EP1313433A1

EP1313433A1 - Use of quaternized protein hydrolyzates

Info

Publication number: EP1313433A1
Application number: EP01976113A
Authority: EP
Inventors: Elke Weimann; Maya Hohle
Original assignee: Cognis Deutschland GmbH and Co KG
Current assignee: BASF Personal Care and Nutrition GmbH
Priority date: 2000-08-29
Filing date: 2001-08-18
Publication date: 2003-05-28
Also published as: JP2004513082A; US20040022754A1; WO2002017862A1; DE10042445A1

Abstract

The invention relates to the use of quaternized protein hydrolyzates as color protection and UV protection for keratin fibers treated with semipermanent colorants.

Description

Use of quaternized protein hydrolyses

Field of the Invention

The invention is in the field of hair treatment compositions and relates to the use of selected cationic compounds for protecting tinted hair.

State of the art

The most important hair treatment agents include hair dyes, which are divided into permanent and semi-permanent colors; the latter are also known as tints or colorations. While permanent hair colors, as the name already expresses, are intended to give hair a permanent new color, tints are mainly used by consumers who only want a new hair color temporarily or only want to change the original shade slightly.

In the course of hair care, shampoos do not differentiate between unwanted dirt deposits on the keratin fibers and those - namely hair dyes - that should actually remain there for a long time. Even if modern colorations have a fairly good adhesive power, they will inevitably be rinsed out over the course of 10 to 20 hair washes, while the consumer would usually welcome longer liability. Manufacturers of hair treatment products can try to meet this wish in two directions: either the adhesion of the colorants is improved or "intelligent" shampoos are developed, which are able to distinguish between dirt deposits and hair dyes on the keratin fibers.

The object of the present invention was to pursue the latter approach and to make available substances which, as a component of hair treatment compositions which are usually rinsed out after use, in particular shampoos, conditioners, treatments and the like, ensure that the hair dyes remain on the fibers while dirt is removed. simultaneously they should give the hair improved protection against UV rays, especially against UV-B rays.

Description of the invention

The present invention relates to the use of quaternized protein hydrolyzates as color and UV protection for keratin fibers treated with semi-permanent dyes.

Surprisingly, it was found that the addition of quaternized protein hydrolyzates to commercially available hair treatment agents, such as shampoos or conditioners, significantly reduces the amount of rinsing out of semi-permanent hair dyes during use and thus increases the sustainability of the hair tint. At the same time, it was found that the protection of the hair against UV-B radiation is significantly improved.

Cationic protein hydrolysates

Cationic protein hydrolyzates are known substances whose use in hair treatment compositions is well known; in this context, reference is made, for example, to international patent application WO 96/25141 and German patent DE 19505005 (Cognis). What is new, however, is that these compounds can be used specifically to protect tinted hair. The applicant found that plant products, which are produced on the basis of breakdown products of pea, rice, almond, potato, soy, silk and in particular wheat proteins (e.g. gluten), are particularly distinguished for this purpose. The acidic, alkaline and / or enzymatic hydrolysis of these starting materials generally leads to products which have an average molecular weight in the range from 100 to 30,000, preferably 100 to 10,000 and in particular 2,000 to 5,000 and dalton.

For hydrolysis, an aqueous suspension of the protein-containing starting material is typically, if appropriate, together with the adsorbents, such as activated carbon, at changing pH values over a period of 1 to 24 hours in the optimum temperature of the proteinases and peptidases used below 70 and preferably below 60 ° C., for example degraded at 30 to 55 ° C. After the hydrolysis, it is recommended that pH in the acidic range, for example to shift to pH = 3 to 4. If the digestion is carried out in the presence of calcium oxide or calcium hydroxide as the base, calcium peptides are formed which have to be filtered off from the residue. If the alkali peptides are desired, it is advisable to treat the calcium peptides with soda or potash solution and then to separate the poorly soluble calcium carbonate. It is also possible to precipitate the calcium in the form of calcium sulfate or calcium oxalate. The sparingly soluble salts are preferably separated off in the presence of filter aids via filter chutes or filter presses. Aqueous vegetable protein hydrolyzate solutions are obtained, which can be concentrated if necessary, for example using downdraft evaporators. The hydrolyzates obtainable generally have a solids content of about 5 to 50% by weight.

The cationization of the vegetable hydrolysates obtained in this way takes place between the free amino and / or carboxyl groups of the oligopeptide and a halogen group of the quaternary ammonium salt used, hydrogen halide being split off. The preferred quaternary ammonium salts follow the formula (I)

[R ^ I ^ -CZ ^ X] shark (I)

in which R ^{1 represents} an alkyl and / or alkenyl radical with 1 to 22 carbon atoms, R ² and R ³ independently of one another for an alkyl radical with 1 to 4 carbon atoms, Z for an optionally hydroxyl-substituted alkylene radical and X and Hai independently of one another for chlorine or bromine stand. In a particular embodiment of the invention, the quaternary ammonium salts used are N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides and in particular N, N-dimethyl -N- (n-dodecyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium chloride.

As already mentioned, the reaction between the protein hydrolyzates and the quaternary ammonium salts takes place with the elimination of hydrogen halide and is catalyzed by alkali bases. The choice of these bases is not critical per se, but concentrated aqueous solutions of sodium or potassium hydroxide are preferably used. The pH during the reaction is therefore preferably in the range from 8 to 12 and in particular around 10. It has proven advantageous to use the molar It should be chosen so that p / 10 to p / 100 mol and preferably p / 20 to p / 50 mol of quaternary ammonium salts are present in a 1 mol of a protein hydrolyzate which has an average of p mol of peptide units. In other words, for a 1 mol of a protein hydrolyzate which has an average of 100 peptide units (p = 100), 1 to 10 mol (p / 100 to p / 10) and preferably 2 to 5 (p / 50 to p / 20) Quaternary ammonium salts are used. The reaction usually takes place at a temperature in the range from 20 to 90, preferably 40 to 60 ° C; the reaction time is typically 1 to 24 and in particular 4 to 12 hours. It has proven to be advantageous to adjust the end product to a neutral pH by adding mineral acid and to stabilize it against microbial attack in the usual manner, for example by adding PHB esters.

The amount of quaternized protein hydrolyzate used can be 1 to 10, preferably 2 to 8 and in particular 4 to 6% by weight, based on the final formulation.

Industrial applicability

The hair treatment compositions which contain the quaternized protein hydrolyzates to be used according to the invention can, as further auxiliaries and additives, mild surfactants, oil bodies, emulsifiers, pearlescent waxes, consistency enhancers, thickeners, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, biogenic active ingredients , UV light protection factors, antioxidants, deodorants, antidandruff agents, film formers, hydrotropes, solubilizers, preservatives, perfume oils, dyes and the like.

surfactants

Anionic, nonionic, cationic and / or amphoteric or amphoteric surfactants can be present as surface-active substances, the proportion of these agents usually being about 1 to 70, preferably 5 to 50 and in particular 10 to 30% by weight. Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, fatty sulfate amate sulfates, hydroxy (ether) sulfate ethersulfates, hydroxy (sulfate) ether sulfates, hydroxy (ether) sulfate, hydroxy (ether) sulfate, Mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids, such as, for example, acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (in particular vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides, especially glucoronic acid, or glucoramic acid derivatives, and glucoronic acid nuclei (glucoronic acid) derivatives, in particular, glucoronic acid (G) -glucoronic acid (G) -glucoronic acid (G) -glucoric acid-derived (G) -glucoramic acid-derived (G) -glucoramic acid (G) -glucoric acid-derived (especially glucoric acid) vegetable glucoric acid derivatives Wheat-based products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds, such as, for example, dimethyldistearylammonium chloride, and esterquats, in particular quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, relevant reviews are, for example, J.Falbe (ed.), "Factors in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J.Falbe (ed.), "Catalysts , Tenside und Mineralöladditive ", Thieme Verlag, Stuttgart, 1978, pp. 123-217. Typical examples of particularly suitable mild, ie particularly skin-compatible, surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, α-olefin sulfonates, fatty acid gluco amide fatty acids, alkyl carboxylates, fatty acid gluco amide fatty acids, fatty acid gluco amide fatty acids, fatty acid gluco amide fatty acids, fatty acid glucoamides, fatty acid glucosacid fatty acids, fatty acid glucamate fatty acids, fatty acid glucosacid fatty acids, fatty acid glucosaccharides, fatty acid glucosacids, fatty acid fatty acids, fatty acid glucosaccharides, fatty acid fatty acids, fatty acid fatty acids, fatty acid fatty acids, fatty acid fatty acids, fatty acid fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids, fatty acids; , the latter preferably based on wheat proteins.

oil body

Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear or branched C ₆ -C ₂₂ fatty alcohols or esters of branched C ₆ -C ₄ come as oil bodies, for example ₁₃ - carboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, such as myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl rucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl stearate, cetyl stearate, cetyl stearate, Cetylerucat, sostearylisostearat Stearylmyristat, stearyl, stearyl, Stearylisostearat, stearyl, stearyl, Stearylerucat, isostearyl, isostearyl, Isostearylstearat, I, Isostearyloleat, Isosteaiγlbehenat, Isostearyloleat, oleyl, oleyl palmitate, oleyl stearate, oleyl isostearate, oleate, Oleylbehenat, oleyl, Behenylmy- ristat, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenylerucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. In addition, esters of linear C ₅ -C ₂₂ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of are suitable. ₈ -C ₃₈ alkyl hydroxy carboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols (cf. DE 19756377 AI), in particular dioctyl malates, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol ) and / or Guerbet alcohols, triglycerides based on Cs-fatty acids, liquid mono- / di- / triglyceride mixtures based on C ₆ -C ₁₈ fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids , In particular benzoic acid, esters of C ₂ -C ₂ -dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C. ₆ -C ₂₂ fatty alcohol carbonates, such as, for example, dicaprylyl carbonates (Cetiol® CC), Guerbet carbonates based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and / or branched C ₆ -C ₂₂ alcohols (e.g. Finsolv®

TN), linear or branched, symmetrical or asymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, such as e.g. Dicaprylyl ether (Cetiol® OE), ring opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicon methicone types, etc.) and / or aliphatic or naphthenic hydrocarbons, e.g. such as squalane, squalene or dialkylcyclohexanes.

emulsifiers

Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

> Adducts of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms, with alkylphenols with 8 to 15 carbon atoms in the alkyl group and Alkylamines with 8 to 22

Carbon atoms in the alkyl radical; > Alkyl and / or alkenyl oligoglycosides with 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs;

> Adducts of 1 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil; > Adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;

> Partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated, branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide; > Partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (eg sorbitol), alkyl glucosides (eg methyl glucoside, butyl glucoside, lauryl glucoside) as well as cellulose glucosides saturated and / or unsaturated, linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 mol ethylene oxide;

> Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE 1165574 PS and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol. > Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

> Wool wax alcohols;

> Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

> Block copolymers e.g. Polyethylene glycol 30 dipolyhydroxystearate; > Polymer emulsifiers, e.g. Pemulen types (TR-1, TR-2) from Goodrich;

> Polyalkylene glycols as well

> Glycerine carbonate.

The addition products of ethylene oxide and / or of propylene oxide onto fatty alcohols, fatty acids, alkylphenols or onto castor oil are known, commercially available products. These are mixtures of homologs, the average degree of alkoxylation of which is the ratio of the amounts of ethylene oxide and / or propylene oxide and Substrate with which the addition reaction is carried out corresponds. C ₂ ₈ fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE 2024051 PS as refatting agents for cosmetic preparations Alkyl and / or alkenyl oligoglycosides, their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. With regard to the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to preferably about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.

Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid, Isostearinsäurediglycerid, oleic acid monoglyceride, oleic acid diglyceride, Ricinolsäuremoglycerid, Ricinolsäurediglycerid, linoleic acid monoglyceride, Linolsäurediglycerid, Linolensäuremonoglycerid, Linolensäurediglycerid, Erucasäuremonoglycerid, Erucasäurediglycerid, Weinsäuremonoglycerid, Weinsäurediglyce- chloride, Citronensäuremonoglycerid, Citronendiglycerid, Apfelsäuremonoglycerid, Malic acid diglyceride and their technical mixtures, which may still contain small amounts of triglyceride from the manufacturing process. Addition products of 1 to 30, preferably 5 to 10, mol of ethylene oxide onto the partial glycerides mentioned are also suitable.

As sorbitan sorbitan, sorbitan sesquiisostearate, Sorbitandii- come sostearat, sorbitan triisostearate, sorbitan monooleate, sorbitan, sorbitan, Sorbitanmonoerucat, Sorbitansesquierucat, Sorbitandierucat, Sorbitantrieru- cat, Sorbitanmonoricinoleat, Sorbitansesquiricinoleat, Sorbitandiricinoleat, Sorbitantriricino- leat, Sorbitanmonohydroxystearat, Sorbitansesquihydroxystearat, Sorbitandihydroxystearat, Sorbitantrihydroxystearat, Sorbitanmonotartrat , Sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan citrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan malimaleate, sorbitan trimaleate and their technical mixtures. Addition products of 1 to 30, preferably 5 to 10, moles of ethylene oxide onto the sorbitan esters mentioned are also suitable.

Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearates (Dehymuls® PGPH), polyglycerol-3 diisostearates (Lameform® TGI), polyglyceryl-4 isostates (Isolan® GI 34), polyglyceryl-3 oleates, diisostearoyl polyglyearylate-3 (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), PolygIyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether ( Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyce- ryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate Isostearate and their mixtures. Examples of other suitable polyol esters are the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like which are optionally reacted with 1 to 30 mol of ethylene oxide.

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylm -hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are also ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C _{8 /} i ₈ alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts , Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylamino-butyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group. Typical anionic emulsifiers are also aliphatic fatty acids with 12 to 22 carbon atoms, such as, for example, palmitic acid, stearic acid or behenic acid, and dicarboxylic acids with 12 to 22 carbon atoms, such as, for example, azelaic acid or sebacic acid. Particularly preferred ampholytic surfactants are N-coconut alkyl aminopropionate, coconut acylaminoethyl aminopropionate and C ₂ -C ₈ -acyl sarcosine. Finally, cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.

Fats and waxes Typical examples of fats are glycerides, that is to say solid or liquid vegetable or animal products which essentially consist of mixed glycerol esters of higher fatty acids, and waxes include natural waxes, such as candelilla wax, carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax and sugar cane - wax, ouricury wax, montan wax, beeswax, shellac wax, walrus, lanolin (wool wax), pretzel fat, ceresin, ozokerite (earth wax), petrolatum, paraffin waxes, micro waxes; chemically modified waxes (hard waxes), such as, for example, montan ester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as, for example, polyalkylene waxes and polyethylene glycol waxes. In addition to fats, fat-like substances such as lecithins and phospholipids can also be used as additives. The person skilled in the art understands the term lecithins as those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Lecithins are therefore often used in the professional world as phosphatidylcholines (PC). Examples of natural lecithins are the cephalins, which are also referred to as phosphatidic acids and are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. In contrast, phospholipids are usually understood to be mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally classed as fats. In addition, sphingosines or sphingolipids are also suitable.

Perlqlanzwachse

Pearlescent waxes, for example, are: alkylene glycol esters, especially ethylene glycol stearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof. Consistency quencher and thickener

Suitable consistency agents are primarily fatty alcohols or hydroxy fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and, in addition, partial glycerides, fatty acids or hydroxy fatty acids. A combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred. Suitable thickeners are, for example, Aerosil types (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl and hydroxypropyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, Polyacrylates, (e.g. Carbopole® and Pemulen types from Goodrich; Synthalene® from

Sigma; Keltrol types from Kelco; Seppic Sepigel types; Salcare types from Allied Colloids), polyacrylamides, polymers, polyvinyl alcohol and polyvinyl pyrrolidone. Bentonites, such as e.g. Bentone® Gel VS-5PC (Rheox), which is a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate. Surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides as well as electrolytes such as table salt and ammonium chloride are also suitable.

stabilizers

Metal salts of fatty acids, such as e.g. Magnesium, aluminum and / or zinc stearate or ricinoleate are used.

polymers

Suitable cationic polymers are, for example, cationic cellulose derivatives, e.g. a quaternized hydroxyethyl cellulose, which is marketed under the name Polymer JR 400® by

Amerchol is available, cationic starch, copolymers of diallylammonium salts and acrylic amides, quaternized vinylpyrrolidone / vinylimidazole polymers such as e.g. Luviquat® (BASF),

Condensation products of polyglycols and amines, quaternized collagen polypeptides, such as, for example, lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as, for example, amodimethicones, copolymers of adipic acid and dimethylaminohydroxiaminodiethyl (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyl-diallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides, as described for example in FR 2252840 A, and their crosslinked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally microcrystalline, condensation - Products from dihaloalkylene, such as, for example, dibromobutane with bisdialkylamines, such as, for example, bis-dimethylamino-l, 3-propane, cationic guar gum, such as, for example, Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese Ammonium salt polymers such as Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.

Anionic, zwitterionic, amphoteric and nonionic polymers include, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and polyesters and their esters, uncrosslinked , Acrylamido-propyltrimethylammonium chloride / acrylate copolymers, octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymers, vinyl pyrrolidone / teraminate / vinyl acrylate methacrylate / vinyl methacrylate methacrylate / methacrylate / vinyl methacrylate / methacrylate / vinyl amide / dimethylaminoethyl methacrylate and / or methyl acrylate / vinyl amide / dimethylamino-cellulose methacrylate / methacrylate / vinyl amide / dimethylamino-cellulose-methacrylate / methacrylate-methyl-methacrylate-methacrylate / acrylate / vinyl amide / dimethylamino-cellulose-methacrylate / acrylate / vinyl amide / dimethylamino-cellulose-methacrylate-methacrylate / acrylate / vinyl amide / dimethylamino / cellulose methacrylate / acrylate / vinyl amide / vinyl amide / dimethylamino / cellulose methacrylate / acrylate / vinyl methacrylate and silicones in question. Other suitable polymers and thickeners are in Cosm.Toil. 108, 95 (1993).

Silicone Compounds

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl modified silicone compounds which are both liquid and resinous at room temperature can. Simethicones, which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates, are also suitable. A detailed overview of suitable volatile silicones can also be found by Todd et al. in Cosm.Toil. 91, 27 (1976).

UV light protection filters and antioxidants

UV light protection factors are understood to mean, for example, organic substances (light protection filters) which are liquid or crystalline at room temperature and are capable of absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, eg heat. UVB filters can be oil-soluble or water-soluble. Examples of oil-soluble substances are:

> 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, e.g. 3- (4-methylbenzylidene) camphor as described in EP 0693471 B1;

> 4-aminobenzoic acid derivatives, preferably 2-ethyl-hexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; > Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene);

> Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester; > Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4 ^v -methylbenzophenone, 2,2 ^Λ -dihydroxy-4-methoxybenzophenone;

> Esters of benzalmalonic acid, preferably 4-methoxybenzmalonic acid di-2-ethylhexyl ester;

> Triazine derivatives, such as 2,4,6-trianilino- (p-carbo-2 ^Λ -ethyl-r-hexyloxy) -l, 3,5-triazine and octyl triazone, as described in EP 0818450 AI or dioctyl butamido triazone

(Uvasorb® HEB);

> Propane-l, 3-diones, such as l- (4-tert.ButyIphenyl) -3- (4 ^λ methoxyphenyl) propan-l, 3-dione;

> Ketotricyclo (5.2.1.0) decane derivatives, as described in EP 0694521 B1.

Possible water-soluble substances are:

> 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts;

> Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;

> Sulfonic acid derivatives of 3-benzylidene camphor, e.g. 4- (2-oxo-3-bornylidene-methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane are particularly suitable as typical UV-A filters, such as, for example ^, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione, 4-tert-butyl- 4'-methoxydibenzoylmethane (Parsol® 1789), l-phenyl-3- (4-sopropylphenyl) propane-1,3-dione and enamine compounds, as described in DE 19712033 AI (BASF). The UV-A and UV-B filters can of course also be used in mixtures. Particularly favorable combinations consist of the derivatives of benzoyl methane ,, for example 4-tert-butyl 4 ^λ methoxydibenzoylmethane (Parsol 1789) and 2-cyano-3,3-phenylcinnamate-2-ethyl-hexyl ester (Octocrylene), in combination with Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate and / or propyl 4-methoxycinnamate and / or isoamyl 4-methoxycinnamate. Such combinations are advantageously combined with water-soluble filters such as, for example, 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts.

In addition to the soluble substances mentioned, insoluble light protection pigments, namely finely dispersed metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The oxides and salts are used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or shape which differs from the spherical shape in some other way. The pigments can also be surface treated, i.e. are hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, e.g. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. So-called micro- or nanopigments are preferably used in sunscreens. Micronized zinc oxide is preferably used. Other suitable UV light protection filters can be found in the overview by P.Finkel in SÖFW-Journal 122, 543 (1996) and Parf.Kosm. 3, 11 (1999).

In addition to the two aforementioned groups of primary light stabilizers, secondary light stabilizers of the antioxidant type can also be used, which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin. Typical examples of this are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-camosine, L-camosine and their derivatives (e.g. Anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiou-racil and other thiols (eg thioredoxin, Glutathione, cysteine, cystine, cystamine and their Glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distea rylthiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. buthioninsulfoximines, homocysteine sulfoximine, butioninsulfones, penta-, hexa-, heptathioninsulfoximine) in very low tolerable dosages (e.g. pmol kg), also (metal) chelators (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, oleic acid, oleic acid), folic acid and their derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg Ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin, rutinic acid and its derivatives, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, camosolene, camosol , Butyl-hydroxyanisole, nordihydroguajakh resin acid, nordihydroguajaretic acid, trihydroxybutyrophenon, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and its derivatives (eg ZnO, ZnSO ₄ ) selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide) and the derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances which are suitable according to the invention.

Bioqene active ingredients

Examples of biogenic active substances are tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy) ribonucleic acid and its fragmentation products, β-glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudo-ceramides, essentielle ceramides, Plant extracts, such as To understand prunus extract, Bambaranus extract and vitamin complexes.

film formers

Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds. Antidandruff agents

Piroctone olamine (1-hydroxy-4-methyl-6- (2,4,4-trimythylpentyl) -2- (1H) -pyridinone monoethanolamine salt), Baypival® (climbazole), Ketoconazol®, (4-acetyl -l - {- 4- [2- (2.4-dichlorophenyl) r-2- (1H-imidazol-l-ylmethyl) -l, 3-dioxylan-c-4-ylmethoxyphenyl} piperazine, ketoconazole, elubiol, selenium disulfide, sulfur colloidal sulfur polyehtylenglykolsorbitanmonooleat, Schwefelrizinolpolyehtoxylat, Schwfel tar distillate, salicylic acid (or in combination with hexachlorophene), undecylenic acid monoethanolamide sulfosuccinate Na salt, Lamepon® UD (protein undecylenic acid condensate), zinc pyrithione, magnesium pyrithione Aluminiumpyrithion and / dipyrithione magnesium sulfate in question ,

hydrotropes

Hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used to improve the flow behavior. Polyols which are suitable here, be sitting ^¬ preferably 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols can also contain further functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

> Glycerin;

> Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecu ^¬ weight of 100 to 1000 daltons; > technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;

> Methyl compounds, such as, in particular, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;

> Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical, such as methyl and butyl glucoside;

> Sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or mannitol,

> Sugar with 5 to 12 carbon atoms, such as glucose or sucrose;

> Aminosugars such as glucamine;

> Dialcohol amines, such as diethanolamine or 2-amino-l, 3-propanediol.

preservative Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid as well as the silver complexes known under the name Surfacine® and the other classes of substances listed in Appendix 6, Parts A and B of the Cosmetics Ordinance.

Perfume oils and flavors

Perfume oils include mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, cumin, juniper), fruit peel (bergamot, lemon, Oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme) ), Needles and twigs (spruce, fir, pine, mountain pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, such as civet and castoreum, are also suitable. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylatepionate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, α-Isomethylionon and Methylcedrylketon, to the alcohols Anethol,

Citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes and balsams. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Essential oils of low volatility, which are mostly used as aroma components, are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Preferably, bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, Cyclovertal, lavandin oil, muscatel Sage oil, ß-Damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evernyl, Iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, Romilllat, Irotyl and Floramat used alone or in mixtures.

dyes

The dyes which can be used are the substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes" by the Dye Commission of the German Research Foundation, Verlag Chemie, Weϊnheim, 1984, pp. 81-106. Examples are culinary red A (CI 16255), patent blue V (CI42051), indigotine (C.L73015), chlorophylline (CI75810), quinoline yellow (CI47005), titanium dioxide (CI77891), indanthrene blue RS (CI 69800) and Madder varnish (CI58000). Luminol may also be present as the luminescent dye. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.

The total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40,% by weight, based on the composition. The agents can be produced by customary cold or hot processes; the phase inversion temperature method is preferably used.

Examples

Examples 1 and 2, Comparative Examples VI and V2. Gray strands of Caucasian woman's hair were first tinted with chestnut brown and then washed 10 or 20 times with shampoos with or without the quaternized protein hydrolysates according to Table 1. The extent to which the tint was washed out was then determined on the one hand with the aid of image analysis as gray level and spectrocolometrically (Microflash V4.0, Data Color International). At the same time, strands treated in this way were irradiated with 4 fluorescent lamps for 24 or 48 h and thus exposed to UV-B rays. The damage was then determined photometrically using the fluorescence method with dansyl chloride. The results are summarized in Table 1. Examples 1 and 2 are in accordance with the invention, Examples VI and V2 are used for comparison.

It can be seen that when the cationic surfactants are used according to the invention, less graying is achieved in comparison, ie less hair dye is rinsed out. Furthermore, the higher fluorescence intensity shows that less UV-B damage has occurred.

Table 1

Color protection through quaternized protein hydrolyzates (quantities as% by weight)

Claims

claims

1. Use of quaternized protein hydrolyzates as color and UV protection for keratin fibers treated with semi-permanent dyes.

2. Use according to claim 1, characterized in that one uses quaternized vegetable protein hydrolyzates

3. Use according to claims 1 and / or 2, characterized in that quaternized wheat protein hydrolyzates are used.

4. Use according to at least one of claims 1 to 3, characterized in that quaternized protein hydrolyzates are used which - based on the protein content - have an average molecular weight of 100 to 30,000 daltons.

5. Use according to at least one of claims 1 to 4, characterized in that quaternized protein hydrolyzates are used which are obtained by reacting protein hydrolyzates with quaternary ammonium salts of the formula (I),

I

[ ^l -N ⁺ - (Z) -X] shark ^' (I)

in which R ^{1 represents} an alkyl and / or alkenyl radical with 1 to 22 carbon atoms, R ² and R ³ independently of one another for an alkyl radical with 1 to 4 carbon atoms, Z for an optionally hydroxyl-substituted alkylene radical and X and Hai independently of one another for chlorine or bromine.

6. Use according to at least one of claims 1 to 5, characterized in that quaternized protein hydrolyzates are used which are obtained by reacting protein hydrolyzates with N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3 -chloro-n-propyl) - ammonium halides. Use according to at least one of claims 1 to 6, characterized in that quaternized protein hydrolyzates are used, which are obtained by reacting protein hydrolyzates with N, N-dimethyl-N- (n-dodecyl) -N- (2-hydroxy-3-chloro -n-propyl) - receives ammonium chloride.

Use according to at least one of claims 1 to 7, characterized in that the quaternized protein hydrolyzates are used in amounts of 1 to 10% by weight, based on the final formulation.