Patent Application
20080247982
The invention relates to cleansing hair treatment products, for example hair shampoos, comprising both anionic and cationic surfactants.
Frequent bleaching, perming and coloring, but also frequent washing of the hair with degreasing surfactants, results in damage to the hair structure. The hair becomes brittle and loses its shine. In addition, the hair becomes electrostatically charged during combing, and the roughened, degreased hair surface causes matting and knotting of the hair. This makes combing more difficult. Despite this, many consumers wish to wash their hair daily on account of an increased need for hygiene.
To care for the hair, after hair washing, after-treatment products are often applied in a second step. As so-called hair cures, in the form of haircare rinses, aerosol foams or else in emulsion form as so-called cream rinses, these are rinsed out of the hair with water after a contact time of a few minutes. Leave-on products, e.g. in the form of conditioner sprays, hair fluids or styling products, for shaping and care, remain on the hair.
As active ingredients for improving the hair structure, such products comprise, inter alia, cationic polymers or cationic surfactants, i.e. quaternary ammonium compounds, such as cetyltrimethylammonium chloride on its own or in combination with various wax-like additives, such as, for example, hydrocarbons, fatty alcohols and fatty acids, which attach to the hair and improve its combability and shine.
On account of the consumer need for quicker and easier haircare, so-called two-in-one products have also been developed, through which hair washing and care take place at the same time. A series of care active ingredients is available for producing such conditioning shampoos.
These include oils and oil-like substances, such as, for example, liquid hydrocarbon compounds, fatty alcohols, monocarboxylic acid esters, polyalcohol esters, silicones, both soluble silicones, such as, for example, dimethicone copolyols, and insoluble silicones, for example polydimethylsiloxanes, and cationic surface-active compositions and cationic polymers.
Hair shampoos comprising anionic surfactants and cationic surfactants, however, cannot be formulated to be clear and stable on account of the reaction of these components to form so-called electroneutral salts.
It is an object of the present invention to provide cleansing and simultaneously conditioning, care hair shampoos which comprise both anionic and cationic surfactants and, despite the incompatibility of the components, are stable and form clear solutions.
Surprisingly, it has now been found that this aim can be achieved through a surfactant system in which the following are present: the anionic surfactants alkyl ether sulfate and/or alkyl sulfate, the anionic surfactant secondary alkanesulfonate, betaine and/or alkyl ether carboxylate, a nonionic surfactant.
The invention thus provides hair treatment products, preferably shampoos, comprising
a1) alkyl ether sulfate or
a2) alkyl sulfate or mixture thereof
b) secondary alkanesulfonate,
c1) betaine or
c2) ether carboxylate or mixture thereof,
d) one or more nonionic surfactants
and
e) a cationic surfactant.
The individual components are described below:
a1) Alkyl Ether Sulfates
These are water-soluble salts or acids of the formula RO(A)mSO3M in which R is an unsubstituted C10-C24-alkyl or hydroxyalkyl radical, preferably a C12-C20-alkyl or hydroxyalkyl radical, particularly preferably C12-C18-alkyl or hydroxyalkyl radical.
A is an ethoxy or propoxy unit, m is a number greater than 0, preferably between about 0.5 and about 6, particularly preferably between about 0.5 and about 3, and M is a hydrogen atom or a cation, such as, for example, sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation. Specific examples of substituted ammonium cations are methyl-, dimethyl-, trimethylammonium and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations, and those which are derived from alkylamines, such as ethylamine, diethylamine, triethylamine or mixtures thereof. Examples which may be mentioned are C12 to C18-fatty alcohol ether sulfates, where the content of EO is 1, 2, 2.5, 3 or 4 mol per mole of the fatty alcohol ether sulfate, and in which M is sodium or potassium.
a2) Alkyl Sulfates
These are water-soluble salts or acids of the formula ROSO3M, in which R is a C10-C24-hydrocarbon radical, preferably a C10-C20-alkyl or hydroxyalkyl radical, particularly preferably a C12-C18-alkyl or hydroxyalkyl radical.
M is hydrogen or a cation, e.g. an alkali metal cation (e.g. sodium, potassium, lithium) or ammonium or substituted ammonium, e.g. methyl-, dimethyl- and trimethylammonium cations, alkanolammonium, e.g. triethanolammonium and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations, derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof.
Components a1 and a2 are used individually or in any combination with one another in concentrations of from 1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3 to 12% by weight and very particularly preferably 4 to 10% by weight.
In secondary alkanesulfonates, the alkyl group can either be saturated or unsaturated, branched or linear and optionally substituted by a hydroxyl group. The sulfo group can be at any position of the C chain, where the primary methyl groups at the start of the chain and the end of the chain have no sulfonate groups. The preferred secondary alkanesulfonates contain linear alkyl chains having about 9 to 25 carbon atoms, preferably about 10 to about 20 carbon atoms and particularly preferably about 13 to 17 carbon atoms. The cation is, for example, sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium. It is also possible to use mixtures of different cations.
Very particular preference is given to secondary C13-17-alkanesulfonate, Na salt, which is available, for example, under the trade name Hostapur® SAS (Clariant), Leuna-Alkansulfonat or Emulgator E30 (Leuna-Tenside GmbH) or Marlon® PS (Sasol).
Secondary alkanesulfonates are used additionally to components a1 and/or a2. The mixing ratio of sec. alkanesulfonate:(a1 and/or a2) is here generally 9.9:0.1 parts by weight,
preferably 9.8 to 5:0.2 to 5 parts by weight,
particularly preferably 4.9 to 2.5:5.1 to 7.5 parts by weight,
and very particularly preferably 2.4 to 0.1:7.6 to 9.9 parts by weight.
c1) Betaines
Betaines can either be carbobetaines or sulfobetaines.
Preference is given to the carboxymethylammonium betaines, in particular C8- to C18-alkyldimethylcarboxymethylammonium betaines, C8- to C18-alkylamidopropyldimethylcarboxymethylammonium betaines and C8- to C18-alkyldipolyethoxycarboxymethylammonium betaines.
Further suitable betaines are, for example, the N-carboxyethylammonium betaines analogous to the compounds listed above, for whose synthesis chloropropionic acid and salts thereof are used instead of chloroacetic acid or salts thereof. Examples thereof are the C12-C18-alkylaminopropionates and C12-C18-alkyliminodipropionates as alkali metal and mono-, di- and trialkylammonium salts.
A preferred sulfobetaine is C12-C18-alkyldimethylsulfopropylbetaine.
c2) Ether carboxylate
Ether carboxylates preferably have the general formula
R—(O—CH2—CH2)n—O—CH2—COOX
where R can be n-alkyl, isoalkyl, cycloalkyl, alkylaryl, arylalkyl and/or aryl. Preferably, the radical R contains 8 to 18 carbon atoms and is derived from fatty alcohols, Ziegler alcohols, oxo alcohols, Guerbet alcohols and alkylphenols. Preference is given here to C8- to C18-alkyl ether carboxylates, and octyl-, nonyl-, and tributylphenol ether carboxylic acids.
Particularly preferred radicals R are C8-alkyl, C12/14-alkyl, iso-C13-alkyl, C14/15-oxoalkyl, C16/18-alkyl, lauryl, oleyl, and/or tallow fatty alkyl.
The index n=1 to 20, preferably 1 to 15, particularly preferably 1 to 12 and very particularly preferably 2 to 10.
X is hydrogen, sodium, potassium, ammonium and/or alkanolammonium, in particular triethanolammonium.
In the hair treatment products according to the invention, components c1 and c2 are used individually or in combination in a concentration of from 0.5 to 15% by weight, preferably from 1 to 10% by weight and particularly preferably from 2 to 7% by weight.
Suitable nonionic surfactants are, in particular, the ethoxylates of long-chain, aliphatic, synthetic or native alcohols with a C8- to C22-alkyl radical. These can contain about 1 to about 25 mol of ethylene oxide.
The alkyl chain of the aliphatic alcohols can be linear or branched, primary or secondary, saturated or else unsaturated.
Preference is given to the condensation products of C10- to C18-alcohols with about 2 to about 18 mol of ethylene oxide per mole of alcohol. The alcohol ethoxylates can have a narrow homolog distribution of the ethylene oxide (“narrow range ethoxylates”) or a broad homolog distribution of the ethylene oxide (“broad range ethoxylates”). Particular preference is given to the C9-C11 oxo alcohol with 6 to 10 mol of EO and the C12/C14-fatty alcohol with 5 to 9 mol of EO. Very particular preference is given to the C11-oxo alcohol-8EO-ethoxylate and the C12/14-fatty alcohol-7EO-ethoxylate. The oxyethylated alcohols preferably have an HLB value of from 10 to 15, preferably 11 to 14.
The use concentration is generally 1 to 30% by weight, preferably 5 to 25% by weight and particularly preferably 10 to 20% by weight.
The quantitative ratio of anionic surfactant to nonionic surfactant is generally 1:4 to 4:1, preferably 1:2 to 2:1, very particularly preferably 0.8:1 to 1.5:1.
Suitable cationic surfactants are, for example, quaternary ammonium salts, such as di(C10-C24)-alkyldimethylammonium chloride or bromide, preferably di(C12-C18)-alkyldimethylammonium chloride or bromide; (C10-C24)-alkyldimethylethylammonium chloride or bromide; (C10-C24)-alkyltrimethylammonium chloride or bromide, preferably cetyltrimethylammonium chloride or bromide and (C20-C22)-alkyltrimethylammonium chloride or bromide; (C10-C24)-alkyldimethylbenzylammonium chloride or bromide, preferably (C12-C18)-alkyldimethylbenzylammonium chloride; N—(C10-C18)-alkylpyridinium chloride or bromide, preferably N—(C12-C16)-alkylpyridinium chloride or bromide; N—(C10-C18)-alkylisoquinolinium chloride, bromide or monoalkyl sulfate; N—(C12-C18)-alkylpolyoylaminoformylmethylpyridinium chloride; N—(C12-C18)-alkyl-N-methylmorpholinium chloride, bromide or monoalkyl sulfate; N—(C12-C18)-alkyl-N-ethylmorpholinium chloride, bromide or monoalkyl sulfate; (C16-C18)-alkylpentaoxyethylammonium chloride; diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride; salts of N,N-diethylaminoethylstearylamide and -oleylamide with hydrochloric acid, acetic acid, lactic acid, citric acid, phosphoric acid; N-acylaminoethyl-N,N-diethyl-N-methylammonium chloride, bromide or monoalkyl sulfate and N-acylaminoethyl-N,N-diethyl-N-benzylammonium chloride, bromide or monoalkyl sulfate, where acyl is preferably stearyl or oleyl.
The weight fraction of the cationic surfactants in the hair treatment products according to the invention (e.g. in the case of hair conditioner) is preferably in the range from 1 to 10% by weight, particularly preferably 2 to 7% by weight, especially particularly preferably 3 to 5% by weight.
In a particularly preferred embodiment, the hair treatment products according to the invention comprise, as solvent, propanediol, glycerol or ethanol in concentrations of from 1 to 10% by weight, preferably from 1 to 5% by weight.
In a further particularly preferred embodiment, the pH of the formulations is adjusted to a value between 5 and 12 by adding acidic or alkaline substances. Acidic substances can be, for example, inorganic or organic acids, such as, for example, sulfuric acid, phosphonic acids, citric acid. Alkaline substances are, for example, sodium hydroxide solution, potassium hydroxide solution and soda.
The hair treatment products according to the invention are preferably liquid and clear. However, by adding further ingredients as are customary for such products, it is also possible for opaque or milky cloudy formulations or those with a pearlescent effect to result.
The following further customary constituents can additionally be present in the hair treatment products according to the invention:
anionic, nonionic, cationic, zwitterionic or amphoteric surfactants, and auxiliaries and additives, such as emulsifiers, superfatting agents, biogenic active ingredients, film formers, preservatives, pearlizing agents, dyes.
Anionic surfactants are, in particular, the following compounds and mixtures thereof:
alkali metal salts, ammonium salts, amine salts and salts of amino alcohols of the following compounds: alkylamide sulfates and ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, α-olefinsulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinamates, alkyl sulfoacetates, alkylpolyglycerol carboxylates, alkyl phosphates, alkyl ether phosphates, alkyl sarcosinates, alkyl polypeptidates, alkyl amidopolypeptidates, alkyl ethionates, alkyl taurates, salts of saturated and unsaturated fatty acids, such as oleic acid, ricinoleic acid, palmitic acid, stearic acid, copra oil acid salt or hydrogenated copra oil acid salts, and alkyl polyethoxycarboxylates.
Nonionic surfactants are, in particular, polyethoxylated, polypropoxylated or polyglycerolated ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerolated fatty acid esters, polyethyloxylated esters of fatty acids and of sorbitol, polyethoxylated or polyglycerolated fatty amides.
Further amphoteric or zwitterionic surfactants, additionally to the carbobetaines and sulfobetaines mentioned at the start, are aminoglycinates and amphoteric imidazolinium compounds, cycloimidinium compounds, such as alkylimidazolines, asparagine derivatives, where the alkyl group in these surface-active agents preferably has 1 to 22 carbon atoms.
Cationic polymers which are used in the shampoos according to the invention in addition to the cationic surfactants are preferably homopolymers and copolymers based on diallyldimethylammonium chloride (DADMAC).
Copolymers based on DADMAC comprise, as further components, other vinylic monomers, such as, for example, vinylimidazole, vinylpyrrolidone, vinyl alcohol, vinyl acetate, (meth)acrylic acid (ester), acrylamide, styrene, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid (AMPS), etc.
The total surfactant content of the hair treatment products according to the invention is preferably 5 to 40% by weight, preferably 10 to 30% by weight, in particular 15 to 25% by weight.
Homopolymers based on DADMAC are also obtainable under the trade names Dodigen® 3954, Dodigen 4033 and Genamin® PDAC (Clariant).
The hair treatment products according to the invention can comprise, as auxiliaries and additives, emulsifiers, such as, for example, nonionic emulsifiers, for example oxyethylated or polyglycerolated fatty alcohols, e.g. oleic alcohol, polyoxyethylated with 10 to 30 mol of ethylene oxide, stearyl alcohol with 10 to 15 or 20 mol of ethylene oxide, oleic alcohol, polyglycerolated with 4 mol of glycerol, synthetic fatty alcohols having 9 to 15 carbon atoms, polyoxyethylated with 5 to 10 mol of ethylene oxide, sorbitan esters, monoglycerides, polysorbates, polyethylene glycol mono/di-fatty acid esters, highly ethoxylated fatty acid esters, and high molecular weight silicone compounds, such as, for example, dimethylpolysiloxane and phosphoric acid esters in an amount of from 1 to 25% by weight, or ionic emulsifiers, such as optionally oxyethylated alkyl sulfates, e.g. sodium lauryl sulfate, ammonium lauryl sulfate, ammonium lauryl sulfate, sodium cetylstearyl sulfate, triethanolamine stearyl sulfate, monoethanolamine lauryl sulfate, sodium lauryl ether sulfate, and monoethanolamine lauryl ether sulfate, these latter emulsifiers being present in concentrations between 0.5 and 15% by weight. Superfatting agents which may be used are substances such as, for example, polyethoxylated lanolin derivatives, lecithin derivatives and fatty acid alkanolamides, the latter serving as foam stabilizers at the same time. The thickeners used are preferably hydrogenated castor oil, salts of long-chain fatty acids, preferably in amounts up to 5% by weight and in particular in amounts of from 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium and titanium stearates or the sodium and/or potassium salts of behenic acid, and also polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethylcellulose and hydroxyethylcellulose, also relatively high molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone, and electrolytes such as sodium chloride and ammonium chloride.
Biogenic active ingredients are to be understood as meaning, for example, plant extracts, protein hydrolyzates and vitamin complexes. Customary film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives and similar compounds. Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentadiol or sorbic acid. Suitable pearlizing agents are, for example, glycol distearic esters, such as ethylene glycol distearate, but also fatty acid monoglycol esters or triethylene glycol distearate. Dyes which can be used are the substances approved and suitable for cosmetic purposes, as are listed, for example, in the publication “Kosmetische Färbemittel” [Cosmetic Colorants] from the Dyes Commission of the German Research Society, published in Verlag Chemie, Weinheim, 1984, pp. 81-106. These dyes are usually used in concentrations of from 0.001 to 0.1% by weight, based on the total mixture. The desired viscosity can be established by adding water and/or organic solvents or by adding a combination of organic solvents and thickeners. With the hair treatment products according to the invention it is possible to improve the shine, the dry combability and the reduction in the regreasing of the hair. Furthermore, an antistatic and feel-improving effect and a pleasant skin feel are found. They have the effect that dry hair is relaxed, shiny and easy to detangle.
The hair shampoos according to the invention are also particularly well suited for colored, tinted or dyed hair since they bring about better fixing of the hair coloration and reduce its washing-out.
A hair shampoo with a total surfactant content of 27% (active ingredient) was prepared.
The anionic surfactants used were Genapol LRO and Hostapur SAS 60, the betaine used was Genagen CAB 818, the nonionic surfactant used was C12/14-alkyl-7EO ethoxylate and the cationic surfactant used was Genamin BTLF.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2004 053 967.7 | Nov 2004 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP05/11852 | 11/5/2005 | WO | 00 | 1/22/2008 |
