WO2022233478A1

WO2022233478A1 - Protection of hair against environmental influence with a phenol and multivalent cations

Info

Publication number: WO2022233478A1
Application number: PCT/EP2022/055961
Authority: WO
Inventors: Katharina Madita BODE; Volker Scheunemann; Camille Grosjacques
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2021-05-05
Filing date: 2022-03-09
Publication date: 2022-11-10
Also published as: DE102021111719A1

Abstract

The invention relates to cosmetic agents for treating a keratin material, comprising a) 0.001 to 20 wt% of an inorganic and/or organic salt comprising a multivalent cation and b) 0.001 to 10 wt% hydroxytyrosol, the pH value of the cosmetic agent being pH 1 to pH 7. The invention also relates to a method in which the cosmetic agent according to the invention is used and to the use of the cosmetic agent according to the invention.

Description

"Preservation of the hair structure against environmental influences comprising a phenol and multivalent ions"

The invention relates to cosmetic agents, in particular shampoos and conditioners, with a combination of active ingredients for gentle and effective cleaning or care of the hair.

The structure of human hair is influenced by external and internal factors. External factors include, in particular, the use of care products, especially the frequency and intensity of hair washing, chemical and environmental influences (tinting, coloring, hair bleaching, permanent or temporary hair shaping, chlorinated water in swimming pools, various types of environmental toxins, etc.), mechanical influences (strong drafts e.g. by shaping the hair) and thermal influences (hot blow-drying, permanent waves or the influence of ultraviolet light e.g. by exposure to the sun). The internal factors include a balanced diet rich in vitamins, drinking enough fluids or taking medication, if necessary.

In order to compensate for structural damage to the hair, it has long been customary to subject hair to an after-treatment using care products. Such care products affect the natural structure and properties of the hair. For example, following after-treatments, the wet and dry combability of the hair, the hold and fullness of the hair can be optimized or the hair can be protected from increased split ends.

During the treatment, the hair is usually treated with special active substances, for example antioxidants. Depending on the formulation, the treatment improves the combability, hold and fullness of the hair and reduces damage, the rate of split ends and brittleness.

Multifunctional cosmetic products containing care products are known in the prior art. These multifunctional cosmetic products include, in particular, the so-called "2 in 1" shampoos, which not only clean the hair, but also condition it. Such products are highly valued by consumers because their product performance means that they have at least one process step, for example conditioning with a classic hair conditioner, are superfluous.These cosmetic products are often provided primarily as cleaning agents, but they also have a care effect and reduce structural damage.

However, sustainably reducing or preventing hair damage remains a challenge. One problem is that many antioxidants are not stable in water-based products. Nor can they be combined with multivalent salts in such a way that a synergistic effect is achieved. Restoring the hair structure after damage is also important. The common term for restoring or improving the hair structure is the "repair effect". The lasting success of the repair effect is still a challenge in the development of cosmetic products. Both the repair effect and the protective effect are not ideal in the case of cosmetic compositions in the prior art due to the instability of the antioxidants.

The object on which the invention is based is to provide a cosmetic agent which prevents or reduces a damaging effect on keratinic fibers. Furthermore, the object on which the invention is based is to provide a cosmetic agent which has a repairing effect on keratinic fibers.

The object on which the invention is based is achieved by the subject matter of claim 1. A first subject matter of the invention is therefore a cosmetic agent for the treatment of a keratin material, in particular for the treatment of human hair, comprising a) 0.001 to 10% by weight of an organic and /or inorganic salt, based on the total weight of the cosmetic agent, comprising a polyvalent cation, preferably a divalent or trivalent cation, more preferably a trivalent cation, and b) 0.001 to 10% by weight of hydroxytyrosol, based on the total weight of the cosmetic agent , wherein the pH of the cosmetic agent is between pH 1 and pH 7.

The combination of the organic or inorganic salt and hydroxytyrosol protects the hair from damage and has a repairing effect. In particular, the combination of the antioxidant and the organic or inorganic salt protects against structural damage from chemical treatment and environmental stress such as UV light exposure. A synergistic repair effect is achieved. With the organic or inorganic salt in combination with the antioxidant it is possible to strengthen the hair structure.

In the context of the present invention, “keratinic material” should be understood to mean, in particular, human hair. A multivalent cation is understood to mean a cation that has more than a single positive formal charge.

Hydroxytyrosol is a phenolic acid also known as 2-(3,4-dihydroxyphenyl)ethanol.

When the terms "inorganic salt", "organic salt", "inorganic and organic salt" or "inorganic or organic salt" are used in the context of the present invention, the terms refer to the salts comprising the multivalent cation. According to the present invention, the salt may be either an inorganic salt or an organic salt, or both an inorganic salt and an organic salt are used. According to a preferred embodiment, the organic and/or inorganic salt comprises a multivalent cation selected from the group consisting of an alkaline earth metal cation, the trivalent aluminum cation and the trivalent lanthanum cation, the counter ion of the multivalent cation being a cosmetically acceptable anion. The preferred alkaline earth metal cations are magnesium and calcium.

According to further preferred embodiments, the multivalent cation is a trivalent cation selected from the group consisting of La(III), Al(III), Bi(III), Ce(III), Ga(III) and Fe(III).

The cosmetically acceptable anion is preferably selected from the group consisting of hydroxide, halide, more preferably chloride or bromide; the anion of a carboxylic acid; the anion of a hydroxycarboxylic acid, more preferably lactate, citrate, or tartrate; the anion of an amino acid, more preferably glycinate; the anion of a dicarboxylic acid; and the anion of a tricarboxylic acid, more preferably citrate. It is also preferred that the organic and/or inorganic salt is a mixture of the aforesaid polyvalent cations and aforesaid counter ions, or is a hydrate of the aforesaid organic and/or inorganic salts.

According to preferred embodiments, the inorganic salt is selected from the group consisting of aluminum lactate, aluminum chloride hexahydrate, lanthanum chloride, lanthanum chloride heptahydrate, calcium hydroxide, magnesium hydroxide, calcium chloride, and magnesium chloride, or the organic salt is trimagnesium citrate. Further preferred embodiments relate to cosmetic agents in which the inorganic salt is selected from the group consisting of BiCb, AlCb, GaCb, CeCl3 and FeCb. The most preferred organic and/or inorganic salt is selected from the group consisting of aluminum lactate and lanthanum chloride.

According to preferred embodiments of the present invention, the cosmetic agent comprises 0.01 to 8% by weight, preferably 0.05 to 5% by weight, of the organic and/or inorganic salt, based on the total weight of the cosmetic agent.

According to further preferred embodiments of the present invention, the cosmetic agent comprises 0.02 to 7% by weight, preferably 0.04 to 6% by weight, of hydroxytyrosol, based on the total weight of the cosmetic agent.

When the inorganic or organic salt is limited to one or more specific inorganic or organic salts in the cosmetic according to the present invention, apart from these, nothing else is included in the cosmetic product. The inorganic or organic salt consists of the specific salt(s).

According to further preferred embodiments, the preferably used amounts of the inorganic and/or organic salt and the preferred amounts of hydroxytyrosol can be combined. According to a preferred embodiment of the present invention, the proportion by weight of the organic and/or inorganic salt in the cosmetic agent is greater than the proportion by weight of hydroxytyrosol.

The preferred pH of the cosmetic composition is from pH 2 to less than pH 7, more preferably from pH 3 to pH 6. The preferred pH values can be combined with preferred levels of inorganic or organic salt or with preferred levels of hydroxytyrosol . Accordingly, preferred embodiments include cosmetic agents that are acidic.

The care effect can be supported by the use of cationic surfactants. According to a preferred embodiment, the cosmetic agent comprises a cationic surfactant. According to preferred embodiments, the cationic surfactant is selected from the group consisting of one

• Alkylammonium salt of the formula RiFkRsF NTX, where one or two of Ri, R ₂ , R3, and R ₄ is a branched or unbranched C ₄ - to C ₂₆ -, preferably a branched or unbranched Cs to C ₂₀ -, more preferably a branched or unbranched C ₁₄ - to cis-alkyl group and the rest of Ri, R ₂ , R3, and R ₄ are hydrogen, methyl or ethyl, and X is a cosmetically acceptable anion, preferably chloride, bromide or methosulfate, with preference being given to the alkylammonium salt of Formula R _I R ₂ R3R ₄ N ⁺ X- is selected from the group consisting of cetrimonium chloride and behentrimonium chloride;

• alkylamidopropyltrimonium salt;

• Alkylenamidopropyltrimonium salt, more preferably undecylenamidopropyltrimonium methosulfate;

• Quaternium-87 and mixtures thereof; wherein the cationic surfactant is contained in the cosmetic in an amount of 0 to 10% by weight, preferably 0.01 to 8% by weight, more preferably 0.2 to 5% by weight, based on the total weight of the cosmetic is.

When the cationic surfactant is an alkylammonium salt of the formula R _I R ₂ R 3 R ₄ N ⁺ X-, one or two of Ri, R ₂ , R 3 , and R ₄ represent a branched or unbranched C ₄ - to C ₂₆ -, preferably a branched or unbranched Cs- to C ₂₀ -, more preferably a branched or unbranched C ₁₄ - to Cis- alkyl group, the remainder of R 1 , R ₂ , R 3 , and R ₄ being hydrogen, methyl or ethyl and X- represents a cosmetically acceptable anion. Preferably the cosmetically acceptable anion is chloride, bromide or methosulfate.

According to a preferred embodiment, the alkyl ammonium salt of the formula RiF^RsF N X- is selected from the group consisting of cetrimonium chloride and behentrimonium chloride.

Also in a preferred embodiment, the cationic surfactant is an alkylamidoamine. The alkylamidoamine can exist in aqueous solution as a quaternized salt. Alkylamidoamines are usually prepared by _amidating natural or synthetic C8-C24 fatty acids and fatty acid cuts with di-(Ci-C3)alkylaminoamines. According to the invention, particularly suitable compounds from this class of substances are, for example, the compounds known under the INCI names stearamidopropyl dimethylamine, behenamidopropyl dimethylamine or brassicamidopropyl dimethylamine. Most preferably, an alkylamidopropyltrimonium salt is used as a quaternized alkylamidoamine.

Another preferred cationic surfactant is the alkylenamidopropyltrimonium salt, especially undecylenamidopropyltrimonium methosulfate.

Also particularly preferred are cationic surfactants, the imidazolium compounds known under the INCI names Quaternium-27, Quaternium-83, Quaternium-87 and Quaternium-91. Quaternium-87 is very particularly preferred among these.

Mixtures of one or more of the abovementioned cationic surfactants can also be used in the cosmetic agents.

Typically, the cationic surfactant is present in the cosmetic in amounts of 0 to 10% by weight, preferably 0.01 to 8% by weight, more preferably 0.2 to 5% by weight, based on the total weight of the cosmetic .

According to a preferred embodiment, the cosmetic agent comprises a cationic polymer. The cationic polymer is preferably selected from the group consisting of

• a cationic cellulose polymer, preferably polyquaternium-10 and/or polyquaternium-24 and/or polyquaternium-67 and/or polyquaternium-72;

• a cationic guar derivative,

• a chitosan,

• cationic honey,

• polyquaternium-37, • Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, and mixtures thereof.

Preferably, the cationic polymer is present in an amount of 0 to 10% by weight, more preferably 0.01 to 8% by weight, still more preferably 0.2 to 5% by weight based on the total weight of the cosmetic in the cosmetic funds included.

In addition or as an alternative to the cationic surfactant, the cosmetic agent can contain a cationic polymer. Accordingly, the cosmetic agent can contain a cationic surfactant, it can contain a cationic polymer, or it can contain a cationic surfactant and a cationic polymer.

According to preferred embodiments, the cosmetic agent contains one or more other care components. According to preferred embodiments, these are selected from the group consisting of a silicone, preferably an aminofunctional silicone or an alkoxylated dimethicone, more preferably an ethoxylated or propoxylated dimethicone, a polyol, a protein hydrolyzate, preferably the hydrolyzates of keratin, silk protein or wheat protein, a protein or a proteolipid.

The preferred proteolipid in the cosmetic composition is a proteolipid of the formula I R'-X-R" (I) in which

R 'is a straight-chain or branched, saturated or unsaturated hydrocarbon radical having 11 to 24 carbon atoms,

R" means a protein, a peptide or a protein hydrolyzate,

X is -C(O)O- or -N ⁺ (R'"2)-R ^IV - or -N(R'")R ^IV - or -C(O)—NCR^R ^V -,

R ^m is -(CH ₂ )x-CH3 with x = 0-22 and

R ^IV is -CH ₂ -CH(OH)-CH ₂ - or -(CH ₂ )x- where x = 0-22;

R ^v and R ^VI are independently -H or -(CH ₂ )x-CH3 where x = 0-22; with the proviso that when X is -C(O)O, R" is keratin or a keratin hydrolyzate.

Preferred silicones are described below:

Particularly preferred silicones are silicones of the formula Si-I(CH3)3Si-[0-Si(CH3) ₂ ]x-0-Si(CH3) ₃ (Si-I), in which x is a number from 0 to 100 , preferably from 0 to 50, more preferably from 0 to 20 and especially 0 to 10. Preferred silicones that can be used in the context of the present invention have viscosities of 0.2 to 2 mm ² s- ¹ at 20° C., with silicones having viscosities of 0.5 to 1 mm ² s- ¹ being particularly preferred. Particularly preferred amino-functional silicones are those of the formula Si-II

M(RaQbSiO(4-ab)/2)x(RcSiO(4-c)/2)y M(Si-II), wherein in the above formula, R is hydrocarbyl or hydrocarbyl having from 1 to about 6 carbon atoms, Q is a polar radical of the general formula -R ¹ is HZ, wherein R ¹ is a divalent linking group bonded to hydrogen and the radical Z composed of carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms or carbon, hydrogen - and nitrogen atoms, and Z is an organic amino-functional residue containing at least one amino-functional group; "a" takes values in the range from about 0 to about 2, "b" takes values in the range from about 1 to about 3, "a" + "b" is less than or equal to 3, and "c ' is a number ranging from about 1 to about 3, and x is a number ranging from 1 to about 2000, preferably from about 3 to about 50, and most preferably from about 3 to about 25, and y is a number ranging from from about 20 to about 10,000, preferably from about 125 to about 10,000, and most preferably from about 150 to about 1000, and M is a suitable silicone end group as is known in the art, preferably trimethylsiloxy. Non-limiting examples of the groups represented by R include alkyl groups such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl and the like; alkenyl radicals such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; cycloalkyl radicals such as cyclobutyl, cyclopentyl, cyclohexyl and the like; phenyl radicals, benzyl radicals, halohydrocarbon radicals such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, and sulfur-containing radicals such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; preferably R is an alkyl group containing from 1 to about 6 carbon atoms, and most preferably R is methyl. Examples of R1 include methylene, ethylene, propylene, hexamethylene, decamethylene, _-CH2CH (CH3) ^CH2- , phenylene, naphthylene, _{-CH2CH2SCH2CH2-} , -CH2CH2OCH2-, -OCH2CH2-, _-OCH2CH2CH2- , -CH2CH (CH3)C(0) _0CH2 -, -( _CH2 )3CC(0)0CH2 _CH2 -, -C6H4C6H4-, -C6H4CH2C6H4-; and -(CH ₂ )3C(0)SCH ₂ CH2-a.

Z is an organic, amino-functional residue containing at least one amino functional group. A possible formula for Z is NH(CH 2 ) z NH 2 where z is 1 or more. Another possible formula for Z is -NH(CH 2 ) z (CH 2 ) zz NH where both z and zz are independently 1 or more, this structure encompassing diamino ring structures such as piperazinyl. Z is most preferably an -NHCH2CH2NH2 residue. Another possible formula for Z is -N(CH2)z(CH2)zzNX2 or -NX2 where each X of X2 is independently selected from the group consisting of hydrogen and alkyl groups having 1 to 12 carbon atoms, and zz is zero.

Q is most preferably a polar amine functional group of the formula -CH2CH2CH2NHCH2CH2NH2. In the formulas, "a" takes on values ranging from about 0 to about 2, "b" takes on values in the range from about 2 to about 3, "a" + "b" is less than or equal to 3, and "c" is a number ranging from about 1 to about 3. The molar ratio of the R _a Qb SiO( _4-a -b)/ ₂ units to RcSiO( _4-C)/2 units ranges from about 1:2 to 1:65, preferably from about 1:5 to about 1:65, and most preferably from about 1:5 to about 1:65 about 1:15 to about 1:20. When one or more silicones of the above formula are employed, the various variable substituents in the above formula may vary with the various silicone components present in the silicone blend.

According to a preferred embodiment, the cosmetic agent contains polyols as a further care component. Polyols are polyhydric alcohols. These are predominantly well tolerated by the skin and, as solvents, ensure that the cosmetic agents that can be obtained with them are not too solid or too difficult or too slow to dissolve. These advantageous properties are particularly evident in the case of glycerin.

Preferred polyhydric alcohols are alditols such as mannitol, isomalt, lactitol, sorbitol and xylitol, threitol, erythritol and arabitol, 1,2-propylene glycol, 1,3-butylene glycol, dipropylene glycol, glycerol or diglycerol, particularly preferably 1,2-propylene glycol, 1 ,3-butylene glycol, dipropylene glycol or glycerin contained in the cosmetic. The polyhydric alcohols, in particular 1,2-propylene glycol, 1,3-butylene glycol, dipropylene glycol and glycerol, are preferably present in the cosmetic agent in amounts of 2 to 30% by weight, more preferably 5 to 15% by weight.

Oils are used as further preferred cosmetic active ingredients. The cosmetic agent preferably comprises a mineral oil or a vegetable oil. The mineral oil can be selected from alkanes, in particular from an alkane mixture that has two or more alkanes that differ from one another in the number of carbon atoms. The preferred vegetable oil used is either modified or unmodified. Preferred vegetable oils are apricot kernel oil, argan oil, jojoba oil, marula oil, almond oil, olive oil, coconut oil and/or sunflower oil.

The cosmetic agent contains shea butter (INCI name Butyrospermaum Parkii (Shea) butter) or argan oil as very particularly preferred cosmetic active ingredients. The cosmetic agent contains shea butter (INCI name Butyrospermaum Parkii (Shea) butter) and argan oil as very particularly preferred cosmetic active ingredients.

According to preferred embodiments, the cosmetic agent contains the other care components, based on the total weight of the cosmetic agent, in amounts of 0.01 to 15% by weight, more preferably in amounts of 0.05 to 10% by weight, even more preferably in amounts of 0 .15 to 5% by weight in the cosmetic composition. These preferred amounts relate to the other care components, provided this is not different, for example in the case of the polyol is specified. Selected other care components can be contained in other preferred amounts in the cosmetic agent.

The cleaning compositions or the care compositions contain surfactant. According to preferred embodiments, the cosmetic agent comprises a nonionic surfactant, an amphoteric surfactant and/or an anionic surfactant, preferably a cationic surfactant together with a further surfactant selected from the group consisting of a nonionic surfactant and an amphoteric surfactant. According to this preferred embodiment, the cosmetic agent comprises a nonionic surfactant and an amphoteric surfactant, or a nonionic surfactant and an anionic surfactant, or an amphoteric surfactant and an anionic surfactant. For use as a care product, it is preferred if the cosmetic agent contains a cationic surfactant with a further surfactant. It is thus preferred if the cosmetic agent contains a cationic surfactant and a nonionic surfactant, or a cationic surfactant and an amphoteric surfactant.

The cosmetic agent according to the preferred embodiment comprises the nonionic surfactant selected from the group consisting of C6 to Cie, preferably Cs to Cie, more preferably C10 to Ci ₄ -alkylpolyglucosides, preferably cocoglucoside or decylglucoside; polyglyceryl alkylates, preferably PEG 7 glyceryl cocoate; cocamide MEA; and alkyl glycol ethers composed of Cs to C24, preferably C12 to C18, alkyl groups and 1 to 8, preferably 2 to 5, ethylene oxide units.

When the nonionic surfactant is an alkyl polyglucoside this is preferably selected from C6 to C18, more preferably Cs to Cie, most preferably C10 to Cu alkyl polyglucosides. It is particularly preferred when the alkyl polyglucoside is coco glucoside or decyl glucoside.

Another group of preferred nonionic surfactants is that of the polyglyceryl alkylates. These are polyglycerol adducts with fatty acid esters, fatty acid alkanolamides or fatty acid glucamides, or ethylene oxide and polyglycerol adducts with fatty acid esters, fatty acid alkanolamides or fatty acid glucamides. Particularly preferred is the PEG 7 glyceryl cocoate.

Furthermore, according to a preferred embodiment, the nonionic surfactants are alkyl glycol ethers consisting of a Cs to C24, preferably C12 to Cis, alkyl group and 1 to 8, preferably 2 to 5, ethylene oxide units.

According to preferred embodiments, the cosmetic agents contain 0.3 to 10% by weight, more preferably 0.5 to 8% by weight, even more preferably 0.75 to 6% by weight and in particular 1 to 5% by weight of nonionic surfactant . The cosmetic agents can contain an amphoteric surfactant. Amphoteric surfactants or zwitterionic surfactants are surfactants that have both a negatively and a positively charged functional group.

According to preferred embodiments, the cosmetic composition contains an amphoteric surfactant, which is preferably a Ce-ie, preferably Cio-i6-alkylamido-(Ci-4-alkyl) betaine, a Ce-ie-, preferably C10-16-alkylamido-(Ci - ₄ -alkyl)sultaine, a Cio-18-alkylamphoacetate or a Cio-18-alkylamphodiacetate. In particular, according to preferred embodiments, the amphoteric surfactant is selected from the group consisting of cocamidopropylbetaine, amophoacetate, preferably disodium amphodiacetate, cocobetaine and mixtures thereof. The cocamidopropyl betaine is a particularly preferred fatty acid amide derivative which is particularly suitable as an amphoteric surfactant.

Suitable zwitterionic surfactants are also the so-called betaines, such as the N-alkyl-N,N-dimethylammonium glycinates, for example coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl -S-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and cocoacylaminoethyl-hydroxyethylcarboxymethylglycinate. Other examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylaminopropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each with about 8 to 24 C atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and Ci2-Ci8-acylsarcosine.

According to preferred embodiments, the cosmetic agents contain 0.3 to 20% by weight, preferably 0.5 to 8% by weight, more preferably 0.75 to 6% by weight and in particular 1 to 5% by weight amphoteric surfactant .

If several surfactants, i.e. also several cationic or several nonionic or several amphoteric or several nonionic and amphoteric surfactants or several cationic and nonionic surfactants or several cationic and amphoteric surfactants are contained in the cosmetic agent, the amounts in % by weight always relate to the sum the surfactants.

Anionic surfactants are preferably included in cleaning compositions. When the cosmetic is a cleansing composition, anionic surfactants and no cationic surfactants are contained in the cosmetic. Preferred anionic surfactants are acyl glutamates, acyl isethionates, acyl sarcosinates and acyl taurates, each with a linear or branched acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, which in particularly preferred embodiments consists of an octanoyl, decanoyl, lauroy| , Myristoyl, palmitoyl and stearoyl radical is selected, esters of tartaric acid, citric acid or succinic acid or the salts of these acids with alkylated glucose, in particular the products with the INCI name Disodium Coco-Glucoside Citrate, Sodium Coco-Glucoside Tartrate and Disodium Cocoglucoside Sulphosuccinates, alkyl polyglycol ether sulfates and ether carboxylic acids with 8 to 18 carbon atoms in the alkyl group and up to 12 ethoxy groups in the molecule, sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkylpolyoxyethyl ester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 ethoxy groups.

More preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acid salts with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkylpolyoxyethyl ester 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups. Particularly preferred anionic surfactants are the alkali metal or ammonium salts of lauryl ether sulfate with a degree of ethoxylation of 2 to 4 EO.

The object on which the invention is based is also achieved by the subject matter of claim 9. A third subject matter of the present invention is therefore a method for treating a keratinic material, in particular for treating human hair, in which the cosmetic agent according to the invention is applied to the keratinic material, in particular applied to human hair and then rinsed out with water.

This process is a rinse-off process. The cosmetic product in this case is a cleaning product or a "2 in 1" cosmetic product. The exposure time, i.e. the time between application and rinsing, is significantly shorter than with the method in which the cosmetic agent is a leave-on cosmetic agent. The exposure time is therefore preferably less than 5 minutes.

The object on which the invention is based is also achieved by the subject matter of claim 10. A fourth subject matter of the present invention is therefore the use of the cosmetic agent according to the invention to reduce or prevent harmful effects from chemical treatments of the keratin material, from air and water pollution free radicals or by UV radiation; or as a means of exerting a repair effect. The cosmetic agent according to the invention is preferably used as a conditioner, hair treatment, shampoo, as a “2 in 1” cosmetic agent or in the form of a spray.

Features relating to preferred embodiments of the first subject matter of the invention, which are only described above in relation to this, of course apply correspondingly to the second, third and fourth subject matter as features of preferred embodiments.

The following examples are intended to explain the subject matter of the present invention without restricting it in any way.

Shampoo:

Ingredient 1.1 1.2 1.3 1.4 V

Sodium Laureth Sulfate 10.0 10.0 12.0 12.0 10.0

Ammonium Lauryl Sulfate 4.0 4.0 2.0 2.0 4.0

Cocoamidopropyl Betaine 4.0 4.0 4.0

Cocobetaine 4.0 - 4.0 Hydroxytyrosol 0.05 0.05 0.05 0.05 Lanthanum Chloride 0.1 0.1 0.1 0.1 Cocamide MEA 0.8 0.8 0.8 0.8 0 .8 PEG-7 glyceryl cocoate 1.0 1.0 1.0 1.0 1.0 nicotinamide 0.3 0.3 0.3 0.3 0.3 citric acid 0.8 0.8 0.8 0, 8 0.8

Hydrolyzed Keratin (Prosina) 0.3 0.3 0.3 0.3 0.3

Panthenol 0.5 0.5 0.5 0.5 0.5

Sodium chloride 1.3 1.3 1.3 1.3 1.3

preservatives, perfume q.s. q.s. q.s. q.s. q.s. Water ad 100 ad 100 ad 100 ad 100 ad 100

Ingredient 2.1 2.2 2.3 2.4

Sodium Laureth Sulfate 10.0 10.0 12.0 12.0 Ammonium Lauryl Sulfate 4.0 4.0 2.0 2.0 Cocoamidopropyl Betaine 4.0 4.0 Disodium Aphodiacetate 4.0 4.0 Hydroxytyrosol 0.05 0 .05 0.05 0.05 Lanthanum Chloride 0.1 0.1 0.1 0.1 Cocamide MEA 0.8 0.8 0.8 0.8 Decyl Glucoside 1.0 1.0 1.0 1.0 Nicotinamide 0.3 0.3 0.3 0.3

citric acid 0.8 0.8 0.8 0.8

Hydrolyzed Keratin (Prosina) 0.3 0.3 0.3 0.3

Panthenol 0.5 0.5 0.5 0.5

sodium chloride 1.3 1.3 1.3 1.3

preservatives, perfume q.s. q.s. q.s. q.s.

Water ad 100 ad 100 ad 100 ad 100

Hair shampoo sulfate-free:

Hair conditioner:

Hair treatment:

care spray:

Claims

Patent Claims:

1. Cosmetic agent for treating a keratinic material, comprising a) 0.001 to 10% by weight of an organic and/or inorganic salt, based on the total weight of the cosmetic agent, comprising a multivalent cation, and b) 0.001 to 10% by weight. % Hydroxytyrosol, based on the total weight of the cosmetic agent, the pH of the cosmetic agent being between pH 1 and pH 7.

2. Cosmetic agent according to claim 1, wherein the organic and / or inorganic salt comprises a divalent or trivalent cation, preferably a trivalent cation, which is more preferably selected from the group consisting of an alkaline earth metal cation, the trivalent aluminum cation and the trivalent lanthanum cation, wherein the counterion of the multivalent cation is a cosmetically acceptable anion, preferably selected from the group consisting of hydroxide, halide, more preferably chloride or bromide; the anion of a carboxylic acid; the anion of a hydroxycarboxylic acid, more preferably lactate, citrate, or tartrate; the anion of an amino acid, more preferably glycinate; the anion of a dicarboxylic acid; and the anion of a tricarboxylic acid, more preferably citrate.

3. Cosmetic agent according to claim 1 or claim 2, wherein the organic and/or inorganic salt is selected from the group consisting of aluminum lactate, lanthanum chloride, lanthanum chloride heptahydrate, calcium hydroxide, magnesium hydroxide, calcium chloride, magnesium chloride and trimagnesium citrate, with preference being given to the organic and/or inorganic salt or inorganic salt selected from the group consisting of aluminum lactate and lanthanum chloride.

4. Cosmetic agent according to one of claims 1 to 3, wherein the cosmetic agent based on the total weight of the cosmetic agent

0.01 to 8% by weight, preferably 0.05 to 5% by weight, of the organic and/or inorganic salt, and the cosmetic agent contains 0.02 to 7% by weight, based on the total weight of the cosmetic agent. %, preferably 0.04 to 6 wt /or inorganic salt in the cosmetic agent is greater than the weight fraction of hydroxytyrosol.

5. Cosmetic agent according to one of claims 1 to 4, comprising a cationic surfactant, which is preferably selected from the group consisting of

• an alkylammonium salt of the formula RiF^RsF N X-, where one or two of Ri, R2, R3, and R4 is a branched or unbranched C4 to C26, preferably a branched or unbranched Cs to C20, more preferably a branched or unbranched C14 to Cis-alkyl group and the others from R 1 , R 2 , R 3 , and R 4 are hydrogen, methyl or ethyl, and X represents a cosmetically acceptable anion, preferably chloride, bromide or methosulfate, with preference being given to the alkyl ammonium salt of the formula R _I R ₂ R3R ₄ N ⁺ X- is selected from the group consisting of cetrimonium chloride and behentrimonium chloride;

• alkylamidopropyltrimonium salt;

6. Cosmetic agent according to any one of claims 1 to 5, comprising a nonionic surfactant, an amphoteric surfactant and / or an anionic surfactant, preferably comprising a cationic surfactant together with a further surfactant selected from the group consisting of a nonionic surfactant and an amphoteric surfactant.

7. Cosmetic agent according to one of claims 1 to 6, wherein the nonionic surfactant is selected from the group consisting of C6 to C18, preferably Cs to C16, more preferably C10 to Cu alkyl polyglucosides, preferably cocoglucoside or decyl glucoside; polyglyceryl alkylates, preferably PEG 7 glyceryl cocoate; cocamide MEA; and alkyl glycol ethers composed of Cs to C24, preferably C12 to Cis, alkyl groups and 1 to 8, preferably 2 to 5, ethylene oxide units.

8. Cosmetic agent according to one of claims 1 to 6, wherein the amphoteric surfactant is a C8-18, preferably Cio-i6-alkylamido (Ci- ₄ -alkyl) betaine, a Cs-is-, preferably Cio-16-alkylamido - (Ci- ₄ -alkyl)sultaine, a Cio-18-alkylamphoacetate or a Cio-18-alkylamphodiacetate; wherein the amphoteric surfactant is selected in particular from the group consisting of cocamidopropylbetaine, amophoacetate, preferably disodium amphodiacetate, cocobetaine and mixtures thereof.

9. A method for treating a keratinic material, in which a cosmetic agent according to any one of claims 1 to 8 is applied to the keratinic material, preferably applied immediately after cleaning the keratinic material, and is left there for a period of 2 minutes or more to next cleaning or less, preferably from 5 minutes or more to 12 hours or less; or in which a cosmetic agent according to one of Claims 1 to 8 is applied to the keratinic material, massaged in and then rinsed out with water.

10. Use of a cosmetic agent according to any one of claims 1 to 8 to reduce or prevent harmful effects from chemical treatments of the keratin material, from air and water pollution, from free radicals or from UV radiation; or as a means of exerting a repair effect.