Patent Grant
8246938
The present invention relates to hydrogen peroxide-free hair-treatment agents based on a special combination of an acetylpyridinium salt with an anionic, zwitterionic and/or amphoteric surfactant, and use of the agent for increasing the hair-conditioning properties.
Today, human hair is treated with hair-cosmetic preparations in many different ways. These include, for example, the cleaning of hair with shampoos, conditioning and regeneration with rinses and deep conditioners as well as the bleaching, coloring and shaping of hair with colorants, tints, waving agents and styling preparations.
Not least owing to the severe stressing of hair, for example, by coloring or permanent waves, by frequent cleaning of hair with shampoos and subsequent blow drying with hot air, by mechanical stresses such as combing and styling, or by environmental stresses such as sunlight, sea water or chlorinated water, the importance of care products with as long-lasting an action as possible is increasing. While consumers can minimize the degree of damage to their hair by reducing hair-cosmetic treatments, it is not possible to avoid environmental influences altogether. Hair can be damaged by stress, both externally and in its structure, giving it an unattractive appearance that can become noticeable as a lack of smoothness, softness, gloss, as well as poorer combability, hair breakage or split ends.
It has therefore been customary for a long time to subject the hair to a special after-treatment to deliver care substances to the hair and scalp which impart an attractive external appearance to the hair again and reinforce the hair structure as well as caring for the scalp and protecting it from drying out. In these after-treatments, the hair is treated with special active substances, for example, quaternary ammonium salts or special polymers, generally in the form of a rinse. As a result of this treatment, depending on the formulation, combability, hold, fullness and gloss of the hair can be improved and the rate of split ends reduced.
Due to coloring, permanent waves or blonding and subsequent washing and conditioning, the hair can perceptibly lose volume and fullness so that cleaning and conditioning (which are absolutely necessary after a coloring, bleaching or permanent waving operation) also entail significant disadvantages for the aesthetics of the hair.
Despite various efforts relating to hair care and regeneration in the last few decades, new problems in hair treatment are still appearing which require new solutions. The search for new ingredients with a positive effect on hair structure consequently remains highly topical. This invention disclosure is directed towards a novel agent for the care of hair which has a structuring effect on hair fibers making it possible to reverse damage already present in the hair in the sense of a “repair effect”.
The present invention therefore provides cleaning and/or conditioning hair-treatment agents which do not have a negative effect on hair volume and hair fullness, particularly in previously colored, bleached and/or shaped hair. In particular, the present application provides agents for the regeneration of environmental influences, UV light irradiation, heat or special hair treatments.
There is a particular focus on providing an agent that develops a conditioning action not only by acting on the external layer of the hair (cuticle), but which is able to diffuse into the hair fibers, thereby strengthening the hair fibers over the entire cross section of the cortex.
To quantify hair damage or strengthening of hair fibers after a hair treatment, the tensile properties of individual hair fibers are often determined. Stress-strain curves obtained here pass through three different regions, it being possible to determine the modulus of elasticity (E modulus, Young's modulus) from tensile measurements in Hooke's range (up to 5% elongation) as a characteristic measured value.
Surface damage or abrasion damage, which affects the cuticle in particular, changes tensile values only slightly. Active substances present in commercial deep conditioners and rinses are mainly cationic surfactants or polymers. These cationic compounds attach themselves to the outside of the cuticle by electrostatic interactions with the anionic groups of the hair. No structural improvement in the interior of the hair fibers can be achieved with these care products.
Damage with negative effects on the structure of the cortex and the strength of the hair results in reduced values of the modulus of elasticity. Substances that improve the strength of the hair structure lead to an increase in the modulus of elasticity. Determination of tensile values, particularly the modulus of elasticity, is therefore an ideal test method for identifying substances with a hair-structuring effect.
It has now been found that it is possible to achieve the above objects by providing hair-cleaning and/or conditioning agents which, in addition to an anionic zwitterionic and/or amphoteric surfactant, contain at least one acetylpyridinium derivative in the form of an acetylpyridinium salt.
Acetylpyridinium derivatives according to the invention are already known from the literature as agents for producing coloring on hair (DE 19745356) or agents for lightening hair (DE102007047685). There is no description in this context of the positive effects of the substances according to the invention on hair quality in hydrogen peroxide-free agents. It was not predictable, therefore, that the object according to the invention can be achieved by use of a combination of acetylpyridinium derivatives and certain surfactant systems.
The present invention therefore firstly provides a cosmetic hair-treatment agent free from hydrogen peroxide and/or the addition compounds thereof to organic and inorganic compounds, containing, in a cosmetic carrier,
wherein R1 is a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 hydroxyalkyl group, a C1-C6 alkoxy-C2-C6 alkyl group, a carboxy-C1-C6 alkyl group, an aryl-C1-C6 alkyl group, a heteroaryl-C1-C6 alkyl group, an aryl group or a heteroaryl group; and X− is a physiologically acceptable anion.
These agents are particularly capable of strengthening hair in the interior of its fibers and reducing structural damage. Overall, when the agent is used a “repair effect” is observed.
The agents contain the active substances in a cosmetic carrier. This cosmetic carrier is preferably aqueous, alcoholic or aqueous-alcoholic. Such carriers include creams, emulsions, gels or surfactant-containing foaming solutions such as shampoos, foam aerosols or other preparations suitable for application to hair. An aqueous carrier contains, within the meaning of the invention, at least 40 wt. %, in particular at least 50 wt. %, water. Aqueous-alcoholic carriers within the meaning of the present invention are water-containing compositions containing 3 to 70 wt. % of a C1-C4 alcohol, in particular ethanol or isopropanol. The agents can also contain other organic solvents, such as methoxybutanol, ethyl diglycol, 1,2-propylene glycol, n-propanol, n-butanol, n-butylene glycol, glycerol, diethylene glycol monoethyl ether and diethylene glycol mono-n-butyl ether. All water-soluble organic solvents are preferred here.
Preferred agents additionally contain a non-aqueous solvent, with particularly preferred agents containing the solvent in a concentration of 0.1 to 30 wt. %, preferably 1 to 20 wt. % and most preferably 2 to 10 wt. %, based on total agent.
The agent according to the invention is free from hydrogen peroxide and/or the addition compounds thereof to organic and inorganic compounds. It is therefore, in particular, not to be understood as a lightening or bleaching agent. Agents which are free from hydrogen peroxide and/or the addition compounds thereof to organic and inorganic compounds are those agents having hydrogen peroxide and/or the addition compounds thereof to organic and inorganic compounds in a total amount of 0.5 wt. % or less, particularly 0.1 wt. % or less, and most particularly 0.01 wt. % or less. Hydrogen peroxide and/or the addition compounds thereof to organic and inorganic compounds are, within the meaning of the present invention, hydrogen peroxide itself or solid addition compounds of hydrogen peroxide to inorganic or organic compounds such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidinone n H2O2 (n is a positive integer greater than 0), urea peroxide and melamine peroxide, as well as peroxo salts such as ammonium peroxodisulfate, alkali metal peroxodisulfates, ammonium peroxomonosulfate, alkali metal peroxomonosulfates, alkali metal peroxodiphosphates and alkaline earth metal peroxides.
As a first essential ingredient, agents according to the invention contain an acetylpyridinium derivative according to formula (I). Examples of residues mentioned as substituents of the compounds of formula (I) are listed below:
In one embodiment of the present invention, compounds according to formula (I) wherein R in the general structure (I) is a C1-C6 alkyl group, a C2-C6 alkenyl group or a C2-C6 hydroxyalkyl group are preferred.
It is particularly preferred according to the invention if R is a C1-C6 alkyl group, preferably methyl, ethyl, n-propyl or isopropyl and particularly preferably methyl.
It is preferred if the anion X− according to formula (I) is chosen from halide, particularly chloride, bromide and iodide, benzenesulfonate, p-toluenesulfonate, C1-C4 alkyl sulfonate, trifluoromethane sulfonate, acetate, trifluoroacetate, perchlorate, ½ sulfate, hydrogen sulfate, tetrafluoroborate, hexafluorophosphate or tetrachlorozincate. It is particularly favorable according to the invention if the physiologically acceptable anion X− is a halide ion (particularly chloride or bromide), hydrogen sulfate, ½ sulfate, p-toluenesulfonate, benzenesulfonate or acetate.
It has been shown that acetylpyridinium derivatives according to formula (I) have particularly advantageous properties according to the invention if they carry the acetyl group in either the 2- or 4-position on the pyridine ring. Another embodiment of the present invention is an agent containing as acetylpyridinium derivative according to formula (I) at least one 2-acetylpyridinium derivative and/or 4-acetylpyridinium derivative.
Suitable acetylpyridinium derivatives here are the physiologically acceptable salts which contain as cation an acetylpyridinium derivative chosen from 4-acetyl-1-methylpyridinium, 4-acetyl-1-allylpyridinium, 4-acetyl-1-(2-hydroxyethyl)pyridinium, 2-acetyl-1-methylpyridinium, 2-acetyl-1-allylpyridinium and 2-acetyl-1-(2-hydroxyethyl)pyridinium.
In particular, those agents wherein the acetylpyridinium derivative according to formula (I) is chosen from 4-acetyl-1-methylpyridinium p-toluenesulfonate, 4-acetyl-1-methylpyridinium benzenesulfonate, 4-acetyl-1-methylpyridinium bromide, 4-acetyl-1-methylpyridinium chloride, 4-acetyl-1-methylpyridinium hydrogen sulfate, 4-acetyl-1-methylpyridinium acetate, 4-acetyl-1-allylpyridinium p-toluenesulfonate, 4-acetyl-1-allylpyridinium benzenesulfonate, 4-acetyl-1-allylpyridinium bromide, 4-acetyl-1-allylpyridinium chloride, 4-acetyl-1-allylpyridinium hydrogen sulfate, 4-acetyl-1-allylpyridinium acetate, 2-acetyl-1-methylpyridinium p-toluenesulfonate, 2-acetyl-1-methylpyridinium benzenesulfonate, 2-acetyl-1-methylpyridinium bromide, 2-acetyl-1-methylpyridinium chloride, 2-acetyl-1-methylpyridinium hydrogen sulfate, 2-acetyl-1-methylpyridinium acetate, 2-acetyl-1-allylpyridinium p-toluenesulfonate, 2-acetyl-1-allylpyridinium benzenesulfonate, 2-acetyl-1-allylpyridinium bromide, 2-acetyl-1-allylpyridinium chloride, 2-acetyl-1-allylpyridinium hydrogen sulfate and/or 2-acetyl-1-allylpyridinium acetate are suitable according to the invention.
Particularly advantageous agents here are those wherein the acetylpyridinium derivative according to formula (I) is chosen from 4-acetyl-1-methylpyridinium p-toluenesulfonate and/or 2-acetyl-1-methylpyridinium p-toluenesulfonate, in particular 4-acetyl-1-methylpyridinium p-toluenesulfonate.
In one embodiment, the agents contain the acetylpyridinium derivatives of formula (I) in an amount of 0.05 to 10 wt. %, preferably 0.1 to 7.5 wt. %, more preferably 0.2 to 6.5 wt. % and in particular 0.5 to 5 wt. %, based on total weight of the ready-to-use agent.
As another essential ingredient, agents according to the invention contain at least one surface-active agent chosen from anionic, amphoteric and/or zwitterionic surfactants.
Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These have an anionic group that imparts water-solubility such as a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group with about 8 to 30 C atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups, as well as hydroxyl groups, can be present in the molecule. Examples of suitable anionic surfactants are, each in the form of the sodium, potassium and ammonium salts as well as the mono-, di- and trialkanol ammonium salts with 2 to 4 C atoms in the alkanol group,
Preferred anionic surfactants for all hair-treatment agents according to the invention are
Also particularly preferred are agents having as anionic surfactant at least one linear and branched, optionally unsaturated fatty acid with 10 to 22 C atoms, and/or an ether carboxylic acid of alkyl polyglycosides of the formula R-(Gly)xCH2COOH, wherein R is an alkyl group with 10 to 18 C atoms, Gly is a glycoside chosen from pyranosides, and x is a number from 1 to 5.
As fatty acids it is possible to use linear and/or branched, saturated and/or unsaturated fatty acids with 6 to 30 carbon atoms. Preferred are fatty acids with 10 to 22 carbon atoms. Typical examples of these fatty acids are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, isopalmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid, as well as technical mixtures thereof, obtained, for example, during compressive cleaving of natural fats and oils, the oxidation of aldehydes from Roelen's oxo synthesis or the dimerization of unsaturated fatty acids. Fatty acid blends obtainable from coconut oil or palm oil are generally particularly preferred; use of stearic acid is especially preferred.
A preferred embodiment of the present invention is one wherein the agent contains at least one anionic surfactant as surface-active agent.
Those surface-active compounds that carry at least one quaternary ammonium group and at least one carboxylate, sulfonate or sulfate group in the molecule are referred to as zwitterionic surfactants. Particularly suitable zwitterionic surfactants are betaines such as N-alkyl-N,N-dimethyl ammonium glycinates, for example, cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example, cocoacyl aminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines with 8 to 18 C atoms in the alkyl or acyl group, and cocoacyl aminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.
Amphoteric surfactants are surface-active compounds which, apart from a C8-C24 alkyl or acyl group, contain in the molecule at least one free amino group and at least one —COOH or —SO3H group and are capable of forming internal salts. Examples of suitable amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkyl amidopropyl glycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids with, in each case, about 8 to 24 C atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-cocoalkyl aminopropionate, cocoacyl aminoethyl aminopropionate and C12-C18 acyl sarcosine.
Hair-treatment agents are generally those such as shampoos, which in a preferred embodiment contain at least one anionic surfactant and at least one amphoteric and/or zwitterionic surfactant in a ratio of anionic surfactant(s) to amphoteric and/or zwitterionic surfactant(s) of from 3:1 to 1:2, preferably from 2:1 to 1:1.
A combination of alkyl ether sulfates and dialkali metal cocoamphodiacetates in a ratio of from 3:1 to 1:2, preferably from 2:1 to 1:1, has proved to be a surfactant combination with the most effective scalp care for hair-treatment agents according to the invention that are formulated as a shampoo.
The invention relates to those agents wherein the surface-active agents chosen from the group of anionic, amphoteric and/or zwitterionic surfactants are present in a total amount of 0.1 to 50 wt. %, preferably 0.5 to 25 wt. %, more preferably 1 to 20 wt. % and in particular 2 to 15 wt. %, based on total weight of the ready-to-use agent.
It is furthermore the aim of the present invention to provide the hair and scalp with skin- and hair-care substances on a lasting basis.
The above-mentioned active substances comprise at least one substance from the group of protein hydrolyzates, vitamins, amino acids, plant extracts and/or ectoine, used in agents according to the invention in an amount of 0.001 to 10 wt. %, preferably in an amount of 0.01 to 7.5 wt. % and in particular in an amount of 0.1 to 5 wt. %, based on total weight of the agent.
Another embodiment of the present invention is one wherein the agent also contains at least one conditioning substance from the group of protein hydrolyzates, vitamins, amino acids, plant extracts and/or ectoine.
It may be preferred that several substances from the above-mentioned group of active skin- and hair-care substances are present in the agent. A combination of at least one vitamin and at least one plant extract, an amino acid or ectoine or a combination of at least one protein hydrolyzate and at least one plant extract, an amino acid or ectoine, is preferred according to the invention. Particularly preferred is the combination of vitamins and amino acids, vitamins and ectoine, and protein hydrolyzates and amino acids.
Vitamins, provitamins and vitamin precursors, as well as derivatives thereof that are preferred according to the invention are those representatives generally allocated to 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). β-Carotene is the provitamin of retinol. Suitable as a vitamin A component are, for example, vitamin A acid and esters thereof, vitamin A aldehyde and vitamin A alcohol and esters thereof, such as palmitate and acetate. Agents according to the invention contain the vitamin A component preferably in amounts of 0.01 to 1 wt. %, based on total preparation.
The vitamin B group or vitamin B complex includes, inter alia:
The above compounds of the vitamin B group are present in agents according to the invention preferably in amounts of 0.01 to 2 wt. %, more preferably 0.03 to 1 wt. %, based on total agent.
Vitamin C (ascorbic acid). Vitamin C is used in the agents preferably in amounts of 0.01 to 3 wt. %, based on total agent. Use in the form of the palmitic ester, glucosides or phosphates may be preferred. Use in combination with tocopherols may likewise be preferred.
Vitamin E (tocopherols, in particular α-tocopherol). Tocopherol and its derivatives, including in particular esters such as acetate, nicotinate, phosphate and succinate, are present in the agents preferably in amounts of 0.01 to 1 wt. %, based on total agent.
Vitamin F. The term “vitamin F” is usually understood to mean essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid.
Vitamin H. The compound (3aS,4S,6aR)-2-oxohexahydrothienol[3,4-d]-imidazole-4-valeric acid is referred to as vitamin H, but its trivial name biotin has now become accepted. Biotin is present in the agents preferably in amounts of 0.0001 to 1.0 wt. %, in particular in amounts of 0.001 to 0.01 wt. %.
Agents according to the invention preferably contain vitamins, provitamins and vitamin precursors from the groups A, B, E and H. It is also possible for several vitamins and vitamin precursors to be present simultaneously. In a particularly preferred embodiment, the hair-treatment agents contain D-panthenol, optionally in a mixture with one of the other aforementioned vitamin components, to support the moisture-retaining capacity of the scalp and/or hair.
Suitable protein hydrolyzates according to the invention are product mixtures obtained by acid-, base- or enzyme-catalyzed degradation of proteins. The term “protein hydrolyzates” includes total hydrolyzates, individual amino acids and derivatives thereof as well as mixtures of various amino acids. Polymers built up from amino acids and amino acid derivatives are also understood according to the invention under the term “protein hydrolyzates”. The latter include polyalanine, polyasparagine, polyserine, etc. Other examples of compounds that can be used are L-alanyl-L-proline, polyglycine, glycyl-L-glutamine or D/L-methionine-S-methyl sulfonium chloride. It is also possible to use β-amino acids and derivatives thereof such as β-alanine, anthranilic acid or hippuric acid. The molecular weight of protein hydrolyzates that can be used is from 75, the molecular weight of glycine, to 200,000. The molecular weight is preferably 75 to 50,000 and most particularly preferably 75 to 20,000 Daltons.
According to the invention, protein hydrolyzates of plant and animal, marine or synthetic origin can be used in an amount of 0.01 to 10 wt. %, preferably 0.05 to 5 wt. % and in particular 0.1 to 3 wt. %, based on total weight of the agent according to the invention.
Animal protein hydrolyzates include elastin, collagen, keratin, silk and milk protein hydrolyzates, which may also be present in the form of salts. These products are marketed, for example, with the trademarks Dehylan® (Cognis), Promois® (Interorgana), Collapuron® (Cognis), Nutrilan® (Cognis), Gelita-Sol® (Deutsche Gelatine Fabriken Stoess & Co), Lexein® (Inolex), Kerasol® (Croda) or ProSina® (Croda).
Suitable protein hydrolyzates of vegetable origin include soy, almond, pea, potato, rice and wheat protein hydrolyzates. These products are obtainable, for example, with the trademarks Gluadin® (Cognis), DiaMin® (Diamalt), Lexein® (Inolex), Hydrosoy® (Croda), Hydrolupin® (Croda), Hydrosesame® (Croda), Hydrotritium® (Croda) and Crotein® (Croda).
Although use of protein hydrolyzates as such is preferred, amino acid mixtures obtained otherwise can also be used in their place. Also possible is the use of derivatives of protein hydrolyzates, for example, in the form of their fatty acid condensation products. Such products are marketed, for example, with the names Lamepon® (Cognis), Lexein® (Inolex), Crolastin® (Croda) or Crotein® (Croda).
The addition of a keratin, collagen or silk protein hydrolyzate to the active substance combination according to the invention has proved particularly suitable. Keratin hydrolyzate is particularly preferred in relation to an increase in the moisture-retaining capacity.
As a further preferred active skin- and/or hair-care substance, agents according to the invention can contain, with particular preference, one or more amino acids. Amino acids also have a skin-moisturizing action and, owing to their buffer effect, stabilize the acid mantle of the skin (i.e., they are used for (scalp) skin protection). Suitable amino acids according to the invention come from glycine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, tryptophan, proline, aspartic acid, glutamic acid, asparagine, glutamine, serine, threonine, cysteine, methionine, lysine, arginine, histidine, β-alanine, 4-aminobutyric acid (GABA), betaine, L-cystine (L-cyss), L-carnitine, L-citrulline, L-theanine, 3′,4′-dihydroxy-L-phenylalanine (L-dopa), 5′-hydroxy-L-tryptophan, L-homocysteine, S-methyl-L-methionine, S-allyl-L-cysteine sulfoxide (L-alliin), L-trans-4-hydroxyproline, L-5-oxoproline (L-pyroglutamic acid), L-phosphoserine, creatine, 3-methyl-L-histidine, L-ornithine, it being possible to use both the individual amino acids and mixtures.
Preferred agents contain one or more amino acids in relatively narrow ranges of quantities. Preferred hair-treatment agents contain as care substance, based on total weight of the agent, 0.01 to 5 wt. %, preferably 0.02 to 2.5 wt. %, more preferably 0.05 to 1.5 wt. %, even more preferably 0.075 to 1 wt. %, and in particular 0.1 to 0.25 wt. % amino acid(s), preferably from the group of glycine and/or alanine and/or arginine and/or serine and/or valine and/or lysine and/or leucine and/or threonine. Particularly preferred for use in agents according to the invention are the amino acids glycine, alanine and/or arginine.
As another preferred active skin and/or hair-care substance, the agents can particularly preferably contain plant extracts for mechanical and sensory strengthening of the hair.
These extracts are usually produced by extraction of the whole plant. In individual cases, however, it may also be preferred to produce the extracts exclusively from flowers and/or leaves of the plant.
According to the invention, the extracts of green tea, oak bark, echinacea, stinging nettle, witch hazel, hops, henna, chamomile, burdock root, horsetail, whitethorn, lime-tree blossom, almond, aloe vera, pine needles, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckoo flower, wild thyme, yarrow, thyme, melissa, rest harrow, coltsfoot, marshmallow, meristem, moringa, ginseng and ginger root in particular are preferred.
Most particularly preferred owing to their hair-strengthening action and their supporting action in relation to hair fullness are the extracts of green tea, chamomile, almond, aloe vera and moringa. According to the invention, a moringa extract is particularly preferred, for example, a product marketed with the trade name Puricare® LS 9658 or Moringa Oleifera®.
Plant extracts can be used according to the invention in both pure form and dilute form. When used in dilute form, they usually contain approx. 0.2-80 wt. % active substance and, as solvent, the extracting agent or mixture of extracting agents used to obtain them.
Furthermore, it may be preferred to use mixtures of more than one, in particular two, different plant extracts in agents according to the invention. Particularly preferred hair-treatment agents contain, based on their weight, 0.001 to 10 wt. %, preferably 0.005 to 5 and in particular 0.01 to 2 wt. %, plant extracts (corresponding to the active substance content of the extract).
As an additional active skin- and/or hair-care substance, the agents can also preferably contain ectoine ((4S)-2-methyl-1,4,5,6-tetrahydropyrimidine-4-carboxylic acid). Preferred hair-treatment agents according to the invention contain, based on their weight, 0.001 to 10 wt. %, preferably 0.01 to 5 wt. %, particularly preferably 0.05 to 2.5 wt. % and in particular 0.1 to 1 wt. % (S)-2-methyl-1,4,5,6-tetrahydro-4-pyrimidine carboxylic acid (ectoine) as well as the physiologically acceptable salts of this compound and/or (S,S)-5-hydroxy-2-methyl-1,4,5,6-tetrahydro-4-pyrimidine carboxylic acid (hydroxyectoine) as well as the physiologically acceptable salts of this compound.
Another embodiment of the present invention is one wherein the agent contains D-panthenol, keratin hydrolyzate, glycine, serine, arginine, Moringa oleifera extract and/or ectoine as an additional conditioning component.
In another embodiment of the invention, the hair-treatment agents also contain, based on their weight, in addition to the active substance combination according to the invention, a mixture of 0.01 to 2 wt. %, preferably 0.05 to 1.5 wt. % and in particular 0.1 to 1 wt. % D-panthenol and 0.01 to 2 wt. %, preferably 0.05 to 1.5 wt. % and in particular 0.1 to 1 wt. % glycine, serine and/or arginine.
In another embodiment of the invention, the hair-treatment agents also contain, based on their weight, in addition to the active substance combination according to the invention, a mixture of 0.01 to 2 wt. %, preferably 0.05 to 1.5 wt. % and in particular 0.1 to 1 wt. % D-panthenol and 0.01 to 2 wt. %, preferably 0.05 to 1.5 wt. % and in particular 0.1 to 1 wt. % ectoine.
In another embodiment of the invention, the hair-treatment agents also contain, based on their weight, in addition to the active substance combination according to the invention, a mixture of 0.01 to 2 wt. %, preferably 0.05 to 1.5 wt. % and in particular 0.1 to 1 wt. % D-panthenol and 0.01 to 2 wt. %, preferably 0.05 to 1.5 wt. % and in particular 0.1 to 1 wt. % moringa extract.
Depending on the desired treatment, the agent according to the invention can be formulated as a shampoo, leave-in or rinse-off conditioner, deep conditioner, hair-conditioning spray emulsion or foam aerosol. It is generally a leave-on or rinse-off conditioner, deep conditioner, hair-conditioning spray emulsion or foam aerosol if the agent also contains at least one cationic surfactant.
Another embodiment of the present invention is therefore provided wherein the agent is formulated as a shampoo, leave-in or rinse-off conditioner, deep conditioner, hair-conditioning spray emulsion or foam aerosol.
According to another preferred embodiment, the hair-treatment agent is a hair-conditioning agent which additionally contains cationic surfactants.
The invention therefore also relates to those agents having, based on their total weight, 0.1 to 10 wt. %, preferably 0.15 to 7.5 wt. %, more preferably 0.2 to 6.5 wt. % and in particular 0.25 to 5 wt. % cationic surfactants.
These are generally leave-on or rinse-off conditioners, deep conditioners, hair-conditioning spray emulsions or foam aerosols.
Cationic surfactants are generally chosen from quaternary ammonium compounds, esterquats and amidoamines.
Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methyl ammonium chlorides, for example, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 22 carbon atoms.
Esterquats are known substances having both at least one ester function and at least one quaternary ammonium group as structural element. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanol alkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines. Products of this type are marketed, for example, with the trademarks Stepantex®, Dehyquart® and Armocare®. The products Armocare® VGH-70, an N,N-bis(2-palmitoyloxyethyl)dimethyl ammonium chloride, and Dehyquart® F-75, Dehyquart® C-4046, Dehyquart® L80 and Dehyquart® AU-35 are examples of these esterquats.
Alkyl amidoamines are generally produced by amidation of natural or synthetic fatty acids and fatty acid blends with dialkylamino amines. A particularly suitable compound according to the invention from this group of substances is stearamidopropyl dimethylamine, commercially available as Tegoamid® S 18.
Use of cationic surfactants is not limited to hair-conditioning agents according to the invention. Indeed, hair-cleaning agents according to the invention can also contain cationic surfactants to increase skin compatibility and mildness.
In another embodiment, to increase skin mildness and reduce skin irritation, hair-treatment agents according to the invention also contain at least one nonionic surfactant in an amount of 0.1 to 10 wt. %, preferably 0.15 to 7.5 wt. %, more preferably 0.2 to 6.5 wt. % and in particular 0.25 to 5 wt. %, based on total weight of the agent.
These nonionic surfactants include:
Suitable nonionic surfactants are in particular the alkylene oxide addition products to saturated linear fatty alcohols and fatty acids as well as C8-C22 alkyl mono- and oligoglycosides and ethoxylated analogs thereof. In particular, non-ethoxylated compounds have proved particularly suitable.
Particularly preferred are alkyl polyglycosides of the formula RO—(Z)x, wherein R consists of C8-C10 alkyl groups, C12-C14 alkyl groups, substantially of C8-C16 alkyl groups, C12-C16 alkyl groups or C16-C18 alkyl groups. The alkyl polyglycosides that can be used according to the invention contain, on average, 1.1 to 5 sugar units. Alkyl polyglycosides with x values of 1.1 to 2.0 are preferred. Most particularly preferred are alkyl glycosides in which x is 1.1 to 1.8.
In another preferred embodiment of the present invention the ready-to-use agent has a pH value from 2.0 to 9.0, preferably 2.5 to 7.0. Particularly preferred and especially skin-compatible are agents in a pH range from 3.0 to 6.0. The pH values within the meaning of the present invention are pH values measured at a temperature of 22° C.
The pH value is generally adjusted with pH regulators. To adjust the pH value, one skilled in the art is familiar with acidifying and alkalinizing agents common in cosmetics. The alkalinizing agents that can be used to adjust the pH value are typically chosen from inorganic salts, particularly alkali and alkaline earth metals, organic alkalinizing agents, particularly amines, basic amino acids and alkanolamines, and ammonia. Preferred acidifying agents are food acids such as citric acid, acetic acid, malic acid or tartaric acid, as well as dilute mineral acids.
In addition to the compulsory components of the combination of active substances, hair-treatment agents according to the invention can, in a preferred embodiment, also contain additional hair-care substances which can support or increase the action according to the invention still further.
These preferred additional active substances are chosen from natural and synthetic oil components, active anti-dandruff substances, cationic polymers, UV filters and/or silicones.
Cationic polymers can preferably be used according to the invention. Suitable cationic polymers according to the invention are polymers having in the main and/or side chain groups that can be “temporarily” or “permanently” cationic. According to the invention, those polymers which, independently of the pH value of the agent, have a cationic group are referred to as “permanently cationic”. These are generally polymers having a quaternary nitrogen atom, for example, in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers wherein the quaternary ammonium group is linked via a C1-4 hydrocarbon group to a polymer main chain built up from acrylic acid, methacrylic acid or derivatives thereof, have proved particularly suitable.
A suitable homopolymer is the optionally crosslinked, poly(methacryloyloxyethyl trimethyl ammonium chloride) having the INCI name Polyquaternium-37. Crosslinking may optionally take place with the aid of olefinically polyunsaturated compounds such as divinylbenzene, tetraallyl oxyethane, methylene bisacrylamide, diallyl ether, polyallyl polyglyceryl ether, or allyl ethers of sugars or sugar derivatives, such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose.
The homopolymer is used preferably in the form of a non-aqueous polymer dispersion having a polymer content of no less than 30 wt. %. Polymer dispersions of this type are commercially available under the names Salcare® SC 95 and Salcare® SC 96.
Copolymers with the above-mentioned cationic monomer units contain as nonionogenic monomer units preferably acrylamide, methacrylamide, acrylic acid C1-C4 alkyl esters and methacrylic acid C1-C4 alkyl esters. Among these nonionogenic monomers, acrylamide is particularly preferred. These copolymers can also be crosslinked, as in the homopolymers described above. A preferred copolymer according to the invention is the crosslinked acrylamide-methacryloyloxyethyl trimethyl ammonium chloride copolymer. Copolymers of this type are available commercially with the name Salcare® SC 92.
Other preferred cationic polymers include:
It is also possible to use as cationic polymers, polymers known by the names Polyquaternium-24 (e.g., the commercial product Quatrisoft® LM 200). Likewise, the copolymers of vinylpyrrolidone, available as the commercial products Copolymer 845 (manufacturer: ISP), Gaffix® VC 713 (manufacturer: ISP), Gafquat®ASCP 1011, Gafquat®HS 110, Luviquat® 8155 and Luviquat® MS 370 can be used according to the invention.
Other cationic polymers according to the invention are “temporarily cationic” polymers. These polymers generally contain an amino group present at certain pH values as a quaternary ammonium group and thus in cationic form. For example, chitosan and derivatives thereof, freely available on the market, for example, with the trade names Hydagen® CMF, Hydagen® HCMF, Kytamer® PC and Chitolam® NB/101, are preferred.
In a particularly preferred embodiment, the agents also contain a cationic polymer for increasing deposition of active cosmetic skin- and hair-care substances and for skin and hair conditioning. This is preferably a cationic guar derivative and/or Polyquaternium-7 (Merquat 550), Polyquaternium-6, Polyquaternium-10, Polyquaternium-67 (SoftCat® polymers) and or Salcare® SC 95 or Salcare® SC 96. The cationic polymer(s) is (are) used in agents according to the invention in an amount of 0.01 to 10 wt. %, preferably from 0.05 to 5 wt. % and in particular from 0.1 to 3 wt. %, based on total weight of the agent.
Another preferred component according to the invention is an oil, which can be chosen from natural and synthetic oil components and/or fatty substances. In particular, conditioning agents according to the invention contain at least one oil and/or fat component.
As natural (vegetable) oils, triglycerides and mixtures of triglycerides are generally used. Preferred natural oils within the meaning of the invention 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 seed oil, cuckoo flower oil, thistle oil, macadamia nut oil, grape seed oil, amaranth seed 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, cocoa butter and shea butter.
In particular, mineral oils, paraffin oils and isoparaffin oils as well as synthetic hydrocarbons are used as mineral oils. One hydrocarbon that can be used according to the invention is 1,3-di-(2-ethylhexyl)cyclohexane (Cetiol® S), available as a commercial product.
Furthermore, a dialkyl ether can be used as the oil component. Dialkyl ethers that can be used include, in particular, di-n-alkyl ethers with a total of 12 to 36 C atoms, in particular 12 to 24 C atoms, such as di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl n-octyl ether, n-octyl n-decyl ether, n-decyl n-undecyl ether, 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 di-n-octyl ether, commercially available with the name Cetiol® OE.
Agents according to the invention contain the oil component(s) preferably in a quantitative range of 0.1 to 7 wt. %, in particular from 0.25 to 5 wt. %, based on total weight of the agent.
In another preferred embodiment, the action of the combination of active substances according to the invention can be optimized still further by additional fatty substances. Additional fatty substances are fatty alcohols as well as natural and synthetic waxes, which can be present both in solid form and as a liquid in aqueous dispersion.
The amount used in this case is 0.1 to 15 wt. %, based on total agent. In a preferred embodiment, the amount is 0.5 to 10 wt. %, with amounts of 1 to 5 wt. % being most particularly advantageous.
Saturated, mono- or polyunsaturated, branched or unbranched fatty alcohols with C6-C30, preferably C10-C22 and most particularly preferably C12-C22 alkyl chains can be used as fatty alcohols. Within the meaning of the invention, it is possible to use, for example, decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, erucyl alcohol, ricinol alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, capryl alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, as well as Guerbet alcohols thereof, this list being intended to be of an exemplary and not a limiting nature. Fatty alcohols preferably originate from natural fatty acids; however, it can generally be assumed that they are obtained from the esters of the fatty acids by reduction. It is likewise possible to use those fatty alcohol blends produced by reduction of naturally occurring triglycerides, such as beef tallow, palm oil, ground-nut oil, rape seed oil, cotton seed oil, soybean oil, sunflower oil and flax oil or fatty acid esters obtained from transesterification products thereof with corresponding alcohols, and thus represent a mixture of different fatty alcohols. Such substances can be purchased, for example, with the names Stenol®, e.g. Stenol® 1618, or Lanette®, e.g. Lanette® O, or Loral®, e.g. Lorol® C8, Lorol® C14, Lorol® C18, Lorol® C8-18, HD-Ocenol®, Crodacol®, e.g. Crodacol® CS, Novol®, Eutanol® G, Guerbitol® 16, Guerbitol® 18, Guerbitol® 20, Isofol® 12, Isofol® 16, Isofol® 24, Isofol® 36, Isocarb® 12, Isocarb® 16 or Isocarb® 24. It is also possible to use wool wax alcohols, commercially available, for example, with the names Corona®, White Swan®, Coronet® or Fluilan®.
As natural or synthetic waxes, it is possible according to the invention to use solid paraffins or isoparaffins, carnauba waxes, beeswaxes, candellila waxes, ozokerites, ceresin, sunflower wax, fruit waxes, such as for example apple wax or citrus wax, microwaxes of PE or PP. Waxes of this type are obtainable, for example, through Kahl & Co., Trittau.
Other fatty substances include:
Anti-dandruff agents also contribute towards improving agents according to the invention, since the reduction or inhibition of dandruff is also associated with better skin compatibility and a lower irritation potential for the scalp. Preferred agents therefore additionally contain at least one cosmetically acceptable active anti-dandruff substance. This is added to the compositions in an amount of 0.05 to 5 wt. %, preferably 0.1 to 3.0 wt. % and in particular 0.3 to 2.0 wt. % (based on total agent) and is chosen from piroctone olamine, climbazole, zinc pyrithione, ketoconazole, salicylic acid, sulfur, selenium sulfides, tar preparations, undecenoic acid derivatives, burdock root extracts, poplar extracts, stinging nettle extracts, walnut shell extracts, birch extracts, willow bark extracts, rosemary extracts and/or arnica extracts. Salicylic acid, climbazole, zinc pyrithione and piroctone olamine are preferred according to the invention.
Furthermore, in a preferred embodiment, an agent can also contain UV filters, since UV filters protect the scalp from the effects of elevated sun irradiation. In addition, it is known that certain active substances can cause skin irritation in combination with elevated sunlight or UV light irradiation, and it is therefore preferred according to the invention if the agents additionally contain a UV filter.
UV filters used according to the invention can be chosen from substituted benzophenones, p-aminobenzoic acid esters, diphenyl acrylic acid esters, cinnamic acid esters, salicylic acid esters, benzimidazoles and o-aminobenzoic acid esters.
Examples of UV filters that can be used according to the invention are 4-aminobenzoic acid, N,N,N-trimethyl-4-(2-oxoborn-3-ylidene methyl)aniline methyl sulfate, 3,3,5-trimethylcyclohexyl salicylate (homosalate), 2-hydroxy-4-methoxybenzophenone (benzophenone-3; Uvinul®M 40, Uvasorb® MET, Neo Heliopan®BB, Eusolex®4360), 2-phenylbenzimidazole-5-sulfonic acid and potassium, sodium and triethanolamine salts thereof (phenyl benzimidazole sulfonic acid; Parsol® HS; Neo Heliopan®Hydro), 3,3′-(1,4-phenylene dimethylene)bis(7,7-dimethyl-2-oxobicyclo-[2.2.1]hept-1-yl methanesulfonic acid) and salts thereof, 1-(4-tert.-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione (butyl methoxydibenzoylmethane; Parsol®1789, Eusolex®9020), α-(2-oxoborn-3-ylidene)toluene-4-sulfonic acid and salts thereof, ethoxylated 4-aminobenzoic acid ethyl ester (PEG-25 PABA; Uvinul®P 25), 4-dimethyl aminobenzoic acid 2-ethylhexyl ester (octyl dimethyl PABA; Uvasorb®DMO, Escalol®507, Eusolex®6007), salicylic acid 2-ethylhexyl ester (octyl salicylate; Escalol®587, Neo Heliopan®OS, Uvinul®018), 4-methoxycinnamic acid isopentyl ester (isoamyl p-methoxycinnamate; Neo Heliopan®E 1000), 4-methoxycinnamic acid 2-ethylhexyl ester (octyl methoxycinnamate; Parsol®MCX, Escalol®557, Neo Heliopan®AV), 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (benzophenone-4; Uvinul®MS 40; Uvasorb®S 5), 3-(4′-methylbenzylidene)-D,L-camphor (4-methylbenzylidene camphor; Parsol®5000, Eusolex®6300), 3-benzylidene camphor (3-benzylidene camphor), 4-isopropyl benzyl salicylate, 2,4,6-trianilino-(p-carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine, 3-imidazol-4-yl acrylic acid and ethyl esters thereof, polymers of N-{(2 and 4)-[2-oxoborn-3-ylidene methyl]benzyl}acrylamide, 2,4-dihydroxybenzophenone (benzophenone-1; Uvasorb®20 H, Uvinul®400), 1,1′-diphenylacrylonitrile acid 2-ethylhexyl ester (octocrylene; Eusolex®OCR, Neo Heliopan®Type 303, Uvinul®N 539 SG), o-aminobenzoic acid menthyl ester (menthyl anthranilate; Neo Heliopan®MA), 2,2′,4,4′-tetrahydroxybenzophenone (benzophenone-2; Uvinul®D-50), 2,2′-dihydroxy-4,4′-dimethoxybenzophenone (benzophenone-6), 2,2′-dihydroxy-4,4′-dimethoxybenzophenone-5-sodium sulfonate and 2-cyano-3,3-diphenylacrylic acid 2′-ethylhexyl ester. 4-Aminobenzoic acid, N,N,N-trimethyl-4-(2-oxoborn-3-ylidene methyl)aniline methyl sulfate, 3,3,5-trimethylcyclohexyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-phenylbenzimidazole-5-sulfonic acid and potassium, sodium and triethanolamine salts thereof, 3,3′-(1,4-phenylene dimethylene)bis(7,7-dimethyl-2-oxobicyclo-[2.2.1]hept-1-yl methanesulfonic acid) and salts thereof, 1-(4-tert.-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione, α-(2-oxoborn-3-ylidene)toluene-4-sulfonic acid and salts thereof, ethoxylated 4-aminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, salicylic acid 2-ethylhexyl ester, 4-methoxycinnamic acid isopentyl ester, 4-methoxycinnamic acid 2-ethylhexyl ester, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, 3-(4′-methylbenzylidene)-D,L-camphor, 3-benzylidene camphor, 4-isopropyl benzyl salicylate, 2,4,6-trianilino-(p-carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine, 3-imidazol-4-yl acrylic acid and ethyl ester thereof, polymers of N-{(2 and 4)[2-oxoborn-3-ylidene methyl]benzyl}acrylamide are preferred. 2-Hydroxy-4-methoxybenzophenone, 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 1-(4-tert.-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione, 4-methoxycinnamic acid 2-ethylhexyl ester and 3-(4′-methylbenzylidene)-D,L-camphor are most particularly preferred according to the invention.
Two preferred UV filters with cationic groups are the compounds cinnamic acid amidopropyl trimethyl ammonium chloride (Incroquat®UV-283) and dodecyl dimethyl-aminobenzamidopropyl dimethyl ammonium tosylate (Escalol® HP 610), available as commercial products.
The UV filters are present in agents according to the invention generally in amounts of 0.1 to 5 wt. %, preferably 0.4 to 2.5 wt. %, based on total agent.
Particularly preferred are hair-treatment agents having at least one silicone. Silicones bring about excellent conditioning properties on the hair. In particular, they improve combability of the hair in the wet and dry state and in many cases have a positive effect on the handle and softness of the hair. It is therefore desirable to add at least one silicone component, in particular in the case of hair conditioning agents. This is/these are chosen from:
The above-mentioned silicone components are added to the agents based on total weight of the agent, in an amount of 0.1 to 10 wt. %, preferably 0.2 to 7.5 wt. % and in particular 0.3 to 5 wt. % (based on the active substance content of silicone).
In another preferred embodiment, the agents can contain emulsifiers. Emulsifiers cause formation of water- or oil-stable adsorption layers at the phase interface, which protect the dispersed droplets from coalescence and thus stabilize the emulsion. Emulsifiers, like surfactants, are therefore constructed from a hydrophobic molecular moiety and a hydrophilic molecular moiety. Hydrophilic emulsifiers preferentially form O/W emulsions and hydrophobic emulsifiers preferentially form W/O emulsions. An emulsion is a droplet-like distribution (dispersion) of one liquid in another liquid with the expenditure of energy to create stabilizing phase interfaces by means of surfactants. Choice of these emulsifying surfactants or emulsifiers is governed here by substances to be dispersed and the particular outer phase, and also the finely divided nature of the emulsion. Emulsifiers which can be used according to the invention include:
Agents according to the invention contain emulsifiers preferably in amounts of 0.1-25 wt. %, in particular 0.5-15 wt. %, based on total agent.
Compositions according to the invention can preferably contain at least one nonionogenic emulsifier with an HLB value of 8 to 18. Nonionogenic emulsifiers with an HLB value of 10 to 15 may be particularly preferred according to the invention.
Furthermore, the agents can contain other active substances, auxiliary substances and additives, in particular
One skilled in the art chooses these additional substances according to the desired properties of the agents.
The present invention also provides for use of hair-treatment agents according to the invention for reducing hair damage in the interior of the hair and for increasing the elasticity of the hair.
The present invention also provides for use of hair-treatment agents according to the invention for restructuring the hair cortex.
The present invention also provides for use of hair-treatment agents according to the invention for improving the condition of the hair.
With regard to further embodiments of the uses according to the invention, the statements regarding the agents according to the invention apply mutatis mutandis.
The following examples explain the invention without limiting it thereto:
All data are—unless specified otherwise—in percent by weight.
Hair-care Shampoo 1—
Hair-care Shampoo 2—
Hair-care Shampoo 3—
Hair-care Shampoo 4—
The following commercial products were used:
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2009 003 154 | May 2009 | DE | national |
This application is a continuation of International Patent Application No. PCT/EP2010/055033 filed 16 Apr. 2010, which claims priority to German Patent Application No. 10 2009 003 154.5 filed 15 May 2009, both of which are incorporated herein by reference.
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| 6371993 | Moeller et al. | Apr 2002 | B1 |
| 20070160553 | Kripp et al. | Jul 2007 | A1 |
| 20110047712 | Gross et al. | Mar 2011 | A1 |
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| 20110162671 | Gross et al. | Jul 2011 | A1 |
| Number | Date | Country |
|---|---|---|
| 102007047685 | Jul 2008 | DE |
| 9213829 | Aug 1992 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20120121528 A1 | May 2012 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/EP2010/055033 | Apr 2010 | US |
| Child | 13296337 | US |
