to DE-A-37 25 030, lpolyglycol ether Sulfates and ethercarboxylic acids having Sulfated hydroxyalkyl polyethylene and/or hydroxyalky 10 to 18 carbon atoms in the alkyl group and up to 12 glycol lene propylene glycol ethers according to DE-A-3723 ether groups in the molecule and SulfoSuccinic mono and 354, dialkyl esters having 8 to 18 carbon atoms in the alkyl group and SulfoSuccinic monoalkyl polyoxyethyl esters having 8 to Sulfonates of unsaturated fatty acids having 8 to 24 carbon 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl atoms and 1 to 6 double bonds according to DE-A-39 groupS. 26 344, 35 Zwitterionic Surfactants is the term used to describe those esters of tartaric acid and citric acid with alcohols, which Surface-active compounds which carry at least one quater represent addition products of about 2-15 molecules of nary ammonium group and at least one -COO or -SOs ethylene oxide and/or propylene oxide onto fatty alco group in the molecule. Particularly suitable Zwitterionic hols having 8 to 22 carbon atoms, surfactants are the so-called betaines, such as N-alkyl-N,N- 40 dimethylammonium glycinates, for example cocoalkyldim alkyl and/or alkenyl ether phosphates of the formula (VI) ethylammonium glycinate, N-acylaminopropyl-N,N- dimethylammonium glycinate S, for example (VI) cocoacylaminopropyldimethylammonium glycinate, and O 2-alkyl-3-carboxymethyl 3-hydroxyethylimidazolines hav O-P-OR30 45 ing in each case 8 to 18 carbon atoms in the alkyl or acyl group, and cocoacylaminoethylhydroxyethyl carboxymeth OX ylglycinate. A preferred Zwitterionic Surfactant is the fatty acid amide derivative known under the INCI name Coca in which R’ is preferably an aliphatic hydrocarbon radical midopropyl Betaine. having 8 to 30 carbon atoms, R is hydrogen, a radical 50 Ampholytic Surfactants are understood as meaning those (CH2CH2O),R or X, n is numbers from 1 to 10 and X is Surface-active compounds which, apart from a C-C-alkyl hydrogen, an alkali metal or alkaline earth metal or or -acyl group in the molecule, contain at least one free NR'R'R'R'', where R to R', independently of one amino group and at least one -COOH or -SOH group another, are a C to C-hydrocarbon radical, and are capable of forming internal Salts. Examples of 55 Suitable ampholytic Surfactants are N-alkylglycines, Sulfated fatty acid alkylene glycol esters of the formula N-alkylpropionic acids, N-alkylaminobutyric acids, (VII) N-alkyliminodipropionic acids, N-hydroxyethyl-N- alkyla mid op ropylgly cine S, N-alkyl taurine S, RCO (AlkO)SOM (VII) N-alkylsarcosines, 2-alkylaminopropionic acids and alky 60 laminoacetic acids having in each case about 8 to 24 carbon in which RCO is a linear or branched, aliphatic, satu atoms in the alkyl group. Particularly preferred ampholytic rated and/or unsaturated acyl radical having 6 to 22 Surfactants are N-cocoalkylaminopropionate, cocoacylami carbon atoms, Alk is CHCH, CHCHCH and/or noethylaminopropionate and C-C-acylsarcosine. CHCHCH, n is numbers from 0.5 to 5 and M is a Nonionic Surfactants contain, as hydrophilic group, e.g. a cation, as are described in DE-A 19736 906.5, 65 polyol group, a polyalkylene glycol ether group or a com monoglyceride Sulfates and monoglyceride ether Sulfates bination of polyol and polyglycol ether group. Such com of the formula (VIII): pounds are, for example, US 6,858.216 B2 15 16 addition products of from 2 to 50 mol of ethylene oxide Such Sugars are, for example, glucose, fructose, galactose, and/or 0 to 5 mol of propylene oxide onto linear and arabinose, ribose, Xylose, lyxose, allose, altrose, mannose, branched fatty alcohols having 8 to 30 carbon atoms, gulose, idose, talose and Sucrose. Preferred Sugar building onto fatty acids having 8 to 30 carbon atoms and onto blocks are glucose, fructose, galactose, arabinose and alkylphenols having 8 to 15 carbon atoms in the alkyl Sucrose, glucose is particularly preferred. grOup, The alkyl polyglycosides which can be used according to addition products, terminally capped with a methyl or the invention contain, on average, 1.1 to 5 Sugar units. Alkyl C-C-alkyl radical, of from 2 to 50 mol of ethylene polyglycosides with X values of from 1.1 to 2.0 are pre oxide and/or 0 to 5 mol of propylene oxide onto linear ferred. Very particular preference is given to alkyl glyco and branched fatty alcohols having 8 to 30 carbon sides in which X is 1.1 to 1.8. atoms, onto fatty acids having 8 to 30 carbon atoms and The alkoxylated homologs of Said alkyl polyglycosides onto alkylphenols having 8 to 15 carbon atoms in the can also be used according to the invention. These homologs alkyl group, Such as, for example, the products obtain can, on average, contain up to 10 ethylene oxide and/or able under the trade names Dehydol(R) LS, Dehydol(R) propylene oxide units per alkyl glycoside unit. LT (Cognis), 15 Preferred nonionic Surfactants have proven to be the C-Co-fatty acid mono- and diesters of addition prod alkylene oxide addition products onto Saturated linear fatty ucts of from 1 to 30 mol of ethylene oxide onto alcohols and fatty acids having in each case 2 to 30 mol of glycerol, ethylene oxide per mole of fatty alcohol or fatty acid. Preparations with excellent properties are likewise obtained addition products of from 5 to 60 mol of ethylene oxide if they comprise, as nonionic Surfactants, fatty acid esters of onto castor oil and hydrogenated castor oil, ethoxylated glycerol. polyol fatty acid esters, Such as, for example, the com These compounds are characterized by the following mercial product Hydagen(R) HSP (Cognis) or Sovermol parameters. The alkyl radical R contains 6 to 22 carbon products (Cognis), atoms and may either be linear or branched. Preference is alkoxylated triglycerides, 25 given to primary linear aliphatic radicals and aliphatic alkoxylated fatty alkyl esters of the formula radicals methyl-branched in the 2-position. Such alkyl radi cals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, R7CO-(OCHCHR), OR, (DX) 1-cetyl and 1-Stearyl. Particular preference is given to 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. If So-called “OXO alco in which RCO is a linear or branched, saturated and/or hols' are used as Starting materials, compounds with an odd unsaturated acyl radical having 6 to 22 carbon atoms, number of carbon atoms in the alkyl chain predominate. R is hydrogen or methyl, R' is linear or branched The compounds containing alkyl groups used as Surfac alkyl radicals having 1 to 4 carbon atoms and W is tant may in each case be uniform Substances. It is, however, numbers from 1 to 20, usually preferred to start, in the preparation of these amine oxides, 35 Substances, from native vegetable or animal raw materials, thus giving mixtures of Substances with different alkyl chain hydroxy mixed ethers, as are described, for example, in lengths dependent on the raw material in question. DE-A 19738866, For the Surfactants which represent addition products of Sorbitan fatty acid esters and addition products of ethylene ethylene oxide and/or propylene oxide onto fatty alcohols or oxide onto Sorbitan fatty acid esters, Such as, for 40 derivatives of these addition products, it is possible to use example, the polySorbates, either products with a “normal’ homolog distribution, or Sugar fatty acid esters and addition products of ethylene those with a narrowed homolog distribution. “Normal” oxide onto Sugar fatty acid esters, homolog distribution is understood as meaning here mix addition products of ethylene oxide onto fatty acid tures of homologs which are obtained in the reaction of fatty alkanolamides and fatty amines, 45 alcohol and alkylene oxide using alkali metals, alkali metal fatty acid N-alkylglucamides, hydroxides and alkali metal alkoxides as catalysts. Nar alkyl polyglycosides corresponding to the general for rowed homolog distributions are obtained, by contrast, mula RO-(Z), where R is alkyl, Z is Sugar, and X is when, for example, hydrotalcites, alkaline earth metal Salts the number of Sugar units. The alkyl polyglycosides of ethercarboxylic acids, alkaline earth metal oxides, which can be used according to the invention can 50 hydroxides or alkoxides are used as catalysts. The use of contain just a certain alkyl radical R. Usually, however, products with narrowed homolog distribution may be pre these compounds are prepared Starting from natural fats ferred. and oils or mineral oils. In this case, the alkyl radicals These surfactants are used in amounts of 0.1-45% by R are mixtures corresponding to the Starting com weight, preferably 1-30% by weight and very particularly pounds or corresponding to the respective work-up of 55 preferably 1-15% by weight, based on the overall agent. these compounds. In a preferred embodiment, nonionic, Zwitterionic and/or Particular preference is given to those alkyl polyglyco amphoteric Surfactants, and mixtures thereof, may be pre sides in which R consists ferred. essentially of C- and Co-alkyl groups, According to the invention, it is likewise possible to use 60 cationic Surfactants of the quaternary ammonium compound essentially of C- and C-alkyl groups, type, the ester quat type and the amidoamine type. Preferred essentially of C- to C-alkyl groups or quaternary ammonium compounds are ammonium halides, essentially of C- to C-alkyl groups or in particular chlorides and bromides, Such as alkyltrimethy essentially of Co- to C-alkyl groups. lammonium chlorides, dialkyldimethylammonium chlorides AS Sugar building block Z, it is possible to use any mono 65 and trialkylmethylammonium chlorides, e.g. cetyltrimethy or oligosaccharides. Usually, SugarS having 5 or 6 carbon lammonium chloride, Stearyltrimethylammonium chloride, atoms, and the corresponding oligosaccharides are used. distearyldimethyl-ammonium chloride, lauryldimethylam US 6,858.216 B2 17 18 monium chloride, lauryldimethylbenzylammonium chloride Fatty acid esters of Sugars and Sugar alcohols, Such as and tricetylmethylammonium chloride, and the imidazolium Sorbitol, compounds known under the INCI names Quaternium-27 polyglycerols and polyglycerol derivatives, Such as, for and Quaternium-83. The long alkyl chains of the abovemen example, polyglycerol poly-12-hydroxy Stearate tioned surfactants preferably have 10 to 18 carbon atoms. (commercial product Dehymuls(R PGPH), Ester quats are known Substances which contain either at linear and branched fatty acids having 8 to 30 carbon least one ester function or at least one quaternary ammonium atoms and their Na, K, ammonium, Ca, Mg, and Zn group as Structural element. Preferred ester quats are quat Salts. ernized ester Salts of fatty acids with triethanolamine, quat The agents according to the invention comprise the emul ernized ester Salts of fatty acids with diethanolalkylamines sifiers preferably in amounts of 0.1-25% by weight, in and quaternized ester Salts of fatty acids with 1,2- particular 0.5-15% by weight, based on the overall agent. dihydroxypropyldialkylamines. Such products are Sold, for Preferably, the compositions according to the invention example, under the trade names StepanteXCR), Dehyduart(R) can comprise at least one nonionic emulsifier with an HLB and Armocare(R). The products Armocare(R) VGH-70, an value of from 8 to 18, according to the definitions given in N,N-bis(2-palmitoyloxyethyl)dimethylammonium chloride, 15 Rompp Lexikon Chemie (Ed. J. Falbe, M. Regitz), 10th and also DehyduartCE) F-75, DehyguartCE) C-4046, Dehy edition, Georg Thieme Verlag Stuttgart, New York, (1997), quartCE) L80 and DehyduartCE AU-35 are examples of Such page 1764. Nonionogenic emulsifiers with an HLB value of ester quats. 10-15 may be particularly preferred according to the inven The alkylamidoamines are usually prepared by amidation tion. of natural or Synthetic fatty acids and fatty acid cuts with Among Said emulsifier types, the emulsifiers which do not dialkylaminoamines. A particularly Suitable compound from contain ethylene oxide and/or propylene oxide in the mol this group of Substances according to the invention is ecule may be very particularly preferred. Stearamidopropyldimethylamine available commercially In a further preferred embodiment of the invention, the under the name Tegoamid(R) S 18. effect of the active ingredient according to the invention can The cationic Surfactants are present in the agents used 25 be further optimized by fatty substances. Fatty Substances according to the invention preferably in amounts of from are understood as meaning fatty acids, fatty alcohols, natural 0.05 to 10% by weight, based on the overall agent. Amounts and Synthetic waxes, which may either be in Solid form or of from 0.1 to 5% by weight are particularly preferred. else in liquid form in aqueous dispersion, and natural and In a further preferred embodiment, the action of the active Synthetic cosmetic oil components. ingredient according to the invention can be increased by Fatty acids which can be used are linear and/or branched, emulsifiers. Such emulsifiers are, for example: Saturated and/or unsaturated fatty acids having 6-30 carbon addition products of from 4 to 30 mol of ethylene oxide atoms. Preference is given to fatty acids having 10-22 and/or 0 to 5 mol of propylene oxide onto linear fatty carbon atoms. Examples thereof which can be mentioned are alcohols having 8 to 22 carbon atoms, onto fatty acids the isoStearic acids, Such as the commercial products Emer having 12 to 22 carbon atoms and onto alkylphenols 35 SolR 871 and Emersol(R) 875, and isopalmitic acids, such as having 8 to 15 carbon atoms in the alkyl group, the commercial product Edenor(E) IP 95, and all other fatty C-C-fatty acid mono- and diesters of addition prod acids sold under the trade names Edenor(R) (Cognis). Further ucts of from 1 to 30 mol of ethylene oxide onto polyols typical examples of Such fatty acids are caproic acid, having 3 to 6 carbon atoms, in particular onto glycerol, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, ethylene oxide and polyglycerol addition products onto 40 isotridecanoic acid, myristic acid, palmitic acid, palmitoleic methyl glucoside fatty acid esters, fatty acid alkanola acid, Stearic acid, isoStearic acid, oleic acid, elaidic acid, mides and fatty acid glucamides, petroSelic acid, linoleic acid, linolenic acid, elaeoStearic C-C2-alkyl mono- and oligoglycosides and ethoxylated acid, arachidic acid, gadoleic acid, behenic acid and erucic analogs thereof, where degrees of oligomerization of acid, and technical-grade mixtures thereof which are from 1.1 to 5, in particular 1.2 to 2.0, and glucose as 45 produced, for example, during the pressurized cleavage of Sugar component are preferred, natural fats and oils, in the Oxidation of aldehydes from the Roelen OXO Synthesis or the dimerization of unsaturated fatty mixtures of alkyl (oligo)glucosides and fatty alcohols, for acids. Particular preference is usually given to the fatty acid example the commercially available product Mon cuts which are obtainable from coconut oil and palm oil; tanov(E) 68, 50 particular preference is usually given to the use of Stearic addition products of from 5 to 60 mol of ethylene oxide acid. onto castor oil and hydrogenated castor oil, The use amount here is 0.1-15% by weight, based on the partial esters of polyols having 3-6 carbon atoms with overall agent. In a preferred embodiment, the amount is Saturated fatty acids having 8 to 22 carbon atoms, 0.5-10% by weight, amounts of 1-5% by weight being very Sterols. Sterols are understood as meaning a group of 55 particularly advantageous. Fatty alcohols which can be used Steroids which carry a hydroxyl group on the 3rd are Saturated, mono- or polyunsaturated, branched or carbon atom of the Steroid backbone and are isolated unbranched fatty alcohols having C-Co-, preferably both from animal tissue (Zoosterols) and from Veg Co-C- and very particularly preferably C-C-carbon etable fats (phytosterols). Examples of Zoosterols are atoms. For the purposes of the invention, it is possible, for cholesterol and lanosterol. Examples of Suitable phy 60 example, to use decanol, octanol, octenol, dodecenol, tosterols are ergosterol, Stigmasterol and Sitosterol. decenol, octadienol, dodecadienol, decadienol, oleyl Sterols are also isolated from fungi and yeasts, these alcohol, erucyl alcohol, ricinol alcohol, Stearyl alcohol, being termed micosterols. isoStearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl Phospholipids. These are understood as meaning prima alcohol, arachidyl alcohol, capryl alcohol, capric alcohol, rily the glucose phospholipids which are obtained, for 65 linoleyl alcohol, linolenyl alcohol and behenyl alcohol, and example, as lecithins or phosphatidylcholines from, for Guerbet alcohols thereof, the intention being for the char example, egg yolk or plant Seeds (e.g. Soybeans). acter of this list to be exemplary and nonlimiting. However, US 6,858.216 B2 19 20 the fatty alcohols originate from preferably natural fatty Synthesis or the dimerization of unsaturated fatty acids. acids, in which case it is usually possible to Start from an Examples of the fatty alcohol components in the ester isolation of the esters of the fatty acids by reduction. oils are isoproyl alcohol, caproic alcohol, caprylic According to the invention, it is likewise possible to use alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl those fatty alcohol cuts which are produced by reducing alcohol, isotridecyl alcohol, myristyl alcohol, cetyl naturally occurring triglycerides Such as beef tallow, palm alcohol, palmoleyl alcohol, Stearyl alcohol, isoStearyl oil, peanut oil, rape oil, cottonseed oil, Soybean oil, Sun alcohol, oleyl alcohol, elaidyl alcohol, petroSelinyl flower oil and linseed oil or fatty acid esters arising from alcohol, linolyl alcohol, linolenyl alcohol, elaeoStearyl their transesterification products with corresponding alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohols, and thus represent a mixture of different fatty alcohol, erucyl alcohol and brassidyl alcohol, and alcohols. Such Substances are available commercially, for technical-grade mixtures thereof which are produced, example, under the names StenolE), e.g. Stenole) 1618 or for example, during the high-pressure hydrogenation of Lanette(R), e.g. Lanette(R) O or Lorole), e.g. Lorolf C8, technical-grade methyl esters based on fats and oils or Lorol& C14, Lorol& C18, Lorol& C8-18, HD-Ocenol?F), aldehydes from the Roelen OXO Synthesis, and as mono Crodacole), e.g. Crodacole CS, NovolcE), Eutanole G, 15 mer fraction in the dimerization of unsaturated fatty Guerbitol(R) 16, Guerbitol(R) 18, Guerbitol(R) 20, Isofol(R) 12, alcohols. According to the invention, particular prefer Isofol(R) 16, Isofol(R) 24, Isofol(R) 36, IsocarbCE) 12, IsocarbCE) ence is given to isopropyl myristate (Rilanit(R) IPM), 16 or IsocarbCR 24. According to the invention, it is also of isononanoic acid C16-18-alkyl esters (Cetiol(R) SN), course possible to use wool wax alcohols, as are available 2-ethylhexyl palmitate (Cegesoft(R 24), 2-ethylhexyl commercially, for example, under the names Corona.E, stearate (Cetiol{R 868), cetyl oleate, glycerol White Swan(R), CoronetOR or Fluilan(R). The fatty alcohols are tricaprylate, coconut fatty alcohol caprate/caprylate used in amounts of 0.1-20% by weight, based on the total (CetiolCE) LC), n-butyl stearate, oleyl erucate (CetiolB) preparation, preferably in amounts of 0.1-10% by weight. J 600), isopropyl palmitate (Rilanit(RIPP), oleyl oleate Natural or Synthetic waxes which can be used according (CetiolCE), hexyl laurate (Cetiol{RA), di-n-butyladipate to the invention are Solid paraffins or isoparaffins, carnauba 25 (CetiolCE) B), myristyl myristate (Cetiol(R) MM), cet waxes, beeswaxes, candelilla waxes, OZokerite, ceresine, earyllisononanoate (Cetiole) SN), decyl oleate (CetiolB) Spermaceti wax, Sunflower wax, fruit waxes, Such as, for V). example, apple wax or citrus wax, microcrystalline waxes of Dicarboxylic esters, such as di-n-butyl adipate, di(2- PE or PP. Such waxes are available, for example, from Kahl ethylhexyl) adipate, di(2-ethylhexyl) Succinate and & Co., Trittau. disotridecyl acelate, and diol esters, Such as ethylene The natural and Synthetic cosmetic oily bodies which can glycol dioleate, ethylene glycol diisotridecanoate, pro increase the effect of the active ingredient according to the pylene glycol di(2-ethylhexanoate), propylene glycol invention include, for example: disoStearate, propylene glycol diperlargonate, butane Vegetable oils. Examples of Such oils are Sunflower oil, diol diisoStearate, neopentyl glycol dicaprylate, olive oil, Soybean oil, rapeseed oil, almond oil, jojoba 35 Symmetrical, asymmetrical or cyclic esters of carbonic oil, orange oil, wheatgerm oil, peach kernel oil and the acid with fatty alcohols, for example described in DE-A liquid fractions of coconut oil. Also Suitable, however, 19756 454, glycerol carbonate or dicaprylyl carbonate are other triglyceride oils, Such as the liquid fractions of (Cetiolce CC), beef tallow and Synthetic triglyceride oils. mono-, di- and trifatty acid esters of Saturated and/or Liquid paraffin oils, isoparaffin oils and Synthetic 40 unsaturated linear and/or branched fatty acids with hydrocarbons, and di-n-alkyl ethers having a total of glycerol, such as, for example, Monomuls(R 90-018, between 12 and 36 carbon atoms, in particular 12 to 24 Monomuls(E) 90-L12 or Cutina(E) MD. carbon atoms, Such as, for example, di-n-octyl ether, The use amount is 0.1-50% by weight, based on the di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, overall agent, preferably 0.1-20% by weight and particu di-n-dodecyl ether, n-hexyl n-octyl ether, n-octyl 45 larly preferably 0.1-15% by weight, based on the total agent. n-decyl ether, n-decyl n-undecyl ether, n-undecyl The total amount of oil and fatty components in the agents n-dodecyl ether and n-hexyl n-undecyl ether and according to the invention is usually 6-45% by weight, di-tert-butyl ether, diisopentyl ether, di-3-ethyl decyl based on the overall agent. Amounts of 10-35% by weight ether, tert-butyl n-octyl ether, isopentyl n-octyl ether are preferred according to the invention. and 2-methylpentyl n-octyl ether. The compounds 1,3- 50 In addition, it has been found that the effect of the active di(2-ethylhexyl)cyclohexane (Cetiol(R) S) and di-n- ingredient according to the invention can be increased if it octyl ether (CetiolCE) OE), available as commercial is combined with hydroxycarboxylic esters. Preferred products, may be preferred. hydroxycarboxylic esters are complete esters of glycolic Ester oils. Ester oils are understood as meaning the esters acid, lactic acid, malic acid, tartaric acid or citric acid. of Co-Co-fatty acids with C-Co-fatty alcohols. Pref 55 Further hydroxycarboxylic esters which are suitable in prin erence is given to the monoesters of fatty acids with ciple are esters of B-hydroxypropionic acid, of tartronic acid, alcohols having 2 to 24 carbon atoms. Examples of of D-gluconic acid, Sugar acid, mucic acid or glucuronic fatty acid components used in the esters are caproic acid. Suitable as alcohol component of these esters are acid, caprylic acid, 2-ethylhexanoic acid, capric acid, primary, linear or branched aliphatic alcohols having 8–22 lauric acid, isotridecanoic acid, myristic acid, palmitic 60 carbon atoms, e.g. fatty alcohols or Synthetic fatty alcohols. acid, palmitoleic acid, Stearic acid, isoStearic acid, oleic In this connection, particular preference is given to the esters acid, elaidic acid, petroSelic acid, linoleic acid, lino of C-Cls-fatty alcohols. Esters of this type are available lenic acid, elaeoStearic acid, arachidic acid, gadoleic commercially, e.g. under the trade name CoSmacol E) from acid, behenic acid and erucic acid, and technical-grade EniChem, Augusta Industriale. The use amount of the mixtures thereof, which are produced, for example, 65 hydroxycarboxylic esters here is 0.1-15% by weight, based during the preSSurized cleavage of natural fats and oils, on the agent, preferably 0.1-10% by weight and very during the oxidation of aldehydes from the Roelen oxo particularly preferably 0.1-5% by weight. US 6,858.216 B2 21 22 Likewise, the combination of the active ingredient with Panthenol and its derivatives and also nicotinamide and Vitamins, provitamins and Vitamin precursors and deriva biotin are particularly preferred. tives thereof has proven advantageous. Finally, the action of the active ingredient can also be In this connection, according to the invention, preference increased through the combined use of plant extracts. is given to those Vitamins, provitamins and Vitamin precur Usually, these extracts are prepared by extraction of the Sors which are usually assigned to the groups A, B, C, E, F whole plant. However, it may also be preferred in individual and H. cases to prepare the extracts exclusively from flowers and/or The group of Substances referred to as Vitamin A includes leaves of the plant. retinol (vitamin A) and 3,4-didehydroretinol (vitamin A). With regard to the plant extracts which can be used B-caroteine is the provitamin of retinol. Suitable as Vitamin according to the invention, reference is made in particular to A component are, according to the invention, for example the extracts which are listed in the table starting on page 44 Vitamin A acid and esters thereof, Vitamin A aldehyde and of the 3rd edition of the introduction to the ingredient Vitamin A alcohol, and esters thereof, Such as the palmitate declaration of cosmetic products, published by the Indus and the acetate. The preparations used according to the trieverband Körperpflege- und Waschmittel e.V. (IKW), invention comprise the Vitamin A component preferably in 15 Frankfurt. amounts of 0.05-1% by weight, based on the overall prepa According to the invention, the extracts from green tea, ration. oak bark, Stinging nettle, hamamelis, hops, chamomile, The vitamin B group or the vitamin B complex include, burdock, horsetail, whitethorn, lindenblossom, almond, aloe inter alia, Vera, Spruce needle, horse chestnut, Sandalwood, juniper, vitamin B (thiamine) coconut, mango, apricot, lemon, wheat, kiwi, melon, orange, grapefruit, Sage, rosemary, birch, mallow, lady's-Smock, vitamin B (riboflavin) wild thyme, yarrow, thyme, melissa, restharrow, coltsfoot, vitamin B. Under this term are often listed the com marshmallow, meristem, ginseng and root ginger, in pounds nicotinic acid and nicotinamide (niacinamide). particular, are preferred. According to the invention, preference is given to 25 Particular preference is given to the extracts from green nicotinamide, which is present in the agents used tea, oak bark, Stinging nettle, hamamelis, hops, chamomile, according to the invention preferably in amounts of burdock, horsetail, linden blossom, almond, aloe Vera, from 0.05 to 1% by weight, based on the overall agent. coconut, mango, apricot, lemon, wheat, kiwi, melon, orange, Vitamin B (pantothenic acid and panthenol). Within this grapefruit, Sage, rosemary, birch, lady's-Smock, wild thyme, group, preference is given to using panthenol. Deriva yarrow, restharrow, meristem, ginseng and root ginger. tives of panthenol which can be used according to the Very particularly Suitable for the use according to the invention are, in particular, the esters and ethers of invention are the extracts from green tea, almond, aloe Vera, panthenol, and also cationically derivatized panthenols. coconut, mango, apricot, lemon, wheat, kiwi and melon. Individual representatives are, for example, panthenol The extractants used for the preparation of Said plant triacetate, panthenol monoethyl ether and its 35 extracts may be water, alcohols and mixtures thereof. Of the monoacetate, and the cationic panthenol derivatives alcohols, preference is given in this connection to lower disclosed in WO 92/13829. Said compounds of the alcohols, Such as ethanol and isopropanol, but in particular Vitamin B type are present in the agents used accord polyhydric alcohols, Such as ethylene glycol and propylene ing to the invention preferably in amounts of 0.05-10% glycol, both as a Sole extractant and also in a mixture with by weight, based on the overall agent. Amounts of 40 water. Plant extracts based on water/propylene glycol in the 0.1-5% by weight are particularly preferred. ratio 1:10 to 10:1 have proven particularly suitable. Vitamin B (pyridoxine and pyridoxamine and pyridoxal). According to the invention, the plant extracts can be used Vitamin C (ascorbic acid). Vitamin C is used in the agents both in pure form and also in dilute form. If they are used used according to the invention preferably in amounts of in dilute form, they usually comprise about 2-80% by from 0.1 to 3% by weight, based on the overall agent. The 45 weight of active Substance and, as Solvent, the extractant or use in the form of the palmitic ester, the glucosides or extractant mixture used in their isolation. phosphates may be preferred. The use in combination with In addition, it may be preferred to use mixtures of two or tocopherols may likewise be preferred. more, in particular two, different plant extracts in the agents Vitamin E (tocopherols, in particular C-tocopherol) Toco according to the invention. pherol and its derivatives, which covers, in particular, the 50 In addition, it has been found that the effect of the active esters, Such as the acetate, the nicotinate, the phosphate and ingredient according to the invention in cosmetic agents can the Succinate, are present in the agents used according to the be further increased in combination with Substances which invention preferably in amounts of 0.05-1% by weight, contain primary or Secondary amino groups. Examples of based on the Overall agent. Such amino compounds which may be mentioned are Vitamin F. The term “vitamin F is usually understood as 55 ammonia, monoethanolamine, 2-amino-2-methyl-1- meaning essential fatty acids, in particular linoleic acid, propanol, 2-amino-2-methylpropanediol, and basic amino linolenic acid and arachidonic acid. acids, Such as, for example, lysine, arginine or histidine. Vitamin H. Vitamin H is used to refer to the compound These amines can of course also be used in the form of the (3aS,4S,6aR)-2-oxohexahydrothienol 3,4-dimidazole-4- corresponding Salts with inorganic and/or organic acids, Valeric acid, which has in the meantime become known by 60 Such as, for example, in the form of ammonium carbonate, the trivial name biotin. Biotin is present in the agents used ammonium citrate, ammonium oxalate, ammonium tartrate according to the invention preferably in amounts of from or lysine hydrochloride. The amines are used together with 0.0001 to 1.0% by weight, in particular in amounts of from the active ingredient according to the invention in ratios of 0.001 to 0.01% by weight. from 1:10 to 10:1, preferably 3:1 to 1:3 and very particularly The agents used according to the invention preferably 65 preferably in Stoichiometric amounts. comprise Vitamins, provitamins and Vitamin precursors from In addition to the active ingredient which is obligatorily the groups A, B, E and H. required according to the invention and the further, above US 6,858.216 B2 23 24 mentioned preferred components, these preparations can in With regard to further optional components and the principle comprise all further components known to the amount of these components used, reference is made person skilled in the art for Such cosmetic agents. expressly to the relevant handbooks known to those skilled Further active ingredients, auxiliaries and additives are, in the art, e.g. the monograph by Kh. Schrader, Grundlagen for example: und Rezepturen der Kosmetika Principles and formulations thickeners, Such as gelatin or plant gums, for example of cosmetics), 2nd edition, Hithig Buch Verlag, Heidelberg, agar agar, guar gum, alginates, Xanthan gum, gum 1989. arabic, karaya gum, carob Seed grain, linseed gums, With regard to the nature according to which the active dextrans, cellulose derivatives, e.g. methylcellulose, ingredient according to the invention is applied to the keratin hydroxyalkylcellulose and carboxymethylcellulose, fibers, in particular human hair, and also to the skin, there are Starch fractions and derivatives, Such as amylose, amy in principle no limitations. Suitable formulation forms of lopectin and dextrins, clays and phyllosilicates, Such as, these preparations are, for example, creams, lotions, for example, bentonite or completely Synthetic Solutions, tonics, emulsions, Such as W/O, O/W, PIT emul hydrocolloids, Such as, for example, polyvinyl alcohol, Sions (emulsions in accordance with the teaching of phase the Ca, Mg or Zn Soaps, 15 inversion, called PIT), microemulsions and multiple emulsions, coarse, unstable, Single- or multiphase shaking Structurants, Such as maleic acid and lactic acid, mixtures, gels, Sprays, aerosols and foam aeroSols. These are perfume oils, usually formulated on an aqueous or aqueous-alcoholic dimethyl isosorbide, basis. Alcoholic components which may be used here are cyclodextrins, lower alkanols and also polyols, Such as propylene glycol Solvents and Solubility promoters, Such as ethanol, and glycerol. Ethanol and isopropanol are preferred alco isopropanol, ethylene glycol, propylene glycol, glyc hols. Water and alcohol may be present in the aqueous erol and diethylene glycol, alcoholic base in a weight ratio of from 1:10 to 10:1. Water fiber Structure-improving active ingredients, in particular and aqueous-alcoholic mixtures which comprise up to 50% mono-, di- and oligosaccharides, Such as, for example, 25 by weight, in particular up to 25% by weight, of alcohol, glucose, galactose, fructose, fruit Sugar and lactose, based on the mixture of alcohol/water, may be preferred bases in accordance with the invention. The pH of these quaternized amines, Such as methyl-1-alkylamidoethyl-2- preparations may in principle be from 2-11. It is preferably alkylimidazolinium methoSulfate, between 2 and 7, values from 3 to 5 being particularly defoamers, Such as Silicones, preferred. To set the pH, virtually any acid or base which can dyes for coloring the agent, he used for cosmetic purposes can be used. Usually, the antidandruff active ingredients, Such as piroctone acids used are food acids. Food acids are understood as olamine, Zinc omadine and climbazole, meaning those acids which are consumed in the course of light protection agents, in particular derivatized usual eating and have positive effects on the human organ benzophenones, cinnamic acid derivatives and 35 ism. Food acids are, for example, acetic acid, lactic acid, tartaric acid, citric acid, malic acid, ascorbic acid and triazines, gluconic acid. For the purposes of the invention, the use of further Substances for adjusting the pH, Such as, for citric acid and lactic acid is particularly preferred. Preferred example, C- and B-hydroxycarboxylic acids, bases are ammonia, alkali metal hydroxide S, active ingredients, Such as allantoin and bisabolol, 40 monoethanolamine, triethanolamine and N,N,N',N'-tetrakis cholesterol, (2-hydroxypropyl)ethylenediamine. comple Xing agents, Such as EDTA, NTA, Preparations which remain on the skin and the hair have B-alaninediacetic acid and phosphonic acids, proven particularly effective and can therefore represent Swelling and penetration Substances, Such as glycerol, preferred embodiments of the teaching according to the propylene glycol monoethyl ether, carbonates, 45 invention. “Remaining on the skin and the hair' is under hydrogencarbonates, guanidines, ureas and primary, stood according to the invention as meaning those prepara Secondary and tertiary phosphates, tions which, in the course of treatment, are not rinsed off the skin or rinsed out of the hair again after a period of from a ceramides. Ceramides are understood as meaning few Seconds to one hour using water or an aqueous Solution. N-acylsphingosine (fatty acid amides of sphingosine) 50 Rather, the preparations remain on the Skin or the hair until or synthetic analogs of Such lipids (so-called the next wash. pseudoceramides), According to a preferred embodiment for application to opacifiers, such as latex, styrene/PVP and styrene/ the hair, these preparations are formulated as hair treatment acrylamide copolymers, or hair conditioner. The preparations of the invention pearlizers, Such as ethylene glycol mono- and distearate 55 according to this embodiment can, following expiry of this and also PEG-3 distearate, contact time, be rinsed out with water or an at least pre pigments, dominantly water-containing agent; however, as Stated reducing agents, Such as, for example, thioglycolic acid above, they are preferably left on the hair. In this connection, and derivatives thereof, thiolactic acid, cysteamine, it may be preferred to apply the preparation according to the thiomalic acid and C.-mercaptoethaneSulfonic acid, 60 invention to the hair prior to the application of a cleaning propellants, Such as propane-butane mixtures, NO, dim agent, a waving agent or other hair-treatment agents. In this case, the preparation according to the invention Serves as ethyl ether, CO2 and air, color protection for the Subsequent applications. antioxidants, According to further embodiments, the agents according deoxy Sugars, 65 to the invention may, however, also, for example, be clean plant glycosides, ing agents for skin and hair, Such as Shampoos, make-up polysaccharides, Such as fucose or rhamnose. removers, face cleansers, care agents for Skin and hair, Such US 6,858,216 B2 25 26 as rinses, day creams, night creams, face masks, or setting about 45 minutes and then rinsed out with water or a agents for the hair, Such as hair-setting agents, setting foams, Surfactant-containing agent, or is entirely left on the hair. In Styling gels and low-waving agents, permanent shaping this connection, reference is made expressly to the known agents, Such as permanent-waving and neutralization agents monographs, e.g. Kh. Schrader, Grundlagen und Rezepturen and pretreatment agents or afterrinses used in particular in der Kosmetika Principles and formulations of cosmetics), the course of a permanent-waving process or coloring pro 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, which CCSS. State the relevant knowledge of the person skilled in the art. In a particular embodiment of the agents according to the AS already mentioned above, within the scope of the invention, it may be preferred for the agents to be in the form teaching according to the invention, it is also possible, of a microemulsion. For the purposes of the invention, although less preferable, to incorporate the active ingredient microemulsions are likewise understood as meaning directly into the colorant or tint. So-called “PIT" emulsions. These emulsions are in principle The composition of the colorant or tint is not subject to Systems with the 3 components water, oil and emulsifier any limitations in principle. which, at room temperature, are in the form of an oil-in AS dye (precursor), it is possible to use water (O/W) emulsion. As these systems are heated, micro 15 oxidation dye precursors of the developer and coupler emulsions form in a certain temperature range (usually type, referred to as the phase inversion temperature or “PIT), natural and Synthetic direct dyes and which, upon further heating, convert to water-in-oil (W/O) precursors of nature-analogous dyes, such as indole and emulsions. Upon Subsequent cooling, O/W emulsions are indoline derivatives, and again formed, although, even at room temperature, they are mixtures of representatives of one or more of these groups. in the form of microemulsions with an average particle The oxidation dye precursors of the developer type cus diameter of less than 400 nm, in particular with a particle tomarily used are primary aromatic amines with a further diameter of about 100-300 nm. Details regarding these very free or Substituted hydroxyl or amino group situated in the stable, low-viscosity systems, for which the term “PIT para or ortho position, diaminopyridine derivatives, hetero emulsions' has generally been adopted, are given in a large 25 cyclic hydrazones, 4-aminopyrazole derivatives, and 2,4,5, number of publications, for which the publications in 6-tetraaminopyrimidine and derivatives thereof. Suitable Angew. Chem.97, 655-669 (1985) and Adv. Colloid Inter de Veloper components are, for example, face Sci 58, 119-149 (1995) are mentioned by way of p-phenylenediamine, p-tolylenediamine, p-aminophenol, representation. o-aminophenol, 1-(2-hydroxyethyl)-2,5-diaminobenzene, According to the invention, preference may be given to 30 N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(2,5- those micro- or “PIT" emulsions which have an average diaminophenoxy)ethanol, 4-amino-3-methylphenol, 2,4,5,6- particle diameter of about 200 nm. tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, The microemulsions according to the invention can be 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6- prepared, for example, by firstly determining the phase dia minopy rimidine, 2-di- methylamino-4,5,6- inversion temperature of the System by heating a sample of 35 tria minopy rimidine, 2-hydroxymethylamino-4- the emulsion prepared in the customary manner and, using aminophenol, bis(4-aminophenyl)amine, 4-amino-3- a conductivity measuring instrument, determining the tem fluorophenol, 2-amino methyl-4-amino phenol, perature at which the conductivity decreases greatly. The 2-hydroxy methyl-4-aminophenol, 4-amino-2- decrease in the specific conductivity of the O/W emulsion ((diethylamino)methyl)phenol, bis(2-hydroxy-5- initially present generally decreases over a temperature 40 a minophenyl)methane, 1,4-bis(4-aminophenyl) range from 2 to 8 C. from originally more than 1 mS/cm to diazacycloheptane, 1,3-bis(N(2-hydroxyethyl)-N(4- values below 0.1 mS/cm. This temperature range corre a minophenylamino))-2-propanol, 4-amino-2-(2- Sponds then to the phase inversion temperature range. After hydroxyethoxy)phenol, 1,10-bis(2,5-diaminophenyl)-1,4,7, the phase inversion temperature range is thus known, the 10-tetraoxadecane, and 4,5-diaminopyrazole derivatives as emulsion, initially prepared as is customary, comprising oil 45 claimed in EP 0740 741 and WO 94/08970, such as, for component, nonionogenic emulsifier, at least parts of water example, 4,5-diamino-1-(2-hydroxyethyl)pyrazole. Particu and optionally further components can be heated to a larly advantageous developer components are temperature which is within or above the phase inversion p-phenylenediamine, p-tolylenediamine, p-aminophenol, temperature range, then cooled, and, where appropriate, 1-(2-hydroxyethyl)-2,5-diaminobenzene, 4-amino-3- further components and the remaining water can be added. 50 methylphenol, 2-aminomethyl-4-aminophenol, 2,4,5,6- Alternatively, the microemulsion can also be prepared tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, directly at a temperature which is within or above the phase 4-hydroxy-2,5,6-triaminopyrimidine. inversion temperature range. The microemulsion prepared in Oxidation dye precursors of the coupler type which are this way is then cooled to a temperature below the phase used are usually m-phenylenediamine derivatives, inversion temperature range, usually room temperature. 55 naphthols, resorcinol and resorcinol derivatives, pyrazolo In a very particularly preferred embodiment, the active nes and m-aminophenol derivatives. Examples of such cou ingredient is used in agents for coloring keratin fibers. In this pler components are connection, the active ingredient according to the invention m-aminophenol and derivatives thereof such as, for can in principle be added directly to the colorant. Preferably, example, 5-amino-2-methylphenol, 5-(3- the active ingredient is applied to the colored keratin fiber, 60 hydroxypropylamino)-2-methylphenol, 3-amino-2- but in a separate Step, either directly after the actual dyeing chloro - 6 - methyl phenol, 2-hydroxy-4- process, or in Separate treatments, where appropriate even aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, days or weeks after the dyeing process. 3-trifluoroacetylamino-2-chloro-6-methylphenol, The term dyeing process includes here all processes 5-amino-4-chloro-2-methylphenol, 5-amino-4- known to the person skilled in the art in which a colorant is 65 methoxy-2-methylphenol, 5-(2'-hydroxyethyl)amino applied to the, optionally dampened, hair, and the colorant is 2-methylphenol, 3-(diethylamino)phenol, either left on the hair for a period between a few minutes and N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- US 6,858.216 B2 27 28 (methylamino) benzene, 3-(ethylamino)-4- nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro methylphenol and 2,4-dichloro-3-aminophenol, 6-ethylamino-1-hydroxy-4-nitrobenzene. o-aminophenol and derivatives thereof, Naturally occurring direct dyes are, for example, henna m-diaminobenzene and derivatives thereof, Such as, for red, henna neutral, henna black, chamomile blossom, 5 Sandalwood, black tea, buckthorn bark, Sage, logwood, example, 2,4-diaminophenoxyethanol, 1,3-bis(2,4- madder root, catechu, cedar and alkanna root. diaminophenoxy)propane, 1-methoxy-2-amino-4-(2- It is not necessary for the oxidation dye precursors or the hydroxyethylamino) benzene, 1,3-bis(2,4- direct dyes to each represent uniform compounds. Rather, it dia mino phenyl) propane, 2,6-bis(2- is possible that, as a result of the preparation processes for hydroxyethylamino)-1-methylbenzene and 1-amino-3- the individual dyes, further components are present in minor bis(2-hydroxyethyl)aminobenzene, amounts in the hair colorants according to the invention, o-diaminobenzene and derivatives thereof, Such as, for provided that these do not adversely affect the coloring example, 3,4-diaminobenzoic acid and 2,3-diamino-1- result, or have to be excluded for other reasons, e.g. toxi methylbenzene, cological reasons. With regard to the dyes which can be used in the hair di- or trihydroxybenzene derivatives, Such as, for 15 colorants and tints according to the invention, reference is example, resorcinol, resorcinolmonomethyl ether, also made expressly to the monograph by Ch. Zviak, The 2-methylresorcinol, 5-methylre Sorcinol, 2,5- Science of Hair Care, chapter 7 (pages 248-250; direct dimethylre Sorcinol, 2-chloro re Sorcinol, dyes), and chapter 8, pages 264-267; oxidation dye 4-chlorore Sorcinol, pyro gallol and 1,2,4- precursors), published as volume 7 of the series “Dermatol trihydroxybenzene, ogy” (Ed. Ch., Culnan and H. Maibach), Verlag Marcel pyridine derivatives, Such as, for example, 2,6- Dekker Inc., New York, Basle, 1986, and the “European dihydroxypyridine, 2-amino-3-hydroxypyridine, Inventory of Cosmetic Raw Materials”, published by the 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2- European Commission, available in diskette format from the methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4- Bundesverband Deutscher Industrie- und Handelsunterneh dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 25 men flir Arzneimittel, Reformwaren und Körperpflegemittel 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine e.V., Mannheim. and 3,5-diamino-2,6-dimethoxypyridine, The precursors of nature-analogous dyes used are, for naphthalene derivatives, Such as, for example, 1-naphthol, example, indoles and indolines, and their physiologically 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, compatible Salts. Preference is given to those indoles and 2-hydroxyethyl-1-naphth ol, 1,5- indolines which have at least one hydroxyl or amino group, dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7- preferably as Substituent on the six-membered ring. These dihydroxynaphthaiene, 1,8-dihydroxynaphthalene, 2,7- groups can carry further Substituents, e.g. in the form of an dihydroxynaphthalene and 2,3-dihydroxynaphthalene, etherification or esterification of the hydroxyl group or an morpholine derivatives, Such as, for example, alkylation of the amino group. Particularly advantageous 6 - hydroxybenzo morpholine and 35 properties are shown by 5,6-dihydroxyindoline, N-methyl 6-aminobenzomorpholine, 5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6- quinoxaline derivatives, Such as, for example, 6-methyl dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic 1,2,3,4-tetrahydroquinoxaline, acid, 6-hydroxyindoline, 6-amino indoline and pyrazole derivatives, Such as, for example, 1-phenyl-3- 40 4-aminoindoline, and 5,6-dihydroxyindole, N-methyl-5,6- methylpyrazol-5-one, dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5, indole derivatives, Such as, for example, 4-hydroxyindole, 6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6- 6-hydroxyindole and 7-hydroxyindole, dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, methylenedioxybenzene derivatives, Such as, for 6-aminoindole and 4-aminoindole. example, 1-hydroxy-3,4-methylenedioxybenzene, 45 Within this group, particular emphasis is given to 1-amino-3,4-methylene dioxybenzene and 1-(2'- N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6- hydroxyethyl)amino-3,4-methylenedioxybenzene. dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, Particularly Suitable coupler components are 1-naphthol, N-butyl-5,6-dihydroxyindoline and, in particular, 5,6- 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, dihydroxyindoline and N-methyl-5,6-dihydroxyindole, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, 50 N-ethyl-5,6-dihydroxy in dole, N-propyl-5, 6 - resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3- dihydroxyindole, N-butyl-5,6-dihydroxyindole and, in aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2.5- particular, 5,6-dihydroxyindole. dimethyl resorcinol and 2,6-dihydroxy-3,4- The indoline and indole derivatives in the colorants used dimethylpyridine. for the purposes of the method according to the invention Direct dyes are usually nitrophenylene diamines, 55 lacuna be used either as free bases or else in the form of nitroaminophenols, azo dyes, anthraquinones or indophe their physiologically compatible Salts with inorganic or nols. Particularly Suitable direct dyes are the compounds organic acids, e.g. the hydrochlorides, the Sulfates and known under the international names or trade names HC hydrobromides. Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic When using dye precursors of the indoline or indole type, Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, 60 it may be preferred to use these together with at least one Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, amino acid and/or at least one oligopeptide. Preferred amino Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse acids are amino carboxylic acids, in particular Violet 4, Disperse Black 9, Basic Brown 16 and Basic C.-aminocarboxylic acids and (D-aminocarboxylic acids. Of Brown 17, and 1,4-bis(B-hydroxyethyl)amino-2- the C-aminocarboxylic acids, particular preference is given nitrobenzene, 4-amino-2-nitrodiphenylamine-2-carboxylic 65 in turn to arginine, lysine, ornithine and histidine. A very acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, hydroxyethyl particularly preferred amino acid is arginine, in particular in 2-nitrotoluidine, picramic acid, 2-amino-6-chloro-4- free form, but also used as the hydrochloride. US 6,858.216 B2 29 30 Hair colorants, particularly if the coloration is carried out Fe", Mn, Mn', Li+, Mg, Ca" and Al". Particularly oxidatively, whether with atmospheric oxygen or other oxi suitable in this connection are Zn'", Cut" and Mn". The dizing agents Such as hydrogen peroxide, are usually metalions can in principle be used in the form of any desired adjusted to be slightly acidic to alkaline, i.e. to pH values in physiologically compatible Salt. Preferred Salts are the the range from about 5 to 11. For this purpose, the colorants acetates, Sulfates, halides, lactates and tartrates. By using comprise alkalinizing agents, usually alkali metal or alkaline these metal Salts, it is possible both to accelerate the devel earth metal hydroxides, ammonia or organic amines. Pre opment of the coloration and also to influence the color ferred alkalinizing agents are monoethanolamine, nuance in a targeted manner. monoisopropanolamine, 2-amino-2-methylpropanol, The active ingredient according to the invention can also 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3- be used in products for the cleaning of Surfaces Such as glass, propanediol, 2-amino-2-methylbutanol and triethanolamine, porcelain, plastic, textiles, leather, Surface coatings or wood. and also alkali metal and alkaline earth metal hydroxides. In The active ingredient is particularly Suitable, for example, particular, monoethanolamine, triethanolamine and for use in manual and machine dishwashing detergents, glass 2-amino-2-methylpropanol and 2-amino-2-methyl-1,3- cleaners, bathroom and toilet cleaners, and also floor clean propanediol are preferred within this group. The use of 15 erS and floorcare compositions. ()-amino acids, Such as (D-aminocaproic acid, as alkalinizing agent is also possible. EXAMPLES If the actual hair colors are formed in the course of an oxidative process, then customary oxidizing agents, Such as, Unless noted otherwise, all amounts are parts by weight. in particular, hydrogen peroxide or addition products thereof 1. Deodorant Roll-on onto urea, melamine or Sodium borate, can be used. The oxidation with atmospheric oxygen as the Sole oxidizing agent may, however, be preferred. In addition, it is possible to carry out the oxidation using enzymes, where the enzymes Constituent Chemical name INCI name % by wt. are used both for generating oxidizing percompounds, and 25 Methocel(R) E4M Premium Hydroxy- Hydroxy- O.8 also for intensifying the action of a Small amount of oxi EP (DOW) propylmethyl- propylmethyl dizing agents present, or else enzymes are used which cellulose cellulose Water 49.2 transfer electrons from Suitable developer components HYDAGEN (R) HCMF Chitosan Chitosan O.2 (reducing agents) to atmospheric oxygen. Preference is (Cognis) given here to oxidases, Such as tyrosinase, ascorbate oxidase Glycolic acid (Merck) Glycolic acid Glycolic acid O.08 Water ad 100 and laccase, or else glucose oxidase, uricase or pyruvate Ethanol 25.0 oxidase. Mention may also be made of the procedure to 2,5-Dihydro-5-methoxy- 0.5 intensify the action of Small amounts (e.g. 1% and below, 2-furanone based on the overall agent) of hydrogen peroxide using CETIOL(R) HE (Cognis) Polyol fatty PEG-7-glyceryl 3.0 peroxidases. 35 acid ester cocoate Expediently, the preparation of the oxidizing agent is then mixed directly prior to coloring the hair with the preparation 2. Deodorant Pump Spray containing the dye precursors. The ready-to-use hair coloring preparation formed here should preferably have a pH in the range from 6 to 10. Particular preference is given 40 to application of the hair colorants in a weakly alkaline INCI medium. The application temperatures can be in a range Constituent Chemical name declaration % by wt. between 15 and 40 C., preferably at the temperature of the Ethanol 40.O Scalp. After a contact time of about 5 to 45, in particular 15 HYDAGEN (R) C.A.T. Triethyl Triethyl 2.O 45 citrate citrate to 30, minutes, the hair colorant is removed from the hair to Water ad 100 be colored by rinsing out. Afterwashing with a shampoo is Tetrahydro-5-oxo-2- 3.0 dispensed with if a Strongly Surfactant-containing carrier, furanecarboxylic acid e.g. a color Shampoo, has been used. HYDAGEN (R) DCMF Chitosan Chitosan O1 Glycolic acid (Merck) Glycolic acid O.04 Particularly in the case of hair which is difficult to color, pH 4.0 the preparation containing the dye precursors can be applied 50 to the hair without prior mixing with the oxidation compo nent. Then, after a contact time of from 20 to 30 minutes 3. Aftershave Cream optionally after interim rinsing-the oxidation component is applied. After a further contact time of from 10 to 20 minutes, the hair is then rinsed and, if desired, after 55 Shampooed. In this embodiment, according to a first variant INCI in which the prior application of the dye precursors is Constituent Chemical name declaration % by wt. thought to effect better penetration into the hair, the corre EMUL.GADE (R) SE Mixture of Glyceryl 4.0 sponding agent is adjusted to a pH of about 4 to 7. According (Cognis) partial Stearate (and) glycerides, Ceteareth-20 to a Second variant, an air oxidation is firstly attempted, 60 fatty (and) where the applied agent preferably has a pH of from 7 to 10. alcohols, wax Ceteareth-12 In the case of Subsequent accelerated post-Oxidation, the use esters and (and) Cetearyl of peroxydisulfate Solutions which have been made acidic as ethoxylated Alcohol (and) fatty alcohols Cetyl Palmitate oxidizing agents may be preferred. LANETTE (R) O Cetylstearyl Cetearyl 1.O In addition, the development of the coloration can be 65 (Cognis) alcohol Alcohol Supported and increased by adding certain metal ions to the MYRITOL (R) 312 Caprylic? Caprylic? 3.0 agent. Such metal ions are, for example, Zn, Cui", Fe'", US 6,858.216 B2 31 32 5. Rich Nightcare -continued

INCI Constituent Chemical name declaration % by wt. Constituent Chemical name INCI name % by wt. EMULGADE (R) PL 68/50 Mixture of Cetearyl 3.0 (Cognis) capric tri- Capric (Cognis) alkyl poly- Glucoside glyceride Triglyceride glycoside and (and) Cetearyl CETOL (R) PGL Hexyldecanol 7.0 cetylstearyl Alcohol (Cognis) (and) alcohol Hexyldecyl LANETTE (R) O (Cognis) Cetylstearyl Cetearyl 4.0 Laurate alcohol Alcohol DC (R) 190 Dimethicone 0.5 CETIOL(R) J 600 (Cognis) Liquid wax Oleyl Erucate 4.0 (Dow Corning) ester CETIOL(R) V (Cognis) Decyl oleate Decyl Oleate 4.0 GLUADIN (R) AGP Partial Hydrolyzed 0.5 CETIOL(R) OE (Cognis) Di-n-octyl Dicaprylyl 4.0 (Cognis) hydrolyzate Wheat Protein 15 ether Ether from wheat MYRITOL (R) 318 (Cognis) Caprylic? Caprylic? 3.5 Allantoin O1 capric Capric Panthenol (50%) 0.5 triglyceride Triglyceride Baysilon (R) M350 Dimethicone 0.5 Water ad 100 (Bayer) (R)-(-)-4- O.3 COPHEROL (R) F 1300 RRR-(c)- Tocopherol 1.O hydroxymethyl-y- (Cognis) Tocopherol butyrolactone (Merck) Water ad 100 CETOL (R) PGL Hexyldecanol 1.O Glycerol 86% Glycerin 3.0 (Cognis) (and) Carbopol (R) 981 2% Carbomer 1O.O Hexyldecyl strength Laurate 25 KOH2O% O.3 LIPOCUTIN (R) (Cognis) Aqua (and) 5.0 KOH, 20% strength Potassium 0.5 Lecithin (and) Hydroxide Cholesterol HYDAGEN (R) B Bisabolol O.2 (and) Decetyl (Cognis) Phosphate Ethanol 1.O.O D.L-2-hydroxy-3,3- 2.O dimethyl-y- butyrolactone Viscosity (mPas), Brookfield RVF, 137 500 4. Moisturizing Cream Containing Vitamin E 23 C., sp.TE, 4 rpm, with Helipath

35

INCI 6. All-purpose Cream Constituent Chemical name declaration % by wt. EMUL.GADE (R) PL Mixture of Cetearyl 5.0 68/50 alkyl Glucoside Constituent Chemical name INCI name % by wt. polyglycoside (and) Cetearyl 40 and Alcohol DEHYMULS (R) PGPH Polyglycerol Polyglyceryl 4.5 cetylstearyl (Cognis) poly-12- poly-12 alcohol hydroxy- hydroxy LANETTE (E) E Powder Sodium Sodium O.25 Stearate Stearate (Cognis) cetylstearyl Cetearyl MYRITOL (R 331 (Cognis) Cocoglycerides 5.0 sulfate Sulfate 45 CETIOL(R) OE (Cognis) Di-n-octyl Dicaprylyl 5.0 CUTINA (R) GMS Glycerol Glyceryl 2.O ether Ether (Cognis) mOnOStearate Stearate Tetrahydro-5-oxo-2- 1.O MYRITOL (R) 312 Caprylic? Caprylic? 5.0 furanecarboxylic acid (Cognis) capric Capric Zinc stearate Zinc stearate 1.O triglyceride Triglyceride (Barlocher) CETIOL(R) LC (Cognis) Caprylic? Coco- 5.0 50 Glycerol (86%) Glycerin 5.0 capric esters Caprylate? MgSO.7HO 0.5 of saturated Caprate Water ad 100 fatty alcohols Viscosity (mPas), Brookfield RVF, ca. 200 OOO C12-C18 23 C., spindle TE, 4 rpm, with Helipath EUTANOL (R) G 16 2-Hexyldeconal Hexyldecanol 2.O (Cognis) (Guerbet 55 alcohol) COPHEROL(R) F 1300 RRR-(c)- Tocopherol 1.O 7. Rich W/O Cream (Cognis) Tocopherol Wacker silicone oil Dimethicone 0.5 AK 350 (Wacker) (S)-(+)-4- 1.5 Constituent Chemical name INCI name % by wt. hydroxymethyl-y- 60 butyrolactone (Merck) DEHYMULS (R) PGPH Polyglycerol Polyglyceryl 3.0 Glycerol 86% Glycerin 3.0 (Cognis) poly-12- poly-12 D-Panthenol USP 0.5 hydroxy- hydroxy Water ad 100 Stearate Stearate Viscosity (mPas), Brook. RVF, 23. C., 1SO OOO LAMEFORM (R) TGI Triglycerol Polyglyceryl- 3.0 sp.TE, 4 rpm, with Helipath 65 (Cognis) disostearate 3 Diisostearate US 6,858.216 B2 33 34

-continued -continued

Constituent Chemical name INCI name % by wt. Constituent Chemical name INCI name % by wt. Beeswax 8100 Beeswax Cera Alba 3.0 (Kahl & Co.) KOH, 20% strength Potassium O.3 Zincum (E) N29 Zinc stearate Zinc Stearate 1.O Hydroxide (Barlocher) Viscosity (mPas)/Brookfield, RVF, 287 500 CETIOL(R) OE (Cognis) Di-n-octyl Dicaprylyl 3.0 23 C., spindle TE, 4 rpm, with Helipath ether Ether pH 6-7 CETIOL(R) LC (Cognis) Caprylic? Coco 6.O capric esters Caprylate? of saturated Caprate fatty alcohols 9. Lipstick C12-C18 MYRITOL (R 312 (Cognis) Caprylic? Caprylic? 8.0 capric Capric 15 triglyceride Triglyceride Constituent Chemical name INCI name % by wt. Almond Oil Almond oil Almond Oil 8.0 MYRITOL (R) 318 Caprylic?capric Caprylic? 14.O Dihydro-3-hydroxy-4,4- 1.O (Cognis) triglyceride Capric dimethyl-2(3H)- Triglyceride furanone MYRITOL (R) PC Propylene gly- Propylene 6.O COPHEROL (R) F 1300 RRR-(c)- Tocopherol 1.O (Cognis) col octanoate? Glycol (Cognis) Tocopherol decanoate Dicaprylate/ Glycerol Glycerin 5.0 Dicaprate MgSO4 x 7HO 1.O EUTANOL(R) G (Cognis) 2-Octyldodec- Octyldodecanol 17.0 Water ad 100 anol (Guerbet Viscosity (mPas), Brookfield, RVF, 1SO OOO alcohol) 23 C., spindle TE, 4 rpm, with Helipath 25 Candelilla Wax Candelilla 7.0 Cea Carnauba Wax Carnauba cera 5.5 Beeswax 8100 (Kahl) Cera alba 6.5 8. Natural Tinting Day Cream GENEROL (R) 122 N Refined soy- Soybean 2.5 (Cognis) bean sterol (Glycine Soya) Sterol MONOMULS (R) 90 L 12 Molecularly Glyceryl 3.0 Constituent Chemical name INCI name % by wt. (Cognis) distilled lauric Laurate acid EMUL.GADE (R) SE Mixture of Glyceryl 6.O monoglyceride (Cognis) partial Stearate (and) DEHYMULS (R) PGPH Polyglycerol Polyglyceryl-2 4.0 glycerides, Ceteareth-20 35 (Cognis) poly-12- Dipolyhy fatty alcohols, (and) hydroxy- droxy-stearate wax esters and Ceteareth-12 Stearate ethoxylated (and) Cetearyl Castor oil Ricinus 18.0 fatty alcohols Alcohol (and) communis Cetyl 4-Hydroxy-2,5- 1.O Palmitate 40 dimethyl-3(2H)- CUTINA (R) MD Mixture of Glyceryl 2.O furanone (Cognis) mono- and Stearate Color pigments 2.O diglycerides of HYDAGEN (R) CMF Chitosan Chitosan 1O.O palmitic and (Cognis) solution Glycolate stearic acid COPHEROL (R) F 1300 RRR-(c)- Tocopherol 2.O CETOL (R) MM Myristyl Myristyl 1.O (Cognis) Tocopherol (Cognis) myristate Myristate 45 MYRITOL (R) 312 Caprylic?capric Caprylic? 5.0 (Cognis) triglyceride Capric Triglyceride 10. Cold-wave Neutralizer CETIOL(R) SN (Cognis) Ester of a Cetearyl 5.0 branched fatty Isononanoate acid with 50 saturated fatty Constituent Chemical name INCI name % by wt. alcohols C16-C18 DEHYTON (R) K True betaine. Cocamidopro- 6.O CETIOL(R) OE (Cognis) Di-n-octyl Dicaprylyl 5.0 (Cognis) Fatty acid amide pyl Betaine ether Ether derivative with Grape Seed Oil Grape Seed Oil 0.5 55 betaine Copherol (R) 1250 RRR-(c)- Tocopheryl 1.O Structure (Cognis) Tocopheryl Acetate (ca. 32%) acetate NUTRILAN (R) H Protein partial Hydrolyzed 5.0 D.L-3,3-Dimethyl-2- 2.O (Cognis) hydrolyzate Collagen hydroxy-y- (ca. 36%) butyrolactone LAMEQUAT (R) L Cationized Laurdimonium 3.0 Eusolex (E) 8020 4 Isopropyl 1.O 60 (Cognis) protein Hydroxypropyl (Merck) dibenzoyl hydrolyzate Hydrolyzed methane (ca. 36%) Collagen Vitamin A palmitate O.2 Hydrogen peroxide 7.5 Titanium dioxide 1.O 35% strength Talc 1.O Keltrol T Xanthan Gum 15.O Glycerol 86% strength Glycerin 5.0 65 (1% swelling) Water ad 100 Water ad 100 US 6,858.216 B2 35 36 13. Leave-on Hair Treatment -continued

Constituent Chemical name INCI name % by wt. % Constituent Chemical name INCI name by wt. S(+)-2-Hydroxy-3,3- 1.O DEHYOUART (R) F 75 Mixture of Distearoylethyl O.7 dimethyl-y-butyro (Cognis) ester quat and Hydroxyethyl lactone (Aldrich) fatty alcohol monium Methosulfate pH 3.5 1O (and) Cetearyl Alcohol DEHYMULS (R) PGPH Polyglycerol Polyglyceryl-2 1.O 11. Cold-wave Neutralizer, in Emulsion Form (Cognis) poly-12- Dipolyhydroxy hydroxystearate stearate LANETTE (R) O Cetylstearyl Cetearyl Alcohol 3.0 15 (Cognis) alcohol EUTANOL (R) G 2-Octyl- Octyldodecanol O.2 % Constituent Chemical name INCI name by wt. (Cognis) dodecanol (Guerbet DEHYQUART (R) C 4046 Mixture of ester Cetearyl 3.0 alcohol) (Cognis) quat, fatty Alcohol (and) CETOL (R) J 6OO Liquid wax Oleyl Erucate O.1 alcohol and Dipalmitoyl (Cognis) ester nonionic ethyl Hydroxy PLANTACARE (R) 1200 C12–C16 fatty Lauryl Glucoside 2.5 emulsifier ethylmonium UP (Cognis) alcohol Methosulfate glycoside (and) (ca. 50%) Ceteareth-20 4-Hydroxy-2,5- 1.O Water ad 100 25 dimethyl-3(2H)- TURPINAL (R) SL Etidronic Acid O.3 (Cognis) furanone Hydrogen peroxide Hydrogen 7.5 Water ad 100 (35%) Peroxide GLUADIN (R) W40 Partial Hydrolyzed Wheat 2.0 PLANTACARE (R) 2000 C8-C16 fatty Decyl 1.O (Cognis) hydrolyzate Protein UP (Cognis) alcohol Glucoside from wheat glycoside (ca. 40%) DL-2-Hydroxy-3,3- 0.5 Panthenol (50%) O.7 dimethyl-y- pH 4 butyrolactone Viscosity (mPas)/Brookfield, RVF 68OO (Aldrich) 23 C., spindle 5, 10 rpm pH 2.7 35 Viscosity (mPas), Brookfield RVT, 36OO 23 C., sp. TC, 10 rpm 14. Leave-on Hair Treatment

12. Sprayable Hair Treatment, Leave-on 40 % by Constituent Chemical name INCI name wt. % by Sepigel (R) 305 Polyacrylamide 3.0 Constituent Chemical name INCI name wt. (Seppic) (and) C13-14 Isoparaffin MONOMULS (R) 60–35 C Hydrogenated Hydrogenated 1.24 45 (and) Laureth-7 (Cognis) palm glycerides Palm COMPERLAN (R) KD Coconut fatty Cocamide DEA 2.O Glycerides (Cognis) acid diethanol EUMULGN (R) B1 Polyoxyethylene- Ceteareth-12 2.76 amide (Cognis) 12 cetylstearyl Dihydro-3-hydroxy- 3.0 alcohol 4,4-dimethyl CETIOL(R) S (Cognis) Hydrocarbon Dioctylcyclo- 9.O 50 2(3H)-furanone hexane (Aldrich) CETIOL(R) OE (Cognis) Di-n-octyl ether Dicaprylyl 9.O Water ad Ether 1OO Dow Corning DC 345 (R) Cyclomethicone 2.O PLANTACARE (R) 12OO C12-C16 fatty Lauryl Glucoside 0.5 (Dow Corning) UP (Cognis) alcohol 2,5-Dihydro-5- 2.O 55 glycoside methoxy-2-furanone (ca. 50%) (Merck) CETOL (R) J 6OO Liquid wax Oleyl Erucate 0.5 Water ad (Cognis) ester 1OO COPHEROL (R) 12SO RRR-(c)- Tocopherol O.2 GLUADIN (R) WO Cationized wheat Laurdimonium 2.85 (Cognis) Tocopheryl (Cognis) protein Hydroxypropyl acetate hydrolyzate Hydrolyzed 60 GLUADIN (R) ALMOND Partial Hydrolyzed Sweet 3.0 (ca. 31%) Wheat Protein (Cognis) hydrolyzate Almond Protein PLANTACARE (R) 2000 C8-C16 Decyl 1.OO from almonds UP (Cognis) fatty alcohol Glucoside (ca. 22%) glycoside GLUADIN (R) WO Cationized Laurdimonium O.8 (ca. 50%) (Cognis) wheat protein Hydroxypropyl Viscosity mPas &100 65 hydrolyzate Hydrolyzed Wheat (ca. 31%) Protein US 6,858.216 B2 37 38 17. Hair Mask -continued

% by % by Constituent Chemical name INCI name wt. Constituent Chemical name INCI name wt. DEHYOUART (R) F 75 Mixture of ester Distearoylethyl 3.0 Ethanol 1.O.O (Cognis) quat and fatty Hydroxyethyl pH alcohol monium Viscosity (mPas)/Brookfield RVF, Methosulfate 1O (and) Cetearyl 23 C., spindle 4, 10 rpm Alcohol LANETTE (R) O Cetylstearyl Cetearyl Alcohol 4.0 (Cognis) alcohol 15. Hair Rinse CUTINA (R) GMS Glycerol Glyceryl Stearate 1.O (Cognis) mOnOStearate 15 EUMUL.GIN (R) B 2. Polyoxyethylene Ceteareth-20 1.5 (Cognis) 20 cetylstearyl alcohol % by 4-Hydroxy-2,5- 2.O Constituent Chemical name INCI name wt. dimethyl-3(2H)- furanone DEHYOUART (R) C 4046 Mixture of Cetearyl Alcohol 4.0 NUTRILAN (R) KERATIN Partial Hydrolyzed 5.0 (Cognis) ester quat, (and) W (Cognis) hydrolyzate from Keratin fatty alcohol Dipalmitoylethyl keratin and nonionic Hydroxyethyl (ca. 20%) emulsifier monium Metho Panthenol O.8 sulfate (and) Aloe Vera Gel 2.O Ceteareth2O Water ad CETOL (R) SN Ester of a Cetearyl 1.O 25 1OO (Cognis) branched fatty Isononanoate pH 3-4 acid with saturated fatty alcohols C16-C18 18. Intensive Hair Treatment GLUADIN (R) ALMOND Partial Hydrolyzed Sweet 2.1 (Cognis) hydrolyzate Almond Protein from almonds (ca. 22%) % Dihydro-3-hydroxy 1.5 Constituent Chemical name INCI name by wt. 4,4-dimethyl 2(3H)-furanone 35 DEHYOUART (R) L8O Mixture of ester Dicocoylethyl 2.5 (Aldrich) (Cognis) quat and Hydroxyethyl Water propylene glycol monium Metho (ca. 75%) sulfate (and) pH 3.5 Propylene Glycol Viscosity (mPas)/Brookfield RVF, 4OOO CUTINA (R) GMS Glycerol Glyceryl Stearate 0.5 23 C., spindle 4, 10 rpm 40 (Cognis) mOnOStearate LANETTE (R) O Cetylstearyl Cetearyl Alcohol 4.0 (Cognis) alcohol HYDAGEN (R) HSP Trimethylol- 0.5 16. Hair Treatment (Cognis) propane Hydroxy methylstearate Ether 45 Dihydro-3-hydroxy 3.0 % by 4,4-dimethyl Constituent Chemical name INCI name wt. 2(3H)-furanone (Aldrich) Dehyguart (R. L. 80 Mixture of ester Dicocoylethyl LAMESOFT (R) PO 65 Mixture of alkyl Coco-Glucoside 2.5 (Cognis) quat and Hydroxyethyl (Cognis) polyglycoside (and) Glyceryl propylene glycol monium Metho 50 and fatty acid Oleate (ca. 75%) sulfate (and) monoglyceride Propylene Glycol Water ad 100 LANETTE (R) O Cetylstearyl Cetearyl Alcohol 3.5 pH 3.5 (Cognis) alcohol Viscosity (mPas), Brook. RVF, 23. C., 4400 MONOMULS (R) 60-35 C Hydrogenated Hydrogenated 1.O spindle 4, 10 rpm (Cognis) palm glycerides Palm Glycerides 55 EUMULGN (R) B 2. Polyoxyethylene Ceteareth-20 (Cognis) 20 cetylstearyl alcohol 19. Hair Ends Fluid COSMEDIA (R) GUAR Guar hydroxy Guar Hydroxy C 261 (Cognis) propyltrimethyl propyl ammonium Trimonium 60 chloride Chloride Constituent Chemical name INCI name % by wt. Tetrahydro-5-oxo 2.O 2-furanecarboxylic HYDAGEN (R) HCMF Chitosan powder Chitosan 0.4 acid, Nasalt (Cognis) Water ad Glycolic acid Glycolic acid O.2 1OO (Merck) pH 3.5 65 Glycerol 86% Glycerin 55.0 Tylose (R. H 100.000 0.4 US 6,858.216 B2 39 40 22. Setting Foam -continued Constituent Chemical name INCI name % by wt. YP (Hoechst) 5 % by R-(-)-2-Hydroxy- 3.0 3,3-dimethyl-y- Constituent Chemical name INCI name wt. butyrolactone (Aldrich) HYDAGEN (R) HCMF Chitosan powder Chitosan 0.4 GLUADIN (R) R Partial Hydrolyzed Rice 4.0 1O (Cognis) (Cognis) hydrolyzate from Protein (and) rice (ca. 27%) Hydrolyzed Glycolic acid glycolic acid O.2 Vegetable Protein (Merck) Panthenol 50% 1.O Dihydro-3-hydroxy- 1.O Ethanol 1.O.O Water ad 100 15 4,4-dimethyl pH 4.5 2 (3H)-furanone (Aldrich) 20. Leave-on Hair Milk DEHYQUART (R) A Cetyltrimethyl- Cetrimonium 1.O 2O (Cognis) ammonium chloride Chloride (ca. 25%) GLUADIN (R) W40 Partial Hydrolyzed Wheat 2.0 % Constituent Chemical name INCI name by wt. (Cognis) hydrolyzate from Protein DEHYOUART (R) L 80 Mixture of Dicocoylethyl 2.0 25 wheat (ca. 40%) (Cognis) brighteners and Hydroxyethyl Water ad propylene glycol monium Metho (ca. 75%) sulfate (and) 1OO Propylene Glycol LAMESOFT (R) PO 65 Mixture of alkyl Coco Glucoside 2.0 (Cognis) polyglycoside (and) Glyceryl 3O and fatty acid Oleate 23. Styling Wax monoglyceride Tetrahydro-5-oxo- 2.0 2-furanecarboxylic acid, K salt Water ad 100 Constituent Chemical name INCI name % by wt. pH 3.5 35 CUTINA (R) MD Mixture of mono- Glyceryl 5.0 (Cognis) and diglycerides Stearate 21. Pump Spray Setting Composition of palmitic and stearic acid 40 EUMUL.GIN (R) B 1. Polyoxyethylene- Ceteareth-12 1.O Constituent Chemical name INCI name % by wt. (Cognis) 12 cetylstearyl alcohol HYDAGEN (R) HCMF Chitosan powder Chitosan 1.O (Cognis) CETIOL(R) V Decyl oleate Decyl Oleate 5.0 Glycolic acid 0.4 45 (Cognis) (Merck) 2,5-Dihydro-5- 0.5 Paraffin oil 1O.O methoxy-2-furanone HYDAGEN (R) HCMF Chitosan powder Chitosan O.8 (Merck) (Cognis) PLANTACARE (R) 1200 C12–C16 fatty Lauryl O.2 UP (Cognis) alcohol glycoside Glucoside 50 Glycolic acid 0.4 (ca. 50%) (Merck) GLUADIN (R) WO Cationized wheat Laurdimonium 1.O (Cognis) protein Hydroxypropyl D.L-4-Hydroxy- 1.O hydrolyzate Hydrolyzed methyl-y-butyro Wheat Protein lactone (Merck) Ethanol 40.O Water ad 100 55 Water ad 100 pH 4.0 24.2-in-1 Shampoo

Constituent Chemical name INCI name % by wt. TEXAPON (R) N 70 Sodium lauryl Sodium Laureth 12.O (Cognis) ether sulfate Sulfate with 2 mol of EO (ca. 70%) US 6,858.216 B2 41 42

-continued Constituent Chemical name INCI name % by wt. DEHYTON (R) PK 45 Fatty acid amide Cocamidopropyl 2.5 (Cognis) derivative with Betaine betaine structure (ca. 45%) PLANTACARE (R) 818 C8-C16 fatty Coco Glucoside 3.0 UP (Cognis) alcohol glycoside (ca. 50%) LAMESOFT (R) PO 65 Cocoglucoside Coco Glucoside 3.0 (Cognis) (and) glyceryl (and) Glyceryl oleate Oleate COSMEDIA (R) GUARC Guar hydroxy Guar Hydroxy O.3 261 N (Cognis) propyltrimethyl propyl Trimonium ammonium chloride Chloride EUPERLAN (R) PK 12OO Liquid dispersion Coco Glucoside 5.0 (Cognis) of pearlescence (and) Glycol imparting Distearate (and) substances and Glycerin auxiliaries Sodium chloride 1.2 D.L-4-Hydroxy O.3 methyl-Y-butyro lactone (Merck) Euxyl (R) K 400 O.1 (Schulke & Mayr) Water ad 100 pH 5.5 Viscosity (mPas), Brookfield RFT, 63OO 23 C., sp.4, 10 rpm

25. Conditioning Shampoo 3O 26. Baby Shampoo

% % by Constituent Chemical name INCI name by wt. 35 Constituent Chemical name INCI name wt. Water ad TEXAPON (R) N 70 Sodium lauryl Sodium Laureth 1O.O 1OO (Cognis) ether sulfate Sulfate Polymer (R) JR 400 Polyguaternium- 0.4 with 2 mol of EO (Americhol) 1O (ca. 70%) TEXAPON (R) K 14 S Sodium lauryl Sodium Myreth 11.0 PLANTACARE (R) 818 C8-C16 fatty Coco Glucoside 4.0 40 Special 70% myristyl ether Sulfate (Cognis) sulfate (ca. 70%) UP (Cognis) alcohol glycoside DEHYTON (R) PK 45 Fatty acid amide Cocamidopropyl 5.0 (ca. 50%) (Cognis) derivative with Betaine DEHYTON (R) K Fatty acid amide Cocamidopropyl 5.0 betaine structure (Cognis) derivative with Betaine (ca. 45%) betaine structure 45 PLANTACARE (R 818 C8–C16 fatty Coco Glucoside 5.0 UP (Cognis) alcohol glycoside (ca. 30%) (ca. 50%) LAMESOFT (R) PO 65 Cocoglucoside Coco Glucoside 1.5 LAMESOFT (R) PO 65 Coco-glucoside Coco Glucoside 5.0 (Cognis) (and) glyceryl (and) Glyceryl (Cognis) (and) glyceryl (and) Glyceryl oleate Oleate oleate Oleate EUPERLAN (R) PK3OOO Liquid dispersion Glycol 3.2 50 Euxyl (R) K 400 1,2-Dibromocyano- O1 AM (Cognis) of pearlescence- Distearate (and) (Schülke & Mayr) butane and 2 imparting Laureth 4 (and) phenoxyethanol substances and Cocamidopropyl Sodium chloride 18 pH 5.5 amphoteric Betaine Viscosity (mPas), Brookfield RVF, 3900 surfactant 55 23 C., spindle 4, 10 rpm Dihydro-3-hydroxy 1.5 4,4-dimethyl 2(3H)-furanone 27. Pearlescent Care Shampoo (Aldrich) Polymer JR (R 400 Polyguaternium O.3 (Americhol) 1O 60 Sodium Chloride 1.5 % Water ad 100 Constituent Chemical name INCI name by wt. pH 5.5 TEXAPON (R) NSO Sodium lauryl Sodium Laureth 29.O Viscosity (mPas), Brookfield RVF, 85OO (Cognis) ether sulfate Sulfate 23 C., spindle 4, 10 rpm 65 (ca. 28%) PLANTACARE (R 818 C8–C16 fatty Coco Glucoside 5.0 US 6,858.216 B2 44 29. Foam Bath -continued

% Constituent Chemical name INCI name by wt. 5 % by Constituent Chemical name INCI name wt. UP (Cognis) alcohol glycoside TEXAPON (R) NSO Sodium lauryl Sodium Laureth 27.0 (ca. 50%) ether sulfate Sulfate TEXAPON (E) SB 3. KC Sulfosuccinic Disodium Laureth 3.8 (ca. 28%) (Cognis) half-ester based Sulfosuccinate PLANTACARE (R 818 C8–C16 fatty Coco Glucoside 9.O on an alkylpoly UP alcohol glycoside glycol ether, di (ca. 50%) Nasalt (ca. 40%) DEHYTON (R) PK 45 True betaine, Cocamidopropyl 4.0 HYDAGEN (R) HSP Trimethylol- 0.5 fatty acid amide Betaine (Cognis) propane Hydroxy derivative with 15 betaine structure methylstearate (ca. 45%) Ether GLUADIN (R) W40 Partial Hydrolyzed Wheat 4.0 EUPERLAN (R) PK3000 Liquid dispersion Glycol 3.0 hydrolyzate from Protein AM (Cognis) of pearlescence- Distearate (and) wheat Dihydro-3-hydroxy- 1.O imparting Laureth-4 (and) 4,4-dimethyl substances and Cocamidopropyl 2(3H)-furanone amphoteric Betaine (Aldrich) surfactant Sodium chloride Sodium Chloride O.3 NaCl 2.0 Water ad Water ad 100 1OO 25 pH 5.5 Viscosity (mPas), Brook.RVF, 23. C., 41OO spindle 4, 10 rpm 30. Cleansing Milk

28. Cream Hair Color Constituent Chemical name INCI name % by wt. EMUL.GADE (R) SE Mixture of partial Glyceryl 6.O (Cognis) glycerides, fatty Stearate (and) % by alcohols, wax Ceteareth2O Constituent Chemical name INCI name wt. 35 esters and (and) ethoxylated fatty Cetearethl2 Lanette (R) O Cetylstearyl Cetearyl Alcohol 17.0 alcohols (and) Cetearyl (Cognis) alcohol Alcohol (and) CUTINA (R) AGS Ethylene glycol Glycol 1.5 Cetyl Palmitate (Cognis) distearate Distearate EUTANOL (R) G 2-Octyldodecanol Octyldodecanol 7.0 EUMULGN (R) B2 Polyoxyethylene-20 Ceteareth-20 3.0 40 (Cognis) (Guerbet Alcohol) (Cognis) cetylstearyl Dihydro-3-hydroxy- 2.O alcohol 4,4-dimethyl EUMULGN (R) B1 Polyoxyethylene-12 Ceteareth-12 3.0 2(3H)-furanone (Cognis) cetylstearyl (Aldrich) alcohol CETOL (R) 868 Isooctyl stearate Octyl Stearate 8.0 EUMULGN (R) OS Polyoxyethylene-5 Oleth-5 1.O (Cognis) (Cognis) oleylcetyl alcohol 45 Glycerol 86% Glycerin 3.0 Eumulgin (R) O10 Polyoxyethylene-10 Oleth-10 1.O Carbopol (R) 981 Carbomerf2% 1O.O (Cognis) oleylcetyl alcohol (Goodrich) Swelling COMPERLAN (R) KD Coconut fatty acid Cocamide DEA 5.0 NaOH 10% O.8 (Cognis) diethanolamide Water ad 100 Water ad Viscosity (mPas), Brookfield RVF, 8 OOO 1OO 50 23 C., spindle 5, 10 rpm DEHYOUART (R) L 80 Mixture of ester Dicocoylethyl 1.5 (Cognis) quat and propylene Hydroxyethyl glycol monium Metho sulfate (and) 31. All-purpose Cleaner Propylene Glycol Propylene glycol 5.0 55 p-Aminophenol O.35 p-Tolylenediamine O.85 Constituent Chemical name % by wt. 2-Methylresorcinol O.14 6-Methyl-m- O.42 GLUCOPON (R) 215 CSUP Alkyl polyglycoside 3.5 aminophenol (Cognis) Dihydro-3-hydroxy- 1.O DEHYDOL (R) 04 DEO Fatty alcohol ethoxylate 1.7 4,4-dimethyl 60 (Cognis) 2(3H)-furanone Citric acid 9.6 (Aldrich) Acetic acid 2.4 Sodium sulfite O.6 Tetrahydro-5-oxo-2- O.2 EDTA Tetrasodium O.2 furanecarboxylic acid EDTA Water ad 100 Ammonia, 28% 5.0 65 pH 2.0-2.5 US 6,858.216 B2 45 46 32. Hand Dishwashing Detergent -continued Phenonip (R) O.8 Water ad 100 Constituent Chemical name % by wt. "Cetylstraryl alchohol + 20 EO (INCI name: Ceteareth-20) (COGNIS) C13/17-alkanesulfonate Alkanesulfonate C13/17 19.5 *Trimethylhexadecylammonium chloride ca. 25% active subtance (INCI (ca. 60%) name:N,N,N-Trimethyl-2-(methyl-1-oxo-2-propenyl)oxyethaneaminium Cetrimonium Chloride) (COGNIS) chlo TEXAPON (R) N 70 (Cognis) Lauryl ether sulfate, ride monopolyer (50% active substance; INCI name: Polyguaternium-37 Nasalt (ca. 70%) (and) Propylenglycol Dicaprilate Dicaprilate (and) PPG-1 Trideceth-6) DEHYTON (R) K (Cognis) Fatty acid amide 13.3 (ALLIEDCationized COLLOIDS) wheat protein hydrolyzate ca. 31% active substance (INCI derivative with betaine name: Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein) COGNIS) structure ca. 30 D.L- Methyl hydroxybenzoate-ethyl hydroxybenzoate-propyl hydroxybenzoate 3,3-alkyl polyglucoside butyl hydroxybenzoate-phenoxyethanol mixture (ca. 28% active substance; ca. 50% 15 INCI name: Phenoxyethanol, Methylparaben, Ethylparaben, Propylparaben, GLUCOPON (R) 6OO CS UP 14.O Butylparaben) (NIPA) (Cognis) 36. Hair Rinse Ethanol 5.0 Dimethyl-2-hydroxy-y- 0.5 butyrolactone Eumulgin (R) B2 O.3 (Aldrich) Cetylfstearyl alcohol 3.3 Water ad 100 Isopropyl myristate 0.5 pH 5-6 Paraffin oil perliquidum 15 cSt. DAB 9 O.3 Dehyguart (R) L80° 0.4 25 Cosmedia Guar (R) C 261 1.5 Promois (R) Milk-CAQ 3.0 33. Fabric Softener Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone 0.5 Citric acid 0.4 Phenonip (R) O.8 Water ad 100 Constituent Chemical name % by wt. Bis(cocoylethyl)hydroxyethylmethylammonium methosulfate (ca. 76% DEHYQUART (E) AU 56 Ester quat (Cognis, 16.7 active substance in propylene glycol; INCI name: Dicocoylethyl Hydroxy ca. 80%) ethylmonium Methosulfat, Propylene Glycol) (COGNIS) Calcium chloride (25%) 0.5 Guar hydroxypropyltrimethylammonium chloride; INCI name: Guar Dihydro-3-hydroxy-4,4- O.65 Hydroxypropyl Trimonium Chloride (COGNIS) dimethyl-2(3H)- 35 INCI name: Cocodimonium Hydroxypropyl Hydrolyzed Casein (SEIWA furanone KASEI) Water ad 100 37. Hair Treatment

34. Floor Cleaner 40 Dehyguart (R) F75' 4.0 Cetylfstearyl alcohol 4.0 Paraffin oil perliquidum 15 cSt DAB 9 1.5 Constituent Chemical name % by wt. Dehyguart (R) A-CA 4.0 Salcare (R) SC 96 1.5 DEHYPON (R) LS 54 Fatty alcohol alkoxylate 7.0 Amisafe-LMA-60 (E) 1.O (Cognis) 45 Gluadin (R) W 20 3.0 DEHYPON (R) LT 104 Fatty alcohol alkoxylate, 2.O Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone 0.5 (Cognis) terminally capped Citric acid O.15 Butyl diglycol 1O.O Phenonip (R) O.8 Na cumenesulfonate 3.0 Water ad 100 (40%) (R)-(-)-4- 50 Fatty alcohols-methyltriethanolammonium methylsulfate dialkyl ester Hydroxymethyl-y- mixture (INCI name: Distearoylethyl Hydroxyethylmonium Methosulfate, butyrolactone Cetearyl Alcohol) (COGNIS) Water ad 100 'INCI name Hydroxypropyl Arginine Lauryl/Myristyl Ether HCl pH 6.5-7.5 (Anomoto)'Wheat protein hydrolyzate (20% active substance in water; INCI name: Aqua (and) Hydrolized Wheat Protein (and) Sodium Benzoate (and) Phe 55 noxyethanol (and) Metyhlparaben (and) Propylparaben (COGNIS) 35. Hair Rinse 38. Hair Treatment

Eumulgin (R) B2' O.3 Cetylfstearyl alcohol 3.3 60 Dehyguart (R) L80 2.O Isopropyl myristate 0.5 Cetylfstearyl alcohol 6.O Paraffin oil perliquidum 15 cSt. DAB 9 O.3 Paraffin oil perliquidum 15 cSt DAB 9 2.O Dehyguart (R) A-CA 2.O Rewoquat (R) W 75'? 2.O Salcare (R) SC 96 1.O Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone 0.5 Citric acid 0.4 Cosmedia Guar (R) C261 0.5 Gluadin (R) WQ' 2.O 65 Sepigel (R) 305" 3.5 Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone 0.5 Honeyquat (R) 50' 1.O US 6,858.216 B2 47 48

-continued -continued NaCl 0.5 Gluadin (R) WO 2.5 Water ad 100 Guadin (E) W 20 3.0 Citric acid O.15 'Sodium lauryl ether sulfate ca. 28% active substance; (INCI name: Sodium Laureth Sulfate) (COGNIS) Phenonip (R) O.8 °INCI name: Sodium Cocoamphoacetate ca. 30% active substance Water ad 100 COGNIS)Quaternized hydroxyethylcellulose (INCI name: Polyquaternium-10) UNION CARBIDE) '1-Methyl-2-nortallow-alkyl-3-tallow-fatty acid amidoethylimidazolinium Polyol fatty acid ester (INCI name: PEG-7 Glyceryl Cocoate) (COGNIS) methosulfate (ca. 75% active substance in propylene glycol; INCI name: *Sodium salt of 2-pyrrolodinone-5-carboxylic acid (AJINOMOTO) Quaternium-27, Propylene Glycol) (WITCO) *INCI name: Hydroxypropyltrimonium Hydrolyzed Wheat Protein 'Copolymer of acrylamide and 2-acrylamido-2-methylpropanesulfonic (COGNIS) acid (INCI name: Polyacrylamide (and) C-C Isoparaffin (and) Laureth 42. Shampoo 7) (SEPPIC) 15 ''INCI name: Hydroxypropyltrimonium Honey (BROOKS)

39. Hair Treatment Texapon (R) NSO 43.O Dehyton (R) K’ 1.O.O Plantacare (R) 1200 UP2 4.0 Euperlan (R) PK3000? 1.6 Dehyguart (R) F75 O.3 Arquad (R) 316 O.8 Salcare (R) SC 96 5.0 Polymer JR (R 400 O.3 Gluadin (R) WO 1.5 Gluadin (R) WO 4.0 Dow Corning (R) 200 Fluid, 5 cSt 1.5 Glucamate (E) DOE 120 0.5 Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone 0.5 Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone 0.5 Gafquat (R) 755N 1.5 25 Sodium chloride O.2 Biodocarb (R)'7 O.O2 Water ad 100 Perfume oil O.25 Water ad 100 *INCI name: Cocamidopropyl Betaine ca. 30% active substance COGNIS) "Polydimethylsiloxane (INCI name: Dimethicone) (DOW CORNING) C12-C16 fatty alcohol glycoside ca. 50% active substance (INCI name: "Dimethylaminoethyl methacrylate-vinylpyrrollidone copolymer, quater Lauryl Glucoside) (COGNIS) nized with diethyl sulfate (19% active substance in water; INCI name: 'Liquid disperion of pearlescence-imparting substances and amphoteric Polyquaternium-11) (GAF) surfactant (ca. 62% active substance; CTFA name: Glycol Distearate (and) Glycerin (and) Laureth-4 (and) Cocoamidopropyl Betaine) (COGNIS) '73-Iodo-2-propynyl-n-butylcarbamate (INCI name: Iodopropylnyl 'Tri-Cio-alkylmethylammonium chlordie (AKZO) Butylcarbamate) (MILKER & GRUNING) 'Ethoxylated methyl glucoside dioleate (CFTA name: PEG-120 Methyl Glucose Dioleate) (AMERCHOL) 40. Hair Treatment 35 43. Shampoo

Sepigel (R) 305 5.0 Dow Corning (R) Q2-5220' 1.5 40 Texapon (R) N 70° 21.0 Promois (R) Milk O' 3.0 Plantacare (E) 1200 UP 8.0 Polymer P1 corresponding to DE 3929173 O6 Gluadin (R) WO 1.5 Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone 0.5 Cutina (R) EGMS O.6 Genamin (E) DSAC' O.3 Honeyquat (R) 50 2.0 Phenonip (R) O.8 Ajidew (R) NL 50 2.8 Perfume oil O.25 Antil (R) 141 1.3 Water ad 100 45 Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone 0.5 Sodium chloride O.2 'Silicone-glycol copolymer (INCI name: Dimethicone Copolyol) (DOW Magnesium hydroxide ad pH 4.5 CORNING)'INCI name Hydropropyltrimonium Hydrolyzed Casein ca. 30% active Water ad 100 substance2Dimethyldistearylammonium (SEIWA KASEI) chloride (INCI name: Distearyldimonium *Sodium lauryl ether sulfate with 2 mol of EO ca. 70% active substance 50 (INCI name: Sodium Laureth Sulfate) (COGNIS) Chloride) (CLARIANT) Ethylene glycol monostearate (ca. 25.35% monoester, 60-70% diester; INCI name: Glycol Stearate) (COGNIS) 41. Shampoo INCI name: Hydroxypropyltrimonium Honey (ca. 50% active substance) (BROOKS)Polyoxyethylene-propylene glycol dioleate (40% active substance; INCI name: Propylene Glycol (and) PEG-55 Propylene Glycol Oleate) 55 Texapon (R) NSO' 40.O (GOLDSCHMIDT) Dehyton (R) G’ 6.O Polymer JR 400 (R2 0.5 44. Shampoo Cetiol (R) HE2 0.5 Ajidew (R) NL 50° 1.O Gluadin (R) WOT 2.5 Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone 0.5 60 Texapon (R) K 14 S SO.O Guadin (E) W 20 0.5 Dehyton (R) K 1.O.O Panthenol (50%) O.3 Plantacare (R) 818 UP7 4.5 Vitamin E O.1 Polymer P1, corresponding to DE 3929 973 O.6 Vitamin H O.1 Cutina (R) AGS 2.0 Citric acid 0.5 D-Panthenol 0.5 Sodium benzoate 0.5 65 Glucose 1.O Perfume 0.4 Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone 0.5 US 6,858.216 B2

-continued -continued Salicyclic acid 0.4 Salcare (R) SC 96 1.O Sodium chloride 0.5 5 Water ad 100 Gluadin (R) WO 2.O Water ad 100 71-Hydroxyethane-1,1-diphosphonic acid (60% active substance; INCI name: Etidronic Acid) (COGNIS) Sodium lauryl myristyl ether sulfate ca. 28% active substance (INCI Acrylic ester-methacrylic acid copolyer (25% active substance) (BASF) name: Sodium Myreth Sulfate) (COGNIS) 'C8-C16 fatty alcohol glycoside ca. 50% active substance (INCI name: Coco oric CONS ( 10 The coloring cream had a pH of 10.0. It brought about an Ethylene glycol stearate (ca. 5-15% monoester, 85-95% diester; INCI intensive red tinting of the hair. name: Glycol Distearate) (COGNIS) 48.. Tinting ShShampoo 45. Hair Treatment 15 Texapon (R) N 70 14.O Dehwton (E) K 1.O.O LuviE. K30200 O.2O.6 S. s RLM 45 NV 14.7 Rol 0.5 Plantacare (E) 1200 UP 4.0 Polymer P1, corresponding to DE 3929 973 O.6 Polymer P1, corresponding to DE 39 29 973 O.3 Dehyguart (R) A-CA' 1.O 2O Cremophor (R) RH 40 O.8 Gluadin (R) W 4O2 1.O Dye C.I. 12 719 O.O2

Natrosol (R) 250 HR 1.1 E.C -..: : i. S. Gphylyoxy-4-dimethyl-2GH)-lumnone W 0.52.O Sir 3-hydroxy-4,4-dimethyl-2(3H)-furanone--,-- 0.5 San O ad 100 Dye C.I. 56059 O.O3 25 Preservative 0.25 Quaternized cellulose derivative (95% active substance; CFTA name: Perfume oil 5. C.S. Polyguaternium-4) (DELFT NATIONAL) Eutanol (BG O.3 Polyvinylpyrrolidone (95% active substance; CFTA name: PVP) (BASF) Gluadin (R) WO 1.O 'Cetyltrimethylammonium chloride (INCI name: Cetrimonium Chhloride) Egypt (R) 50 6. COGNIS) Salcare (R) SC 96 O. *Partial hydrolyzate from wheat ca. 40% active substance (INCI name: 3O Water ad 100 Hydrolyzed Wheat Gluten Hydrolyzed Wheat Protein) (COGNIS) 'Hydroxyethylcellulose (AQUALON) 'Lauryl alcohol + 4.5 ethylene oxide acetic acid sodium salt (20.4% active substance) (CHEM-Y) 'Castor oil, hydrogenated + 45 ethylene oxide (INCI name: PEG-40 46. Coloring Cream Hydrogenated Castor Oil) (BASF) 2-Octyldodecanol (Guerbet Alcohol) (INCI name: Octyldodecanol) 35 (COGNIS) C12 18-fatty alcohol 1.2 Upon washing the hair with this tinting Shampoo, the hair EumulginLanette (E) (R)O' B 2. 4.0O.8 IS given a gloSSy1 pale-DIondele-blonde Snade.shad Cutina (R) KD 16 2.O 49. Cream Permanent Wave Sodium sulfite 0.5 40 L(+)-ascorbic acid 0.5 Ammonium sulfate 0.5 1.2-Propylene glycol 1.2 Polymer JR (R 400 O.3 Waving cream p-Aminophenol O.35 Pl (R) 810 UPS2 5.0 p-Tolylenediamine O.85 45 antacare 2-Methylresorcinol O.14 Thioglycolic acid 8.O 6-Methyl-m-aminophenol O42 Turpinal B SL 0.5 Cetiol (R) OE 0.5 Ammonia (25% strength) 7.3 Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone 0.5 Ammonium carbonate 3.0 Honeyquat (R) 50 1.O Cetylfstearyl alcohol 5.0 Ajidew (R) NL 50 1.2 Guerbet Alcohol 4.0 Gluadin (R) WO 1.O 50 Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone 0.5 Ammonia 1.5 Salcare (R) SC 96 3.0 Water ad 100 Gluadin (R) WO 2.O Perfume oil C.S. “Cetylstearyl alcohol (INCI name: Cetearyl Alcohol) (COGNIS) Water ad 100 'Self-emulsifying mixture of mono/diglycerides of higher saturated fatt acids with SiN stearate (INCI E. Glyceryl S. SE) y 55 *Cs-CoAlkyl glucoside with degree of oligomerization 1.6 (ca. 60% COGNIS) active substance) (COGNIS) Di-n-octyl ether (INCI name: Dicaprylyl Ether) (COGNIS) 47. Developer Dispersion for Coloring Cream 12 Plantacare (E) 810 UP 5.0 60 Hydrogenated castor oil 2.O Potassium bromate 3.5 Texapon (R) NSO 2.1 Nitrillotriacetic acid O.3 Hydrogen peroxide (50% strength) 12.0 Citric acid O.2 Turpinal (R) SL7 1.7 Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone 0.5 Latekoll (R) D 12.0 Merquat (R) 550 0.5 Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone 0.5 65 Hydagen (R) HCMF 0.5 Gluadin (R) WO O.3 Gluadin (R) WO 0.5 US 6,858.216 B2 S1

-continued formula (I) O O R6 Perfume oil C.S. Water ad 100 R5 Dimethyldiallylammonium chloride-acrylamide copolymer (8% active 1. 4 substance; INCI name: Polyguarternium-7) (MOBILOIL) R R2 R3 R 'Chitosan powder (INCI name: Chitosan) (COGNIS) formula (II) O O R10 50. Face Tonics 1O R9 R7 R8 SO.1 50.2 50.3 wherein the radicals R to R', independently of one Pluronic (R) L. 64 3.0 4.0 5.0 Dihydro-3-hydroxy-4,4- 0.25 O.25 0.25 15 another, are Selected from the group consisting of dimethyl-2 (3H)-furanone hydrogen, -OH, a methyl, methoxy, an aminomethyl or Dipropylene glycol 1.O.O 1O.O 1.O.O hydroxymethyl radical, Emulsifier TD9/PEG4OHCO 0.5 0.5 0.5 Fragrance O.2 O.2 O.2 a-C-C-Saturated or mono- or diunsaturated, branched Zn gluconate O.OS O.O7 O.10 or linear hydrocarbon radical, Hydagen (R) CMF' 3.5 6.O 9.5 a-C-C-Saturated or mono- or diunsaturated, branched Water (NaOH to pH = 5) ad 100 ad 100 ad 100 or linear mono-, di- or trihydroxy hydrocarbon radical, EO-PO-EO block polymer (EO = 40% by weight), OH number = 39.1 a-C-C-Saturated or mono- or diunsaturated, branched Trideceth 9 and PEG40-hydrogenated castor oil or linear mono-, di- or triamino hydrocarbon radical, a 'Solution of chitosan (ca. 1% by weight) in a 0.4% strength aqueous gly group -OR', where R' is selected from a -C-C- colic acid solution 25 Saturated or mono- or diunsaturated, branched or linear 51. Hydrogels hydrocarbon radical, a -C-C-Saturated or mono- or diunsaturated, branched or a linear mono-, di- or tri hydroxy hydrocarbon radical, a group -NR'R'', where R'' and R' independently of 51.1 51.2 one another, are Selected from hydrogen, methyl, a Pluronic (R) L64 3.0 3.0 -C-C-Saturated or mono- or diunsaturated, Methocel(R) E4M O.3 O.2O branched or linear hydrocarbon radical or a -C-C- Dihydro-3-hydroxy-4,4-dimethyl- O.25 0.25 Saturated or mono- or diunsaturated, branched or linear 2(3H)-furanone mono-, di- or trihydroxy hydrocarbon radical, Dipropylene glycol 1O.O 1.O.O 35 Emulsifier TD9/PEG4OHCO 0.5 O.SO a group -COOR", where R' is selected from hydrogen, Fragrance O.2 O.2O methyl, a -C-C-Saturated or mono- or Zn gluconate O.OS O.10 diunsaturated, branched or linear hydrocarbon radical, Hydagen (R) CMF 3.5 8.O Water (NaOH to pH = 5) ad 100 ad 100 a-C-C-Saturated mono- or diunsaturated, branched 40 or linear mono-, di- or trihydroxy hydrocarbon radical Methylhydroxypropylcellulose (DOW) or a -C-C-Saturated or mono- or diunsaturated, branched or linear mono-, di- or triamino hydrocarbon 52. Skin Emulsions (O/W) radical, a group -CONR'R'', where R' and R'' are indepen 45 dently selected from hydrogen, methyl, a -C-C- Saturated or mono- or diunsaturated, branched or linear 52.1 52.2 hydrocarbon radical, a -C-C-Saturated mono- or Emulgade (R) SE 8.0 8.0 diunsaturated, branched or linear mono-, di- or trihy Cutina (R) MD-A 1.5 1.5 Cetylfstearyl alcohol 1.5 1.5 droxy hydrocarbon radical or a -C-C-Saturated or Myritol (R. 318° 1.O.O 1.O.O 50 mono- or diunsaturated, branched or linear mono-, di 2-Ethylhexyl stearate 5.0 5.0 or triamino hydrocarbon radical, Dimethylpolysiloxane (350 at) 1.O 1.O Controx (R) KS O.OS O.OS a group -COR', where R' is selected from methyl, a PHB propyl ester O.2 O.2 -C-C-Saturated or mono- or diunsaturated, PHB methyl ester O.2 O.2 branched or linear hydrocarbon radical, a -C-C- Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanone 0.5 0.25 55 Saturated or mono- or diunsaturated, branched or linear 1.2-Propylene glycol 3.0 3.0 mono-, di- or trihydroxy hydrocarbon radical or a Hydagen (R) CMF 3.0 8.0 Zn gluconate O.04 O.10 -C-C-Saturated or mono- or diunsaturated, Water (NaOH to pH = 5) ad 100 ad 100 branched or linear mono-, di- or triamino hydrocarbon radical, and Mixture of: glyceryl stearate, ceteareth-20, ceteareth-12, cetearyl alcohol and cetylpalmitate (COGNIS) 60 a group -OCOR'', where R7 is methyl, a -C-C- 'Glyceryl stearate (COGNIS) Saturated or mono- or polyunsaturated, branched or "Caprylic?capric triglyceride (COGNIS) linear hydrocarbon radical, a -C-Cio-Saturated or Tocopherol and hydrogenated tallow glycerides citrate (COGNIS) mono- or polyunsaturated, branched or linear mono-, What is claimed is: di-, tri- or polyhydroxy hydrocarbon radical or a 65 -C-Cio-Saturated or mono- or polyunsaturated, 1. A cosmetic agent comprising a 2-furanone derivative of branched or linear mono-, di-, tri- or polyamino hydro the formula (I) and/or of the formula (II): carbon radical, US 6,858.216 B2 S3 S4 with the proviso that when R and Rare -OH and R' or 6. The cosmetic agent as claimed in claim 5, wherein R' R" are hydrogen, the remaining groups R and R'' are not and R, independently are selected from the group consist a dihydroxyethyl radical. ing of 2. The cosmetic agent of claim 1, wherein R', R and R', hydrogen, -OH, methyl, methoxy, aminomethyl, independently are Selected from the group consisting of 5 hydroxymethyl, hydrogen, -OH, methyl, methoxy, aminomethyl, -C-C-saturated or mono- or diunsaturated, branched hydroxymethyl, or linear mono-, di- or trihydroxy hydrocarbon radical, a group -OR', where R' is selected from a -C-C- a-C-C-Saturated or mono- or diunsaturated, branched Saturated or mono- or diunsaturated, branched or linear or linear mono-, di- or trihydroxy hydrocarbon radical, 1O hydrocarbon radical or a -C-C-Saturated or mono a-C-C-Saturated or mono- or diunsaturated, branched or diunsaturated, branched or linear mono-, di- or or linear mono-, di- or triamino hydrocarbon radical, a trihydroxy hydrocarbon radical, group -OR', where R' is selected from a -C-C- a group -COOR'', where R'' is selected from hydrogen, Saturated or mono- or diunsaturated, branched or linear methyl, a -C-C-Saturated or mono- or hydrocarbon radical or a -C-C-Saturated or mono- 15 diunsaturated, branched or linear hydrocarbon radical or diunsaturated, branched or linear mono-, di- or or a -C-C-Saturated mono- or diunsaturated, trihydroxy hydrocarbon radical, branched or linear mono-, di- or trihydroxy hydrocar a group -COOR", where R' is selected from hydrogen, bon radical, methyl, a -C-C-Saturated or mono- or a group -COR', where R' is selected from methyl, a diunsaturated, branched or linear hydrocarbon radical, 2O -C-C-Saturated or mono- or diunsaturated, a -C-C-Saturated or mono- or diunsaturated, branched or linear hydrocarbon radical or a -C-C- branched or linear mono-, di- or trihydroxy hydrocar- Saturated or mono- or diunsaturated, branched or linear bon radical or a -C-C-Saturated or mono- or mono-, di- or trihydroxy hydrocarbon radical, and diunsaturated, branched or linear mono-, di- or triamino a group -OCOR'', where R7 is selected from methyl, a hydrocarbon radical, -C-Cio-Saturated and/or mono- or polyunsaturated, 25 branched or linear hydrocarbon radical or a -C-Cio a group -COR', where R' is selected from a methyl, Saturated or mono- or polyunsaturated, branched or a -C-C-Saturated or mono- or diunsaturated, linear mono-, di-, tri- or polyhydroxy hydrocarbon branched or linear hydrocarbon radical, a -C-C- radical. Saturated or mono- or diunsaturated, branched or linear 7. The cosmetic agent of claim 6, wherein R and R', mono-, di- or trihydroxy hydrocarbon radical or a 30 independently are Selected from the group consisting of: -C-C-Saturated or mono- or diunsaturated, hydrogen, -OH, methyl, methoxy, aminomethyl, branched or linear mono-, di- or triamino hydrocarbon hydroxymethyl, radical, and a group -OCOR'', where R'' is selected from methyl, a a-C-C-Saturated or mono- or diunsaturated, branched -C-Cio-Saturated or mono- or polyunsaturated, 35 or linear mono-, di- or trihydroxy hydrocarbon radical, branched or linear hydrocarbon radical, a -C-Cio a group -OR'', where R'' is selected from a -C-C- Saturated or mono- or polyunsaturated, branched or Saturated or mono- or diunsaturated, branched or linear linear mono-, di-, tri- or polyhydroxyalkyl radical or a hydrocarbon radical or a -C-C-Saturated or mono -C-Cio-Saturated or mono- or polyunsaturated, or diunsaturated, branched or linear mono-, di- or branched or linear mono-, di-, tri- or polyaminohydro- 40 trihydroxy hydrocarbon radical, carbon radical. a group -COOR'', where R'' is selected from hydrogen, 3. The cosmetic agent of claim 2, wherein R, R and R, methyl, a -C-C-Saturated or mono- or independently are Selected from the group consisting of: diunsaturated, branched or linear hydrocarbon radical hydrogen, -OH, methyl, methoxy, aminomethyl, or a -C-C-Saturated mono- or diunsaturated, hydroxymethyl, 45 branched or linear mono-, di- or trihydroxy hydrocar bon radical, and a-C-C-Saturated or mono- or diunsaturated, branched a group-OCOR'', where R'' is selected from methyl, a or linear hydrocarbon radical, -C-Cio-Saturated or mono- or polyunsaturated, a-C-C-Saturated or mono- or diunsaturated, branched branched or linear hydrocarbon radical or a -C-Cio or linear mono-, di- or trihydroxy hydrocarbon radical 50 Saturated or mono- or polyunsaturated, branched or and linear mono-, di-, tri- or polyhydroxy hydrocarbon a-C-C-Saturated or mono- or diunsaturated, branched radical. or linear mono-, di- or triamino hydrocarbon radical. 8. The cosmetic agent of claim 7, wherein R and R, 4. The cosmetic agent of claim 3 wherein R, R, R and independently are Selected from the group consisting of: R", independently are Selected from the group consisting 55 hydrogen, -OH, methyl, methoxy, aminomethyl, of: hydroxymethyl, hydrogen, -OH, methyl, methoxy, aminomethyl, a-C-C-Saturated or mono- or diunsaturated, branched hydroxymethyl, or linear mono-, di- or trihydroxy hydrocarbon radical, a-C-C-Saturated or mono- or diunsaturated, branched and or linear hydrocarbon radical, 60 a group -OR', where R' is selected from a -C-C- a-C-C-Saturated or mono- or diunsaturated, branched Saturated or mono- or diunsaturated, branched or linear or linear mono-, di- or trihydroxy hydrocarbon radical hydrocarbon radical or a -C-C-Saturated or mono and or diunsaturated, branched or linear mono-, di- or a-C-C-Saturated or mono- or diunsaturated, branched trihydroxy hydrocarbon radical. or linear mono-, di- or triamino hydrocarbon radical. 65 9. The cosmetic agent of claim 8, wherein the compound 5. The cosmetic agent of claim 4 wherein the 2-furanone of formula (I) is dihydro-3-hydroxy-4,4-dimethyl-2(3H)- derivative has the formula (I). furanone. US 6,858.216 B2 SS 10. The cosmetic agent of claim 9 which in addition 15. The cosmetic agent of claim 14 which in addition contains a polymer. contains a vitamin, a provitamin, a Vitamin precursor or 11. The cosmetic agent of claim 10 which in addition derivatives thereof. contains a protein hydrolyzate and/or derivative thereof. 16. The cosmetic agent of claim 15 which in addition 12. The cosmetic agent of claim 11 which in addition contains a Substance which contains primary or Secondary contains a Surfactant. amino groups. 13. The cosmetic agent of claim 12 which in addition 17. A method of treating human or animal skin comprising contains an emulsifier. applying to Said skin the cosmetic agent of claim 1. 14. The cosmetic agent of claim 13 which in addition contains a Solid fatty Substance. k k k k k