Hair care shampoo containing polylysine

Abstract

The present invention provides a hair care shampoo based on specific amounts of epsilon-polylysine and anionic surfactants. Hair care shampoos can be used to improve the detangling, combability, smoothness and sensory properties of hair.

Description

[0001] The invention relates to hair care shampoos based on specific amounts of epsilon-polylysine and anionic surfactants, which are essentially free of chemically modified polymers. The invention further relates to the use of the hair care shampoos to improve the care properties of hair, in particular to improve detangling, combability, smoothness, shine, volume, and the sensory properties of hair.

[0002] With the help of cosmetic cleaning products, such as hair shampoos, human hair and the scalp can be cleansed and freed from sebum, styling product residues and other impurities.

[0003] Hair shampoos typically contain (usually anionic) surfactants, which, depending on the type and amount of surfactant(s), remove not only dirt and sebum, but also lipids and proteins from the hair and / or scalp with each cleansing process. This can cause damage to the hair structure and / or dryness of the scalp, particularly with frequent cleansing. This can manifest itself visually or haptically, for example, in a lack of shine and / or smoothness of the hair, a dull feeling, the appearance of split ends and / or hair breakage, and an irritated and / or itchy scalp.

[0004] Damage to the hair structure or hair fibers, especially split ends and / or hair breakage, can also be further aggravated by environmental influences (such as intense sunlight), mechanical stress (such as combing under the heat of a hairdryer) and chemical influences (such as dyeing, shaping or straightening the hair).

[0005] To prevent, reduce, and / or (at least superficially) eliminate hair damage, hair shampoos have often been enriched with conditioning ingredients, usually combinations of silicone oils and cationic polymers. This primarily smoothed hair and made it easier to comb. Cationic polymers also have an antistatic effect on hair fibers.

[0006] The disadvantage of this conventional combination of silicones and cationic polymers is the occurrence of a so-called build-up effect. This occurs because both silicones and cationic polymers coat the hair fibers with a wafer-thin film, which builds up further with each use of a shampoo based on this conditioning blend and can ultimately lead to unwanted weighting of the hair.

[0007] In addition, shampoos containing silicones can often only be satisfactorily stabilized by adding other synthetic polymers.

[0008] For reasons of sustainability, efforts are also being made to replace synthetic or chemically modified active ingredients and excipients in cosmetic products with natural and biodegradable active ingredients and excipients.

[0009] The provision of caring hair shampoos that are 'low in' or 'free from' chemically modified polymers - possibly also 'low in' or 'free from' silicones - is therefore a relevant task in the field of cosmetics.

[0010] Known alternative active ingredients cannot yet adequately cover all needs.

[0011] The objective of this application was to provide hair care shampoos with high care performance that ensure an optimal balance between gentle yet thorough cleansing, long-lasting and sustainable care of the scalp and hair, and good tolerability. Ideally, the supporting effect of chemically modified polymers should be avoided.

[0012] Epsilon-polylysine is a biotechnologically derived multifunctional active ingredient that has so far been used primarily in Asia as a preservative or as a component of preservative mixtures. Furthermore, epsilon-polylysine is known for its excellent anti-dandruff efficacy, especially in combination with other anti-dandruff active ingredients (e.g., from DE 102011079536, DE 102011079540, DE 102011077067).

[0013] The synergistic combination of epsilon-polylysine with anionic surfactants to significantly improve hair care-relevant parameters has not been described so far.

[0014] It has now been discovered that even the addition of extremely small amounts of epsilon-polylysine anionic surfactants to shampoos imparts exceptionally good hair care properties – particularly with regard to the care parameters of detangling, combability, smoothness, shine, volume, and improved sensory properties of hair. What was particularly surprising was that the improvement in hair care properties could be achieved in the absence of any cationic care polymers, and that the care effect was greater than in corresponding shampoos that even contain higher amounts of cationic polymers as care components.

[0015] A further advantage of the hair care shampoos according to the invention is that additional care components—such as silicones—can be optionally added without requiring stabilization by chemically modified polymers, especially polymers containing (meth)acrylic units. However, even the optional addition of silicones did not lead to undesirable weighting of the hair after regular use of hair care shampoos based on epsilon-polylysine and anionic surfactants.

[0016] A first subject of the invention is therefore a hair care shampoo which is contained in a cosmetic carrier - based on the total weight of the hair care shampoo - a) 0.00001 - 1.0% by weight of epsilon polylysine b) contains 5.0 - 20 wt.% of at least one anionic surfactant, wherein the hair care shampoo is substantially free of chemically modified polymers.

[0017] The first subject matter of the invention summarized above will now be presented in more detail.

[0018] Unless otherwise stated, all amounts expressed in % are by weight and are expressed based on the total weight of the hair care shampoo.

[0019] A suitable cosmetic carrier for the hair care shampoos according to the invention is, for example, water or a mixture of water and alcohols. Lower alkanols and polyols such as propylene glycol and glycerin can serve as the alcoholic component. Ethanol, n-propanol, and isopropanol are preferred lower alcohols. Water and alcohol(s) can be present in a weight ratio of 1:20 to 99:1. Water or aqueous-alcoholic mixtures containing up to 50% by weight, preferably up to 25% by weight, and in particular up to 15% by weight of alcohols (based on the total weight of the alcohol / water mixture) can be preferred cosmetic carriers.

[0020] "Substantially free of" as used herein means that chemically modified polymers are present in the hair care shampoo in less than 0.01% by weight, preferably less than 0.005% by weight, more preferably less than 0.001% by weight, and most preferably not at all.

[0021] “Chemically modified polymers” in the sense of the present invention are understood to mean any chemically modified cationic polymers, even if they are based on natural starting materials such as starch, cellulose or gums.

[0022] Furthermore, “chemically modified polymers” in the sense of the present invention are understood to mean any stabilizing and / or thickening polymers that comprise acrylic or methacrylic units.

[0023] Hair care shampoos according to the invention are preferably substantially free, particularly preferably free, of cationic polymers and / or polymers comprising (meth)acrylic units. Hair care shampoos according to the invention are particularly preferably substantially free or free of cationic polymers falling under the INCI name "Polyquaternium," cationic guar, starch, or cellulose polymers, and polymers comprising (meth)acrylic units.

[0024] As the first essential ingredient, the hair care shampoos according to the invention contain - based on their total weight - 0.00001 - 1.0 wt.% epsilon-polylysine.

[0025] For the purposes of the present invention, “epsilon-polylysine” is understood to mean an oligo- or homopolymer of the natural amino acid lysine, which is also referred to as epsilon-polylysine due to its linkage in the ε-position.

[0026] Particularly preferably, "epsilon-polylysine" in the context of the present invention refers to epsilon-poly-L-lysine. This is a polyelectrolyte that is soluble in polar solvents (such as water). Physiologically acceptable salt and solution forms of epsilon-poly-L-lysine are also suitable for use in the hair care shampoos according to the invention.

[0027] Epsilon-poly-L-lysine is available by bacterial fermentation, for example from the strain Streptomyces albulus.

[0028] Due to its polycationic charge, epsilon-poly-L-lysine has a high affinity for hair, which has a negative net charge.

[0029] It has been found that epsilon-poly-L-lysine with a linear molecular structure and a specific degree of polymerization is particularly suitable for use in the hair care shampoos according to the invention.

[0030] Particularly suitable are compounds of the following formula in which n stands for integers from 2-50. More preferably, n represents integers from 10-40 and especially from 25-35.

[0031] Particularly suitable is epsilon-poly-L-lysine with a linear molecular structure and a specific average molecular weight in the range of 200 - 7,500 g / mol, more preferably 1,000 - 6,000 g / mol and in particular 3,500 - 5,500 g / mol.

[0032] Compared to polylysine with a dendritic structure, epsilon-poly-L-lysine, with its previously defined linear molecular structure, can deposit better on the hair fibers and even penetrate deeper into the cuticle and outer hair cortex. This not only achieves a smoothing, detangling, and conditioning effect on the outer hair fibers, but also, to a certain extent, repairs and / or strengthens the inner structure of the hair fiber.

[0033] Epsilon-polylysine, especially epsilon-poly-L-lysine, is preferably used in the hair care shampoos according to the invention within narrower quantity ranges. A particularly suitable amount of epsilon-poly-L-lysine (based on the total weight of the hair care shampoo) is 0.00005-0.5 wt.%, more preferably 0.0001-0.4 wt.%, particularly preferably 0.0005-0.3 wt.%, most preferably 0.001-0.25 wt.%, and especially 0.005-0.1 wt.%.

[0034] As a second essential ingredient, the hair care shampoos according to the invention contain - based on their total weight - 5.0 - 20.0 wt.% of at least one anionic surfactant.

[0035] All anionic surface-active substances suitable for cosmetic use on the human or animal body are suitable as anionic surfactants (or emulsifiers). These are characterized by a water-solubilizing anionic group, such as a carboxylate, sulfate, sulfonate, or phosphate group, and a lipophilic alkyl group with approximately 8 to 30 carbon atoms. Additionally, the molecule may contain glycol or polyglycol ether groups, ester, ether, and amide groups, as well as hydroxyl groups.

[0036] Suitable anionic surfactant types that can be used in the hair care shampoos according to the invention include, for example: - linear and branched fatty acids with 8 to 30 C atoms (soaps), - Ethercarboxylic acids of the formula RO-(CH2-CH2O) x -CH2-COOH, in which R is a linear or e, saturated or unsaturated alkyl group with 8 to 30 C atoms and x = 0 or 1 to 16, and their physiologically acceptable salts, - Acylsarcosides with 8 to 24 C atoms in the acyl group (sarcosinate surfactants), - Acyltaurides with 8 to 24 C atoms in the acyl group (taurate surfactants), - Acyl isethionates with 8 to 24 C atoms in the acyl group (isethionate surfactants), - Acylglutamates with 8 to 24 C atoms in the acyl group (glutamate surfactants) - sulfosuccinic acid mono- and / or dialkyl esters with 8 to 24 C atoms in the alkyl group and sulfosuccinic acid mono-alkylpolyoxyethyl esters with 8 to 24 C atoms in the alkyl group and 1 to 6 oxyethyl groups (sulfosuccinate surfactants), - Alpha-olefinsulfonates with 8 to 24 C atoms (alpha-olefinsulfonate surfactants), - Alkyl sulfates and / or alkyl ether sulfate salts of the formula R-(OCH2CH2) n -O-SO3X, in which R is preferably a straight-chain or saturated or unsaturated alkyl group having 8 to 30 C atoms, x is the number 0 or 1 to 12 and X is an alkali, alkaline earth, ammonium or alkanolamine ion, - Sulfonates of unsaturated fatty acids with 8 to 24 C atoms and 1 to 6 double bonds, - Esters of tartaric acid and citric acid with alcohols, which are addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 C atoms, and / or - Alkyl and / or alkenyl ether phosphates of the formula in which R 1 preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R 2 for hydrogen, a residue (CH2CH2O) n R 1 or X, n for numbers from 0 to 10 and X for hydrogen, an alkali or alkaline earth metal or the group - NR 3 R 4 R5 R 6 stands, with R 3 to R 6 independently of each other standing for a C1 to C4 hydrocarbon residue.

[0037] Preferred for use in the hair care shampoos according to the invention are physiologically acceptable salts of alkyl (ether) sulfates, ether carboxylic acids, sarcosinates, isethionates, taurates, sulfosuccinates, alpha-olefin sulfonates and mixtures thereof.

[0038] Particularly preferred are physiologically acceptable salts of alkyl (ether) sulfates and in particular alkyl (ether) sulfates of the general formula R-(OCH2CH2) n -OSO3X, in which R is a straight-chain or branched, saturated or unsaturated alkyl group having 8 to 24 C atoms, n is the number 0 or 1 to 12, and X is an alkali, alkaline earth, ammonium or alkanolamine ion.

[0039] The at least one anionic surfactant b), preferably at least one physiologically acceptable salt of alkyl (ether) sulfates, ether carboxylic acids, sarcosinates, isethionates, taurates, sulfosuccinates, alpha-olefin sulfonates, and particularly preferably at least one physiologically acceptable salt of alkyl (ether) sulfates, is used in the hair care shampoos according to the invention preferably within narrower quantity ranges. A particularly suitable amount of at least one anionic surfactant b) as defined above (based on the total weight of the hair care shampoo) is 6-17.5 wt.%, particularly preferably 7-15 wt.%.

[0040] The synergistic hair care effect of epsilon-polylysine and anionic surfactants in a cosmetic carrier - preferably containing predominantly water - is particularly significant when the hair care shampoo according to the invention has a pH in the range of preferably 2.5 - 7, more preferably 3 - 6 and in particular 3.5 - 5.5.

[0041] To adjust this pH, virtually any acid or base suitable for cosmetic purposes can be used. Typically, food acids are used. Food acids are those acids that are ingested as part of normal food intake and have positive effects on the human organism. Examples of food acids include acetic acid, lactic acid, tartaric acid, citric acid, malic acid, ascorbic acid, and gluconic acid. For the purposes of the invention, the use of citric acid and / or lactic acid is particularly preferred. Preferred bases are ammonia, alkali metal hydroxides, monoethanolamine, triethanolamine and N,N,N',N'-tetrakis-(2-hydroxypropyl)-ethylenediamine.

[0042] To improve the foaming properties and / or to improve the mildness, it may be advantageous if the hair care shampoos according to the invention contain, in addition to the at least one anionic surfactant b), 0 - 15%, particularly preferably 0.25 - 12.5% ​​and in particular 0.5 - 10% of at least one amphoteric or zwitterionic surfactant and / or one non-ionic surfactant (based on the total weight of the hair care shampoo).

[0043] Suitable zwitterionic or amphoteric surfactants carry both a cationic and an anionic charge in the molecule. Amphoteric surfactants preferably have at least one quaternary ammonium group and at least one -COO - - or -SO3 --group, in addition to a preferably C8-C24 alkyl or acyl group, in the molecule. Furthermore, they are capable of forming internal salts. Particularly preferred amphoteric surfactants are betaines such as N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acyl-aminopropyl-N,N-dimethylammonium glycinate, for example cocoacylaminopropyl dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines, each with 8 to 18 C atoms in the alkyl or acyl group, as well as cocoacylaminoethyl hydroxyethylcarboxymethylglycinate. Particularly preferred are the amphoteric or zwitterionic surfactants known under the INCI names Cocamidopropyl Betaine, Lauramidopropyl Betaine, Cocoampho(di)acetate and / or Lauroapho(di)acetate.

[0044] Suitable non-ionic surfactants and / or emulsifiers can be selected from amine oxides such as the compounds known under the INCI names Cocamine Oxide, Lauramine Oxide and Cocamidopropylamine Oxide, fatty acid alkanolamides such as the compounds known under the INCI names Cocamide MEA and Coamide DEA, mixtures of alkyl (oligo) glucosides and fatty alcohols such as the commercially available product Montanov ® 68, sterols such as zoosterols and phytosterols, phospholipids, alkyl (oligo)glycosides such as the compounds known under the INCI names Caprylyl / Capryl Glucoside, Decyl Glucoside, Lauryl Glucoside and Coco Glucoside, alkoxylated esters such as the compounds known under the INCI names PEG-7 Glyceryl Cocoate and PEG-40 Hydrogenated Castor, polyglycerol esters and / or their salts.

[0045] To further enhance the care properties, it may be advantageous to add at least one other hair care active ingredient, in addition to epsilon-polylysine a), to the hair care shampoos according to the invention in a proportion of 0.01-10 wt.% of the total weight of the hair care shampoo. Amounts used are more preferred, ranging from 0.05-7.5 wt.%, particularly preferably from 0.1-6 wt.%, and especially from 0.25-5 wt.%.

[0046] The at least one hair care active ingredient can preferably be selected from (I) Oils (II) Protein hydrolysates (III) Proteolipids (IV) Amino acids (V) Vitamins (VI) or mixtures thereof.

[0047] The addition of one or more hair care ingredients (I) to (V) to the hair care shampoos according to the invention offers the advantage that, depending on the type and amount of the hair care ingredient(s) (I) to (V), the visually and haptically perceptible external care effects of the hair fibers can be further enhanced. External care effects are understood to include, in particular, increased smoothness, shine, suppleness, volume, and easier combability.

[0048] Suitable oils (I) are understood to mean natural, mineral or synthetic oils, fats, waxes or mixtures thereof.

[0049] The group of suitable natural (vegetable) oils typically includes triglycerides and mixtures of triglycerides. Preferred natural oils are coconut oil, (sweet) almond oil, walnut oil, peach kernel oil, apricot kernel oil, avocado oil, tea tree oil, soybean oil, sesame oil, sunflower oil, tsubaki oil, evening primrose oil, rice bran oil, palm kernel oil, mango kernel oil, meadowfoam oil, safflower oil, macadamia nut oil, grape seed oil, amaranth seed oil, tamanu oil, perilla oil, argan oil, bamboo oil, olive oil, wheat germ oil, pumpkin seed oil, mallow oil, hazelnut oil, safflower oil, canola oil, sasanqua oil, jojoba oil, rambutan oil, cocoa butter, murumuru butter, and / or shea butter.

[0050] Mineral oils, paraffin and isoparaffin oils, and synthetic hydrocarbons are particularly used. An example of a suitable hydrocarbon is 1,3-di-(2-ethylhexyl)-cyclohexane (Cetiol), which is available as a commercial product. ®S) or mixtures of medium-chain alkanes (such as Cetiol ® Ultimate).

[0051] A dialkyl ether can also serve as a suitable oil component. Suitable dialkyl ethers include, in particular, 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-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 ether, as well as di-tert-butyl ether, diisopentyl ether, di-3-ethyldecyl ether, tert-butyl n-octyl ether, isopentyl n-octyl ether, and 2-methylpentyl n-octyl ether. Particularly preferred is the di-n-octyl ether, which is commercially available under the name Cetiol ® OE is available.

[0052] Silicone compounds may also be considered as synthetic oils. Suitable silicones can be selected from: (i) polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, which are volatile or non-volatile, straight-chain or cyclic, branched or unbranched; (ii) polysiloxanes containing in their general structure one or more organofunctional groups selected from: a) substituted or unsubstituted aminated groups; b) (perfluorinated groups; c) thiol groups; d) carboxylate groups; e) hydroxylated groups; f) alkoxylated groups; g) acyloxyalkyl groups; h) amphoteric groups; i) bisulfite groups; j) hydroxyacylamino groups; k) carboxy groups; l) sulfonic acid groups; and m) sulfate or thiosulfate groups; (iii) linear polysiloxane(A)-polyoxyalkylene(B) block copolymers of type (AB) n with n > 3; (iv) grafted silicone polymers with a non-silicone-containing organic backbone consisting of an organic main chain formed from organic monomers not containing silicone, to which at least one polysiloxane macromer has been grafted in the chain and optionally at at least one chain end; (v) grafted silicone polymers with a polysiloxane backbone to which non-silicone-containing organic monomers have been grafted, comprising a polysiloxane main chain to which at least one organic macromer not containing silicone has been grafted in the chain and optionally at at least one of its ends; (vi) or mixtures thereof.

[0053] Fats include fatty acids, fatty alcohols and natural and synthetic waxes, which can be in solid form or liquid in aqueous dispersion.

[0054] Fatty acids that can be used are linear and / or branched, saturated and / or unsaturated fatty acids with 6-30 carbon atoms, preferably with 10-22 carbon atoms. Fatty alcohols that can be used are saturated, mono- or polyunsaturated, e or unbranched fatty alcohols with C6-C 30 -, preferably C 10 - C 22 - and especially preferably C 12 - C 22 - carbon atoms.

[0055] Natural or synthetic waxes that can be used include solid paraffins or isoparaffins, carnauba waxes, beeswaxes, candelilla waxes, ozokerites, ceresin, spermaceti, sunflower wax, hardened waxes such as hydrogenated castor oil, fruit waxes such as apple wax or citrus wax, and microwaxes made of PE or PP.

[0056] Other suitable fatty substances include - Ester oils, including esters of C6 - C 30 - Fatty acids with C2 - C 30- fatty alcohols. Examples of particularly suitable ester oils are isopropyl myristate (Rilanit ® IPM), isononanoic acid C16-18 alkyl ester (cetiol ® SN), 2-ethylhexyl palmitate (Cegesoft ® 24), 2-ethylhexyl stearate (Cetiol ® 868), cetyl palmitate, cetyl oleate, glycerol tricaprylate, coconut fatty alcohol caprinate / caprylate (cetiol ® LC), n-butyl stearate, oleyl rucate (cetiol ® J 600), isopropyl palmitate (Rilanit ® IPP), Oleyl Oleate (Cetiol ® ), lauric acid hexyl ester (Cetiol ® A), Di-n-butyl adipate (Cetiol ® B), myristyl myristate (Cetiol ® MM), Cetearyl Isononanoate (Cetiol ® SN), oleic acid decyl ester (Cetiol ® V) - Dicarboxylic acid esters such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, di-(2-ethylhexyl) succinate and di-isotridecyl acelate as well as diol esters such as ethylene glycol dioleate, ethylene glycol di-isotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate, neopentyl glycol dicaprylate, symmetrical, asymmetrical or cyclic esters of carbonic acid with fatty alcohols such as glycerol carbonate or dicaprylyl carbonate (Cetiol ® CC) - ethoxylated or non-ethoxylated mono-, di- and trifatty acid esters of saturated and / or unsaturated linear and / or ene fatty acids with glycerol, such as monomuls ® 90-018, Monomuls ® 90-L12, Cetiol ® HE or Cutina ® MD.

[0057] The weight proportion of oils, fats and / or waxes in the total weight of the hair care shampoos can be 0 to 10 wt.%, preferably 0.01 to 7.5 wt.% and in particular 0.05 to 5 wt.%.

[0058] Hair care shampoos according to the invention preferably contain essentially no silicones. "Essentially no" in this context is to be understood in the same way as previously described.

[0059] For the purposes of the present invention, protein hydrolysates (II) are understood to be degradation products of proteins produced by acidic, basic, or enzymatic reactions. Due to the production process, protein hydrolysates exhibit a molecular weight distribution.

[0060] Suitable protein hydrolysates (II) can be of plant, animal, marine or synthetic origin.

[0061] Preferred protein hydrolysates of plant origin can be selected from the group consisting of soy, almond, pea, moringa, potato, and wheat protein hydrolysates. Such products are available, for example, under the trademarks Gluadin® (Cognis), DiaMin® (Diamalt), Lexein® (Inolex), Hydrosoy® (Croda), Hydrolupin® (Croda), Hydrosesame® (Croda), Hydrotritium® (Croda), Crotein® (Croda), and Puricare® LS 9658 from Laboratoires Serobiologiques.

[0062] Preferred protein hydrolysates of animal origin can be selected from the group consisting of elastin, collagen, keratin, silk, and milk protein hydrolysates, which can also be present in the form of salts. Such products are marketed, for example, under the trademarks Dehylan® (Cognis), Promois® (Interorgana), Collapuron® (Cognis), Nutrilan® (Cognis), Gelita-Sol® (Deutsche Gelatine Fabriken Stoess & Co), Lexein® (Inolex), ProSina® (Croda), and Kerasol® (Croda).

[0063] Preferred protein hydrolysates of marine origin can be selected from the group consisting of collagen hydrolysates from fish or algae, protein hydrolysates from mussels, and pearl hydrolysates. Examples of pearl extracts are the commercial products Pearl Protein Extract BG® or Crodarom® Pearl.

[0064] Particularly preferred protein hydrolysates (II) are - Hydrolyzed keratin, - Hydrolyzed collagen, - Hydrolyzed silk protein, - Hydrolyzed cashmere protein, - Hydrolyzed wheat protein, - Hydrolyzed soy protein, - Hydrolyzed pea protein, - Hydrolyzed hemp seed protein, - Hydrolyzed cottonseed protein, - Hydrolyzed rice protein.

[0065] Furthermore, cationized protein hydrolysates within the meaning of the present invention are to be counted among the protein hydrolysates (II), wherein the underlying protein hydrolysate originates from the same sources as previously stated.

[0066] The weight proportion of protein hydrolysates (II) in the total weight of the hair care shampoo according to the invention can be 0 to 5 wt.%, preferably 0.01 to 3 wt.% and in particular 0.01 to 2.5 wt.%.

[0067] For the purposes of the present invention, proteolipids (III) are understood to mean compounds of the general formulas (1) or (2), R'-X-R'' Formula (1) [R'-X-R''] + Z - Formula (2) where - R' represents a straight-chain or branched, saturated or unsaturated functional hydrocarbon group having 8 to 24 carbon atoms (including mixtures of such R' groups as are found, for example, in natural products such as coconut oil). - R'' represents a protein, a peptide or a protein hydrolysate, - Z - is a physiologically acceptable anion - X -C(O)O- or -N'(R III 2)-R IV - or -N(R III )R IV - or -C(O)-N(R V )R VI represents, - R III -(CH2) x -CH3, where x is 0-22, and - R IV -CH2-CH(OH)-CH2- or -(CH2) x - optionally substituted with one or more -OH groups, where x = 0-22; - R v and R VI independently -H or -(CH2) x-CH3, where x = 0-22;with the proviso that R'' represents keratin or a keratin hydrolysate when X represents -C(O)O-.

[0068] If X is -C(O)O- or -N(R III )R IV - or -C(O)-N(R V )R VI the compound is uncharged and formula (II) applies. If X -N + (R III 2)-R IV -, i.e., the nitrogen is quaternized, a counterion is present and formula (III) applies. The counterion is any suitable physiologically acceptable anion, such as a halide. A preferred cation is chloride.

[0069] More suitably, the or each proteolipid has the formula (IVA):where - R', R III , R'' and Z are as previously defined, - m = 1 to 10, and - Y stands for -H or -OH.

[0070] R'' can be a protein. Alternatively, R'' can be a peptide. R'' can also be a protein hydrolysate. Preferably, R'' is a protein hydrolysate. Such a protein hydrolysate can be keratin-based, i.e., a keratin hydrolysate. Alternatively, R'' can be a plant-based hydrolysate.

[0071] Preferred examples of proteolipids (III) include: - Hydrolyzed steardimonium hydroxypropyl keratin, - Hydrolyzed steardimonium hydroxypropyl collagen, - Hydrolyzed steardimonium hydroxypropyl silk protein, - Hydrolyzed steardimonium hydroxypropyl cashmere protein, - Hydrolyzed steardimonium hydroxypropyl rice protein, - Hydrolyzed steardimonium hydroxypropyl wheat protein, - Hydrolyzed steardimonium hydroxypropyl soy protein, - Hydrolyzed steardimonium hydroxypropyl pea protein, - Hydrolyzed steardimonium hydroxypropyl cottonseed protein, - Hydrolyzed steardimonium hydroxypropyl hemp seed protein, - Hydrolyzed cocodimonium hydroxypropyl keratin, - Hydrolyzed Cocodimonium hydroxypropyl collagen, - Hydrolyzed cocodimonium hydroxypropyl silk protein, - Hydrolyzed cocodimonium hydroxypropyl cashmere protein, - Hydrolyzed cocodimonium hydroxypropyl rice protein, - Hydrolyzed cocodimonium hydroxypropyl soy protein, - Hydrolyzed cocodimonium hydroxypropyl wheat protein, - Hydrolyzed cocodimonium hydroxypropyl pea protein - Hydrolyzed cocodimonium hydroxypropyl cottonseed protein, - Hydrolyzed cocodimonium hydroxypropyl hemp seed protein,

[0072] The weight proportion of proteolipids (III) in the total weight of the hair care shampoo according to the invention can be 0 to 7.5 wt.%, particularly preferably 0.01 to 5 wt.% and in particular 0.01 to 2.5 wt.%.

[0073] Amino acids (IV) within the meaning of the present invention are amino acids as well as physiologically acceptable salts, esters, or acyl derivatives of amino acids. Preferably, (IV) is an amino acid or an amino acid salt. Preferred amino acids (IV) within the meaning of the present invention are alanine, arginine, asparagine, aspartic acid, creatine, cysteic acid, cysteine, cystine, glutamic acid, glutamine, glycine, histidine, hydroxyproline, isoleucine, leucine, lysine, methionine, norleucine, ornithine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, and mixtures and physiologically acceptable salt forms thereof. Aspartic acid, glutamic acid, glycine, serine, valine, and mixtures and physiologically acceptable salt forms thereof are particularly preferred. Aspartic acid, glutamic acid, and mixtures and physiologically acceptable salt forms thereof may be particularly preferred.

[0074] The weight proportion of amino acids (IV) in the total weight of the hair care shampoo according to the invention can be 0 to 7.5 wt.%, particularly preferably 0.01 to 5 wt.% and in particular 0.01 to 2.5 wt.%.

[0075] Suitable vitamins (V) are understood to mean vitamins, provitamins and vitamin precursors as well as their derivatives from groups A, B, C, E, F and H. ➣ The group of substances referred to as vitamin A includes retinol (vitamin A1) and 3,4-didehydroretinol (vitamin A2). Beta-carotene is the provitamin of retinol. Examples of vitamin A components include vitamin A acid and its esters, vitamin A aldehyde, and vitamin A alcohol and its esters, such as palmitate and acetate. The vitamin A component can preferably be present in cosmetic compositions in amounts of 0.005–1% by weight, based on the total composition. ➣ The vitamin B group or vitamin B complex includes, among others: ◯ Vitamin B1 (thiamine) ◯ Vitamin B2 (riboflavin) ◯ Vitamin B3. The compounds nicotinic acid and nicotinamide (niacinamide) are often listed under this name. Nicotinamide is preferred and can be present in cosmetic compositions preferably in amounts of 0.005 to 1% by weight, based on the total composition. ◯ Vitamin B5 (pantothenic acid, panthenol, and pantolactone). Within this group, panthenol and / or pantolactone are preferred. Suitable panthenol derivatives include, in particular, panthenol esters and ethers, as well as cationically derivatized panthenols. Examples include panthenol triacetate, panthenol monoethyl ether and its monoacetate, and cationic panthenol derivatives. The vitamin B5-type compounds mentioned can be present in cosmetic compositions, preferably in amounts of 0.05–5% by weight, based on the total composition. Amounts of 0.1–2% by weight are particularly preferred. ◯ Vitamin B6 (pyridoxine as well as pyridoxamine and pyridoxal) ◯ Vitamin B7 - cf. Vitamin H. ➣ Vitamin C (ascorbic acid). Vitamin C can preferably be used in cosmetic compositions in amounts of 0.01 to 3% by weight, based on the total composition. Use in the form of the palmitic acid ester, glucosides, or phosphates may be preferred. Use in combination with tocopherols may also be preferred. ➣ Vitamin E (tocopherols, especially α-tocopherol). Tocopherol and its derivatives, including in particular esters such as acetate, nicotinate, phosphate, and succinate, can be present in cosmetic compositions preferably in amounts of 0.005-1% by weight, based on the total composition. ➣ Vitamin F. The term “vitamin F” usually refers to essential fatty acids, especially linoleic acid, linolenic acid and arachidonic acid. ➣ Vitamin H. The compound (3aS,4S,6aR)-2-oxohexahydrothienol[3,4-d]imidazole-4-valeric acid is known as vitamin H, but the common name biotin has since become established. Biotin can be present in cosmetic compositions preferably in amounts of 0.0001 to 1.0% by weight, especially in amounts of 0.001 to 0.01% by weight.

[0076] The hair care shampoos according to the invention can particularly preferably contain vitamins, provitamins, and vitamin precursors from groups A, B, E, and H. Panthenol, pantolactone, nicotinamide, and vitamin E acetate are particularly preferred and can be added to the hair care shampoos both individually and in combination in the aforementioned amounts.

[0077] In addition to the previously described care effects on the outer hair fibers, a repair effect or strengthening of the inner hair fibers can also be achieved or enhanced if, in addition to epsilon-polylysine a), at least one further repair agent is added to the hair care shampoos according to the invention in a proportion of 0.01 to 10% by weight based on the total weight of the hair care shampoo. Amounts used are more preferred, ranging from 0.05 to 7.5% by weight, particularly preferably from 0.1 to 6% by weight, and especially from 0.25 to 5% by weight.

[0078] The at least one repair agent for hair fibers can preferably be selected from (i) a mixture of hydroxypropylgluconamide and hydroxypropylammonium gluconate (ii) alpha-hydroxyoctanal or alpha-hydroxyoctanone (iii) a mixture of succinic acid and citric acid (iv) Lanthanum chloride (v) any mixtures of (i) - (iv).

[0079] Under (i) are preferably understood compounds of the following formulas a. and b. in which - R1-R4 are independently hydrogen, a hydrocarbon radical having 1 to 10 carbon atoms, a hydroxyl group, an amino group, a sulfhydryl group, an aryl group or a halogen, and R5 and R6 are independently hydrogen, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aryl group, an alkylaryl group or a heterocyclic group; and - R1'-R4' are independently hydrogen, a hydrocarbon radical having 1 to 10 carbon atoms, a hydroxyl group, an amino group, a sulfhydryl group, an aryl group or a halogen, and R5 and R6 are independently hydrogen, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aryl group or a heterocyclic group, excluding R5' and R6' being simultaneously hydrogen, - the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, the aryl group, the alkylaryl group or the heterocyclic group are substituted by at least one hydroxyl group.

[0080] Suitable compounds of formulas a. and b. are known as mixtures. One possible way of preparing them is disclosed, for example, in patent application US 2017 / 0007518. Preferably, at least one compound of formula a. and at least one compound of formula b. are varied in a molar ratio of 0.1:1 to 99.9:1, more preferably 1:99 to 99:1, particularly preferably 20:80 to 80:20. Most preferably, the molar ratio of compounds of formula a. to compounds of formula b. is 40:60 to 60:40.

[0081] A mixture of hydroxypropylgluconamide and hydroxypropylammonium gluconate in the aforementioned molar ratios is very particularly preferably used in the hair care shampoos according to the invention.

[0082] Such mixtures are available commercially, for example, from Ashland under the trade name Fiberhance ® bm available.

[0083] Under (ii) are preferably understood compounds of the following formula c. R 7 -C(O)-CH(X)-R 8 Formula c. wherein - one of the residues R 7 or R 8 represents H and the other represents a straight-chain or branched, saturated or unsaturated alkyl group having 1 to 15 carbon atoms, where the carbon chain may optionally be substituted by one or more hydroxyl or amino groups, and - X stands for -OH, -NH2, -Cl, -Br, -I or for the following groups: -O-(CH2) n-CH3, where n is 1, 2, 3 or 4, and -O-(CH2) m -OH, where m is the number 1, 2 or 3.

[0084] In particularly suitable compounds according to formula c., one of the radicals R 7 , R 8 represents H and the other represents a saturated alkyl group having 1 to 15 carbon atoms. Particularly preferred compounds of formula (III) are those in which one of the radicals R 7 , R 8 for H and the other for a group -(CH2) o -CH3, where o represents the numbers 3, 4, 5, 6, 7, 8, 9 or 10. Most preferably, one of the residues R 7 or R 8 for H and the other for a butyl, pentyl, hexyl, heptyl or octyl group, in particular a hexyl group.

[0085] Also preferred are alpha-substituted compounds according to formula c., in which the substituent X represents a hydroxyl or an amino group. Particularly preferably, X represents a hydroxyl group.

[0086] Particularly preferred are alpha-substituted compounds of the general formula c., in which • one of the residues R 7 , R 8 for H or for a group -(CH2) o -CH3, where o stands for the numbers 3, 4, 5, 6, 7, 8, 9 or 10, and • X represents a hydroxyl group.

[0087] Very particular preference is given to alpha-substituted compounds of general formula c, which are selected from alpha-hydroxybutanal, alpha-hydroxypentanal, alpha-hydroxyhexanal, alpha-hydroxyheptanal, alpha-hydroxyoctanal, alpha-hydroxybutanone, alpha-hydroxypentanone, alpha-hydroxyhexanone, alpha-hydroxyheptanone, alpha-hydroxyoctanone, or mixtures thereof. Alpha-hydroxyoctanal, alpha-hydroxyoctanone, or mixtures thereof are particularly preferred.

[0088] In addition to the active ingredients described above, the hair care shampoos according to the invention may further contain one or more active ingredients from one or more of the following groups: - Dyes, including both dyes for coloring the compositions and dyes for coloring hair, including oxidation dye precursors, direct dyes, natural dyes and mixtures thereof, and optionally oxidizing and alkalizing agents, - UV filter substances - Perfumes - natural thickeners such as cellulose, starch, xanthan gum, sclerotium gum, succinoglucan, polygalactomannan, pectin, agar, carrageenan, tragacanth, gum arabic, karaya gum, tara gum, gellan, gelatin, alginic acids and their salts - Complexing agents such as EDTA - Anti-dandruff agents such as Piroctone Olamine, Zinc Pyrithione, Climbazole, Propanediol Caprylate - Pearlescent agents and / or opacifiers - Keratin-reducing agents such as mercaptans, thioglycolate salts, if necessary in combination with ammonia or amines - Ceramide - Propellant - Preservatives.

[0089] The first and second subject matter of the invention as well as particularly preferred embodiments are characterized by the following statements: 1. Hair care shampoo containing in a cosmetic carrier - based on the total weight of the hair care shampoo - a) 0.00001 - 1.0% by weight of epsilon polylysine b) 5.0 - 20 wt.% of at least one anionic surfactant, characterized in that the hair care shampoo is substantially free of chemically modified polymers. 2. Hair care shampoo according to claim 1, which is essentially free of cationic polymers and / or polymers comprising (meth)acrylic units. 3. Hair care shampoo according to one of the preceding statements, wherein the epsilon-polylysine a) has a linear molecular structure. 4. Hair care shampoo according to one of the preceding statements, wherein the epsilon-polylysine a) is selected from epsilon-poly-L-lysine with a linear molecular structure comprising 2 to 50 lysine units. 5. Hair care shampoo according to one of the preceding statements, wherein the epsilon-polylysine a) is selected from epsilon-poly-L-lysine with a linear molecular structure comprising 10 to 40 lysine units. 6. Hair care shampoo according to one of the preceding statements, wherein the epsilon-polylysine a) is selected from epsilon-poly-L-lysine with a linear molecular structure comprising 25 to 35 lysine units. 7. Hair care shampoo according to one of the preceding statements, wherein the epsilon-polylysine a) has an average molecular weight in the range of 200 - 7,500 g / mol. 8. Hair care shampoo according to one of the preceding statements, wherein the epsilon-polylysine a) has an average molecular weight in the range of 1,000 - 6,000 g / mol. 9. Hair care shampoo according to one of the preceding statements, wherein the epsilon-polylysine a) has an average molecular weight in the range of 3,500 - 5,500 g / mol. 10. Hair care shampoo according to one of the preceding statements, containing epsilon-polylysine a) in a weight proportion of 0.00005 - 0.5 wt.% of the total weight of the hair care shampoo. 11. Hair care shampoo according to one of the preceding statements, containing epsilon-polylysine a) in a weight proportion of 0.0001 - 0.4 wt.% of the total weight of the hair care shampoo. 12. Hair care shampoo according to one of the preceding statements, containing epsilon-polylysine a) in a weight proportion of 0.0005 - 0.3 wt.% of the total weight of the hair care shampoo. 13. Hair care shampoo according to one of the preceding statements, containing epsilon-polylysine a) in a weight proportion of 0.001 - 0.25 wt.% of the total weight of the hair care shampoo. 14. Hair care shampoo according to one of the preceding statements, containing epsilon-polylysine a) in a weight proportion of 0.005 - 0.1 wt.% of the total weight of the hair care shampoo. 15. Hair care shampoo according to one of the preceding statements, wherein the at least one anionic surfactant b) is selected from physiologically acceptable salts of alkyl (ether) sulfates, ether carboxylic acids, sarcosinates, isethionates, taurates, sulfosuccinates, alpha-olefin sulfonates and mixtures thereof. 16. Hair care shampoo according to one of the preceding statements, wherein the at least one anionic surfactant b) is selected from physiologically acceptable salts of alkyl (ether) sulfates. 17. Hair care shampoo according to one of the preceding statements, containing the at least one anionic surfactant b) in a weight proportion of 6 - 17.5 wt.% of the total weight of the hair care shampoo. 18. Hair care shampoo according to one of the preceding statements, containing the at least one anionic surfactant b) in a weight proportion of 7 - 15 wt.% of the total weight of the hair care shampoo. 19. Hair care shampoo according to any of the preceding statements, which has a pH value in the range of 2.5 - 7. 20. Hair care shampoo according to any of the preceding statements, which has a pH value in the range of 3 - 6. 21. Hair care shampoo according to any of the preceding statements, which has a pH value in the range of 3.5 - 5.5. 22. Hair care shampoo according to one of the preceding statements, containing - based on its total weight - 0.01 to 10 wt.% of at least one further hair care active ingredient other than a), selected from the group of (I) Oils (II) Protein hydrolysates (III) Proteolipids (IV) Amino acids (V) Vitamins (VI) or any mixtures of (I) to (V). 23. Hair care shampoo according to one of the preceding statements, containing - based on its total weight - 0.01 to 10 wt.% of at least one repair agent for hair fibers, selected from (i) a mixture of hydroxypropylgluconamide and hydroxypropylammonium gluconate (ii) alpha-hydroxyoctanal or alpha-hydroxyoctanone (iii) a mixture of succinic acid and citric acid (iv) Lanthanum chloride (v) any mixtures of (i) - (iv). 24. Using a hair care shampoo according to any of the preceding statements to cleanse and condition hair. 25. Use according to claim 25 to improve detangling, combability, smoothness, shine, volume and the sensory properties of hair.

[0090] With regard to preferred embodiments of the use according to the invention, what has been said regarding the composition according to the invention applies mutatis mutandis. Examples:Examples1) Examples of implementation

[0091] The following hair care shampoos were prepared. The quantities given are by weight unless otherwise stated. Hair care shampoos: 1 2 3 4 Epsilon-Poly-L-Lysine* 0,00001 - 1,0 0,0005 - 0,3 0,02 0,06 anionic surfactant 5,0 - 20 7 - 15 Sodium Laureth Sulfate 10 Ammonium Lauryl Sulfate 2 7,5 amphoteric surfactant 0-15 0,25 - 12,5 Cocoamidopropyl Betaine 4 Disodium Cocoamphodiacetate 4 non-ionic surfactant 0-15 0,25 - 12,5 Cocamide MEA 0,8 PEG-7 Glyceryl Cocoate 1 Laureth-2 1,2 Coco Glucoside 3,5 Hair care ingredient 0,01 - 10 Hydrolyzed Keratin 0,3 Hydrolyzed Wheat Protein 0,3 Glycine 0,3 Panthenol 0,5 Niacinamide 0,1 Dimethicone 0,3 Lactic Acid 0,5 Citric Acid 0,8 Sodium Chloride 1,3 1,3 alpha-hydroxyoctanal and / or alpha-hydroxyoctanone 0,01 - 10 Lanthanium Chloride 0,4 Water and, if necessary, other excipients and active ingredients to 100 to 100 to 100 to 100 * with a linear molecular structure and 25 to 35 lysine units 2) Evidence of effectivenessa) Wet combability measurements

[0092] To determine wet combability, the effort required to comb wet hair strands was measured. The hair strands were treated with a medium bleaching agent and then combed while wet. The combing forces applied were recorded. After the baseline measurement, the hair strands were treated with the respective test formulation (see Table 1) (10 minutes, 0.5 g of the respective formulation per g of hair), and then each hair strand was rinsed with 1 liter of water (38°C) for 1 minute.

[0093] The measured values ​​of an untreated strand of hair were compared with those of a strand treated as described.

[0094] The following table shows that the compositions according to the invention significantly improve wet combability.

[0095] Work required for wet combability on medium-bleached hair compared to medium-bleached hair treated with different formulations* 1 2 3 4 5 6 7 average work [mJ] 92.6 97.9 67.0 75.7 78.1 81.2 83.4 * All tested formulations 2-7 are essentially based on the above-mentioned formulation 3. The measurement under "1" was carried out with medium-bleached and untreated hair strands. However, reference shampoo 2 contains neither epsilon-poly-L-lysine nor a cationic polymer; the inventive formulations 3-6 comprise varying amounts of epsilon-poly-L-lysine (3: 0.08 wt.%; 4: 0.15 wt.%; 5: 0.5 wt.%; 6: 1 wt.%), and formulation 7 comprises 0.2 wt.% of the cationic polymer Jaguar. ® Excel (Guar Hydroxypropyltrimonium Chloride).

[0096] Surprisingly, the above results could not be obtained from aqueous solutions containing epsilon-poly-L-lysine or from surfactant solutions containing no or only small amounts (< 5 wt%) of anionic surfactants.

[0097] Furthermore, it was surprising that even with extremely low amounts of epsilon-poly-L-lysine, significantly better wet combability could be achieved than with the formulation containing a cationic polymer (cf. in particular formulations 3, 7). b) Sensory test

[0098] In a second test, 13 trained individuals evaluated prepared hair strands under standardized conditions (white light + additional spotlight at 21°C and approximately 25% relative humidity). An untreated calibration hair strand served as a reference (one strand per condition / treatment, but each strand was randomly evaluated twice by each individual (evaluation was performed on two different days) – a completely randomized study design. Each product (see below) was tested on one strand of hair; all strands had previously been ultra-bleached.

[0099] The tested products were, as described under a), a reference shampoo, to which 0.08 wt.% epsilon-poly-L-lysine was added in one test and 0.5 wt.% epsilon-poly-L-lysine in another test. The second comparison shampoo corresponds to the reference shampoo, to which 0.2 wt.% of the cationic polymer Jaguar was added instead of epsilon-poly-L-lysine. ® Excel (Guar Hydroxypropyltrimonium Chloride) was added.

[0100] The significantly best properties in terms of shine, softness, smoothness were achieved with the composition containing 0.08 wt% epsilon-poly-L-lysine - ahead of the composition containing 0.5 wt% epsilon-poly-L-lysine and the composition containing Jaguar ® Excel (Guar Hydroxypropyltrimonium Chloride). QUOTES CONTAINED IN THE DESCRIPTION

[0000] This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Cited patent literature

[0000] DE 102011079536

[0012] DE 102011079540

[0012] DE 102011077067

[0012] US 2017 / 0007518

[0080]

Claims

[1] Hair care shampoo containing in a cosmetic carrier - based on the total weight of the hair care shampoo - a) 0.00001 - 1.0% by weight of epsilon polylysine b) 5.0 - 20 wt.% of at least one anionic surfactant, characterized by that the hair care shampoo is essentially free of chemically modified polymers. [2] Hair care shampoo according to claim 1, which is substantially free of cationic polymers and / or polymers comprising (meth)acrylic units. [3] Hair care shampoo according to one of the preceding claims, wherein the epsilon-polylysine a) has a linear molecular structure. [4] Hair care shampoo according to one of the preceding claims, wherein the epsilon-polylysine a) is selected from epsilon-poly-L-lysine with a linear molecular structure comprising 2 to 50 lysine units. [5] Hair care shampoo according to one of the preceding claims, wherein the epsilon-polylysine a) has an average molecular weight in the range of 200 - 7,500 g / mol. [6] Hair care shampoo according to one of the preceding claims, wherein the at least one anionic surfactant b) is selected from physiologically acceptable salts of alkyl (ether) sulfates, ether carboxylic acids, sarcosinates, isethionates, taurates, sulfosuccinates, alpha-olefin sulfonates and mixtures thereof. [7] Hair care shampoo according to one of the preceding claims, which has a pH in the range of 2.5 - 7. [8] Hair care shampoo according to one of the preceding claims, containing - based on its total weight - 0.01 to 10 wt.% of at least one further hair care active ingredient different from a), selected from the group of (I) Oils (II) Protein hydrolysates (III) Proteolipids (IV) Amino acids (V) Vitamins (VI) or any mixtures of (I) - (V). [9] Hair care shampoo according to one of the preceding claims, containing - based on its total weight - 0.01 to 10 wt.% of at least one repair agent for hair fibers, selected from (i) a mixture of hydroxypropylgluconamide and hydroxypropylammonium gluconate (ii) alpha-hydroxyoctanal or alpha-hydroxyoctanone (iii) a mixture of succinic acid and citric acid (iv) Lanthanum chloride (v) any mixtures of (i) to (iv). [10] Use of a hair care shampoo according to any one of claims 1 to 9 for improving the detangling, combability, smoothness and sensory properties of hair.