CZ20003202A3 - A composition for treating keratin fibers - Google Patents

Abstract

at least 6% by weight of oil components and at least one non-ionic emulsifier, and are in the form of a microemulsion with a mean droplet size of less than 400 nm, and further contain a UV-absorbing component A of the general formula (I) U-Q, where U represents a UV-absorbing group and Q represents a group containing at least one quaternary ammonium functional group, are very suitable for protecting keratin fibers, especially human hair, against UV radiation.

Description

Technical field

The present invention relates to a composition for treating keratinous fibers, which is in the form of a microemulsion, and a method of treating keratinous fibers using this composition.

State of the art

Nowadays, human hair is affected by hair cosmetics in a variety of ways. These include washing hair with shampoos, hair care and regeneration with rinses and treatments, and bleaching, dyeing and shaping hair with bleaching, coloring and toning products, curling products and styling products. In addition to the actual purpose of using these products, there is an increasing trend towards using these products to provide preventive protection against damage. Protection against the effects of excessive exposure to light, as is the case especially in the mountains and by the sea, due to the ultraviolet component of sunlight, is becoming increasingly important.

The use of products with inorganic pigments or organic UV filters, for example based on benzophenone or cinnamic acid, for protecting the skin and hair from sunlight is known. The disadvantage of these products is that, especially in the case of rinse-off products, the amount of active ingredients on the hair is low. As a result, the desired protective effect cannot usually be achieved in whole or in part with these products.

One attempt to overcome this disadvantage has been to develop new derivatives of known filter agents that contain a cationic group in addition to the UV-absorbing moiety. This significantly increases the amount of these agents on the hair. Problems

However, it also results in an uneven distribution of the adsorbed filtering substances on the hair. These problems can be solved by adding fatty or oily components to the corresponding compositions. However, this can cause problems in formulating products that are stable during storage and, especially in the case of spray products, it is necessary to achieve acceptable spray behavior by simultaneously adding an organic solvent. However, the use of these solvents is undesirable for ecological reasons and the solvents can also negatively affect the desired properties of the composition from the point of view of hair care.

It has now been found that the above problems can be avoided by using special cationic UV-absorbing substances in compositions which are formulated in the form of special microemulsions, so-called PIT emulsions.

It was known to experts that adding ionic components to emulsions

PIT usually leads to a significant increase in the phase inversion temperature. Therefore, the production of these products is usually abandoned either for reasons related to the substances themselves or for economic reasons. This is especially true for quaternary ammonium compounds known as fabric softeners,

2o which in usual amounts often cause an increase in the phase inversion temperature from 20 to 30 °C, thereby causing the critical limit of 100 °C to be exceeded.

It is therefore most surprising that the UV-absorbing substances with cationic groups used according to the invention either do not affect the phase inversion temperature in a measurable way at all or only slightly, i.e. usually significantly below 15°C.

The essence of the invention

The subject of the invention is therefore compositions for treating keratin fibers which contain at least 6% by weight.

oil components and at least one non-ionic emulsifier, and are in the form of a microemulsion with a mean droplet diameter of less than 400 nm, which contain the UV-absorbing component A of the general formula (I)

U-Q (I) where U represents a UV-absorbing group and Q represents a group containing at least one quaternary ammonium functional group.

The term keratin fibers according to the invention means fur, wool, feathers and especially human hair.

The compositions according to the present invention contain an oil component as the first essential component. As an oil component, essentially all water-insoluble oils and fatty substances and mixtures thereof with solid paraffins and waxes are suitable. Insoluble substances are defined according to the present invention as those whose solubility in water is less than 0.1% by weight at 20°C. The melting point of the individual oil or fat components should be as low as possible below the phase inversion temperature of the system and in particular should be below approximately 40°C. Oil and fat components which can be liquid at room temperature, i.e. at a temperature below 25°C, are particularly preferred. When using a plurality of oil and fat components and optionally solid paraffins and waxes, however, it is generally also sufficient if a mixture of oil and fat components or paraffins and waxes meets these conditions.

A preferred group of oil components are vegetable oils. Examples of these oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach oil and liquid portions of coconut oil.

However, other triglyceride oils, such as liquid beef tallow and synthetic triglyceride oils, are also suitable.

• · ··· · · · · · · · · · · · · · 999 99 99

- 4 Another group of compounds usable according to the present invention as oil components are liquid paraffin oils and synthetic hydrocarbons such as di-n-alkyl ethers with a total of between 12 and 36 carbon atoms, especially 12 to 24 carbon atoms, such as 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, nondecyl-n-dodecyl ether and n-hexyl-n-undecyl ether, as well as di-tert-butyl ether, di-isopentyl ether, di-3-ethyldecyl ether, tert-butyl-noctyl ether, isopentyl-n-octyl ether and 2-methylpentyl-n-octyl ether. As commercially available compounds, 1,3-di-(2-ethylhexyl)-cyclohexane (Cetiol®S) and di-n-octyl ether (Cetiol®OE) may be preferred.

Esters of fatty acids and fatty alcohols can also be used as oil components according to the invention. These are preferably monoesters of fatty acids with alcohols having 3 to 24 carbon atoms. This group of substances is the esterification products of fatty acids with 8 to 24 carbon atoms, such as caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid, and their technical mixtures, which are formed, for example, by pressure cracking of natural fats and oils, by reduction of aldehydes from Roelen's oxosynthesis or by dimerization of unsaturated fatty acids, with alcohols such as isopropyl alcohol, caproic acid, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, gehenyl alcohol, erucyl alcohol and brassidyl alcohol as well as their technical mixtures, which enter, for example, during high-pressure hydration of technical methyl esters based on fats and oils or aldehydes from Roelen oxosynthesis and as monomer fractions during dimerization of unsaturated • · · · · ·

- 5 • · · · · · · · · · fatty alcohols. Particularly preferred according to the invention are isopropyl myristate, C16-18 alkyl ester of isononanoic acid (Cetiol®SN),

Stearic acid 2-ethylhexyl ester (Cetiol®868), cetyl oleate, glycerol tricaprylate, coconut fatty alcohol caprylate/caprylate and n-butyl stearate.

The oil components used according to the invention can also be dicarboxylic acid esters such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, di-(2-ethylhexyl) succinate and diisotridecyl acetate and diol esters such as ethylene glycol dioleate, ethylene glycol 10-diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol diisostearate, propylene glycol dipelargonate, butanediol diisostearate and neopentyl glycol dicaprylate.

The total amount of oil and fat components in the compositions of the present invention is usually 6 to 45% by weight, based on the total composition. According to the invention, amounts of 10 to 35% by weight are preferred.

As a second essential ingredient, the compositions according to the present invention contain a nonionic emulsifier.

Such nonionic emulsifiers are, for example:

- condensation products of 4 to 30 mol of ethylene oxide and/or 0 to mol of propylene oxide with straight fatty alcohols with 8 to 22 carbon atoms, fatty acids with 12 to 22 carbon atoms and alkylphenols with 8 to 15 carbon atoms in the alkyl group, mono- and diesters of C ₁₂ -C ₂₂ fatty acids of condensation products of 1 to 30 mol of ethylene oxide with polyols with 3 to 6 carbon atoms, especially glycerol, condensation products of ethylene oxide and polyglycerol with methylglucoside esters of fatty acids, alkanolamides of fatty acids and glucamides of fatty acids, • ·

- 6 C ₈ -C ₂₂ alkyl mono- and -oligoglycosides and their ethoxylated analogues, with oligomerization degrees of 1.1 to 5, especially 1.1 to 1.4, and glucose as the sugar component being preferred, condensation products of 5 to 60 mol of ethylene oxide with castor oil and hardened castor oil, and partial esters of polyols with 3 to 6 carbon atoms with saturated fatty acids with 8 to 22 carbon atoms.

The compositions according to the present invention contain nonionic emulsifiers preferably in an amount of 4 to 15% by weight, in particular 6 to 10% by weight, based on the total composition.

The compositions according to the invention preferably contain at least one nonionic emulsifier with an HLB value of 8 to 18 as defined in the Römpp-Lexikon Chemie (ed. J. Falbe, M. Regitz), 10th edition, Georg Thieme Verlag Stuttgart, New York (1997), p. 1764. Nonionic emulsifiers with an HLB value of 10 to 15 are particularly preferred according to the invention.

Among the nonionic types of emulsifiers mentioned, ethoxylated fatty alcohols with 8 to 22 carbon atoms and 4 to 30 ethoxyl units are preferred.

Another essential component of the compositions according to the invention are 20 special, ultraviolet radiation-absorbing components A, which will be referred to hereinafter for short as UV-absorbers A. These UV-absorbers A have the general structure U-Q.

The structural unit U represents a UV-absorbing group. This group can be essentially derived from the known UV25 filters used in the field of cosmetics, in which one group, usually the hydrogen atom of the UV filter, is replaced by a group Q with a quaternary ammonium functional group.

Compounds from which the structural part U can be derived are, for example: • · • · · · * • · · · · · · · · · · · ♦··

- 7-substituted benzophenones, such as 2,4-dihydroxybenzophenone,

2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and 2,2'-dihydroxy5 -4,4'-dimethoxybenzophenone-5-sodium sulfonate, p-aminobenzoic acid esters, diphenylacrylic acid esters such as 2-cyano-3,3-diphenylacrylic acid ethyl ester and 2-cyano-3,3-diphenylacrylic acid 2'-ethylhexyl ester, cinnamic acid esters such as octylmethoxycinnamate, salicylic acid esters such as octyl salicylate, benzimidazoles, and o-aminobenzoic acid esters.

According to the invention, structural units U which are derived from cinnamic acid amide or from N,N-dimethylaminobenzoic acid amide are preferred.

The structural units U can essentially be chosen so that the absorption maximum of the UV absorber A can lie either in the UVA region (315 to 400 nm) or in the UVB region (280 to 315 nm) or in the

UVC (<280 nm). Particularly preferred are UV-absorbers A with an absorption maximum in the UVB region, especially in the region from about 280 to about 300 nm.

Furthermore, the structural part U, also depending on the structural part Q, is preferably selected such that the molar extinction coefficient of the UV absorber A at the absorption maximum is more than 15,000, in particular more than 20,000.

The structural part Q necessarily contains a quaternary ammonium group. These quaternary ammonium groups can essentially be bonded directly to the structural part U, so that the structural part U represents one of the four substituents of the positively charged nitrogen atom.

- 8 • · · · · ·

Preferably, however, one of the four substituents on the positively charged nitrogen atom is a group, especially an alkylene group with 2 to 6 carbon atoms, which serves as a link between the structural moiety U and the positively charged nitrogen atom.

According to a preferred embodiment of the invention, the group Q has the general structure -(CH ₂ ) _X -N ⁺ R ¹ R ² R ³ X', where x represents an integer from 1 to 4, R ¹ and R ² independently represent C1-4 alkyl groups, R ³ represents a C1-22 alkyl group or a benzyl group and X' represents a physiologically acceptable anion. Within this general structure, x preferably represents 3, R ¹ and R ² are each a methyl group and R ³ is either a methyl group or a saturated or unsaturated, straight or branched hydrocarbon chain with 8 to 22, in particular 10 to 18 carbon atoms.

Physiologically acceptable anions are, for example, inorganic anions such as halides, especially chloride, bromide and fluoride, sulfate ions and phosphate ions, and organic anions such as lactate, citrate, acetate, tartrate, methosulfate and tosylate.

Particularly preferred UV absorbers A are the commercially available compounds cinnamic acid amidopropyltrimethylammonium chloride (Incroquat®UV-283) and dodecyldimethylaminobenzamidopropyl-dimethylammonium tosylate (Escalol® HP 610).

The UV absorbers A are usually present in the compositions according to the invention in an amount of 0.5 to 5% by weight, based on the total composition. Amounts of 1.0 to 2.5% by weight are preferred.

Another essential component of the compositions according to the invention is water.

Finally, the compositions according to the invention must be in the form of a microemulsion with a mean droplet diameter of less than 400 nm, in particular less than 200 nm.

The term microemulsion in the context of the invention refers to the so-called “PIT” emulsions. In the case of these emulsions, these are essentially systems • · ·

- 9 ···· ·· ·· • · · · · · ♦ • · ♦ * · containing 3 components - water, oil and non-ionic emulsifier, which occur at room temperature as an oil-in-water (O/W) emulsion. When this system is heated, microemulsions are formed within a certain temperature range (usually referred to as the phase inversion temperature or "PIT"), which upon further heating transform into water-in-oil (W/O) emulsions. Upon subsequent cooling, O/W emulsions are formed again, but which also occur at room temperature as microemulsions with a mean particle diameter of less than 400 nm, especially with a particle diameter of approximately 100 to 300 nm. Details regarding these very stable low-viscosity systems, for which the term "PIT emulsion" has generally been adopted, are described in a number of publications, of which the articles in Angew. Chem. 97, 655-669 (1985) and Adv. Colloid Interface Sci. 58, 119-149 (1995). Microemulsions or "PIT" emulsions having a mean particle diameter of approximately 200 nm may be preferred according to the invention.

The production of microemulsions according to the invention can be carried out, for example, by first determining the phase inversion temperature of the system, whereby a sample of the emulsion produced in the usual manner is heated and the temperature at which the conductivity drops sharply is determined using a conductivity measuring device. The decrease in the specific conductivity of the originally present O/W emulsion generally falls in the temperature range of 2 to 8 ° C from the original more than 1 mS / cm to values less than 0.1 mS / cm. This temperature range corresponds to the temperature range of phase inversion. If the phase inversion temperature is already known, it is possible first to heat the emulsion produced in the usual manner, consisting of an oil component, a non-ionic emulsifier, at least part of the water and optionally other components, to a temperature within or above the phase inversion temperature range, then cooling is carried out and optionally other components and the remaining water are added. Alternatively, the microemulsion can be produced directly at a temperature within or above the phase inversion temperature range. The microemulsion thus produced is then cooled to a temperature below the phase inversion temperature range, typically room temperature.

from z · · · ·· · ··· ·· ··· ··· ♦* *·

- 10 In addition to the necessary components, the compositions according to the present invention may contain further components depending on the intended use, and the phase inversion temperature may have a decisive influence on the usability of the individual compounds.

According to a preferred embodiment, the compositions according to the present invention contain, in addition to the oil components, which in many cases also contribute to the treatment, at least one further treatment component. These further treatment components are generally selected from non-ionic compounds. However, the use of ionic treatment components is not essentially excluded, especially if they are used in small amounts. In this case, however, the influence of these ionic compounds on the phase inversion temperature should be determined. As a rule, only such ionic compounds are then used whose influence on the phase inversion temperature does not cause further problems in production.

Treating agents are known to those skilled in the art. Examples of such active agents are:

Fatty alcohols with 8 to 22 carbon atoms. These fatty alcohols used can be saturated or unsaturated and straight or branched. For example, decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, erucyl alcohol, ricinol alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, capryl alcohol, capric alcohol, linoleyl alcohol, linolenic alcohol and behenyl alcohol and their Guerbet alcohols are usable within the scope of the present invention, this list being given only by way of example and not intended to be limiting. However, the fatty alcohols preferably originate from natural fatty acids, and it is usually possible to proceed from the production of fatty acid esters by reduction. According to the invention, mixtures of fatty alcohols which are formed by the reduction of naturally occurring triglycerides, such as

- 11 10

« ·«»*»· • ♦ » • · • « • • ♦ · • • * · * • *··

» » beef tallow, palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil and linseed oil, or from fatty acids resulting from transesterification with the corresponding alcohols, thereby obtaining a mixture of various fatty alcohols. The fatty alcohols are preferably used in an amount of 0.3 to 3% by weight, based on the composition as a whole.

Hydrolysates of animal and preferably vegetable proteins, such as in particular hydrolysates of elastin, collagen, keratin, milk proteins, soy proteins, silk proteins, oat proteins, pea proteins, almond proteins and wheat proteins, their condensation products with fatty acids and quaternized protein hydrolysates.

Vitamins and vitamin precursors such as tocopherols, vitamin A, niacin and niacinamide, other B vitamins, vitamin F and especially biotin. In this group of treatment substances, panthenol, its derivatives, in particular esters and ethers of panthenol and cationically derivatized panthenols are further preferred. Specific examples are panthenol triacetate, panthenol monoethyl ether and panthenol monoacetate and the cationic derivatives of panthenol disclosed in WO 92/13829. In this group, panthenol is preferred.

Mono-, di- and oligosaccharides, such as glucose, galactose, fructose, mannose, fruit sugar and lactose.

Plant extracts, which are usually obtained by extraction of whole plants, but in some cases also only from flowers and/or leaves of plants. With regard to plant extracts usable within the scope of the present invention, reference is made in particular to the extracts listed in the table starting on page 44 of the third edition of the guide to the declaration of ingredients of cosmetic products published by the Industrieverband Kórperpflege- und Waschmittel e. V. (IKW), Frankfurt. According to the invention, particularly preferred extracts are

- 12 10

« ···· • · * • · ·· • · • * · • • · · • ·· ·♦ ···

·· ·· * · · · • « · * • ♦ · · • · · * «· ·· oak bark, nettle, hornbeam, hops, chamomile, burdock root, horsetail, hawthorn, linden blossom, almonds, aloe vera, spruce needles, horsetail, sandalwood, juniper, coconut, mango, apricot, lemon, wheat, kiwi, watermelon, orange, grapefruit, sage, rosemary, pears, mallow, meadow cress, thyme, yarrow, thyme, lemon balm, prickly pear, coltsfoot, hibiscus, ginseng and ginger root.

Particularly beneficial are extracts from almond, aloe vera, coconut, mango, apricot, lemon, wheat, kiwi and watermelon.

Mixtures of several, in particular two different plant extracts, may also be present. Water, alcohols and mixtures thereof may be used as the extraction agent for the said plant extracts. Lower alcohols such as ethanol and isopropanol are preferred among the alcohols, but especially polyhydric alcohols such as ethylene glycol, propylene glycol and butylene glycol, either as the sole extraction agent or as a mixture with water. Plant extracts based on water:propylene glycol in a ratio of 1:10 to 10:1 have proven to be particularly suitable. The plant extracts may be used according to the invention both in pure and diluted form. If used in diluted form, they usually contain approximately 2 to 80% by weight of active ingredient and, as a solvent, an extraction agent or a mixture of extraction agents used in their preparation.

Honey extracts, which are obtained in a manner analogous to plant extracts, and usually contain 1 to 10% by weight, in particular 3 to 5% by weight, of the active ingredient. Water/propylene glycol mixtures can also be used as preferred extraction media here.

Ceramides.

Phospholipids, for example soy lecithin, egg lecithin and cephalins.

Silicone oils, especially dialkyl and aryl siloxanes, such as dimethylpolysiloxane and methylphenylpolysiloxane and their alkoxylated and quaternized analogues. Examples of these silicones are the products supplied by Dow Corning under the name DC

190, DC 200 and DC 1401 and commercial products of Dow Corning DC 344 and DC 345, Q2-7224 (manufacturer: Dow Corning;

stabilized trimethylsilyl amodimethicone), Dow Corning® 929 Emulsion (containing hydroxyl-amino-modified silicone, also known as amodimethicone), SM-2059 (manufacturer:

General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternized polydimethylsiloxanes, Quaternium-80).

Alkylamidoamines, which are usually produced by amidation of natural or synthetic fatty acids and mixtures of fatty acids dialkylaminoamines. Typical examples of these fatty acids are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and technical mixtures thereof, which are formed, for example, by pressure cracking of natural fats and oils, by reduction of aldehydes from Roelen oxosynthesis or by dimerization of unsaturated fatty acids. Particularly preferred are usually mixtures of fatty acids which are obtained as coconut oil or palm oil; the use of stearic acid is generally particularly preferred. A particularly preferred compound for carrying out the present invention from this group of substances is stearamido• ·

- 14 ·· · ·

-propyldimethylamine, which can be purchased in stores under the name Tegoamid®S 18.

Esterquats, especially quaternized triethanolamine ester salts of fatty acids, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines.

Cationic surfactants of the quaternary ammonium compound type, in particular ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylio -ammonium chlorides, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, tricetylmethylammonium chloride, behenyltrimethylammonium methosulfate and imidazolinium compounds known under the INCI designations Quaternium-27 and Quaternium-83.

Cationic polymers, especially those containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic polymers are, for example, quaternized cellulose derivatives, which are commercially available under the name

Celquat® and Polymer JR® (especially Celquat® H 100 products,

Celquat® L 200 and Polymer JR® 400), polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic and methacrylic acids, commercially available under the names Merquat® 100 (poly(dimethyldiallylammonium chloride)) and Merquat®

550 (dimethyldiallylammonium chloride-acrylamide copolymer), copolymers of vinylpyrrolidones with quaternized derivatives of dialkylaminoacrylates and dialkylaminomethacrylates, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoalkylmethacrylate copolymers (for example, commercial products

Gafquat®734 and Gafquat®755), vinylpyrrolidone-vinylimidazolium methchloride copolymers, which are offered under

- 15 under the name Luviquat®, quaternized polyvinyl alcohol and polymers with quaternary nitrogen atoms in the main polymer chain known under the trade names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

As regards other compounds, reference can be made to specialist manuals known to those skilled in the art, for example Schrader, Grundlagen und Rezepturen der Kosmetika, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

These additional treatment components are contained in the compositions according to the present invention preferably in amounts of 0.05 to 10, in particular 0.1 to 5% by weight, based on the active substance of the treatment component and the total composition.

According to preferred embodiments, the compositions according to the present invention contain, in addition to the UV absorber A, a further UV filter. All conventional UV filters used in cosmetics are suitable; according to the invention, oil-soluble UV filters and substances with an absorption maximum in the UVB range may be preferred. As regards the other commonly used UV filters, the above-mentioned substances may be mentioned; a preferred further UV filter is 2-ethylhexyl ester of 3,3'-diphenyl20-2-cyanoacrylic acid (OCTOCRYLENE), (2-ethylhexyl) ester of 4-methoxycinnamic acid (OCTYL METHOXYCINNAMATE), 2-hydroxy-4-methoxybenzophenone (BENZOPHENONE-3), isoamyl ester of 4-methoxycinnamic acid (ISOAMYL P-METHOXYCINNAMATE) and 2-phenylbenzimidanol-5-sulfonic acid (PHENYLBENZIMIDAZOLE

SULFONIC ACID). These further UV filters are preferably present in the compositions according to the invention in an amount of 0.1 to 7, in particular 0.2 to 5% by weight, based on the total composition.

According to a first embodiment, the preparations according to the present invention are formulated as hair rinses or hair treatments. Hair rinses are generally formulated so that the active ingredient is rinsed off after the desired exposure time with water or a product, • · · ·

- 16 which at least predominantly contains water. The contact time with the hair is usually short. Hair treatments contain a combination of active ingredients in a higher concentration than hair rinses and are intended for the treatment of severely damaged hair. The exposure time can be short, for example of the same order as the exposure time of hair rinses, but it can be up to 20 minutes depending on the degree of hair damage. These hair treatments according to the present invention are rinsed off after the exposure time with water or a composition which at least predominantly contains water; however, they can also be left on the hair. These compositions can also be advantageously formulated as foam aerosols, in particular as sprays. For this purpose, the compositions can contain propellants. In this variant, however, a formulation in the form of a pump sprayer is preferred, where air serves as the propellant.

According to further embodiments, the compositions according to the invention can be, for example, in the form of washing compositions such as shampoos, fixing compositions such as hair hardeners, hair sprays and waving compositions, compositions for permanently changing the shape of the hairstyle such as permanent wave compositions and fixatives, color changing compositions such as bleaches, oxidation coloring compositions and toning compositions based on direct-acting dyes, hair lotions and compositions for treating the ends of the hair. Depending on the purpose of use, the corresponding viscosities of the compositions can be set. The invention also includes such products which contain separately packaged compositions, firstly the composition according to the invention and then at least one further composition which comprises, for example, precursors of oxidation dyes or oxidizing agents. These separately packaged compositions are mixed either directly before application to the hair or directly on the hair.

Other typical components of the compositions according to the present invention, while in particular in the case of ionic compounds the above-mentioned limitations regarding the range of phase transition temperatures must be taken into account, may therefore be:

• · >··*··* ··· ··· ·· ··

- 17 Anionic, zwitterionic, amphoteric and nonionic polymers, such as vinyl acetate/crotonic acid copolymer, polydimethylsiloxane, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and their esters, uncrosslinked and polyol-crosslinked polyacrylic acids, acrylamidopropyltrimethylammonium chloride/acrylate copolymers, octylacrylamide/methyl methacrylate/tert-butyl aminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers, vinyl pyrrolidone/dimethyl aminoethyl methacrylate/vinyl caprolactam terpolymers and optionally derivatized cellulose ethers.

Anionic surfactants such as, in particular, alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and mono- and dialkyl esters of sulfosuccinic acid with 8 to 18 carbon atoms in the alkyl group and monoalkyl polyoxyethyl ester of sulfosuccinic acid with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups.

- Zwitterionic surfactants, especially so-called betaines such as N-alkyl-N,N-dimethylammonium glycinate, for example coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinate, for example (coconut acyl)aminopropyldimethylammonium glycinate and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-25-imidazoline each with 8 to 18 carbon atoms in the alkyl or acyl group and (coconut acyl)aminoethylhydroxyethylcarboxymethyl glycinate.

Ampholytic surfactants such as N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N30 alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl-glycines, N-alkyltaurines, N-alkylsarcosines, 2• · acids

- 18 alkylaminopropionic and alkylaminoacetic acids each with approximately 8 to 18 carbon atoms in the alkyl group.

Defoamers such as silicones.

Thickening agents such as agar-agar, guar gum, alginates, xanthan gum, gelatin, pectin, hydroxyethyl cellulose and polyacrylamides and their copolymers.

Structurants such as maleic acid.

Perfume oils, dimethylisosorbide and cyclodextrins.

Solubilizers such as ethylene glycol, propylene glycol, glycerol and diethylene glycol.

Dyes for coloring the composition.

Active anti-dandruff ingredients such as Piroctone Olamine, Zinc Omadine and Climbazole.

Other substances for adjusting the pH value.

- Active ingredients such as allantoin, pyrrolidonecarboxylic acids and bisabolol.

Other light-protecting substances.

Consistency modifiers such as sugar esters, polyol esters or polyol alkyl ethers.

- Fats and waxes such as sperm whale, beeswax, montan wax and paraffins.

Swelling and penetrating agents such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidine, urea and primary, secondary and tertiary phosphates.

- Turbidants such as latex, styrene/PVP copolymers and styrene/acrylamide copolymers.

Pearlizing agents such as ethylene glycol monostearate and distearate and PEG-3 distearate.

- 19 • · ·· · ··

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids.

Direct acting dyes.

So-called binding and developing components as intermediates of oxidation dyes.

Reducing agents such as thioglycolic acid and its derivatives, thiolactic acid, cysteamine, thiomalic acid and α-mercaptoethanesulfonic acid.

Oxidizing agents such as hydrogen peroxide, potassium bromate and sodium bromate.

Propellant gases such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ ,

N ₂ and air and antioxidants.

The pH value of the compositions according to the present invention can be essentially between 2 and 11, the person skilled in the art being aware of the known unstable behavior of some substances, for example the basic building block panthenol, in an alkaline environment. The pH value of the compositions according to the invention is preferably between 2 and 7, with values from 3 to 6 being particularly preferred. For setting this pH value, practically any acid usable for cosmetic purposes can be used. Edible acids are usually used. Edible acids are understood to mean those acids that we take in as part of our usual nutrient intake and which have a positive effect on the human body. Edible acids are, for example, acetic acid, lactic acid, tartaric acid, citric acid, malic acid, ascorbic acid and gluconic acid. The use of citric and lactic acid is particularly preferred within the scope of the invention.

The invention also provides a method for treating keratin fibers, especially human hair, in which a

- 20 ·· ·· • ♦ · · • · · ♦ • · · · · • · · · » · · the composition according to any one of claims 1 to 11 and after an exposure time of approximately 1 second to approximately 30 minutes it is rinsed again.

The subject matter of the invention will be further illustrated by the following examples.

Examples of embodiments of the invention

All quantities in the following examples are parts by weight unless otherwise stated. ^{* (a * * * * (a}

1.

UV protection solution (a) Cetiol® SN ¹ 20.0 (a) Cutina® E 24 ² 5.3 (a) Cutina® GMS ³ 3.6 (a) Incroquat® UV-283 ⁴ 2.0 (a) Neo Heliopan® BB ⁵ 1.0 (a) Perfume oil 1.0 (b) Panthenol 0.2 (b) Desalinated water up to 100

Isononanoic acid Ci6-Ciealkyl ester (INCI designation: Cetearyl Isononanoate) (HENKEL)

Glycerol monostearate + 24 EO (INCI designation: PEG-20 Glyceryl Stearate)

Glycerol monostearate (INCI designation: Glyceryl Stearate) (HENKEL)

Trimethylcinnamic acid amidopropylammonium chloride 25 (INCI designation: Cinnamidopropyl Trimethyl Ammonium Chloride) (CRODA)

- 21 ·· ·«

2-Hydroxy-4-methoxybenzophenone (INCI designation:

Benzophenone-3) (HAARMANN & REIMER)

Production procedure: Two separate mixtures, obtained from the components marked (a) and (b), are heated to 85 °C. Then both mixtures are mixed at 85 °C and cooled with constant stirring. ^{* (a * * * * (a * * * * Ce * * * * Ok}

2.

Spray-on hair treatment, leave-on type (a) Monomuls® 60-35 C ⁶ 1.7 (a) Eumulgin® B1 ⁷ 3.5 (a) Cetiol® S ⁸ 7.2 (a) Cetiol® OE ⁹ 7.2 (a) Dow Corning® 344-EU-Fluid ¹⁰ 3.6 (a) Escalol® HP610 ¹¹ 1.5 (a) Perfume oil as required (a) Preservative as required (b) Glycerol 2.0 (b) Water to 100

Mono-diglyceride of fatty acids based on hydrogenated palm oil (INCI designation: Hydrogenated Palm Glycerides) (HENKEL)

Cetylstearyl alcohol + 12 EO (INCI designation: Ceteareth-12) (HENKEL)

1,3-bis(2-ethylhexyl)cyclohexane (INCI designation:

Dioctylcyclohexane) (HENKEL)

Di-n-octyl ether (INCI designation: Dicaprylyl Ether) (HENKEL)

Octamethylcyclotetrasiloxane (INCI designation: Cyclomethicone) (DOW CORNING) • ·

- 22 Dodecyldimethylaminobenzamidopropyldimethylammonium tosylate (ISP)

Production procedure: as in example 1 ⁵ 3. Repair milk, light (a) Emulgade®SE ¹² (a) Eumulgin® B2 ¹³ (a) Cetiol® LC ¹⁴ (a) Cetiol® OE io (a) Incroquat® UV-283 (a) Preservative (b) Gluadin® W40 ¹⁵ (b) Water, demineralized

4.5

1.0

5.0

5.0

1.0 as needed 0.5 to 100

A mixture of partial glycerides-fatty alcohols-fatty alcohol ethoxylates-wax esters (INCI designation: Glyceryl Stearate (and)

Ceteareth-20 (and) Ceteareth-12 (and) Cetearyl Alcohol (and) Cetyl Palmitate) (HENKEL) ¹³ Cetylstearyl Alcohol + 20 EO (INCI designation: Ceteareth-20) (HENKEL) ¹⁴ Caprylic-Capric Acid Ester with C ₁₂ -i8 Fatty Alcohol (INCI designation: Coco-Caprylate/Caprate) (HENKEL) ¹⁵ Wheat Protein Hydrolysate (40% active ingredient in water; INCI designation: Aqua (and) Hydrolyzed Wheat Protein (and) Sodium Benzoate (and) Phenoxyethanol (and) Methylparaben, (and) Propylparaben (HENKEL)

Production procedure as in example 1.

- 23 ··· ·· ·· • · · · · • · · · · • · · · · ·* ··

4. Repair milk, sprayable (a) Emulgade®SE 4.5 (a) Eumulgin® B2 1.0 (a) Cetiol® LC 5.0 (a) Cetiol® OE 5.0 (a) Escalol® HP610 0.5 (a) Preservative as required (b) Promois®Silk 1000 Q ^{15 16 * * * 20 * * * * 25} 0.5 (b) Panthenol 0.5 (b) Water, demineralized to 100

Silk protein hydrolysate (approximately 7% active ingredient in water INCI designation: Aqua (and) Hydrolyzed Silk) (INTERORGANA) Production method as in example 1.

5. Hair protection milk (a) Emulgade®SE (a) Eumulgin® B2 (a) Cetiol® S (a) Cetiol® OE (a) Escalol® HP610 (a) Preservative (a) Neo Heliopan® BB (b) Water

Production as in example 1.

4.5

1.0

5.0

5.0

1.25 as needed 0.75 to 100 • ·

- 24 ··♦ · • · • · ·· * ·« ·«· ···

Forte Hair Protection Milk (a) Emulgade®SE 4.5 (a) Eumulgin® B2 1.0 (a) Cetiol® S 5.0 (a) Cetiol® OE 5.0 (a) Escalol® HP610 2.0 (a) Neo Heliopan® BB 1.5 (a) Copherol®F 1300 ¹⁷ 0.3 (b) Water up to 100 D-α-tocopherol (85% active ingredient; label INCI: Tocopherol) (HENKEL CORP.) Production as in example 1.

7.

Hair repair spray (a) Emulgade®SE 4.5 (a) Eumulgin® B2 1.0 (a) Cetiol® S 5.0 (a) Cetiol® OE 5.0 (a) Incroquat® UV-283 1.0 (a) Copherol®F 1300 0.2 (b) Panthenol 1.0 (b) Water to 100

D-α-tocopherol (85% active ingredient; INCI designation: Tocopherol) (HENKEL CORP.)

Production as in example 1.

• ·

- 25 • ···· • 4 · • · • 4 · ·

444 ·· • 44 444

44

8.

Sunscreen Balm (a) Emulgade®SE 1.6 (a) Eumulgin® B2 0.4 (a) Cetiol® OE 5.0 (a) Myritol®318 ¹⁸ 0.5 (a) Escalol® HP610 1.0 (b) Neo Heliopan® Hydro ¹⁹ 1.5 (b) Hydagen®B ²⁰ 1.0 (b) Carbopol®5984 ²¹ (2% solution in water) 8.0 (b) NaOH, 1% 4.0 (b) Water, demineralized to 100

Fatty acid triglyceride (INCI designation: Caprylic/Capric Triglyceride) (HENKEL)

2-Phenylbenzimidazole-5-sulfonic acid (INCI designation: Phenylbenzimidazole Sulfonic Acid) (HAARMANN & REIMER)

D,L-a-bisabolol (85% active ingredient; INCI designation: Bisabolol) (HENKEL)

Polyacrylic acid (INCI designation: Carbomer) (BF GOODRICH)

Production as in example 1.

9. Protective milk for intensive sun protection (leave-on type) (a) Emulgade®SE 8.0 (a) Eumulgin® B2

2.0 • · ·· *· • · * · · · <*· ♦ ♦ · • · · · • » · • · · · ·» ♦·

(a) Almond oil 2.0 (a) Euthanol® G ²² 2.0 (a) Cetiol® 868 ²³ 9.0 (a) Incroquat® UV-283 0.5 (a) Neo Heliopan® BB 1.0 (a) Neo Heliopan® A V ²⁴ 1.0 (b) Glycerol, 86% 5.0 (b) Water, demineralized up to 100 2-Octyldodecyl alcohol (INCI designation: Octyldodecanol)

(HENKEL)

2-Ethylhexyl stearic acid ester (INCI designation: Octyl

Stearate) (HENKEL) ²⁴ (2-ethylhexyl)ester of 4-methoxycinnamic acid (INCI designation:

Octyl Methoxycinnamate) (HAARMANN & REIMER)

Production as in example 1.

Sunscreen emulsion, sprayable

(a) Emulgade®SE 4.7 (a) Eumulgin® B2 1.3 (a) Cetiol® 868 6.0 (a) Cetiol® SN 6.0 (a) Escalol® HP 610 2.0 (a) Neo Heliopan® E 1000 ²⁵ 4.0 (a) Neo Heliopan® BB 1.0 (a) Copherol®F 1300 1.0 (b) Glycerol, 86% 5.0

··· ♦ · · · » ’ ··· ♦· ··· ··· ·« ··

- 27 (b) Water up to 100

3-(4-methoxyphenyl)-2-propenoic acid 3-methylbutyl ester (INCI designation: Isoamyl-p-methoxycinnamate) (HAARMANN & REIMER)

Production as in example 1.

Claims (5)

PATENT CLAIMS 1. A composition for treating keratin fibers, which contains 5 at least 6% by weight of oil components and at least one non-ionic emulsifier, and is in the form of a microemulsion with a mean droplet size of less than 400 nm, characterized in that it further contains a UV-absorbing component A of the general formula (I) and U-Q (I) where U represents a UV-absorbing group and Q represents a group that contains at least one quaternary ammonium functional group. 15 2. The composition according to claim 1, characterized in that the group Q in the general formula (I) has the general structure -(CH ₂ ) _X -N ⁺ R ¹ R ² R ^{3 4} X, where x represents an integer from 1 to 4, R ¹ and R ² independently represent C _1-4 alkyl groups, R ³ represents a C 1-22 alkyl group or a benzyl group and X 20 represents a physiologically acceptable anionic group. 3. A composition according to claim 2, characterized in that at least two of the groups R ¹ , R ² and R ³ represent methyl groups. 4. The composition according to any one of claims 1 to 3, characterized in that the group U is chosen such that compound A has an absorption maximum in the UVB region. - 29 25 ··· · * • · ·· Means according to someone of claims 1 until 4, mark u j i c i with th e m that the compound And it has molar extinction 15,000. coefficient in maximum absorption at least Means according to someone of claims 1 until 5, mark u j i c i with th e m that it contains at least one oil component of plant origin. Means according to someone from claims 1 up to 6, mark u j i c i with that, f it contains nonionic emulsifier with HLB value of 8 to 18. Means according to someone from claims 1 up to 7, mark u j i c i with that > that as nonionic emulsifier contains at least one ethoxylated fatty alcohol. Means according to someone from claims 1 up to 8, mark u j i c i with that, that it contains at least one more treatment component. Means according to someone from claims 1 up to 9, mark u j i c i with the fact that e contains an additional UV filter. ·· • · · • 4 4 ’ 4 · 4· - 30 11. The composition according to any one of claims 1 to 10, characterized in that it is formulated as a spray. 12. A method for treating keratin fibers, in particular human hair, characterized in that the composition according to any one of claims 1 to 11 is applied to the fibers and rinsed off after a contact time of approximately 1 s to approximately 30 min.