AU1046100A

AU1046100A - Novel use of uv filters, method for colouring keratinic fibres agents for realising this method

Info

Publication number: AU1046100A
Application number: AU10461/00A
Authority: AU
Inventors: Ullrich Bernecker; Manuela Ehlert; Horst Hoffkes; Detlef Hollenberg; Bernd Meinigke
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1998-11-18
Filing date: 1999-11-09
Publication date: 2000-06-05
Also published as: DE19853111A1; JP2002529492A; DE59910913D1; EP1128804B1; ATE279907T1; EP1128804A1; WO2000028957A1; ES2232184T3

Abstract

The present invention relates to the use of UV filters for substantially increasing the laundry fastness of dyes for keratinic fibres. The UV filters can be applied onto the fibres both directly with the colouring agent or in another step of this method. The agents obtained according to the present invention are associated with a combination of a water non-soluble UV filter, of a UV filter comprising a quaternary ammonium group and of a mono-, di- or oligosaccharide in order to substantially increase the laundry fastness of the dyes.

Description

WO 00/28957 1 PCT/EP99/08568 Novel Use of UV Filters, Method for Colouring Keratinic Fibres, Agents for Realizing this Method This invention relates to the use of UV filters for improving the fastness to washing of colors on keratin fibers, to a processes for coloring keratin fibers and to preparations for use in these processes. Among the various products available for the cosmetic treatment of 5 the human body, formulations for modifying or shading the color of the hair occupy a prominent position. Disregarding blonding preparations which lighten the hair oxidatively by degrading the natural hair dyes, there are largely three types of preparations for changing the color of hair which are of importance in the coloring of hair: 10 So-called oxidation colorants are used for permanent, intensive colors with corresponding fastness properties. Oxidation colorants normally contain oxidation dye precursors, so-called primary intermediates and secondary intermediates. The primary intermediates form the actual dyes with one another or by coupling with one or more secondary 15 intermediates under the influence of oxidizing agents or atmospheric oxygen. Although oxidation colorants are distinguished by excellent long lasting coloring results, a mixture of a relatively large number of oxidation dye precursors normally has to be used for natural-looking colors. In many cases, substantive dyes are additionally used for shading. If the dyes 20 formed during color development or directly used have clearly different fastness values (for example UV stability, fastness to perspiration, fastness to washing, etc.), a discernible and hence unwanted change of color can gradually occur. This phenomenon occurs to a greater extent if the hair style has hairs or hair zones damaged to different extents. One example of 25 this are long hairs where the tips exposed for long periods to all kinds of environmental influences are generally damaged to a greater extent than WO 00/28957 2 PCT/EP99/08568 the relatively freshly regrown hair zones. Colorants or tints containing substantive dyes as their coloring component are normally used for temporary colors. Substantive dyes are based on dye molecules which are directly absorbed onto the hair and do 5 not require an oxidative process for developing the color. Dyes such as these include, for example, henna which has been used since ancient times for coloring the body and hair. Corresponding colors are generally far more sensitive to shampooing than the oxidative colors so that an often unwanted change of shade or even a visible "decoloration" then occurs 10 very much more quickly. Finally, a new coloring process has recently attracted considerable interest. In this process, precursors of the natural hair dye melanin are applied to the hair and then form "nature-like" dyes in the hair in the course of oxidative processes. One such process using 5,6-dihydroxyindoline as 15 the dye precursor is described in EP-B1 530 229. If preparations containing 5,6-dihydroxyindoline are applied, in particular repeatedly, people with gray hair can be given back their natural hair color. Color development can be carried out with atmospheric oxygen as sole oxidizing agent so that no other oxidizing agent has to be used. In people with 20 originally medium-blond to brown hair, the indoline may be used as sole dye precursor. By contrast, in people with originally red hair and, more particularly, dark to black hair, satisfactory results can often only be obtained by using other dye components as well, more particularly special oxidation dye precursors. In this case, too, the fastness of the colors can 25 be problematical. Accordingly, there has been no shortage of attempts to improve the fastness of colors on keratin fibers. One development direction is optimization of the dyes themselves or the synthesis of new modified dye molecules. Another development direction is the search for additives for 30 the colorants to increase the fastness of the colors. A known solution to WO 00/28957 3 PCT/EP99/08568 the problem is to add UV filters to the colorant. These filters are applied to the hair together with the dye during the coloring process so that, in many cases, a distinct increase in the stability of the color to the effect of daylight or artificial light is obtained. 5 It has now surprisingly been found that the fastness to washing of colors on keratin fibers can also be significantly increased by the use of UV filters. Fastness to washing in the context of the present invention is understood to be the retention of the original color in regard to shade and/or intensity when the keratinic fiber is exposed to the repeated 10 influence of water-based preparations, more particularly surfactant containing preparations, such as shampoos. Accordingly, the present invention relates to the use of UV filters for improving the fastness to washing of colors on keratin fibers. According to the invention, keratin fibers are understood to include 15 pelts, wool, feathers and in particular human hair. There are no general restrictions on either the structure or the physical properties of the UV filters to be used in accordance with the invention. On the contrary, any cosmetically usable UV filters of which the absorption maximum lies in the UVA range (315-400 nm), the UVB range 20 (280-315 nm) or the UVC range (< 280 nm) may be used. UV filters with an absorption maximum in the UVB range, more particularly in the range from about 280 to about 300 nm, are particularly preferred. The UV filters used in accordance with the invention may be selected, for example, from substituted benzophenones, p-aminobenzoic 25 acid esters, diphenyl acrylic acid esters, cinnamic acid esters, salicylic acid esters, benzimidazoles and o-aminobenzoic acid esters. Examples of UV filters suitable for use in accordance with the invention are 4-aminobenzoic acid, N,N,N-trimethyl-4-(2-oxoborn-3 ylidenemethyl)-aniline methyl sulfate, 3,3,5-trimethyl cyclohexyl salicylate 30 (Homosalate), 2-hydroxy-4-methoxybenzophenone (Benzophenone-3; WO 00/28957 4 PCT/EP99/08568 Uvinul@ M 40, Uvasorb@ MET, Neo Heliopan@ BB, Eusolex@ 4360), 2 phenylbenzimidazole-5-sulfonic acid and potassium, sodium and triethanolamine salts thereof (Phenylbenzimidazole sulfonic acid; Parsol@ HS, Neo Heliopan@ Hydro), 3,3'-(1,4-phenylenedimethylene)-bis-(7,7 5 dimethyl-2-oxo-bicyclo-[2.2.1]hept-1-yl methanesulfonic acid) and salts thereof, 1-(4-tert.-butylphenyl)-3-(4-methoxyphenyl)-propane-1,3-dione (Butyl methoxydibenzoylmethane; Parsol@ 1789, Eusolex@ 9020), c-(2 oxoborn-3-ylidene)-toluene-4-sulfonic acid and salts thereof, ethoxylated 4 aminobenzoic acid ethyl ester (PEG-25 PABA; Uvinul@ P 25), 4 10 dimethylaminobenzoic acid-2-ethylhexyl ester (Octyl Dimethyl PABA; Uvasorb@ DMO, Escalol@ 507, Eusolex@ 6007), salicylic acid-2-ethyl hexyl ester (Octyl Salicylate; Escalol@ 587, Neo Heliopan@ OS, Uvinul@ 018), 4 methoxycinnamic acid isopentyl ester (Isoamyl p-Methoxycinnamate; Neo Heliopan@ E 1000), 4-methoxycinnamic acid-2-ethylhexyl ester (Octyl 15 Methoxycinnamate; Parsol@ MCX, Escalol@ 557, Neo Heliopan@ AV), 2 hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (Benzophenone-4; Uvinul@ MS 40; Uvasorb@ S 5), 3-(4' methylbenzylidene)-D,L-camphor (4-Methylbenzylidene camphor; Parsol@ 5000, Eusolex@ 6300), 3-benzylidene camphor (3-Benzylidene camphor), 20 4-isopropyl benzyl salicylate, 2,4,6-trianilino-(p-carbo-2'-ethylhexyl-1'-oxy) 1,3,5-triazine, 3-imidazol-4-yl acrylic acid and its ethyl ester, polymers of N {(2 and 4)-[2-oxoborn-3-ylidenemethyl]benzyl}-acrylamide, 2,4 dihydroxybenzophenone (Benzophenone-1; Uvasorb@ 20 H, Uvinul@ 400), 1,1'-diphenylacrylonitrile acid-2-ethylhexyl ester (Octocrylene; Eusolex@ 25 OCR, Neo Heliopan@ Type 303, Uvinul@ N 539 SG), o-aminobenzoic acid menthyl ester (Menthyl Anthranilate; Neo Heliopan@ MA), 2,2',4,4' tetrahyd roxybenzophenone (Benzophenone-2; Uvinul@ D-50), 2,2' dihyd roxy-4,4'-dimethoxybenzophenone (Benzophenone-6), 2,2' dihydroxy-4,4'-dimethoxybenzophenone-5-sodium sulfonate and 2-cyano 30 3,3-diphenylacrylic acid-2'-ethyl hexyl ester. Preferred UV filters are 4- WO 00/28957 5 PCT/EP99/08568 aminobenzoic acid, N,N,N-trimethyl-4-(2-oxoborn-3-ylidenemethyl)-aniline methyl sulfate, 3,3,5-trimethyl cyclohexyl salicylate, 2-hydroxy-4 methoxybenzophenone, 2-phenylbenzimidazole-5-sulfonic acid and potassium, sodium and triethanolamine salts thereof, 3,3'-(1,4 5 phenylenedimethylene)-bis-(7,7-dimethyl-2-oxo-bicyclo-[2.2.1]hept-1-yl methanesulfonic acid) and salts thereof, 1-(4-tert.-butylphenyl)-3-(4 methoxyphenyl)-propane-1,3-dione, a-(2-oxoborn-3-ylidene)-toluene-4 sulfonic acid and salts thereof, ethoxylated 4-aminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid-2-ethylhexyl ester, salicylic acid-2-ethyl 10 hexyl ester, 4-methoxycinnamic acid isopentyl ester, 4-methoxycinnamic acid-2-ethyl hexyl ester, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, 3-(4'-methylbenzylidene)-D,L-camphor, 3-benzylidene camphor, 4-isopropyl benzyl salicylate, 2,4,6-trianilino-(p-carbo-2' ethylhexyl-1 '-oxy)-1,3,5-triazine, 3-imidazol-4-yl acrylic acid and its ethyl 15 ester, polymers of N-{(2 and 4)-[2-oxoborn-3-ylidenemethyl]benzyl} acrylamide. According to the invention, 2-hydroxy-4 methoxybenzophenone, 2-phenylbenzimidazole-5-sulfonic acid and potassium, sodium and triethanolamine salts thereof, 1-(4-tert.butylphenyl) 3-(4-methoxyphenyl)-propane-1,3-dione, 4-methoxycinnamic acid-2 20 ethylhexyl ester and 3-(4'-methylbenzylidene)-,D,L-camphor are most particularly preferred. UV filters with a molar extinction coefficient at the absorption maximum of more than 15,000 and more particularly above 20,000 are preferred. 25 It has also been found that, with structurally similar UV filters, the water-insoluble compound in many cases is more effective in the context of the teaching according to the invention than water-soluble compounds which are distinguished from it by one or more additional ionic groups. In the context of the invention, water-insoluble UV filters are UV filters of 30 which no more than 1% by weight and, more particularly, no more than WO 00/28957 6 PCT/EP99/08568 0.1% by weight dissolves in water at 20 0 C. In addition, at least 0.1% by weight and, more particularly, at least 1% by weight of these compounds should dissolve in typical cosmetic oil components at room temperature. Accordingly, it may be preferable in accordance with the invention to use 5 water-insoluble UV filters. In another embodiment of the invention, preferred UV filters contain a cationic group, more particularly a quaternary ammonium group. These UV filters have the general structure U - Q where the structural moiety U is a UV-absorbing group. In principle, this group may 10 be derived from the known, cosmetically usable UV filters mentioned above in which one group, generally a hydrogen atom, of the UV filter is replaced by a cationic group Q, more particularly with a quaternary amino function. Examples of compounds from which the structural moiety U may be derived are 15 - substituted benzophenones, - p-aminobenzoic acid esters, - diphenylacrylic acid esters, - cinnamic acid esters, - salicylic acid esters, 20 - benzimidazoles and - o-aminobenzoic acid esters. According to the invention, preferred structural moieties U are derived from cinnamic acid amide or from N,N-dimethylaminobenzoic acid amide. 25 In principle, the structural moieties U may be selected so that the absorption maximum of the UV filters can lie both in the UVA (315-400 nm) range and in the UVB (280-315 nm) range or in the UVC (< 280 nm) range. UV filters with an absorption maximum in the UVB range, more especially in the range from about 280 to about 300 nm, are particularly preferred. 30 In addition, the structural moiety U may preferably be selected - H 3791 PCT - 12.11.1998 7 In addition, the structural moiety U may preferably be selected even in dependence upon the structural moiety Q - so that the molar extinction coefficient of the UV filter at the absorption maximum is above 15,000 and more particularly above 20,000. 5 The structural moiety Q preferably contains a quaternary ammonium group as the cationic group. In principle, this quaternary ammonium group may be directly attached to the structural moiety U so that the structural moiety U represents one of the four substituents of the positively charged nitrogen atom. However, one of the four substituents at the positively 10 charged nitrogen atom is preferably a group, more particularly an alkylene group containing 2 to 6 carbon atoms, which acts as a link between the structural moiety U and the positively charged nitrogen atom. The group Q advantageously has the general structure -(CH 2 )xN*

R

1

R

2

R

3 X~, where x is an integer of 1 to 4, R' and R 2 independently of one 15 another represent C 1

.

4 alkyl groups, R 3 is a C 1

-

22 alkyl group or a benzyl group and X- is a physiologically compatible anion. In this general structure, x is preferably the number 3, R 1 and R 2 each represent a methyl group and R 3 is either a methyl group or a saturated or unsaturated, linear or branched hydrocarbon chain containing 8 to 22 and more particularly 10 20 to 18 carbon atoms. Physiologically compatible anions are, for example, inorganic anions, such as halides, more particularly chloride, bromide and fluoride, sulfate ions and phosphate ions, and organic anions, such as lactate, citrate, acetate, tartrate, methosulfate and tosylate. 25 Two preferred UV filters containing cationic groups are the compounds obtainable as commercial products cinnamic acid amidopropyl trimethylammonium chloride (Incroquat@ UV-283) and dodecyl dimethylaminobenzamidopropyl dimethylammonium tosylate (Escalol@ HP 610). 30 The teaching according to the invention does of course also H 3791 PCT - 12.11.1998 8 encompass the use of a combination of several UV filters. In this embodiment, a combination of at least one water-insoluble UV filter with at least one UV filter containing a cationic group is preferred. The UV filters are present in the compositions used in accordance 5 with the invention in quantities of normally 0.1 to 5% by weight and preferably 0.4 to 2.5% by weight, based on the composition as a whole. The effect of the UV filters according to the invention may be further increased by using them in combination with at least one mono-, di- or oligosaccharide. Preferred saccharides are glucose, galactose, fructose, 10 mannose, fruit sugar and lactose. Glucose is particularly preferred. The saccharides are present in the compositions according to the invention in quantities of 0.1 to 10% by weight and more particularly 1 to 3% by weight, based on the particular formulation. The effect of the UV filters according to the invention may also be 15 significantly increased by using them in combination with a spreading agent. Spreading agents in the context of the invention are substances which produce a uniform distribution of active principles, more particularly UV filters, on the surface of the keratin fibers. 20 Preferred spreading agents are oil components. Oil components suitable for the purposes of the invention are, in principle, any water-insoluble oils and fatty compounds and mixtures thereof with solid paraffins and waxes. According to the invention, water insoluble substances are defined as substances of which less than 0.1% by 25 weight dissolves in water at 200C. The melting point of the individual oil or fatty components is preferably below about 400C. Oil and fatty components which are liquid at room temperature, i.e. below 250C, can be particularly preferred for the purposes of the invention. However, where several oil and fatty components and optionally solid paraffins and waxes 30 are used, it is generally sufficient if the mixture of the oil and fatty WO 00/28957 9 PCT/EP99/08568 requirements. A preferred group of oil components are vegetable oils. Examples of such oils are sunflower oil, olive oil, soya oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheatgerm oil, peach kernel oil and the liquid 5 fractions of coconut oil. However, other triglyceride oils, such as the liquid fractions of bovine tallow, and synthetic triglyceride oils are also suitable. Another group of compounds particularly preferred for use as oil components in accordance with the invention are liquid paraffin oils and 10 synthetic hydrocarbons and di-n-alkyl ethers containing a total of 12 to 36 carbon atoms and, more particularly, 12 to 24 carbon atoms, such as for example di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n decyl-n-undecyl ether, n-undecyl-n-dodecyl ether and n-hexyl-n-undecyl 15 ether and ditert.butyl ether, diisopentyl ether, di-3-ethyldecyl ether, tert.butyl-n-octyl ether, isopentyl-n-octyl ether and 2-methylpentyl-n-octyl ether. The compounds 1,3-di-(2-ethylhexyl)-cyclohexane and di-n-octyl ether obtainable as commercial products (Cetiol@ S and Cetiol@ OE, respectively) can be preferred. 20 Other oil components suitable for use in accordance with the invention are fatty acid and fatty alcohol esters. The monoesters of fatty acids with alcohols containing 3 to 24 carbon atoms are preferred. This group of substances are products of the esterification of fatty acids containing 8 to 24 carbon atoms such as, for example, caproic acid, 25 caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and the technical mixtures thereof obtained, for example, in the pressure 30 hydrolysis of natural fats and oils, in the reduction of aldehydes from WO 00/28957 10 PCT/EP99/08568 Roelen's oxosynthesis or in the dimerization of unsaturated fatty acids with alcohols such as, for example, isopropyl alcohol, caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, 5 isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and the technical mixtures thereof obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or 10 aldehydes from Roelen's oxosynthesis and as monomer fraction in the dimerization of unsaturated fatty alcohols. According to the invention, iso propyl myristate, isononanoic acid C 16

.

18 alkyl ester (Cetiol@ SN), stearic acid-2-ethylhexyl ester (Cetiol@ 868), cetyl oleate, glycerol tricaprylate, cocofatty alcohol caprate/caprylate and n-butyl stearate are particularly 15 preferred. Other oil components suitable for use in accordance with the invention are dicarboxylic acid esters, such as di-n-butyl adipate, di-(2 ethylhexyl)-ad i pate, di-(2-ethylhexyl)-succinate and diisotridecyl acelate, and diol esters, such as ethylene glycol dioleate, ethylene glycol diisotri 20 decanoate, propylene glycol di-(2-ethylhexanoate), propylene diisostearate, propylene glycol dipelargonate, butanediol diisostearate and neopentyl glycol dicaprylate, and also complex esters, for example diacetyl glycerol monostearate. In addition, fatty alcohols containing 8 to 22 carbon atoms may be 25 used as spreading agents acting in accordance with the invention. The fatty alcohols used in accordance with the invention may be saturated or unsaturated and linear or branched. Examples of fatty alcohols suitable for use in accordance with the invention are decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, 30 erucyl alcohol, ricinolyl alcohol, stearyl alcohol, isostearyl alcohol, cetyl WO 00/28957 11 PCT/EP99/08568 alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, capryl alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol and Guerbet alcohols thereof (this list is purely exemplary and is not intended to limit the invention in any way). However, the fatty alcohols emanate from 5 preferably natural fatty acids, normally being obtained from the esters of the fatty acids by reduction. According to the invention, it is also possible to use the fatty alcohol cuts which are produced by reduction of naturally occurring triglycerides, such as beef tallow, palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil and linseed oil, or fatty acid 10 esters formed from the transesterification products thereof with corresponding alcohols and which therefore represent a mixture of different fatty alcohols. Finally, other oil components preferably used for the purposes of the invention are silicone oils, more particularly dialkyl and alkylaryl siloxanes 15 such as, for example, dimethyl polysiloxane and methylphenyl polysiloxane and alkoxylated and quaternized analogs thereof. Examples of such silicones are the products marketed by Dow Corning under the names of DC 190, DC 200 and DC 1401 and the commercial products DC 344 and DC 345 of Dow Corning, Q2-7224 (manufacturer: Dow Corning; a stabilized 20 trimethyl silyl amodimethicone), Dow Corning@ 929 emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SN-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil@ Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethyl siloxanes, quaternium-80). 25 The total quantity of spreading agents in the preparations used in accordance with the invention is normally 0.5 to 20% by weight, based on the preparation as a whole. According to the invention, quantities of 1 to 5% by weight are preferred. The positive effect of the spreading agents is enhanced if they are 30 used together with cationic or anionic surfactants.

WO 00/28957 12 PCT/EP99/08568 Examples of the cationic surfactants suitable for use in accordance with the invention are, in particular, quaternary ammonium compounds. Preferred quaternary ammonium compounds are ammonium halides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium 5 chlorides and trialkyl methyl ammonium chlorides, for example cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammonium chloride. Alkyl amidoamines, particularly fatty acid amidoamines, such as 10 the stearyl amidopropyl dimethyl amine obtainable as Tego Amid@ S 18, are further distinguished by their ready biodegradability. Quaternary ester compounds, so-called "esterquats", such as the methyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfates marketed under the trade name of Stepantex@ and the corresponding products marketed under the name 15 of Dehyquart@ are also readily biodegradable. One example of a quaternary sugar derivative suitable for use as a cationic surfactant is the commercially available product Glucquat@ 100 (CTFA name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride). Suitable anionic surfactants are any anionic surface-active 20 substances suitable for use on the human body. Such substances are characterized by a water-solubilizing anionic group such as, for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group containing around 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ether, amide and hydroxyl groups and generally 25 ester groups may also be present in the molecule. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids containing 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and, in particular, salts of saturated and in particular unsaturated Ca-22 carboxylic acids, such as oleic 30 acid, stearic acid, isostearic acid and palmitic acid. The anionic surfactants WO 00/28957 13 PCT/EP99/08568 which contain at least one carboxylate group are particularly preferred. It has been found that the effectiveness of the UV filters in increasing fastness to washing is evident both when the UV filter is applied to the keratin fibers together with the actual colorant and when the UV filter 5 is applied with a separate formulation immediately after coloring. The present invention also relates to a process for coloring keratin fibers in the usual way with a colorant, characterized in that the colorant additionally contains a UV filter to increase the fastness of the color to washing. In the process according to the invention, too, the human hair 10 represents the preferred type of keratin fiber. The are no basic restrictions to the composition of the colorant. Suitable dye (precursors) include * oxidation dye precursors of the primary and secondary intermediate type, 15 e natural and synthetic substantive dyes and * precursors of "nature-like" dyes, such as indole and indoline derivatives and mixtures of representatives of one of more of these groups. Oxidation dye precursors of the primary intermediate type are 20 normally primary aromatic amines with another free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6 tetraaminopyrimidine and derivatives thereof. According to the invention, preferred primary intermediates are p-phenylenediamine, p 25 toluylenediamine, p-aminophenol, o-aminophenol, 1-(2'-hydroxyethyl)-2,5 diaminobenzene, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, 2-(2,5-di aminophenoxy)-ethanol, 1-phenyl-3-carboxyamido-4-amino-5-pyrazolone, 4-amino-3-methylphenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-tri aminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6 30 diaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2-hydroxy- WO 00/28957 14 PCT/EP99/08568 ethylaminomethyl-4-aminophenol, 4,4'-d iaminodiphenylamine, 4-amino-3 fluorophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-amino phenol, bis-(2-hydroxy-5-aminophenyl)-methane, 1,4-bis-(4-aminophenyl) diazacycloheptane, 1,3-bis-(N-(2-hydroxyethyl)-N-(4-aminophenylamino)) 5 2-propanol, 4-amino-2-(2-hydroxyethoxy)-phenol and 4,5-diaminopyrazole derivatives according to EP 0 740 741 or WO 94/08970, for example 4,5 diamino-1 -(2'-hydroxyethyl)-pyrazole. Particularly preferred primary intermediates are p-phenylenediamine, p-toluylenediamine, p aminophenol, 1-(2'-hydroxyethyl)-2,5-diaminobenzene, 4-amino-3-methyl 10 phenol, 2-aminomethyl-4-aminophenol, 2,4,5,6-tetraaminopyrimidine, 2 hydroxy-4,5,6-triaminopyrimidine and 4-hydroxy-2,5,6-triaminopyrimidine. m-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as oxidation dye precursors of the secondary intermediate 15 type. According to the invention, preferred secondary intermediates are 1 naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, o aminophenol, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-5 pyrazolone, 2,4-dichloro-3-aminophenol, 1,3-bis-(2,4-diaminophenoxy) 20 propane, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, 2,6-dihydroxypyri dine, 2,6-diaminopyridine, 2-amino-3-hydroxypyridine, 2,6-dihydroxy-3,4 diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 4-amino-2 hydroxytoluene, 2,6-bis-(2-hydroxyethylamino)-toluene, 2,4-diamino 25 phenoxyethanol, 1-methoxy-2-amino-4-(2-hydroxyethylamino)-benzene, 2 methyl-4-chloro-5-aminophenol, 6-methyl-1,2,3,4-tetrahydroquinoxaline, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 2,6-dimethyl-3 aminophenol, 3-amino-6-methoxy-2-methylaminophenol, 2-hydroxy-4 aminophenoxy ethanol, 2-methyl-5-(2-hydroxyethylamino)-phenol and 2,6 30 dihydroxy-3,4-dimethyl pyridine. Particularly preferred secondary WO 00/28957 15 PCT/EP99/08568 intermediates are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5 amino-2-methylphenol, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3 aminophenol, 2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol and 2,6-dihydroxy-3,4-diaminopyridine. 5 Substantive dyes are normally nitrophenylenediamines, nitro aminophenols, azo dyes, anthraquinones or indophenols. Preferred sub stantive dyes are the compounds known under the International names or trade names of HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 10 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 and also 1,4-bis-(p-hydroxyethyl)-amino-2-nitrobenzene, 4 amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydro quinoxaline, hydroxyethyl-2-nitrotoluidine, picramic acid, 2-amino-6-chloro 15 4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino 1 -hydroxy-4-nitrobenzene. The preparations according to the invention may also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, black alder bark, 20 sage, logwood, madder root, catechu, sedre and alkanet. Both the oxidation dye precursors and the substantive dyes are present in the preparations according to the invention in quantities of preferably 0.01 to 20% by weight and more preferably 0.5 to 5% by weight, based on the preparation as a whole. 25 Preferred precursors of natural dyes are indoles and indolines which contain at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups may carry further substituents, for example in the form of an etherification or esterification of the hydroxy group or an alkylation of the amino group. 30 Particularly suitable precursors of natural hair dyes are derivatives of WO 00/28957 16 PCT/EP99/08568 5,6-dihydroxyindoline corresponding to formula (Ila): 43 5 R 0 O R-0 N R I (Ia) R) 10 in which - independently of one another - R 1 is hydrogen, a C1 alkyl group or a C1.4 hydroxyalkyl group,

R

2 is hydrogen or a -COOH group, the -COOH group optionally being present as a salt with a physiologically compatible cation, 15 R 3 is hydrogen or a C1 alkyl group,

R

4 is hydrogen, a C1.4 alkyl group or a group -CO-R , where R 6 is a Cj.4 alkyl group, and

R

5 is one of the groups mentioned for R 4 , and physiologically compatible salts of these compounds with an organic or 20 inorganic acid. Particularly preferred derivatives of indoline are 5,6-dihydroxy indoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxy indoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4 25 aminoindoline. Within this group, particular emphasis is placed on N-methyl-5,6 dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6 dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and, in particular, 5,6 dihydroxyindoline. 30 Other particularly suitable precursors of natural hair dyes are derivatives of 5,6-dihydroxyindole corresponding to formula (11b): WO 00/28957 17 PCT/EP99/08568 R4- 3 5 R-O N R II (Ib) R in which - independently of one another 10 R 1 is hydrogen, a C 1 .4 alkyl group or a C 1 .4 hydroxyalkyl group,

R

2 is hydrogen or a -COOH group, the -COOH group optionally being present as a salt with a physiologically compatible cation,

R

3 is hydrogen or a C 1 .4 alkyl group,

R

4 is hydrogen, a C1.4 alkyl group or a group -CO-R , where R 6 is a C 1

.

4 15 alkyl group, and

R

5 is one of the groups mentioned for R 4 , or physiologically compatible salts of these compounds with an organic or inorganic acid. Particularly preferred derivatives of indole are 5,6-dihydroxyindole, 20 N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6 dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2 carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole. Within this group, particular emphasis is placed on N-methyl-5,6 dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, 25 N-butyl-5,6-dihydroxyindole and, in particular, 5,6-dihydroxyindole. The indoline and indole derivatives may be used both as free bases and in the form of their physiologically compatible salts with inorganic or organic acids, for example hydrochlorides, sulfates and hydrobromides, in the colorants used in the process according to the invention. The indole or 30 indoline derivatives are present in these colorants in quantities of normally 0.05 to 10% by weight and preferably 0.2 to 5% by weight.

WO 00/28957 18 PCT/EP99/08568 Where dye precursors of the indoline or indole type are used, it can be of advantage to use them together with at least one amino acid and/or at least one oligopeptide. Preferred amino acids are aminocarboxylic acids, more particularly a-aminocarboxylic acids and wo-aminocarboxylic 5 acids. Among the a-aminocarboxylic acids, arginine, lysine, ornithine and histidine are particularly preferred. A most particularly preferred amino acid is arginine used more particularly in free form but also as the hydrochloride. The corresponding preparations contain the amino acid or the oligopeptide in quantities of 0.1 to 10% by weight and preferably I to 4% by weight, 10 based on the preparation as a whole. The oxidation dye precursors, the substantive dyes or the precursors of natural dyes do not have to be single compounds. On the contrary, other components may be present in small quantities in the hair colorants according to the invention due to the processes used to produce the 15 individual dyes providing these other components do not adversely affect the coloring result or have to be ruled out for other reasons, for example toxicological reasons. So far as the dyes suitable for use in the hair colorants and tinting compositions according to the invention are concerned, reference is also 20 expressly made to the work by Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; substantive dyes) and Chapter 8, pages 264 267; oxidation dye precursors), published as Volume 7 of the Series "Dermatology" (Ed.: Ch. Culnan and H. Maibach), Marcel Dekker Inc., New York/Basel, 1986, and to the "Europaische Inventar der Kosmetik 25 Rohstoffe" published by the Europsische Gemeinschaft and available in disk form from the Bundesverband Deutscher Industrie- und Handelsunternehmen fur Arzneimittel, Reformwaren und Korperpflegemittel d.V., Mannheim. To produce the colorants, the compulsory and optional constituents 30 mentioned above are incorporated in a suitable water-containing carrier.

WO 00/28957 19 PCT/EP99/08568 For coloring hair, such carriers are, for example, creams, emulsions, gels or even surfactant-containing foaming solutions, for example shampoos, foam aerosols or other formulations suitable for application to the hair. Hair colorants are normally adjusted to a mildly acidic to alkaline pH, 5 i.e. to a pH of about 5 to 11, particularly where coloring is carried out oxidatively with atmospheric oxygen or other oxidizing agents, such as hydrogen peroxide. To this end, the colorants contain alkalizing agents, normally alkali metal or alkaline earth metal hydroxides, ammonia or organic amines. Preferred alkalizing agents are monoethanolamine, 10 monoisopropanolamine, 2-amino-2-methylpropanol, 2-amino-2 methylpropane-1,3-diol, 2-amino-2-ethylpropane-1,3-diol, 2-amino-2 methylbutanol and triethanolamine and alkali metal and alkaline earth metal hydroxides. Within this group, monoethanolamine, triethanolamine and 2-amino-2-methylpropanol and 2-amino-2-methylpropane-1,3-diol are 15 preferred. o-Amino acids, such as o-aminocaproic acid, may also be used as alkalizing agents. The colorants according to the invention may also contain any of the known active substances, additives and auxiliaries typical of such formulations. In many cases, the colorants contain at least one surfactant, 20 both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has been found to be of advantage to select the surfactants from anionic, zwitterionic or nonionic surfactants. Anionic surfactants can be particularly useful. So far as the anionic and cationic surfactants are concerned, 25 reference is made to the foregoing observations. In the context of the invention, zwitterionic surfactants are surface active compounds which contain at least one quaternary ammonium group and at least one -COO( or -SO3(- group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl 30 N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl WO 00/28957 20 PCT/EP99/08568 ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and 5 cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name of Cocamidopropyl Betaine. Ampholytic surfactants are surface-active compounds which, in addition to a C8-18 alkyl or acyl group, contain at least one free amino group 10 and at least one -COOH or -SO 3 H group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkyl aminobutyric acids, N alkyl iminodipropionic acids, N-hydroxyethyl-N-alkyl amidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkyl aminopropionic acids and alkyl 15 aminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkyl amino propionate, cocoacyl aminoethyl aminopropionate and C12-18 acyl sarcosine. Nonionic surfactants contain, for example, a polyol group, a poly 20 alkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Examples of such compounds are - products of the addition of 2 to 30 moles of ethylene oxide and/or 0 to 5 moles of propylene oxide to linear fatty alcohols containing 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms and to 25 alkylphenols containing 8 to 15 carbon atoms in the alkyl group, - C12-22 fatty acid monoesters and diesters of products of the addition of 1 to 30 moles of ethylene oxide to glycerol, - C8-22 alkyl mono- and oligoglycosides and ethoxylated analogs thereof, - products of the addition of 5 to 60 moles of ethylene oxide to castor oil 30 and hydrogenated castor oil, WO 00/28957 21 PCT/EP99/08568 - products of the addition of ethylene oxide to sorbitan fatty acid esters, - products of the addition of ethylene oxide to fatty acid alkanolamides. The compounds containing alkyl groups used as surfactants may be 5 single compounds. In general, however, these compounds are produced from native vegetable or animal raw materials so that mixtures with different alkyl chain lengths dependent upon the particular raw material are obtained. The surfactants representing addition products of ethylene and/or 10 propylene oxide with fatty alcohols or derivatives of these addition products may be both products with a "normal" homolog distribution and products with a narrow homolog distribution. Products with a "normal" homolog distribution are mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides 15 or alkali metal alcoholates as catalysts. By contrast, narrow homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be of advantage. 20 Other active substances, auxiliaries and additives are, for example, - nonionic polymers such as, for example, vinyl pyrrolidone/vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetate copolymers and polysiloxanes, - cationic polymers, such as quaternized cellulose ethers, polysiloxanes 25 containing quaternary groups, dimethyl diallyl ammonium chloride polymers, acrylamide/dimethyl diallyl ammonium chloride copolymers, dimethyl aminoethyl methacrylate/vinyl pyrrolidone copolymers quater nized with diethyl sulfate, vinyl pyrrolidone/imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, 30 - zwitterionic and amphoteric polymers such as, for example, acrylamido- WO 00/28957 22 PCT/EP99/08568 propyl/trimethyl ammonium chloride/acrylate copolymers and octyl acrylamide/methyl methacrylate/tert.butyl aminoethyl methacrylate/2 hydroxypropyl methacrylate copolymers, - anionic polymers such as, for example, polyacrylic acids, crosslinked 5 polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-tert.butyl acrylamide terpolymers, 10 - thickeners, such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, for example methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives, such as amylose, amylopectin and dextrins, clays such as, for example, 15 bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl alcohol, - structurants, such as maleic acid and lactic acid, - hair-conditioning compounds, such as phospholipids, for example soybean lecithin, egg lecithin and kephalins, and also silicone oils, 20 - protein hydrolyzates, more particularly elastin, collagen, keratin, milk protein, soybean protein and wheat protein hydrolyzates, condensation products thereof with fatty acids and quaternized protein hydrolyzates, - perfume oils, dimethyl isosorbide and cyclodextrins, - solvents and solubilizers, such as ethanol, isopropanol, ethylene glycol, 25 propylene glycol, glycerol and diethylene glycol, - antidandruff agents, such as Piroctone Olamine and Zinc Omadine, - other substances for adjusting the pH value, such as for example a and p-hydroxycarboxylic acids, - active principles, such as panthenol, pantothenic acid, allantoin, 30 pyrrolidone carboxylic acids and salts thereof, plant extracts and WO 00/28957 23 PCT/EP99/08568 vitamins, - cholesterol, - consistency factors, such as sugar esters, polyol esters or polyol alkyl ethers, 5 - fats and waxes, such as spermaceti, beeswax and montan wax, - fatty acid alkanolamides, - complexing agents, such as EDTA, NTA and phosphonic acids, - swelling and penetration agents, such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas 10 and primary, secondary and tertiary phosphates, - opacifiers, such as latex, - pearlizers, such as ethylene glycol mono- and distearate, - propellents, such as propane/butane mixtures, N 2 0, dimethyl ether,

CO

2 and air and 15 - antioxidants. To produce the colorants according to the invention, the constituents of the water-containing carrier are used in the usual quantities for this purpose. For example, emulsifiers are used in concentrations of 0.5 to 20 30% by weight while thickeners are used in concentrations of 0.1 to 25% by weight, based on the colorant as a whole. Information on other optional components and the quantities in which they are used can be found in the reference books known to the expert, for example K. Schrader, Grundlagen und Rezepturen der 25 Kosmetika, 2nd Edition, HUthig Buch Verlag, Heidelberg, 1989. If the actual hair colors are developed in an oxidative process, typical oxidizing agents such as, in particular, hydrogen peroxide or adducts thereof with urea, melamine or sodium borate may be used. However, oxidation with atmospheric oxygen as sole oxidizing agent may 30 be preferred. Oxidation may also be carried out with enzymes. In this WO 00/28957 24 PCT/EP99/08568 case, the enzymes may be used both to produce oxidizing per compounds and to enhance the effect of an oxidizing agent present in small quantities. Examples of enzymatic processes include the use of laccases and strengthening of the effect of small quantities (for example 1 % and less, 5 based on the formulation as a whole) of hydrogen peroxide by peroxidases. The preparation of the oxidizing agent is preferably mixed with the preparation of the oxidation dye precursors immediately before coloring of the hair. The ready-to-use hair coloring preparation formed should have a pH value in the range from 6 to 10. In a particularly preferred embodiment, 10 the hair colorant is used in a mildly alkaline medium. The application temperatures may be in the range from 15 to 400C but are preferably at the temperature of the scalp. After a contact time of about 5 to 45 and preferably 15 to 30 minutes, the hair colorant is removed from the hair to be colored by rinsing. There is no need for the hair to be washed with a 15 shampoo where a carrier of high surfactant content, for example a coloring shampoo, has been used. In the particular case of hair which is difficult to color, the preparation containing the oxidation dye precursors may be applied to the hair without preliminary mixing with the oxidation component. The oxidation component 20 is applied after a contact time of 20 to 30 minutes, optionally after rinsing. After another contact time of 10 to 20 minutes, the hair is rinsed and, if desired, shampooed. In a first variant of this embodiment where the preliminary application of the dye precursors is intended to improve penetration into the hair, the corresponding formulation is adjusted to a pH 25 value of about 4 to 7. In a second variant, oxidation with air is initially carried out, the formulation applied preferably having a pH value of 7 to 10. In the subsequent accelerated post-oxidation phase, it can be of advantage to use acidified peroxydisulfate solutions as the oxidizing agent. Whichever of the processes mentioned above is used to apply the 30 colorant according to the invention, development of the color may be WO 00/28957 25 PCT/EP99/08568 supported and enhanced by adding certain metal ions to the colorant. Examples of such metal ions are Zn 2 +, Cu 2 +, Fe2+, Fe 3 +, Mn2+, Mn 4 *, Li*, Mg2+, Ca2+ and A13+. Zn2+, Cu 2 + and Mn2+ are particularly suitable. Basically, the metal ions may be used in the form of a physiologically 5 compatible salt. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. Development of the hair color can be accelerated and the color tone can be influenced as required through the use of these metal salts. As mentioned above, application of the UV filter to increase the 10 fastness of the colors of keratin fibers to washing may also be carried out in a separate step after the actual coloring step. Accordingly, the present invention also relates to a process for coloring keratin fibers, characterized in that, in a first step, the keratin fiber is colored in the usual way and, in a second step, a preparation containing 15 at least one UV filter to increase the fastness of the color to washing is applied and, if desired, is rinsed out again after a contact time of a few seconds to about 20 minutes. In the context of the invention, the expression "colored in the usual way" is understood to mean the procedure known to the expert whereby a 20 colorant is applied to the - optionally wetted - hair and is left on the hair for a time of a few minutes to about 45 minutes. The hair is then rinsed out with water or a surfactant-containing preparation. The second step of the process according to the invention, in which the preparation containing the UF filter is applied, can be: 25 e The above-mentioned rinsing out of the colorant, the water or the surfactant preparation additionally containing a UV filter. * The application of another preparation containing a UV filter after the rinsing step mentioned, this other preparation also being removed from the hair after a contact time of a few seconds to about 20 30 minutes. In this case, the other preparation may be, for example, a WO 00/28957 26 PCT/EP99/08568 hair treatment preparation of the rinse or conditioner type. The application of another preparation containing a UV filter after the rinsing step mentioned, this other preparation remaining on the hair. In this case, the other preparation may be, for example, a hair 5 treatment preparation such as a conditioner, an aftertreatment or a hair spray. This second preparation which is used to apply the UV filter to the hair may contain the other ingredients typical of the type of preparation 10 selected. Reference is specifically made in this connection both to the basic knowledge of the relevant expert, as documented for example by Schrader's work cited above, and to the other ingredients listed above in the description of the colorants. In principle, the way in which this second preparation is made up is not subject to any restrictions either. Creams, 15 lotions, solutions, emulsions, gels, sprays and surfactant-containing foaming solutions, for example shampoos or foam aerosols, are suitable. However, formulation as a so-called PIT emulsion can be less preferred on account of the associated limitations in regard to the other ingredients. Finally, a particularly marked improvement in the fastness to 20 washing of colors on keratin fibers was observed when a preparation containing a combination of a water-insoluble UV filter, a UV filter corresponding to formula (1) and a mono-, di- or oligosaccharide was used. Accordingly, the present invention also relates to a preparation for increasing the fastness to washing of colors on keratin fibers, characterized 25 in that it contains an active-principle combination consisting of at least one water-insoluble UV filter, an least one UV filter corresponding to formula (I) and a mono-, di- or oligosaccharide. According to the foregoing, this preparation may be both the actual colorant and a preparation which is applied to the hair in a second step 30 after the actual coloring step. With regard to the preferred embodiments as WO 00/28957 27 PCT/EP99/08568 to the compulsory ingredients and the other optional components of these preparations according to the invention, reference is made to the foregoing observations. The following Examples are intended to illustrate the invention. 5 Examples All quantities in the following Examples are parts by weight unless otherwise indicated. 10 Colorant formulation Oleic acid 6.5 Propylene glycol 6.5 Isopropanol 12.0 Sodium lauryl ether sulfate + 2 EO 3.5 15 (27% active substance in water) Sodium sulfite 0.2 EDTA disodium salt 0.1 p-Aminophenol HCI 0.5 p-Toluylenediamine sulfate 0.1 20 Resorcinol 0.2 4-Amino-2-nitrodiphenylamine-2'-carboxylic acid 0.1 6-Nitro-1,2,3,4-tetrahydroquinoxaline 0.1 5-Amino-2-methylphenol 0.3 Perfume 0.5 25 Monoethanolamine to pH 9.2 Water to 100 The colorant was mixed with a commercially available primary intermediate (Poly Country Colors) containing 5% hydrogen peroxide in a 30 ratio of colorant to primary intermediate of 40 ml to 50 ml.

WO 00/28957 28 PCT/EP99/08568 Conditioner formulations B1 B2 C1 C16/18 fatty alcohol (1:1) 3.0 3.0 3.0 5 Paraffin oil perliq. 3.0 3.0 3.0 Cetyl trimethyl ammonium chloride 0.8 0.8 0.8 Perfume 0.3 0.3 0.3 Escalol@ HP610 1 1.0 Uvinul@ M 402 - 0.5 10 Water <---------------to100--------+ dodecyl dimethylaminobenzamidopropyl dimethyl ammonium tosylate (ISP) 2 2-hydroxy-4-methoxybenzophenone (INCI name: Benzophenone-3) 15 (BASF) Coloring was carried out on natural white hair tresses (ca. 2 g) of the Virgin White (Alkinco) type. To this end, 8 g of the colorant/primary intermediate mixture were applied to the tress, left thereof for 30 mins. and 20 then rinsed out with water (37*C). The tress was then treated for 2 mins. with the conditioner (B1, B2 and Cl), then washed 6 times with 0.5 ml of a commercially available shampoo, rinsed with water (37*C) and dried. The color intensity of the tress was then evaluated by experts using the following scoring system: 25 color intensity = 1: Virgin White tress before coloring color intensity = 6: tress after coloring, rinsing with water (370C) and drying (no treatment with the conditioner) The following scores were awarded: H 3791 PCT - 12.11.1998 29 Conditioner Score B1 5 B2 5 V1 4 5 Accordingly, the fastness of the colors to washing was significantly higher on the tresses aftertreated in accordance with the invention than on the tresses aftertreated with the comparison preparation.

Claims

1. The use of a UV filter for improving the fastness to washing of colors on keratin fibers.

2. The use claimed in claim 1, characterized in that the UV filter is 5 insoluble in water.

3. The use claimed in claim 1 or 2, characterized in that the UV filter contains a benzophenone unit.

4. The use claimed in claim 1, characterized in that the UV filter contains a cationic group. 10

5. The use claimed in claim 4, characterized in that the UV filter has a general structure corresponding to formula (1): U - Q (I) 15 in which U is a UV-absorbing group and Q is a group containing at least one quaternary ammonium function.

6. The use claimed in claim 5, characterized in that the group Q in general formula (1) has the general structure -(CH 2 )xN*RR 2 R 3 X-, where x is an integer of 1 to 4, R 1 and R 2 independently of one another represent 20 C 1 . 4 alkyl groups, R 3 is a C1-22 alkyl group or a benzyl group and X- is a physiologically compatible anionic group.

7. The use claimed in claim 6, characterized in that at least two of the groups R 1 , R 2 and R 3 are methyl groups.

8. The use claimed in any of claims 5 to 7, characterized in that the 25 group U is selected so that the UV filter A has an absorption maximum in the UVB range.

9. The use claimed in any of claims 1 to 8, characterized in that the UV filter has a molar extinction coefficient at the absorption maximum of at least 15,000. 30

10. The use claimed in at least one of claims 1 to 9, characterized in that WO 00/28957 31 PCT/EP99/08568 the UV filter is used in combination with a mono-, di- or oligosaccharide.

I1. The use claimed in any of claims 1 to 10, characterized in that the UV filter is used in combination with a spreading agent.

12. The use claimed in claim 11, characterized in that the spreading 5 agent is paraffin oil.

13. A process for coloring keratin fibers, characterized in that, in a first step, the keratin fiber is colored in the usual way and, in a second step, a preparation containing at least one UV filter to increase the fastness of the color to washing is applied and, if desired, is rinsed out again after a 10 contact time of a few seconds to about 20 minutes.

14. A process for coloring keratin fibers in the usual way with a colorant, characterized in that the colorant contains a UV filter to increase the fastness of the color to washing.

15. A composition for increasing the fastness to washing of colors on 15 keratin fibers, characterized in that it contains a combination of active substances consisting of e at least one water-insoluble UV filter e at least one UV filter corresponding to formula (1) in claim 5 and e a mono-, di- or oligosaccharide.