EP2099411A2 - Combinaison synergique de protéines de soie et de métaux sélectionnés - Google Patents

Combinaison synergique de protéines de soie et de métaux sélectionnés

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Publication number
EP2099411A2
EP2099411A2 EP07822560A EP07822560A EP2099411A2 EP 2099411 A2 EP2099411 A2 EP 2099411A2 EP 07822560 A EP07822560 A EP 07822560A EP 07822560 A EP07822560 A EP 07822560A EP 2099411 A2 EP2099411 A2 EP 2099411A2
Authority
EP
European Patent Office
Prior art keywords
copolymer
acid
polymers
group
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP07822560A
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German (de)
English (en)
Inventor
Marcus Krueger
Dieter Goddinger
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2099411A2 publication Critical patent/EP2099411A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/98—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution of animal origin
    • A61K8/987—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution of animal origin of species other than mammals or birds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/04—Preparations for permanent waving or straightening the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/413—Nanosized, i.e. having sizes below 100 nm
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers
    • A61K2800/522—Antioxidants; Radical scavengers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers
    • A61K2800/524—Preservatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes

Definitions

  • the invention relates to cosmetic compositions containing a synergistically effective combination of silk proteins and selected metals and to the use of these compositions for the cleansing and / or care of skin and hair.
  • human hair is today treated in a variety of ways with hair cosmetic preparations. These include, for example, the cleansing of hair with shampoos, the care and regeneration with rinses and cures and the bleaching, dyeing and shaping of the hair with dyes, tinting agents, waving agents and styling preparations. In this case, means for changing or nuancing the color of the head hair play a prominent role.
  • the bleaching agents that cause an oxidative lightening of the hair by degradation of the natural hair dyes, so in the field of hair coloring essentially three types of hair dye are of importance:
  • oxidation colorants For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components.
  • the developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components.
  • the oxidation stains are characterized by excellent, long lasting staining results. For natural-looking dyeings but usually has a Mixture of a larger number of oxidation dye precursors are used; In many cases, direct dyes are still used for shading.
  • dyeing or tinting agents which contain so-called direct drawers as a coloring component. These are dye molecules that grow directly on the hair and do not require an oxidative process to form the color. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much more undesirable nuance shift or even a visible "discoloration" occurs much more quickly.
  • the hair is treated with special active ingredients, for example quaternary ammonium salts or special polymers, usually in the form of a rinse.
  • special active ingredients for example quaternary ammonium salts or special polymers, usually in the form of a rinse.
  • this treatment improves the combability, the hold and the fullness of the hair and reduces the splitting rate.
  • These preparations contain, in addition to the usual components, for example for the cleaning of the hair, in addition to active ingredients which were formerly reserved for the hair aftertreatment agents.
  • the consumer thus saves an application step; At the same time, packaging costs are reduced because one product is less needed.
  • active ingredients both for separate aftertreatment agents and for combination preparations generally have a preferential effect on the hair surface.
  • active ingredients are known which give the hair shine, hold, fullness, better wet or dry combabilities or prevent splitting.
  • the internal structural cohesion of the hair fibers which can be greatly influenced, in particular, by oxidative and reductive processes such as dyeing and perming.
  • the object of the present invention is therefore to provide compositions for compositions for the treatment and conditioning of keratinic fibers, in particular for the cleaning and care of keratinic fibers, which can very particularly preferably be applied subsequently to previously oxidatively treated keratinic fibers. At the same time the skin irritation of these agents is reduced. In addition to agents for the oxidative dyeing of hair, the color stability of the coloration is furthermore significantly improved despite the subsequent washing and conditioning process. In means for carrying out a cold wave, the volume and the durability of the cold wave are influenced just as positively in the subsequent application of the compositions according to the invention as the very good combability.
  • protein hydrolysates which are able to significantly restructure the internal structure of fibers, in particular keratinous fibers, are used as care active substances.
  • Structural strengthening that is to say restructuring in the context of the invention, is to be understood as meaning a reduction in the damage of keratinic fibers which has arisen due to the most diverse influences.
  • the restoration of natural strength plays an essential role.
  • Restructured fibers are distinguished, for example, by an improved gloss or by an improved grip or by easier combing.
  • they have an optimized strength and elasticity.
  • Successful restructuring can be physically understood as a melting point increase compared to prove damaged fiber. The higher the melting point of the hair, the firmer the structure of the fiber.
  • Protein hydrolysates have been known for a long time and are widely used in cosmetic products. Reference may be made to the relevant literature, for example in A. Domsch, "The Cosmetic Preparations", Volume II, page 205 and following, Publishing House for the chemical industry, H. Ziolkowsky. However, there is no indication of a restructuring, which is characterized by an increased strength and elasticity to find.
  • a cosmetically very interesting fiber protein is silk.
  • silk By silk one understands the fibers of the cocoon of the mulberry silkworm (Bombyx mori L.).
  • the raw silk fiber consists of a double thread fibroin.
  • sericin holds this double thread together.
  • Silk consists of 70-80% by weight of fibroin, 19-28% by weight of sericin, 0.5-1% by weight of fat and 0.5-1% by weight of dyes and mineral constituents.
  • the essential components of sericin are with about 46 wt.% Hydroxyamino acids.
  • the sericin consists of a group of 5 to 6 proteins.
  • the essential amino acids of sericin are serine (Ser, 37% by weight), aspartate (Asp, 26% by weight), glycine (Gly, 17% by weight), alanine (Ala), leucine (Leu) and tyrosine (Tyr) ,
  • the water-insoluble fibroin belongs to the skieroproteins with a long-chain molecular structure.
  • the main components of the fibroin are glycine (44 wt.%), Alanine (26 % By weight), and tyrosine (13% by weight).
  • Another important structural feature of the fibroin is the hexapeptide sequence Ser-Gly-Ala-Gly-Ala-Gly.
  • hydrolysates or full silk products are known.
  • the raw material under the name Crosilk ® Liquid one for years used successfully raw material in cosmetic compositions.
  • a first subject of the present invention are therefore cosmetic preparations containing an active substance complex consisting of an active ingredient (I) selected from natural silk and / or derivatives thereof and mixtures thereof, and an active ingredient (II) selected from at least one metal and / or at least a salt of these metals, wherein the metal is selected from an element of the 1st and / or 8th subgroup of the periodic table and mixtures thereof.
  • the active ingredient complex used according to the invention significantly synergistically improves the above-described essential internal and external structural features and the strength and elasticity of human hair. Furthermore, this active ingredient complex has an increased antibacterial activity. This is extremely advantageous according to the invention, because if necessary, at least some preservatives can be dispensed with. Finally, the active ingredient complex according to the invention contributes to increased protection against UV radiation. Therefore, in the compositions according to the invention optionally the amount of necessary UV filter can be significantly reduced. Thus, the active ingredient complex according to the invention leads to compositions which in their Ingredients can be limited to a mandatory level and still show excellent cosmetic effect. The corresponding cosmetic compositions containing the active ingredient complex according to the invention thus have a significantly increased compatibility and are particularly mild.
  • a cosmetic composition containing the active ingredient according to the invention is applied complexly following an oxidative treatment of keratinic fibers such as, for example, a coloring, bleaching or a well process, the adverse oxidative damage of the keratinic fibers is significantly and significantly reduced by such treatments.
  • the active ingredient complex according to the invention shows a marked anti-oxidative effect on oxidatively treated keratinic fibers.
  • active ingredients (I) in the active ingredient complex can be used: native sericin, hydrolyzed and / or further derivatized sericin, such as commercial products with the INCI names Sericin, Hydrolyzed Sericin, or Hydrolyzed SiIk, a mixture of the amino acids serine, aspartate and glycine and / or their methyl, propyl, isopropyl, butyl, isobutyl esters, their salts such as, for example, hydrochlorides, sulfates, acetates, citrates, tartrates, in which mixture the serine and / or derivatives thereof contain from 20 to 60% by weight , the aspartate and / or its derivatives to 10 - 40 wt.% And the glycine and / or its derivatives to 5 to 30 wt.% Are included, with the proviso that the amounts of these amino acids and / or their derivatives preferably to 100% by weight, and mixtures thereof.
  • native sericin such as
  • the following can be used complexly as active ingredients (I) in the active ingredient: native fibroin converted into a soluble form, hydrolyzed and / or further derivatized fibroin, especially partially hydrolyzed fibroin, which contains as its main constituent the amino acid sequence Ser-Gly-Ala-Gly-Ala-Gly, the amino acid sequence Ser-Gly-Ala-Gly-Ala-Gly, a mixture of the amino acids glycine, Alanine and tyrosine and / or their methyl, propyl, iso-propyl, butyl, iso-butyl esters, their salts such as hydrochlorides, sulfates, acetates, citrates, tartrates, wherein in this mixture, the glycine and / or its derivatives in amounts of 20 60% by weight, containing alanine and its derivatives in amounts of 10-40% by weight, and the tyrosine and its derivatives in amounts of 0
  • At least one of the active ingredient components (I) of the active ingredient complex is used in the native or at most solubilized form. According to the invention, it is also possible to use a mixture of several active substances (I).
  • the active substances sericin and / or its derivatives and fibroin and / or its derivatives in the ratio of 10:90 to 70:30, in particular 15:85 to 50:50 and very particularly 20:80 to 40: 60 are used based on their respective contents of active substance in the preparations according to the invention.
  • the derivatives of sericin and fibroin hydrolysates include both anionic and cationized protein hydrolysates.
  • the protein hydrolysates of sericin and fibroin according to the invention and the derivatives prepared therefrom can be obtained from the corresponding proteins by chemical, in particular alkaline or acid hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis.
  • the hydrolysis of proteins usually results in a protein hydrolyzate having a molecular weight distribution of about 100 daltons all the way to several thousand daltons.
  • cationic protein hydrolysates of sericin and fibroin and / or derivatives thereof whose underlying protein content has a molecular weight of 100 to 25,000 daltons, preferably 250 to 10,000 daltons.
  • cationic protein hydrolysates of sericin and fibroin also mean quaternized amino acids and mixtures thereof.
  • the quaternization of the protein hydrolysates or amino acids is often carried out using quaternary ammonium salts such as N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides.
  • the cationic protein hydrolysates may also be further derivatized.
  • cationic protein hydrolysates and derivatives those mentioned under the INCI names in the "International Cosmetic Ingredient Dictionary and Handbook", (seventh edition 1997, The Cosmetic, Toiletry and Fragrance Association 1 101 17 th Street, NW, Suite 300, Washington, DC 20036-4702) and commercially available products: Cocodimonium Hydroxypropyl Hydrolyzed Silica, Cocodimonium Hydroxypropyl Silica, Amino Acids, Hydroxyproypltrimonium Hydrolyzed Silica, Lauryldimonium Hydroxypropyl Hydrolyzed Silica, Steardimonium Hydroxypropyl Hydrolyzed Silica, Quaternium 79 Hydrolyzed Silica.
  • anionic protein hydrolysates and derivatives according to the invention are those listed under the INCI names in the International Cosmetic Ingredient Dictionary and Handbook, (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1 101 17 th Street, NW, Suite 300, Washington, DC 20036-4702) and commercially available products: Potassium Cocoyl Hydrolyzed SiCl, Sodium Lauroyl Hydrolyzed SiIk, or Sodium Stearoyl Hydrolyzed SiIk.
  • the active ingredient (I) is also the natural silk itself, the natural colloidal silk brought into solution by known methods and processes and any hydrolyzate and derivative from the complete silk.
  • the natural silk hydrolyzate derivatives include both anionic and cationized protein hydrolysates.
  • the protein hydrolyzates of the natural silk according to the invention and the derivatives prepared therefrom can be obtained from the corresponding proteins by chemical, in particular alkaline or acid hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. In particular, this also includes peptides from the complete silk.
  • the molecular weight of such silk is between 80 D and 400,000 D.
  • a molar weight of 80 D to 100,000 D is preferred, particularly preferred is a molecular weight of 80 D to 60,000 D, very particularly preferred is a molecular weight of 80 D up to 40,000 D, most preferred is a molecular weight of from 80D to 30,000D and most preferably a molecular weight from 80D to 20,000D.
  • the invention also encompasses that the natural silk or its hydrolysates can be derivatized both anionically and cationically.
  • Typical examples of the cationic protein hydrolysates and derivatives of the present invention can be found in the International Cosmetic Ingredient Dictionary and Handbook, (seventh edition 1997, The Cosmetic, Toiletry and Fragrance Association 1 101 17 th Street, NW, Suite 300, Washington, DC 20036 -4702) and are commercially available.
  • the active ingredient (I) in amounts of 0.1 to 99.9 wt .-% based on the total active ingredient complex. Amounts of 50 to 99.9 especially 75 to 99.5 wt% are most preferred, and amounts greater than 90 wt% are most preferred, with amounts greater than 95 wt% being most preferred.
  • the active ingredient (II) according to the invention is at least one metal or at least one metal salt from one of the elements of the first and / or eighth subgroup of the Periodic table and their mixtures.
  • These include the metals iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, as well as copper, silver and gold and their salts.
  • the metals rhodium, palladium, iridium, platinum, silver and gold and salts thereof are preferred.
  • the metals palladium, platinum, silver and gold and salts thereof are particularly preferred. Most preferably, the metals are platinum, silver and gold and their salts.
  • At least one metal is used as active ingredient (II), then this metal is present as finely divided metal dust. Preference is given to a particle size in the range of a few nanometers, the so-called nanoparticles.
  • this metal salt is selected from the physiologically acceptable salts. These are in particular the halides, fluoride, chloride, bromide, the sulfates, the phosphates, acetates, tartrates, citrates, lactates, as well as the salts of these elements with the natural alpha-amino acids.
  • the active ingredient (II) in amounts of 10 ppb - 1 wt .-% based on the total active ingredient complex. Amounts of from 10 ppb to 0.5 wt%, especially from 1 ppm to 0.2 wt%, are most preferred, and amounts of from 5 ppm to 0.2 wt% are most preferred, with amounts of 5 ppm to 0.1% by weight is most preferred.
  • the entire active substance complex is contained in amounts of 0.001-10% by weight, based on the total agent. Quantities of 0.005 to 5, in particular 0.01 to 3 wt .-%, are very particularly preferred.
  • the raw materials are commercially available under the names Fine Silk ® Crystal - called Nano Gold - Nano Gold and Fine-Silk ® Pep.
  • keratinic fibers are understood to mean furs, wool, feathers and, in particular, human hair.
  • fatty substances (D) can be further increased.
  • Fatty substances are to be understood as meaning fatty acids, fatty alcohols, natural and synthetic waxes, which can be in solid form as well as liquid in aqueous dispersion, and natural and synthetic cosmetic oil components.
  • fatty acids (D1) it is possible to use linear and / or branched, saturated and / or unsaturated fatty acids having 6 to 30 carbon atoms. Preference is given to fatty acids having 10 to 22 carbon atoms. Among these could be mentioned, for example, isostearic as the commercial products Emersol ® 871 and Emersol ® 875, and isopalmitic acids such as the commercial product Edenor ® IP 95, and all other products sold under the trade names Edenor ® (Cognis) fatty acids.
  • fatty acids are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and Erucic acid and its technical mixtures, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from the Roelen oxo synthesis or the dimerization of unsaturated fatty acids incurred.
  • Particularly preferred are usually the fatty acid cuttings obtainable from coconut oil or palm oil; In particular, the use of stearic acid is usually preferred.
  • the amount used is 0.1 - 15 wt.%, Based on the total mean.
  • the amount is preferably 0.5-10% by weight, with amounts of 1-5% by weight being particularly advantageous.
  • Fatty alcohols (D2) may be used are saturated, mono- or polyunsaturated, branched or unbranched fatty alcohols with C 6 - C o-3, preferably C10 - C22 and most preferably C 12 - C 22 - carbon atoms.
  • Decanols, octanols, dodecadienol, decadienol, oleyl alcohol, eruca alcohol, ricinoleic alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, caprylic alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol are, for example, decanol, octanolol, dodecadienol, decadienol , as well as their Guerbet alcohols, this list should have exemplary and non-limiting character.
  • the fatty alcohols are derived from preferably natural fatty acids, which can usually be based on recovery from the esters of fatty acids by reduction.
  • those fatty alcohol cuts which are produced by reducing naturally occurring triglycerides such as beef tallow, palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil and linseed oil or fatty acid esters formed from their transesterification products with corresponding alcohols, and thus represent a mixture of different fatty alcohols.
  • Such substances are, for example, under the names Stenol ® such as Stenol ® 1618 or Lanette ® such as Lanette ® O or Lorol ®, for example, Lorol ® C8, Lorol C14 ®, Lorol C18 ®, ® Lorol C8-18, HD-Ocenol ®, Crodacol ® such as Crodacol ® CS, Novol ®, Eutanol ® G, Guerbitol ® 16, Guerbitol ® 18, Guerbitol ® 20, Isofol ® 12, Isofol ® 16, lsofol ® 24, Isofol ® 36, Isocarb ® 12, Isocarb ® 16 or acquire Isocarb® ® 24 for sale.
  • Stenol ® such as Stenol ® 1618 or Lanette ® such as Lanette ® O or Lorol ®
  • Lorol ® C8 Lorol C8-18
  • wool wax alcohols as are commercially available, for example under the names of Corona ®, White Swan ®, Coronet ® or Fluilan ® can be used according to the invention.
  • the fatty alcohols are used in amounts of from 0.1 to 30% by weight, based on the total preparation, preferably in amounts of from 0.1 to 20% by weight.
  • waxes As natural or synthetic waxes (D3) it is possible according to the invention to use solid paraffins or isoparaffins, carnauba waxes, beeswaxes, candelilla waxes, ozokerites, ceresin, spermaceti, sunflower wax, fruit waxes such as, for example, apple wax or citrus wax, microwaxes of PE or PP.
  • Such waxes are available, for example, from Kahl & Co., Trittau.
  • the amount used is 0.1-50 wt.% Based on the total agent, preferably 0.1 to 20 wt.% And particularly preferably 0.1 to 15 wt.% Based on the total agent.
  • Can increase the effect of the active ingredient complex according to the invention are, for example, include: vegetable oils.
  • vegetable oils examples include sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach kernel oil and the liquid portions of coconut oil.
  • triglyceride oils such as the liquid portions of beef tallow as well as synthetic triglyceride oils.
  • the compounds are available as commercial products 1, 3-di- (2-ethyl-hexyl) -cyclohexane (Cetiol ® S), and di-n-octyl ether (Cetiol ® OE) may be preferred.
  • Ester oils are understood as meaning the esters of Ce - C30 fatty acids with C 2 - C 30 fatty alcohols.
  • the monoesters of the fatty acids with alcohols having 2 to 24 carbon atoms are preferred.
  • fatty acid components used in the esters are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and Erucic acid and its technical mixtures, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from the Roelen oxo synthesis or the dimerization of uns
  • fatty alcohol components in the ester oils are isopropyl alcohol, Caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical grade Mixtures obtained, for example, in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols.
  • isopropyl myristate IPM Rilanit ®
  • isononanoic acid C16-18 alkyl ester Cetiol ® SN
  • 2-ethylhexyl palmitate Cegesoft ® 24
  • stearic acid-2-ethylhexyl ester Cetiol ® 868
  • cetyl oleate glycerol tricaprylate, Kokosfettalkohol- caprate / caprylate (Cetiol ® LC)
  • n-butyl stearate oleyl erucate
  • isopropyl palmitate IPP Rilanit ®
  • oleyl Oleate Cetiol ®
  • hexyl laurate Cetiol ® A
  • di-n-butyl adipate Cetiol ® B
  • myrist IPM Rilanit ®
  • Dicarboxylic acid esters such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, di- (2-ethylhexyl) succinate and di-isotridecyl acelate
  • diol esters such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di (2 ethylhexanoate), propylene glycol di-isostearate, propylene glycol di-pelargonat, butanediol di-isostearate, Neopentylglykol- dicaprylate, symmetrical, asymmetric or cyclic esters of carbonic acid with fatty alcohols, for example described in DE-OS 197 56 454, glycerol carbonate or dicaprylyl carbonate (Cetiol ® CC),
  • Fatty acid partial glycerides ie monoglycerides, diglycerides and their technical mixtures. With the use of technical products production reasons may still contain small amounts of triglycerides.
  • the partial glycerides preferably follow the formula (D4-I), CH 2 O (CH 2 CH 2 O) m R 1
  • R 3 in the R 1 , R 2 and R 3 is independently of one another hydrogen or a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18, Carbon atoms are provided with the proviso that at least one of these groups is an acyl radical and at least one of these groups is hydrogen.
  • the sum (m + n + q) is 0 or numbers from 1 to 100, preferably 0 or 5 to 25.
  • R 1 is an acyl radical and R 2 and R 3 are hydrogen and the sum (m + n + q) is 0.
  • Typical examples are mono- and / or diglycerides based on caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic , Linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
  • oleic acid monoglycerides are used.
  • the amount used of the abovementioned oil bodies in the compositions used according to the invention is usually 0.1-30% by weight, based on the total agent, preferably 0.1-20% by weight, and in particular 0.1-15% by weight. ,
  • Another group of substances that can be used as fatty substances are silicones.
  • silicone oils As a further class of substances, which is included as an alternative to the previously described in the compositions of the invention as an active ingredient, the silicone oils (S). Silicone oils cause a wide variety of effects. For example, at the same time they influence the dry and wet combability, the grip of dry and wet hair and the shine. But also the softness and the elasticity of the film, which is formed by film-forming polymers on the hair for the purpose of strengthening and styling, is positively influenced by silicones.
  • silicone oils is understood by the person skilled in the art to mean several structures of organosilicon compounds.
  • the dimethiconols according to the invention can be both linear and branched as well as cyclic or cyclic and branched.
  • Linear dimethiconols can be represented by the following structural formula (S1-I): (SiOHR 1 2 ) -O- (SiR 2 2 -O-) x - (SiOHR 1 2 ) (S1-I)
  • Branched dimethiconols can be represented by the structural formula (S1-II):
  • the radicals R 1 and R 2 are each independently hydrogen, a methyl radical, a C 2 to C 30 linear, saturated or unsaturated hydrocarbon radical, a phenyl radical and / or an aryl radical.
  • the groups represented by R 1 and R 2 include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, 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-
  • R 1 examples include methylene, ethylene, propylene, hexamethylene, decamethylene, -CH 2 CH (CH 3 ) CH 2 -, phenylene, naphthylene, -CH 2 CH 2 SCH 2 CH 2 -, - CH 2 CH 2 OCH 2 - , -OCH 2 CH 2 -, -OCH 2 CH 2 CH 2 -, -CH 2 CH (CH 3 ) C (O) OCH 2 -, - (CH 2 ) 3 CC (O) OCH 2 CH 2 -, C 6 H 4 C 6 H 4 -, -C 6 H 4 CH 2 C 6 H 4 -; and - (CH 2 ) 3 C (O) SCH 2 CH 2 -.
  • R 1 and R 2 are methyl, phenyl and C 2 to C 22 alkyl radicals. Of the C2 to C22 alkyl radicals, lauryl, stearyl and behenyl radicals are particularly preferred.
  • the numbers x, y and z are integers and each run independently from 0 to 50,000.
  • the molecular weights of Dimethicone lie between 1,000 D and 10000000 D.
  • the viscosities are between 100 and 10,000,000 cPs measured at 25 0 C by means of a glass capillary viscometer according to Dow Corning Corporate Test Method CTM 0004 dated 20 July 1970.
  • Preferred viscosities are 1000-5000000 cPs, very particularly preferred viscosities lie between 10,000 and 3,000,000 cps. The most preferred range is between 50,000 and 2,000,000 cps.
  • the teaching of the invention also includes that the dimethiconols may already be present as an emulsion.
  • the corresponding emulsion of the dimethiconols can be prepared both after the preparation of the corresponding dimethiconols from these and the usual methods of emulsification known to the person skilled in the art.
  • both cationic, anionic, nonionic or zwitterionic surfactants and emulsifiers can be used as auxiliaries for the preparation of the corresponding emulsions.
  • the emulsions of Dimethiconole can also directly through
  • Emulsion polymerization process can be prepared. Such methods are also well known to the person skilled in the art. For example, reference may be made to the Encyclopedia of Polymer Science and Engineering, Volume 15, Second Edition, pages 204 to 308, John Wiley & Sons, Inc. 1989. This reference is expressly incorporated herein by reference.
  • the droplet size of the emulsified particles is according to the invention from 0.01 ⁇ m to 10000 ⁇ m, preferably from 0.01 to 100 ⁇ m, very particularly preferably from 0.01 to 20 ⁇ m and most preferably from 0.01 to 10 microns.
  • the particle size is determined by the method of light scattering.
  • branched dimethiconols are used, it is to be understood that the branching is greater than a random branching, which occurs by impurities of the respective monomers randomly.
  • branched dimethiconols are therefore to be understood as meaning that the degree of branching is greater than 0.01%.
  • a degree of branching is greater than 0.1%, and most preferably greater than 0.5%.
  • the degree of branching is determined from the ratio of unbranched monomers, that is, the amount of monofunctional siloxane, to the branching monomers, that is, the amount of tri- and tetrafunctional siloxanes. According to the invention both low branched as well as highly branched Dimethiconole be very particularly preferred.
  • Examples of such products include the following commercial products: Botanisil NU-150M (Botanigenics), Dow Coming 1-1254 Fluid, Dow Corning 2-9023 Fluid, Dow Corning 2-9026 Fluid, Ultrapure Dimethiconol (Ultra Chemical), Unisil SF- R (Universal Preserve), X-21-5619 (Shin-Etsu Chemical Co.), AbN OSW 5 (Degussa Care Specialties), ACC DL-9430 Emulsion (Taylor Chemical Company), AEC Dimethiconol & Sodium Dodecylbenzenesulfonate (A & E Connock (Perfumery & Cosmetics) Ltd.), BC Dimethiconol Emulsion 95 (Basildon Chemical Company, Ltd.), Cosmetic Fluid 1401, Cosmetic Fluid 1403, Cosmetic Fluid 1501, Cosmetic Fluid 1401 DC (all aforementioned Chemsil Silicones, Inc.), Dow Corning 1401 Fluid, Dow Corning 1403 Fluid, Dow Corning 1501 Fluid, Dow Corning 1784 HVF
  • the dimethiconols (S1) are present in the compositions according to the invention in amounts of from 0.01 to 10% by weight, preferably from 0.01 to 8% by weight, particularly preferably from 0.1 to 7.5% by weight and in particular from 0.1 to 5% by weight of dimethiconol based on the composition.
  • the dimethiconols form a separate phase in the compositions according to the invention. In this case, it may be appropriate to homogenize the composition shortly before use by shaking it in the short term.
  • the amount of dimethiconol may be up to 40% by weight, preferably in amounts of up to 25% by weight, based on the total composition.
  • Dimethicones (S2) form the second group of silicones, which are particularly preferred according to the invention.
  • the dimethicones according to the invention can be both linear and branched as well as cyclic or cyclic and branched.
  • Linear dimethicones can be represented by the following structural formula (S2-I): (SiR 1 S) -O- (SiR 2 2 -O-) x - (SiR 1 S) (S2-I)
  • Branched dimethicones can be represented by the structural formula (S2 - II):
  • the radicals R 1 and R 2 are each independently hydrogen, a methyl radical, a C 2 to C 30 linear, saturated or unsaturated hydrocarbon radical, a phenyl radical and / or an aryl radical.
  • the groups represented by R 1 and R 2 include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, 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-
  • R 1 examples include methylene, ethylene, propylene, hexamethylene, decamethylene, -CH 2 CH (CH 3 ) CH 2 -, phenylene, naphthylene, -CH 2 CH 2 SCH 2 CH 2 -, - CH 2 CH 2 OCH 2 - , -OCH 2 CH 2 -, -OCH 2 CH 2 CH 2 -, -CH 2 CH (CH 3 ) C (O) OCH 2 -, - (CH 2 ) 3 CC (O) OCH 2 CH 2 -, C 6 H 4 C 6 H 4 -, -C 6 H 4 CH 2 C 6 H 4 -; and - (CH 2 ) 3 C (O) SCH 2 CH 2 -.
  • R 1 and R 2 are methyl, phenyl and C 2 to C 22 alkyl radicals. Of the C2 to C22 alkyl radicals, lauryl, stearyl and behenyl radicals are particularly preferred.
  • the numbers x, y and z are integers and each run independently from 0 to 50,000.
  • the molecular weights of Dimethicone lie between 1,000 D and 10000000 D.
  • the viscosities are between 100 and 10,000,000 cPs measured at 25 0 C by means of a glass capillary viscometer according to Dow Corning Corporate Test Method CTM 0004 dated 20 July 1970.
  • Preferred viscosities are 1000-5000000 cPs, very particularly preferred viscosities lie between 10,000 and 3,000,000 cps. The most preferred range is between 50,000 and 2,000,000 cps.
  • the teaching of the invention also includes that the dimethicones may already be present as an emulsion.
  • the corresponding emulsion of the dimethicones can be prepared both after the preparation of the corresponding dimethicones from these and the usual methods of emulsification known to the person skilled in the art.
  • both cationic, anionic, nonionic or zwitterionic surfactants and emulsifiers can be used as auxiliaries for the preparation of the corresponding emulsions.
  • the emulsions of dimethicones can also be prepared directly by an emulsion polymerization process. Such methods are also well known to the person skilled in the art. For example, reference may be made to the Encyclopedia of Polymer Science and Engineering, Volume 15, Second Edition, pages 204 to 308, John Wiley & Sons, Inc. 1989. This reference is expressly incorporated herein by reference.
  • the droplet size of the emulsified particles according to the invention is 0.01 ⁇ m to 10000 ⁇ m, preferably 0.01 to 100 ⁇ m, very particularly preferably 0.01 to 20 ⁇ m and most preferably 0.01 to 10 microns.
  • the particle size is determined by the method of light scattering.
  • branched dimethicones are used, it is to be understood that the branching is greater than a random branching, which occurs by impurities of the respective monomers randomly.
  • branched dimethicones are therefore to be understood as meaning that the degree of branching is greater than 0.01%.
  • a degree of branching is greater than 0.1%, and most preferably greater than 0.5%.
  • the degree of branching is determined from the ratio of unbranched monomers, that is, the amount of monofunctional siloxane, to the branching monomers, that is, the amount of tri- and tetrafunctional siloxanes. According to the invention both low branched as well as highly branched Dimethicone be very particularly preferred.
  • the dimethicones (S2) are present in the compositions according to the invention in amounts of from 0.01 to 10% by weight, preferably from 0.01 to 8% by weight, particularly preferably from 0.1 to 7.5% by weight and in particular from 0.1 to 5% by weight of dimethiconone based on the composition.
  • the dimethicones form a separate phase in the compositions according to the invention.
  • it may be appropriate to homogenize the composition shortly before use by shaking it in the short term.
  • the amount of dimethicone may be up to 40% by weight, preferably in amounts of up to 25% by weight, based on the total composition.
  • Aminofunctional silicones or also called amodimethicones (S4), are silicones which have at least one (optionally substituted) amino group.
  • Such silicones may e.g. by the formula (S4-I)
  • R is a hydrocarbon or a hydrocarbon radical having 1 to about 6 carbon atoms
  • Q is a polar radical of the general formula -R 1 HZ, wherein R 1 is a divalent connecting group attached to hydrogen and the Z is an organic, amino-functional radical containing at least one amino-functional group, carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms or carbon, hydrogen and nitrogen atoms; "a” assumes values in the range of about 0 to about 2, “b” assumes values in the range of about 1 to about 3, “a” + “b” is less than or equal to 3, and “c” is a number in the range from about 1 to about 3, and x is a number in the range of 1 to about 2,000, preferably from about 3 to about 50, and most preferably from about 3 to about 25, and y is a number ranging from about 20 to about 10,000, preferably from about 125 to about 10,000, and most preferably from about 150 to about 1,000, and M a suitable silicone end group, as known in the art,
  • 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,
  • R 1 examples include methylene, ethylene, propylene, hexamethylene, decamethylene, -CH 2 CH (CH 3 ) CH 2 -, phenylene, naphthylene, -CH 2 CH 2 SCH 2 CH 2 -, - CH 2 CH 2 OCH 2 - , -OCH 2 CH 2 -, -OCH 2 CH 2 CH 2 -, -CH 2 CH (CH 3 ) C (O) OCH 2 -, - (CHz) 3 CC (O) OCH 2 CH 2 -, -C 6 H 4 C 6 H 4 -, -C 6 H 4 CH 2 C 6 H 4 -; and - (CH 2 ) 3 C (O) SCH 2 CH 2 -.
  • Z is an organic, amino-functional radical containing at least one functional amino group.
  • a possible formula for Z is NH (CH 2 ) Z NH 2 , wherein z is 1 or more.
  • Another possible formula for Z is -NH (CH 2 ) Z (CH 2 ) ZZ NH, wherein both z and zz are independently 1 or more, which structure includes diamino ring structures, such as piperazinyl.
  • Z is most preferably a -NHCH 2 CH 2 NH 2 radical.
  • Z is - N (CH 2 ) Z (CH 2 ) ZZ NX 2 or -NX 2 , wherein each X of X 2 is independently selected from the group consisting of hydrogen and alkyl groups of 1 to 12 carbon atoms, and zz is 0.
  • Q is most preferably a polar, amine functional group of the formula - CH 2 CH 2 CH 2 NH 2 CH 2 CH 2 NH 2 .
  • "a” assumes values in the range of about 0 to about 2
  • "b” assumes values in the range of about 2 to about 3
  • "a” + “b” is less than or equal to 3
  • the molar ratio of the R 3 Q b SiO (4-ab) / 2 units to the R c SiO (4-C) / 2 units is in the range from about 1: 2 to 1:65, preferably from about 1: 5 to about 1:65, and most preferably from about 1:15 to about 1:20.
  • Preferred agents according to the invention are characterized in that they contain an amino-functional silicone of the formula (S4-II)
  • G is -H, a phenyl group, -OH, -O-CH 3 , -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 H 3, -CH 2 CH (CH 3) 2, -CH (CH 3) CH 2 CH 3, -C (CH 3) 3;
  • a is a number between 0 and 3, in particular 0;
  • b is a number between 0 and 1, in particular 1,
  • m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably values from 0 to 1999 and in particular from 49 to 149 and m is preferably from 1 to 2000, in particular from 1 to 10,
  • R ' is a monovalent radical selected from o -N (R ") - CH 2 -CH 2 -N (R") 2 o -N ( R ") 2 o -N
  • Particularly preferred agents according to the invention are characterized in that they contain an amino-functional silicone of the formula (S4-III)
  • n and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably values of 0 to 1999 and in particular of 49 to 149 and m preferably values of 1 to 2000 , in particular from 1 to 10 assumes.
  • silicones are referred to as trimethylsilylamodimethicones according to the INCI declaration.
  • compositions according to the invention which are characterized in that they contain an amino-functional silicone of the formula (S4-IV) are also particularly preferred.
  • n1 and n2 are numbers whose sum (m + n1 + n2) is between 1 and 2,000, preferably between 50 and 150 , where the sum (n1 + n2) preferably assumes values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10.
  • silicones are referred to as amodimethicones according to the INCI declaration.
  • agents according to the invention are preferred in which the amino-functional silicone has an amine number above 0.25 meq / g, preferably above 0.3 meq / g and in particular above 0.4 meq / g ,
  • the amine number stands for the MiIIi- equivalents of amine per gram of amino-functional silicone. It can be determined by titration and also expressed in mg KOH / g.
  • the amodimethicones (S4) are present in the compositions according to the invention in amounts of from 0.01 to 10% by weight, preferably from 0.01 to 8% by weight, particularly preferably from 0.1 to 7.5% by weight and in particular from 0.1 to 5% by weight of amodimethicone based on the composition.
  • the amodimethicones it is also possible for the amodimethicones to form a separate phase in the compositions according to the invention.
  • the amount of amodimethicone may be up to 40% by weight, preferably in amounts of up to 25% by weight, based on the total composition.
  • completely novel polyammonium polysiloxane compounds are known in which the siloxane substructures are optionally connected to each other via ammonium substructures. Such compounds and their use in cosmetic products are described, for example, in the published patent application WO 02/10257.
  • compositions of the invention may contain at least one polyammonium-polysiloxane compound, which is constructed as described below.
  • the polyammonium-polysiloxane compounds contain:
  • A is one of the groups: -CH 2 C (O) O-, -CH 2 CH 2 C (O) O-, -CH 2 CH 2 CH 2 C (O) O-, -OC (O) CH 2 -, -OC (O) CH 2 CH 2 - and / or -OC (O) CH 2 CH 2 CH 2 -,
  • a ' means: -CH 2 C (O) -, -CH 2 CH 2 C (O) -, -CH 2 CH 2 CH 2 C (O) -, -C (O) CH 2 -, -C (O ) CH 2 CH 2 - and / or -C (O) CH 2 CH 2 CH 2 - and
  • E represents a polyalkylene oxide group of the general formulas:
  • S represents -Si (R 1) 2 -O [-Si (R 1) 2 -O] n-Si (R 1) 2 and wherein R 1 is 22 -alkyl Ci-C, Ci-C 22 -Fluoralkyl or aryl, n is 0 to 1000, and when there are several groups S in the polysiloxane compound, they may be the same or different, wherein K is a bivalent or trivalent straight-chain, cyclic or branched C 2 -
  • C 40 hydrocarbon radical which is represented by -O-, -N-, -NR 1 -, -C (O) -, -C (S) -, -N + (R 3 ) - and -
  • N + (R 1 ) (R 3 ) - may be interrupted and substituted with -OH, wherein R 1 is as defined above, or optionally a bond to a divalent radical R 3 , and wherein R 3 is a monovalent or divalent straight chain, cyclic or branched dC 20 hydrocarbyl radical which may be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH, or -AER 2 , wherein A, E and
  • R is as defined above, wherein the radicals K may be the same or different from each other, and in the case where K represents a trivalent radical, the saturation of the third valence over one
  • the polysiloxane compounds according to the invention are characterized in that they have the above-defined components a1) to a4).
  • the polysiloxane compounds are formed by binding of said structural units or radicals a1) to a3) to each other.
  • Component a4) serves to neutralize the positive charges resulting from component a2).
  • the polysiloxane compounds of the invention may be oligomers or polymeric compounds. Oligomeric compounds also include the case described below wherein the polysiloxane compound has only one repeating unit.
  • Polysiloxane compounds of the invention are naturally formed by alternating linkage of divalent radicals.
  • the terminal atom groups result from the terminal atom groups of the starting materials used. This is known per se to the person skilled in the art.
  • the polymeric polysiloxane compounds according to the invention are linear polyammonium-polysiloxane compounds which are composed of the structural components a1) to a3).
  • the linear polymeric polysiloxane compounds according to the invention in particular their formed from the repeat units linear polymeric backbone, by alternating juxtaposition of polyalkylene oxide structural units a1), organic radicals containing at least one, preferably quaternary ammonium group a2) and polysiloxane structural units a3) are constructed. That is, the optionally present in the structural components beyond free valences (as may occur in trivalent radicals as component a2) or trivalent radicals K) are preferably not used to build polymeric side chains or polymeric branches.
  • the main chain of the linear polymeric polysiloxane compounds according to the invention can be built up from the organic radicals containing at least one ammonium group a2) and the polysiloxane structural units a3), and the polyalkylene oxide structural units a1) bind as side chains to the trivalent organic ammonium group radical.
  • the following structures can result: - (polyalkylene oxide structural unit-polysiloxane structural unit-polyalkylene oxide structural unit - preferably quaternary ammonium group radical) x -
  • polysiloxane compounds according to the invention may result which have only one repeating unit. This is known per se to the person skilled in the art. This case leads, for example, to inventive polysiloxane compounds of the structure:
  • the polysiloxane compounds according to the invention preferably consist essentially of the components a1) to a4), the polymeric polysiloxane compounds according to the invention naturally having the terminal groups resulting from the reaction of the monomeric starting materials. However, it is also possible to use monofunctional chain terminators.
  • polyalkylene oxide structural units a) may be divalent radicals of the general formulas:
  • the rest A ' means: -CH 2 C (O) -, -CH 2 CH 2 C (O) -, - CH 2 CH 2 CH 2 C (O) -, -C (O) CH 2 -, -C (O) CH 2 CH 2 - and / or - C (O) CH 2 CH 2 CH 2 -.
  • the polyalkylene oxide structural units a1) may furthermore be a monovalent, ie terminal polyalkylene oxide structural unit of the formula: - AER 2 , in which A and E have the abovementioned meaning, and R 2 is H, straight-chain, cyclic or branched CrC 20 - Hydrocarbon radical which may be interrupted by -O-, or -C (O) - and substituted with -OH and acetylenic, olefinic or aromatic.
  • the component a2) from which the polysiloxane compounds according to the invention are composed is at least one divalent or trivalent organic radical which contains at least one ammonium group.
  • the binding of the radical to the other components of the polysiloxane compounds of the invention is preferably carried out via the nitrogen atom of one or more ammonium groups in the organic radical.
  • divalent or trivalent means that the organic ammonium radical to form bonds in particular to the other components of the polysiloxane compounds according to the invention has two or three free valences.
  • the ammonium radical is expediently represented by an NH 4 + group in which at least two hydrogen atoms are substituted by organic groups.
  • quaternary ammonium group is by general definition (see, for example, Römpp Chemie Lexikon) a group in which all four hydrogen atoms of an NH 4 + group are replaced by organic radicals.
  • the component a2) of the polysiloxane compounds according to the invention is at least one polysiloxane structural unit of the general formula:
  • S is a polysiloxane group of the general formula
  • R 1 is preferably C 1 -C 8 -alkyl, C 1 -C 8 -fluoroalkyl and aryl. Furthermore, R1 is preferably d-ds-alkyl, d-Ce-fluoroalkyl and aryl. Furthermore, R 1 is preferably C r C 6 alkyl, Ci - C 6 - fluoroalkyl, preferably dC 4 fluoroalkyl, and phenyl. More preferably, R 1 is methyl, ethyl, trifluoropropyl and phenyl.
  • C r C 22 -alkyl in the context of the present invention means that the aliphatic hydrocarbon groups have 1 to 22 carbon atoms, which may be straight-chain or branched. Examples which may be mentioned are methyl, ethyl, propyl, n-butyl, pentyl, hexyl, heptyl, nonyl, decyl, undecyl, isopropyl, neopentyl and 1,2,3 trimethylhexyl.
  • C 1 -C 22 -fluoroalkyl in the context of the present invention means aliphatic hydrocarbon compounds having 1 to 22 carbon atoms which may be straight-chain or branched and having at least one fluorine atom are substituted. Examples which may be mentioned are monofluoromethyl, monofluoroethyl, 1,1,1-trifluoroethyl, perfloroethyl, 1,1,1-trifluoropropyl, 1,2,2-trifluorobutyl.
  • aryl in the context of the present invention are unsubstituted or mono or polysubstituted with OH, F, Cl, CF 3 C r C 6 alkyl, C r C 6 alkoxy, C 3 -C 7 - cycloalkyl, C 2 -C 6 alkenyl or phenyl substituted phenyl.
  • the term may optionally also mean naphthyl.
  • K represents a divalent or trivalent straight-chain, cyclic or branched C 2 -C 4O hydrocarbon radical which is represented by -O-, -NH-, -N-, C (O) -, -C (S) -, -N + (R 3 ) -, -NR 1 -, and -N + (R 1 ) (R 3 ) - may be interrupted and substituted with -OH.
  • the group K binds via a carbon atom to the silicon atom of the group S.
  • the group K can, as seen above, also preferably have quaternary ammonium groups, so that ammonium groups result in addition to the ammonium groups in said component a2) in the polysiloxane compounds according to the invention.
  • the polysiloxane compounds according to the invention can, for example in the radical K, have amino groups.
  • the reaction of the polysiloxane compounds according to the invention with acids leads to their protonation.
  • Such protonated amino group-containing polysiloxane compounds are included in the scope of the present invention.
  • the binding of component a3), the polysiloxane structural unit -KSK-, to the other structural components via the radical K preferably does not take place via a nitrogen atom of the radical K.
  • R 1 is as defined above or optionally represents a bond to a divalent radical R 3 , so that a cycle results.
  • R 3 represents a monovalent or divalent straight-chain, cyclic or branched -C 2 o-hydrocarbon radical, interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted with -OH, or -AER 2 , wherein A, E and R 2 are as defined above.
  • the radicals K can be identical or different from one another, and in the case where K represents a trivalent radical, the saturation of the third valence takes place via a bond to the abovementioned organic radical which contains at least one ammonium group.
  • the polysiloxane compounds according to the invention furthermore contain component a4), at least one organic or inorganic anionic acid radical for neutralizing the charges resulting from the (n) ammonium group (s).
  • Organic or inorganic acid radicals are radicals that formally result from the elimination of one or more protons from organic or inorganic acids and include, for example, halides such as fluoride, chloride, bromide, sulfates, nitrates, phosphates, carboxylates such as formate, acetate, propionate etc., sulfonates, sulfates, polyether carboxylates and polyether sulfates etc. Chloride is preferred.
  • the organic or inorganic anionic acid radicals as component a4) of the polysiloxane compounds according to the invention may be identical or different from one another.
  • halide ions preferably result from the reaction of the amines with alkyl halides, while, for example, carboxylates result from the carboxylic acids which can be added in the reaction of bisepoxides with amines.
  • K represents a bivalent or trivalent straight-chain, cyclic or branched C 2 -C 40 hydrocarbon radical which is represented by -O-, -NH-, -N-, -NR 1 -, -C ( O) -, -C (S) - may be interrupted and substituted with -OH, wherein R 1 is as defined above, and wherein the radicals K may be the same or different from each other.
  • organic radical which contains at least one, preferably quaternary ammonium, group is preferably a radical of the general formula:
  • N 1 is a quaternary ammonium group of the general formula - (R 4 ) N + (R 5 ) -, wherein R 4 represents a monovalent or divalent straight chain, cyclic or branched C 1 -C 20 hydrocarbon radical which may be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH, and R 5 is a monovalent straight-chain, cyclic or branched C 1 -C 20 -hydrocarbon radical represents, which may be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted with -OH, or a single bond to a divalent radical R 4 or a tetravalent radical F, and the radicals R 4 and R 5 within the group -N 1 -FN 1 - as well as in the polysiloxane compound may be the same or different
  • F is a divalent or tetravalent straight-chain, cyclic or branched C 2 -C 30 -hydrocarbon radical which is represented by -O-, -NH-, -N-, - C (O) -, -C (S) -, a siloxane chain S , wherein for S the above-mentioned references apply, can be interrupted and substituted with -OH.
  • the abovementioned organic radical which contains at least one, preferably quaternary ammonium, group may furthermore preferably be a radical of the general formula - (R 6 ) N + (R 7 ) -, in which R 6 is a monovalent or divalent straight-chain, cyclic or branched d C 30 -hydrocarbon radical, which is represented by -O-, -NH-,
  • -C (O) -, -C (S) - may be interrupted and substituted with -OH, or R 6 represents a single bond to a trivalent radical K.
  • R 7 is a monovalent straight chain, cyclical or branched C 1 -C 2 0- hydrocarbon radical, interrupted by -O-, -NH-, -C (O) -, -C (S) - may be substituted with -OH and interrupted, or -AER 2 , wherein -AER 2 has the abovementioned meaning, or a single bond to a divalent radical R 6 or to a trivalent radical K.
  • the radicals R 6 and R 7 may be the same or different from each other.
  • the aforementioned organic radical containing at least one ammonium group may further preferably be a radical of the general formula:
  • N 5 is an ammonium group of the general formula
  • R 23 is hydrogen, a monovalent or divalent straight-chain, cyclic or branched C 1 -C 2 0- hydrocarbon radical, interrupted by -O-, -NH-, -C (O) -, -C (S) - interrupted and - OH can be substituted,
  • R 24 is hydrogen, a monovalent straight-chain, cyclic or branched d-C 2 o-
  • a particular embodiment of the polyammonium-polysiloxane compounds (which will be referred to as the first embodiment of component a) of the active ingredient complex), wherein the aforementioned organic radical containing at least one, preferably quaternary ammonium, as component a2) of the polysiloxane compounds according to the invention a radical the general formula:
  • B is -AEKSKEA- and additionally -AE-A'- and -A'-EA-, where S, K, -AE-, - EA-, -AE-A'- and -A'-EA, respectively - and -N 1 -FN 1 - are as defined above, and the proportion of the group -AE-A 'or -A'-EA- in the group B can be chosen such that the mass of -AE-A 'or -A'-EA- is from 0 to 90%, preferably 0% or 0.1 to 50% of the mass of the polysiloxane content S in the polymer.
  • the first embodiment of the polyammonium-polysiloxane compounds preferably relates to linear alkylene-oxide-modified polyquaternary polysiloxanes of the general formula (I 1 )
  • K is a divalent straight-chain, cyclic or branched C 2 -C 20 -
  • Hydrocarbon radical which may be interrupted by -O-, -NH-, -NR 1 -, -C (O) -, -C (S) and substituted by -OH
  • E is a polyalkylene oxide unit of the structure - [CH 2 CH 2 O ] q - [CH 2 CH (CH 3 ) O] r - with, q 1 to 200, r 0 to 200 and
  • a -CH 2 C (O) O-, -CH 2 CH 2 C (O) O- or - CH 2 CH 2 CH 2 C (O) O-, N 1 is a quaternary ammonium structure
  • R 4 represents a monovalent or divalent straight, cyclic or branched dC 20 hydrocarbon radical interrupted by O-, -NH, -C (O) -, -C (S) - and.
  • F is a divalent or tetravalent straight-chain, cyclic or branched C 2 -Cs 0 hydrocarbon radical represented by -O-, -NH-, -N-, -C (O) -, -C (S) -, a siloxane chain S, where S is the above-mentioned references, may be interrupted and substituted with -OH.
  • the possibility of a tetravalent substructure for F means that F can form a branched or ring system with the limiting N 1 , so that F then participates with two bonds at each quaternization of both limiting N 1 .
  • WO 02/10257 for a more detailed illustration, reference is made to the published patent application WO 02/10257, in particular to Example 1 therein.
  • the possibility of a divalent substructure for R 4 means that in these cases it is a cyclic-structure-forming structure in which R 5 in this case is a single bond to R 4 .
  • Examples are morpholinyl and piperidinyl structures. More preferred embodiments of this so-called first embodiment of the invention and processes for the preparation of said polysiloxane compounds of the formula (I) or (I 1 ) are described below.
  • R 4 is preferably -CH 3 , -CH 2 CH 3 , - (CH 2 ) 2 CH 3 , - (CH 2 ) 3 CH 3 , - (CH 2 ) 5 CH 3 , -CH 2 CH 2 OH, - CH 2 CH 2 NHCO-R 14 or -CH 2 CH 2 CH 2 NHCO-R 14 , wherein R 14 denotes a straight-chain, cyclic or branched CrCl 8 -hydrocarbon radical which is represented by -O-, -NH-, -C (O) -, -C (S) - may be interrupted and substituted with -OH.
  • R 4 and R 5 can also together form a cyclic structure of the formulas
  • R 4 is preferably a monovalent or divalent straight chain, cyclic or branched C 1 -C 1 6, more preferably C 3 -C 6 , hydrocarbon radical represented by -O-, -NH-, -C may be interrupted and substituted by -OH, more preferably a C 3 - - (O) -, -C (S) -C 6 - hydrocarbon radical, interrupted by -O-, -NH-, -NR 1 -, -C (O) -, -C (S) - may be interrupted and substituted with - OH, wherein R 1 has the abovementioned meaning.
  • F is preferably a divalent or tetravalent straight-chain, cyclic or branched C 2 -C 20 -hydrocarbon radical which is represented by -O-, -NH-, -N-, - C (O) -, - C (S), a siloxane chain S, where S is the above-mentioned references, interrupted and can be substituted by - OH.
  • R 14 is preferably unsubstituted C 5 -C 7 -hydrocarbon radicals derived from the corresponding fatty acids or hydroxylated C 3 -C 7 radicals which can be attributed to hydroxylated carboxylic acids, preferably saccharide carboxylic acids.
  • R 14 furthermore preferably represents hydroxylated radicals from the group consisting of
  • m is 2 to 100, preferably 2 to 50.
  • n is 0 to 1000, preferably 0 to 100, more preferably 0 to 80 and particularly preferably 10 to 80.
  • q is 1 to 200, preferably 1 to 50, more preferably 2 to 20 and particularly preferably 2 to 10.
  • r is 0 to 200, preferably 0 to 100, more preferably 0 to 50, and even more preferably 0 to 20.
  • a particular embodiment of the invention (which is referred to below as the so-called second embodiment of the polysiloxane compounds) is represented by the polysiloxane compounds of the general formula (II),
  • R 2 -EAN 2 -KSKN 2 -AER 2 (II) wherein S, K, -AE-, -EA- and R 2 have the abovementioned meanings, and N 2 is an organic radical containing at least one quaternary ammonium group, the general formula
  • R 8 is a monovalent or divalent straight-chain, cyclic or branched -C 2 o hydrocarbyl group represented by -0-, -NH-, -C (O) -, - C (S) - may be substituted with -OH and interrupted,
  • R 9 is a monovalent straight-chain, cyclic or branched dC 2 o hydrocarbon radical which may be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH, or a single bond to a divalent radical R 8 or to a trivalent radical K, and the radicals R 8 and R 9 within the polysiloxane compound of the general formula (II) may be identical or different from each other.
  • S is -Si (R 1 ) 2 -O [-Si (R 1 ) 2 -O] n -Si (R 1 ) - with R 1 is Ci-C 22 -alkyl, Ci-C 22 -Fluoralkyl or aryl, n 0 to 1000, K is a divalent or trivalent straight chain, cyclical or branched C 2 -C 2 o-hydrocarbon radical, interrupted by -O-, -N-, -NH-
  • -NR 1 -, -C (O) -, -C (S) - may be interrupted and substituted with -OH, N 2 is a quaternary ammonium structure
  • R 8 is a monovalent or divalent straight-chain, cyclic or branched C 1 -C 20 -hydrocarbon radical which may be interrupted by -O-, -NH-, C (O) -, -C (S) - and substituted by -OH, R 9 R 8 or a single bond to K or R 8 ,
  • A is -CH 2 C (O) O-, -CH 2 CH 2 C (O) O- or -CH 2 CH 2 CH 2 C (O) O-
  • E is a polyalkylene oxide unit of the structure
  • R 16 H straight-chain, cyclic or branched CrC 20 -
  • -OH can be substituted and acetylenic, olefinic or aromatic.
  • K can be branched and then participates with two bonds in the quaternization of N 2 .
  • divalent substructure for R 8 means that in these cases it is a cyclic-structure-forming structure, where R 9 is then a single bond to R 2 .
  • R 8 is preferably -CH 3 , -CH 2 CH 3 , - (CH 2 ) 2 CH 3 , - (CH 2 ) 3 CH 3 , - (CH 2 ) 5 CH 3 , -CH 2 CH 2 OH -CH 2 CH 2 NHCO-R 17 or -CH 2 CH 2 CH 2 NHCO-R 17 , in which R 17 is a straight-chain, cyclic or branched CrCl 8 -hydrocarbon radical which is represented by -O-, -NH-, -C (O) -, -C (S) - may be interrupted and substituted with -OH.
  • R 8 and R 9 may also together form a cyclic structure of the formulas
  • K is preferably a divalent or trivalent straight-chain, cyclic or branched one
  • -C (S) - may be interrupted and substituted with -OH, wherein R 1 is as defined above.
  • Preferred for K are, for example, radicals of the following structures:
  • R 8 is preferably a monovalent or divalent straight-chain, cyclic or branched C 1 -C 6 -hydrocarbon radical which may be interrupted by -O-, -NH-, -C (O), -C (S) - and substituted by -OH ,
  • R 16 is preferably a straight-chain, cyclic or branched C 1 -C -hydrocarbyl radical which may be interrupted by -O- or -C (O) - and substituted by -OH and may be acetylenic or olefinic.
  • R 17 preferably represents unsubstituted C 5 -C 7 -hydrocarbon radicals which are derived from the corresponding fatty acids or hydroxylated C 3 -C 7 radicals which can be attributed to hydroxylated carboxylic acids, preferably to saccharidecarboxylic acids.
  • R 17 is particularly preferably selected from the group selected.
  • n is preferably 0 to 200, more preferably 0 to 80, particularly preferably 10 to 80.
  • q is preferably 1 to 50, more preferably 2 to 20, and particularly preferably 2 to 10.
  • r is preferably 0 to 100, and more preferably 0 to 50.
  • r is preferably 0 to 20, and more preferably 0 to 10.
  • polyammonium-polysiloxane compounds a) as an essential constituent of the active substance complex according to the invention (which is referred to as so-called third embodiment of the polysiloxanes) is represented by the polysiloxane compounds of the general formula (III): - [KSKN 3 Jm- (III )
  • N 3 is an organic radical containing at least one quaternary ammonium group of the general formula
  • R 10 is a monovalent straight chain, cyclic or branched C 1 -C 30 hydrocarbon radical represented by -O-, -NH-, -C (O) -, -C (S) - may be interrupted and substituted by -OH or represents a single bond to K
  • R 11 is -AER 2 , wherein -AER 2 has the abovementioned meaning.
  • the polysiloxane compounds of the third embodiment are alkylene oxide-modified polyparternary polysiloxanes of the general formula (IN ' ),
  • R 10 is a monovalent or divalent straight-chain, cyclic or branched dC 3 o-hydrocarbon radical which is represented by -O-, -NH-,
  • -C (O) -, -C (S) - may be interrupted and substituted with -OH or a
  • A is -CH 2 C (O) O-, -CH 2 CH 2 C (O) O- or - CH 2 CH 2 CH 2 C (O) O- and E is a polyalkylene oxide unit of structure
  • R is H, straight-chain, cyclic or branched C 1 -C 20 -hydrocarbon radical which may be interrupted by -O- or -C (O) - and substituted by -OH and may be acetylenic, olefinic or aromatic
  • K is a divalent or trivalent straight-chain, cyclic or branched C 2 -C 40 -hydrocarbon radical which is represented by -O-, -NH-, -NR 1 -, -N-, -C (O) -, -C (S ) - may be interrupted and substituted with -OH or contains a quaternary ammonium structure N 5 , with N 5 meaning - (R 19 ) N + (R 20 ) -
  • R 19 is a monovalent or divalent straight-chain, cyclic or branched C 1 -C 20 -hydrocarbon radical which may be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH or Is single bond to R 10 , and R 20 is -AE- which is as defined above.
  • R 10 and R 19 are independently of one another preferably -CH 3 , -CH 2 CH 3 , - (CH 2 ) 2 CH 3 , - (CH 2 ) 3 CH 3 , - (CH 2 ) 5 CH 3 , -CH 2 CH 2 OH, -CH 2 CH 2 NHCOR 21 or - CH 2 CH 2 CH 2 NHCOR 21 , wherein R 21 is a straight-chain, cyclic or branched d- Ci ⁇ hydrocarbon radical represented by -O-, -NH-, -C (O ) -, -C (S) - may be interrupted and substituted with - OH.
  • a bivalent substructure for R 10 is a cyclic system-forming structure wherein R 10 then has a single bond to K, preferably to a tertiary amino structure or to the quaternary structure N 5 over R 19 .
  • R 1 in the so-called third embodiment of the polysiloxanes can be referred to the above statements.
  • R 10 is preferably a monovalent or divalent straight-chain, cyclic or branched C 1 -C 25 -hydrocarbon radical which is interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH can.
  • R 19 is a monovalent or divalent straight-chain, cyclic or branched C 1 -C 25 -hydrocarbon radical which may be substituted by -O-, -NH-, -C (O) -, -interrupted and with -OH.
  • K is furthermore preferably a bivalent or trivalent straight-chain, cyclic or branched C 3 -C 30 -hydrocarbon radical which is represented by -O-, -NH-, -NR 1 -, -N-, -C (O) -, -C (S) - may be interrupted and substituted with -OH, more preferably K is -CH 2 CH 2 CH 2 OCH 2 CHOHCH 2 -,
  • R or R is preferably a straight-chain, cyclic or branched C 1 -C 8 -hydrocarbon radical which is interrupted by -O- or -C (O) - and -OH and are acetylenic or olefinic can. More preferably R 2 or R 18 is C r C 6 -alkyl,
  • R 21 is an unsubstituted Ci-Cs hydrocarbon group T which is derived from the corresponding fatty acids or hydroxylated C 3 -C 7 radicals, and in preferred saccharide is derived from the group of hydroxylated carboxylic acids.
  • R 21 is:
  • m is preferably 2 to 100, and more preferably 2 to 50
  • n is 0 to 100, preferably 0 to 80, and particularly preferably 10 to 80
  • q is 1 to 50, preferably 2 to 50 particularly preferably 2 to 20, and more preferably q is 2 to 10
  • r is 0 to 100, preferably 0 to 50, more preferably 0 to 20, and even more preferably r is 0 to 10.
  • polysiloxanes which is referred to below as the so-called fourth embodiment of the polysiloxanes to be used according to the invention
  • N 4 is an organic radical containing at least one quaternary ammonium group of the general formula - (R 12 ) N + (R 13 ) - wherein R 12 is a monovalent or divalent straight chain, cyclic or branched dC 2 o hydrocarbon radical; by -
  • O-, -NH-, -C (O) -, -C (S) - may be interrupted and substituted with -OH,
  • R 13 may have the meanings of R 12 , or represents a single bond to K or R 12 , and the radicals R 12 and R 13 may be the same or different from each other.
  • the polysiloxane compounds of the fourth embodiment are preferably alkylene oxide-modified polyquartezere polysiloxanes of the general formula (IV),
  • R 1 is Ci-C 22 -alkyl, Ci-C 22 fluoroalkyl or aryl, n is 0 to 1000, K is a divalent or trivalent straight-chain, cyclic or branched C 2 -C 2O - represents hydrocarbon radical, interrupted by -O- , -NH-,
  • N is a quaternary ammonium structure - (R 12 ) N + (R 13 ) -, wherein R is 12 is a monovalent or divalent straight-chain, cyclic or branched CrC 20 -
  • R 13 is R 12 or a single bond to K or R 12
  • A is -CH 2 C (O) O-, -CH 2 CH 2 C (O) O- or -CH 2 CH 2 CH 2 C (O) O-
  • K can be branched and then be involved with two bonds in the quaternization of N 4 .
  • R 12 is preferably -CH 3 , -CH 2 CH 3 , - (CH 2 ) 2 CH 3 , - (CH 2 ) 3 CH 3 , - (CH 2 ) 5 CH 3 , -CH 2 CH 2 OH, -CH 2 CH 2 NHCOR 22 or -CH 2 CH 2 CH 2 NHCOR 22 , in which R 22 is a straight-chain, cyclic or branched CrCl 8 -hydrocarbon radical which is represented by -O-, -NH-, -C (O) -, - C (S) - may be interrupted and substituted with -OH.
  • R 12 and R 13 may also together form a cyclic structure of the formulas
  • R 12 is preferably a monovalent or divalent straight-chain, cyclic or branched C 1 -C 6 -hydrocarbon radical which is interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH can.
  • K is preferably a bivalent or trivalent straight-chain, cyclic or branched C 3 -C 6 -hydrocarbon radical which is represented by -O-, -NH-, -NR 1 -, -N-, -C (O ) -, -C (S) - may be interrupted and substituted with -OH, more preferably K is -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 OCH 2 CHOHCH 2 - or
  • R 22 is an unsubstituted C 5 -C 17 hydrocarbon radical derived from the corresponding fatty acids or having hydroxylated C 3 -C 17 radicals which can be attributed to hydroxylated carboxylic acids, preferably saccharide carboxylic acids.
  • R 22 More preferred is R 22 :
  • m is preferably 2 to 100, and particularly preferably 2 to 50.
  • n is 0 to 100, preferably 0 to 80, and particularly preferably 10 to 80.
  • q is 1 to 50, preferably 2 to 50, and particularly preferably 2 to 20, more preferably q is 2 to 10.
  • r is 0 to 100, preferably 0 to 50, and more preferably 0 to 20, more preferably r is 0 to 10.
  • dC 22 -alkyl or d-C 5 -hydrocarbon radical as used above means in the context of the present invention aliphatic hydrocarbon compounds having 1 to 22 carbon atoms or 1 to 30 carbon atoms which may be straight-chain or branched. Examples which may be mentioned are methyl, ethyl, propyl, n-butyl, pentyl, hexyl, heptyl, nonyl, decyl, undecyl, isopropyl, neopentyl, and 1,2,3-trimethylhexyl.
  • C r C 22 fluoroalkyl as used above means in the context of the present invention aliphatic hydrocarbon compounds having 1 to 22 carbon atoms which may be straight-chain or branched and are substituted by at least one fluorine atom. Examples include monofluoromethyl, monofluoroethyl, 1,1,1-trifluoroethyl, perfluoroethyl, 1,1,1-trifluoropropyl, 1,2,2 trifluorobutyl listed.
  • aryl means in the context of the present invention are unsubstituted or mono or polysubstituted with OH, F, Cl, CF3 Cr Ce-alkyl, C r C 6 alkoxy, C 3 -C 7 - cycloalkyl , C 2 -C 6 alkenyl or phenyl substituted phenyl.
  • the term may optionally also mean naphthyl.
  • a particular embodiment of the polysiloxanes according to the invention as constituent a) of the active ingredient complex according to the invention (which is referred to below as the so-called fifth embodiment of the polysiloxanes) is represented by the polysiloxanes of the general formula (V):
  • the groups K, S, -AE-A'- and -A'-EA- within the polysiloxanes of the general formula (V) may be the same or different from each other, and the molar ratio of the group -KSK- and the group -AE-A'- or -A'-EA- in the polysiloxane compound of the general formula (V) of 100: 1 to 1: 100,
  • N 5 is an ammonium group of the general formula - (R 23 ) N + (R 24 ) -, in which
  • R is hydrogen, a monovalent or divalent straight-chain, cyclic or branched dC 2 o hydrocarbon radical which may be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH
  • R 24 represents hydrogen, a monovalent straight-chain, cyclic or branched C 1 -C 20 -hydrocarbon radical which may be interrupted by -O-, -NH-, - C (O) -, C (S) - and substituted by -OH or represents a single bond to a divalent radical R, and the radicals R 23 and R 24 within the group -N 5 -F 1 -N 5 - as well as in the polysiloxane compound may be identical or different,
  • F 1 is a bivalent straight-chain, cyclic or branched hydrocarbon radical which may be interrupted by -O-, -NH-, -N-, -C (O) - or - C
  • the molar ratio of the group -KSK- and the group -AE-A ' or -A ' -EA- in the polysiloxane compound of the general formula (V) is between 100: 1 and 1: 100.
  • This molar ratio can be controlled by the choice of the molar ratio of the starting compounds, in particular the ratio of the ( ⁇ , w-halocarboxylic acid polyalkylene oxide ester compounds and polysiloxane bis-epoxy compounds preferably used according to the invention.
  • the properties of the products depend essentially on the ratio of the starting materials used, as well as the length of the polyalkylene oxide or polysiloxane blocks contained therein.
  • polysiloxanes K is a divalent hydrocarbon radical having at least 4 carbon atoms which has a hydroxyl group and which may be interrupted by an oxygen atom.
  • F1 is a divalent straight-chain, cyclic or branched C 2 -C 30 hydrocarbon radical which is represented by -O-, -NH-, -N-, -C (O) -, -C (S) - or may be interrupted by a group - E -, wherein E is as defined above, and wherein the carbon atoms resulting from the radical E are not counted among the 2 to 30 carbon atoms of the C 2 -C 30 hydrocarbon radical become.
  • R 25 is a monovalent or divalent straight-chain, cyclic or branched C 1 -C 20 -hydrocarbon radical which may be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH, methyl is particularly preferred
  • R 26 is a monovalent straight-chain, cyclic or branched C 1 -C 20 -hydrocarbon radical which may be interrupted by -O-, -NH-, -C (O) -, -C (S) and substituted by -OH, particularly preferably methyl, or one Single bond to a divalent radical R 25 , and the radicals R 25 and R 26 within the group -N 5 -F 2 -N 5 - as well as in the polysiloxane compound may be the same or different from each other, and
  • F 2 is a divalent straight-chain, cyclic or branched hydrocarbon radical which may be interrupted by -O-, -NH-, -N-, -C (O) -, -C (S) -.
  • F 2 is a branched, preferably straight-chain, C 1 -C 6 -alkanediyl group, of which a 1,6-hexanediyl (or hexamethylene) group is preferred.
  • the so-called fifth embodiment of the polysiloxane compounds, -N 5 -F 1 -N 5 - is a group of the formula:
  • R 27 and R 28 are each hydrogen, C 1 -C 6 -alkyl or hydroxy (C 1 -C 6 ) -alkyl, preferably hydrogen, methyl or -CH 2 CH 2 OH, and
  • F 3 is a divalent straight chain, cyclic or branched hydrocarbon radical interrupted by a group -E-, wherein E is as defined above.
  • F 3 is particularly preferably a group of the formula
  • E is as defined above and D is each a single bond or a straight or branched C 1 -C 6 alkanediyl group, with the proviso that D is not a single bond when it binds to a terminal E group oxygen atom.
  • the group -D-E-D- is replaced by a group of the formula
  • D is a C 1 -C 6 straight or branched alkanediyl group and r and q are as defined above.
  • XOD- may be the ethylene oxide and
  • Propylene oxide units may be arranged arbitrarily, e.g. as a random copolymer unit or as a block copolymer unit.
  • v is preferably 1 to 100, more preferably 1 to 70, still more preferably 1 to 40.
  • w is preferably 0 to 100, more preferably 0 to 70, even more preferably 0 to 40.
  • the group -N 5 -F 1 -N 5 is represented by a group of the formula:
  • polysiloxane compounds of the general formula (V) are composed of two different types of the group -N 5 -F 1 -N 5 -.
  • the polysiloxane compounds of the general formula (V) may be cyclic or linear.
  • the terminal groups result either from the bifunctional monomers described below for the preparation or their functionalized derivatives or from monoamines which are added as chain terminators during the polymerization.
  • the terminal groups resulting from the use of the monoamine chain-stopper are preferably present as ammonium groups, either by quaternization or protonation.
  • K is one of the groups of the formula:
  • q is preferably in the range from 1 to 50, in particular 2 to 50, especially 2 to 20 and especially 2 to 10, and r is in the range from 0 to 100, in particular 0 to 50, especially 0 to 20 and especially 0 to 10.
  • the organic or inorganic acid radical for neutralizing the charges resulting from the (n) ammonium group (s) is expediently selected from inorganic radicals such as chloride, bromide, hydrogensulfate, sulfate, or organic radicals such as acetate, Propionate, octanoate, decanoate, dodecanoate, tetradecanoate, hexadecanoate, octadecanoate and oleate, wherein as mentioned above, chloride and bromide preferably result from the reaction of the alkyl halide groups with amine groups.
  • inorganic radicals such as chloride, bromide, hydrogensulfate, sulfate, or organic radicals such as acetate, Propionate, octanoate, decanoate, dodecanoate, tetradecanoate, hexadecanoate, octadecanoate and oleate, wherein as mentioned above
  • polysiloxanes of the fifth embodiment are present in protonated form as amine salts or as amines.
  • the polysiloxanes of the fifth embodiment of the invention are conveniently prepared by one of the methods described in the laid-open specification WO 02/10257.
  • the polyammonium-polysiloxane compounds described above can be obtained for example under the tradename Baysilone ® from GE Bayer Silicones.
  • the products with the names Baysilone TP 391 1, SME 253 and SFE 839 are preferred. Very particular preference is given to the use of Baysilone TP 391 1 as the active component of the compositions according to the invention.
  • polyammonium-polysiloxane compounds described above are very particularly preferred in the compositions according to the invention in an amount of from 0.01 to 10% by weight, preferably from 0.01 to 7.5, particularly preferably from 0.01 to 5.0% by weight from 0.05 to 2.5% by weight each based on the total composition.
  • the ratio of the polyammonium-polysiloxane compounds to a further synergistic active ingredient component selected from the group of polymers, the protein hydrolysates, the silicones, the vitamins and the plant extracts is generally 1: 1000 to 1: 2, preferably 1: 100 to 1: 2 , more preferably 1:50 to 1: 2, and most preferably 1:10 to 1: 2.
  • this mixture is in the inventive compositions in amounts of 0.01 to 10 wt.%, Preferably 0.01 to 8 wt.%, Particularly preferably 0.1 to 7.5 wt .% And in particular 0.1 to 5 wt.% Of silicone mixture based on the composition.
  • the mixture of silicones form a separate phase in the compositions according to the invention.
  • the amount of silicone mixture may be up to 40% by weight, preferably in amounts of up to 25% by weight, based on the total composition.
  • teaching of the invention also includes that a mixture of several fatty substances (D) from different classes of fatty substances, at least two different classes of fatty substances in the inventive
  • compositions can be used.
  • the preferred mixtures of at least two oil and fat components necessarily contain at least one further silicone component in this case.
  • the silicone component in this case is selected from the dimethiconols and the amodimethicones.
  • the total amount of oil and fat components in the compositions according to the invention is usually 0.5-75% by weight, based on the total agent. Amounts of 0.5-35 wt .-% are preferred according to the invention.
  • silicones are the water-soluble silicones. Since these are not strictly speaking the fatty substances, they are discussed in detail here.
  • silicones are sparingly soluble or insoluble in water. However, by suitable substitution, there are water-solubilized silicones.
  • the term "water-soluble” also encompasses "dispersible in water”. Water-dispersed silicones are therefore also included according to the invention.
  • the solubility or dispersibility of silicones can be achieved, for example, by ethoxylation and / or propoxylation of silicones.
  • Water-soluble silicones can be easily recognized by their INCI name. They generally have the addition PEG or PPG before the actual INCI name. Commercial products with the INCI names such as PEG-12 Dimethicone or PEG-Amodimethicone are typical representatives of the water-soluble silicones. These will be described in more detail below.
  • Dimethicone copolyols form a group of the preferred water-soluble silicones. Dimethicone copolyols can be represented by the following structural formulas: (SiR 1 3) - O - (SiR 2 2 - O -) x - (Sirpe - O -) y - (SiR 1 3) (S3 - I)
  • Branched dimethicone copolyols can be represented by the structural formula (S3-III):
  • the radicals R 1 and R 2 are each independently hydrogen, a methyl radical, a C 2 to C 30 linear, saturated or unsaturated hydrocarbon radical, a phenyl radical and / or an aryl radical.
  • the groups represented by R 1 and R 2 include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, 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,
  • R 1 examples include methylene, ethylene, propylene, hexamethylene, decamethylene, -CH 2 CH (CH 3 ) CH 2 -, phenylene, naphthylene, -CH 2 CH 2 SCH 2 CH 2 -, - CH 2 CH 2 OCH 2 - , -OCH 2 CH 2 -, -OCH 2 CH 2 CH 2 -, -CH 2 CH (CH 3 ) C (O) OCH 2 -, - (CH 2 ) 3 CC (O) OCH 2 CH 2 -, C 6 H 4 C 6 H 4 -, -C 6 H 4 CH 2 C 6 H 4 -; and - (CH 2 ) 3 C (O) SCH 2 CH 2 -.
  • R 1 and R 2 are methyl, phenyl and C 2 to C 22 alkyl radicals. Of the C2 to C22 alkyl radicals, lauryl, stearyl and behenyl radicals are particularly preferred.
  • PE stands for a polyoxyalkylene radical.
  • Preferred polyoxyalkylene radicals are derived from ethylene oxide, propylene oxide and glycerol.
  • the numbers x, y and z are integers and each independently run from 0 to 50,000.
  • the molecular weights of the dimethicone copolyols are between 1,000 D and 10000000 D.
  • the viscosities are between 100 and 10,000,000 cPs measured at 25 0 C by means of a glass capillary viscometer according to Dow Corning Corporate Test Method CTM 0004 dated 20 July 1970.
  • Preferred viscosities are from 1000 to 5,000,000 cPs, most preferred viscosities are between 10,000 and 3,000,000 cps. The most preferred range is between 50,000 and 2,000,000 cps.
  • the teaching of the invention also includes that the Dimethiconcopolymere can also be present as an emulsion.
  • the corresponding emulsion of the dimethicone copolyols can be prepared both after the preparation of the corresponding dimethicone copolyols from these and the usual methods of emulsification known to the person skilled in the art.
  • both cationic, anionic, nonionic or zwitterionic surfactants and emulsifiers can be used as auxiliaries for the preparation of the corresponding emulsions.
  • the emulsions of dimethicone copolyols can also be prepared directly by an emulsion polymerization process.
  • the droplet size of the emulsified particles according to the invention is 0.01 ⁇ m to 10000 ⁇ m, preferably 0.01 to 100 ⁇ m, very particularly preferably 0.01 to 20 ⁇ m and most preferably 0.01 to 10 microns.
  • the particle size is determined by the method of light scattering.
  • branched dimethicone copolyols are used, it is to be understood that the branching is greater than a random branching, which occurs by impurities of the respective monomers randomly.
  • branched dimethicone copolyols are therefore to be understood as meaning that the degree of branching is greater than 0.01%.
  • a degree of branching is greater than 0.1%, and most preferably greater than 0.5%.
  • the degree of branching is determined from the ratio of unbranched monomers, that is, the amount of monofunctional siloxane, to the branching monomers, that is, the amount of tri- and tetrafunctional siloxanes.
  • both low-branched and highly branched dimethicone copolyols can be very particularly preferred.
  • the dimethicone copolyols (S3) are present in the compositions according to the invention in amounts of from 0.01 to 10% by weight, preferably from 0.01 to 8% by weight, particularly preferably from 0.1 to 7.5% by weight and in particular from 0.1 to 5% by weight of dimethicone copolyol based on the composition.
  • the dimethicone copolyols it is also possible for the dimethicone copolyols to form a separate phase in the compositions according to the invention.
  • the amount of Dimethiconcopolyol up to 40 wt.%, Preferably in amounts of up to 25 wt.% Based on the total composition.
  • Water-soluble amino-functional silicones, or else PEG-amodimethicones (S5), are silicones which have at least one (optionally substituted) amino group. And further substituted with polyoxyalkylene groups.
  • m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably values of 0 to 1999 and in particular of 49 to 149 and m preferably values of 1 to 2000 , in particular from 1 to 10 and furthermore PE independently of one another represents a polyalkylene oxide block, with the proviso that at least one polyalkylene oxide block must be present.
  • the number of polyalkylene oxide blocks is in each case between 1 and 5000, preferably 1 and 3000 and particularly preferably from 1 to 1000, with 1 to 100 repeat units being most preferred.
  • the polyalkylene oxide is formed in the simplest case of ethylene oxide or propylene oxide or butylene oxide or mixtures thereof or a mixture of ethylene oxide and propylene oxide. Preference is given to the use of ethylene oxide.
  • silicones are referred to as PEG trimethylsilylamodimethicones according to the INCI declaration.
  • Agents according to the invention which are characterized in that they contain a water-soluble amino-functional silicone of the formula (S5 - II) are also particularly preferred.
  • n1 and n2 are numbers whose sum (m + n1 + n2) is between 1 and 2,000, preferably between 50 and 150 in which the sum (n1 + n2) preferably has values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10 and furthermore PE is independently of one another a polyalkylene oxide block, with the proviso that at least one polyalkylene oxide block must be present.
  • the number of polyalkylene oxide blocks is in each case between 1 and 5000, preferably 1 and 3000 and particularly preferably from 1 to 1000, with 1 to 100 repeat units being most preferred.
  • the polyalkylene oxide is formed in the simplest case of ethylene oxide or propylene oxide or butylene oxide or mixtures thereof or a mixture of ethylene oxide and propylene oxide. Preference is given to the use of ethylene oxide.
  • compositions according to the invention are preferred in which the amino-functional silicone has an amine number above 0.25 meq / g, preferably above 0.3 meq / g and in particular above 0.4 meq / g.
  • the amine number stands for the milliequivalents of amine per gram of the amino-functional silicone. It can be determined by titration and also expressed in mg KOH / g.
  • the water-soluble amodimethicones (S5) are present in the compositions according to the invention in amounts of from 0.01 to 10% by weight, preferably from 0.01 to 8% by weight, more preferably from 0.1 to 7.5% by weight and in particular 0.1 to 5% by weight of amodimethicone based on the composition.
  • the amodimethicones it is also possible for the amodimethicones to form a separate phase in the compositions according to the invention.
  • the amount of amodimethicone may be up to 40% by weight, preferably in amounts of up to 25% by weight, based on the total composition.
  • the combination of the active substance complex with surfactants (E) has proved to be particularly advantageous.
  • the compositions used according to the invention contain surfactants.
  • surfactants is understood as meaning surface-active substances which form adsorption layers on the upper and boundary surfaces or which can aggregate in volume phases to give micelle colloids or lyotropic mesophases.
  • anionic surfactants consisting of a hydrophobic radical and a negatively charged hydrophilic head group
  • amphoteric surfactants which carry both a negative and a compensating positive charge
  • cationic surfactants which, in addition to a hydrophobic radical, have a positively charged hydrophilic group
  • nonionic surfactants which have no charges but strong dipole moments and are highly hydrated in aqueous solution.
  • Suitable anionic surfactants (E1) in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule.
  • anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group, linear and branched fatty acids having 8 to 30 C atoms (Soaps), - Ethercarbon Acid the formula RO- (CH2-CH2O) x-CH2-COOH, where R is a linear
  • Alkyl group having 8 to 30 C atoms and x 0 or 1 to 16,
  • Esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 C atoms,
  • R 1 is preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms
  • R 2 is hydrogen, a radical (CH 2 CH 2 O) n R 2 or X
  • n is from 1 to 10
  • X is hydrogen, an alkali metal radical or alkaline earth metal or NR 3 R 4 R 5 R 6 , with R 3 to R 6 independently of one another represent hydrogen or a C 1 to C 4 hydrocarbon radical
  • R 3 to R 6 independently of one another represent hydrogen or a C 1 to C 4 hydrocarbon radical
  • R 3 to R 6 independently of one another represent hydrogen or a C 1 to C 4 hydrocarbon radical
  • R 3 to R 6 independently of one another represent hydrogen or a C 1 to C 4 hydrocarbon radical
  • R 7 CO is a linear or branched, aliphatic, saturated and / or unsaturated acyl group containing 6 to 22 carbon atoms
  • Alk is CH 2 CH 2, CHCH 3 CH 2 and / or CH 2 CHCH 3
  • n is a number from 0.5
  • Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts.
  • Condensation products of Cs - C30 - fatty alcohols with protein hydrolysates and / or amino acids and their derivatives which are known to the skilled person as protein fatty acid condensates, such as Lamepon ® - types Gluadin ® - types Hostapon ® KCG or Amisoft ® - types.
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic acid monoalkylpolyoxyethylester with 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups, Monoglycerdisulfate, alkyl and Alkenyletherphosphate and protein fatty acid condensates.
  • mild anionic surfactants are used as anionic surfactants.
  • the mild anionic surfactants described below the effect of the composition according to the invention is substantially increased.
  • millild surfactants is understood by the person skilled in the art as meaning surfactants which are found in numerous test methods such as the HET-CAM test, the Neutra rottest, the BUS model (bovine and skin model), the human skin model, the Zeize test, the Draize test , have proven to be mild surfactants in the Armflexwashtest or the Duhringhunttest, etc. All test models share the principle of being measured against a standard to which the measurement results are referenced In each of these test models there is a threshold below that of "mild surfactants" becomes. This threshold is for example in the HET-CAM test 1, 5.
  • surfactants which have a relative irritation score of 1, 5 and smaller, for example, in the HET-CAM test are known as "mild.”
  • a surfactant gives a different score in each test model.
  • a cocamidopropyl betaine may even be classified as "irritating" in the HET-CAM test, while in the other test models it is more likely to be considered mild surfactants.
  • a common and accepted classification defines anionic surfactants as mild if they have a relative irritation score of less than 1.5 in the HET-CAM test. According to the invention, however, such anionic surfactants are preferably used and understood as "mild anionic surfactants" which are classified as "mild” in all current test models.
  • acyl lactylates acyl lactylates
  • Ethercarbon Acid the formula RO- (CH 2 -CH 2 O) X -CH 2 -COOH, in which R is a linear
  • Alkyl group having 8 to 30 carbon atoms and x 0 or 1 to 16 and their salts,
  • Acyl isethionates having 8 to 24 carbon atoms in the acyl group are long known, skin-friendly surfactants, which are accessible by esterification of fatty acids with the sodium salt of 2-hydroxyethane-sulfonic acid (isethionic acid). If you for this esterification fatty acids with 8 to 24 carbon atoms, ie z.
  • the Sulfobernsteinklamonoalkyl (C 8 -C 24 ) ester dinatrium salts are prepared by known methods z. B. prepared by reacting maleic anhydride with a fatty alcohol having 8 - 24 carbon atoms to maleic acid monoester of the fatty alcohol and sulfites this with sodium sulfite to Sulfobernsteinklareester.
  • Particularly suitable sulfosuccinic acid esters are derived from fatty alcohol fractions having 12- 18 C atoms, as z. B. from coconut oil or Kokosfett Maschinenmbamethylester are accessible by hydrogenation.
  • Alkylpolyglykolethersulfate of the formula RO (CH 2 -CH 2 O) x -OSO 3 H, in which R is a preferably linear alkyl group having 8 to 30 carbon atoms and x 0 or 1 to 12, esters of tartaric acid and citric acid with alcohols, represent the adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols containing 8 to 22 carbon atoms,
  • OX in the R 1 is preferred for an aliphatic hydrocarbon radical having 8 to 30 carbon atoms
  • R 2 is hydrogen, a radical (CH 2 CH 2 O) n R 2 or X, n is from 1 to 10 and X is hydrogen, an alkali or alkaline earth metal or NR 3 R 4 R 5 R 6 , where R 3 to R 6 independently of one another represent hydrogen or a C 1 - to C 4 -hydrocarbon radical,
  • Glycerol ether sulfates such as monoglyceride sulfates and monoglyceride ether sulfates of the formula (E1-III),
  • Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts.
  • monoglyceride sulfates of the formula (E1-III) are used in which R 8 CO is a linear acyl radical having 8 to 18 carbon atoms, amide-ether carboxylic acids,
  • Condensation products of a water-soluble salt of a water-soluble protein hydrolyzate-fatty acid condensation product are prepared by condensation of C8-C30 fatty acids, preferably of fatty acids having 12-18 C atoms with amino acids, mono-, di- and water-soluble oligopeptides and mixtures of such products as obtained in the hydrolysis of proteins.
  • These protein hydrolyzate-fatty acid condensation products are neutralized with a base and are then preferably present as alkali metal, ammonium, mono-, di- or Trialkanolammoniumsalz.
  • Such products are under the commodity sign Lamepon® ®, Maypon ®, Gluadin® ®, Hostapon® ® KCG or Amisoft ® has long been commercially available,
  • mild anionic surfactants contain polyglycol ether chains, it is particularly preferred that they have a narrow homolog distribution.
  • the number of glycol ether groups it is preferred for the number of glycol ether groups to be from 1 to 20, preferably from 2 to 15, more preferably from 2 to 12.
  • mild anionic surfactants having polyglycol ether without restricted homologue distribution may for example be obtained even if the one hand, the number of polyglycol ether amounts to 4 to 12 and are selected as a counter ion Zn or Mg ions. Examples of these are the commercial product Texapon ASV ®.
  • mild and anionic surfactants mentioned heretofore and in the following can also be used in the form of their salts.
  • Particularly suitable mild anionic surfactants are in each case in the form of the lithium, magnesium, zinc, sodium, potassium and ammonium and the mono-, di- and Trialkanolammoniumsalze with 1 to 4 carbon atoms in the alkanol group.
  • the preferred ammonium ions are in addition to the ammonium ion as such monomethylammonium, dimethylammonium, trimethylammonium, monoethylammonium, diethylammonium, triethylammonium, monopropylammonium, dipropylammonium, tripropylammonium,
  • inventive Teach also the other not explicitly mentioned ammonium ions of these alkanolammonium salts.
  • mild anionic surfactants which are most preferably used in the composition according to the invention are alkyl and / or
  • G glycoside unit derived from a sugar with 5 or 6 carbon atoms, p number from 1 to 10.
  • the mild anionic surfactant is selected from anionic alkyl polyglycosides, ether carboxylic acids, acyl isethionates, protein fatty acid condensates, taurates, sulfosuccinates, fatty acid amide ether sulfates, NRE fatty alcohol ether sulfates, acyl glutamates, and acyl aspartates, and mixtures thereof.
  • anionic alkyl polyglucosides such as alkyl oligoglycoside carboxylates, sulfates, phosphates and / or isethionates, ether carboxylic acids, acyl isethionates and also taurates and mixtures thereof.
  • the mixing ratio of these surfactants is at least 10: 1 to 1:10.
  • Preferred is a mixing ratio of 5: 1 to 1: 5, more preferably from 2.5: 1 to 1: 2.5, and most preferably from about 1, 5: 1 to 1: 1.5.
  • the radical is 0-CH 2 -COONa.
  • alkyl oligoglycoside carboxylate in which the alkyl radical is a lauryl radical.
  • a Laurylglucosidcarboxylat as it is available as Plantapon ® LCG Cognis Germany.
  • the glycoside units G are preferably derived from aldoses or ketoses.
  • the aldoses are used.
  • glucose is particularly suitable for their easy accessibility and technical availability.
  • the alkylglycosides which are particularly preferably used as starting materials are therefore the alkylglucosides.
  • the index p in the general formula (I) indicates the degree of oligomerization, i.
  • the distribution of mono- and oligoglycosides and stands for a number between 1 and 10. While p in a given compound always has to be an integer and can take here especially the values p 1 to 6, the value p for a particular alkyl glycoside an analytic calculated arithmetical variable, which usually represents a fractional number.
  • alkyl glycosides having an average degree of oligomerization p of 1.1 to 3.0 are used. Particular preference is given to those alkyl glycosides whose degree of oligomerization is less than 1.5 and, in particular, lies between 1.1 and 1.4.
  • the alkyl radical R is derived from primary alcohols having 6 to 22, preferably 12 to 18 carbon atoms.
  • Typical examples are caproic alcohol, caprylic alcohol, Capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and Behenylakohol and technical fractions, in addition to the aforementioned saturated alcohols may also contain portions of unsaturated alcohols and are obtained on the basis of natural fats and oils, such as palm oil, palm kernel oil, coconut oil or beef tallow. The use of technical coconut oil is particularly preferred here.
  • the alkyl glycosides can also be derived from synthetic primary alcohols having 6 to 22 carbon atoms, in particular the so-called oxo alcohols, which have a proportion of 5 to 40% by weight of branched isomers.
  • Particularly preferred alkyl radicals are those having 8/10, 12/14, 8 to 16, 12 to 16 or 16 to 18 carbon atoms. Mixtures of the alkyl radicals result in a production starting from natural fats and oils or mineral oils.
  • the alkyl or alkenyl oligoglycoside carboxylates, phosphates, sulfates or isethionates used according to the invention can be prepared by known processes.
  • the carboxylates are prepared, for example, by reacting the alkyloligoglycosides with salts of chlorocarboxylic acids in the presence of bases. For example, it can be reacted with 2-chloroacetic acid sodium salt in the presence of NaOH. In the reaction, both the hydroxyl groups in the ring and the -CH 2 -OH group can be reacted. The degree of conversion depends inter alia on the stoichiometry of the feedstock.
  • the alkyl oligoglycosides are reacted at least on the -CH 2 -OH group, optionally with an agent capable of reacting one or more of the hydroxyl groups on the ring.
  • hydroxyl groups may also be etherified, for example.
  • the preparation of the isethionates is also carried out by known methods of the prior art. It is also known that the products can be used for hair and body care. In particular, aqueous detergent mixtures are described which contain alkyloligoglycoside isethionates and, for example, further anionic surfactants.
  • the preparation of the sulfates is also carried out by known methods. Furthermore, mixtures of APG sulphates with i.a. Alkyl sulfates or alkyl ether sulfates and other ingredients described. It is stated that the surfactant mixtures can be used in products that are used for washing, dyeing, rippling or rinsing hair.
  • the preparation of the sulfates is also carried out according to the prior art.
  • the corresponding alkyl glycoside can be reacted with gaseous sulfur trioxide or with sulfuric acid followed by neutralization.
  • Cosmetic and pharmaceutical preparations containing the alkyloligoglycoside sulfates are also known.
  • detergent mixtures of alkyl oligoglycoside sulfates and alkyl ether phosphates are described which can be used, for example, in hair rinses, hair dyes or hair waving agents.
  • the mild anionic surfactants used according to the invention and particularly preferably the alkyl and / or alkenyl oligoglycoside carboxylates, sulfates, phosphates and / or isoethionates are used in an amount of from 0.1 to 25% by weight, more preferably from 0.1 to 15 wt .-% and most preferably used in an amount of 0.5 to 10.0 wt.%
  • the mild anionic surfactants used can in these agents all or part of the conventional anionic surfactants replace.
  • the mild anionic surfactants according to the invention can be used as the sole anionic surfactant in the compositions, or mixtures of these mild anionic surfactants can be used with each other or with other conventional anionic surfactants. These conventional anionic surfactants are explained in more detail later.
  • the mild anionic surfactants and other anionic surfactants may be present in a weight ratio ranging from 5: 0.05 to 1: 2, more preferably 3: 0.5 to 1: 2, especially 2.5: 0.5 to 1: 1 , 5, and most preferably 1, 5: 1 to 1: 1.5.
  • Zwitterionic surfactants are those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO * " 'or -SO 3 ' " 'group.
  • Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyldimethylammonium glycineate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
  • a preferred zwitterionic surfactant is the fatty
  • Ampholytic surfactants (E3) are understood as meaning those surface-active compounds which, in addition to a C 8 -C 24 -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SOsH group and which are capable of forming internal salts are.
  • ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C Atoms in the alkyl group.
  • ampholytic surfactants are the N-cocoalkylaminopropionate, the Kokosacylaminoethylamino- propionate and the Ci 2 - Ci 8 - acylsarcosine.
  • Nonionic surfactants (E4) contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group as the hydrophilic group. Such compounds are, for example
  • Alkyl group such as those under the sales name Dehydol ®
  • Polyol fatty acid esters such as the commercial product Hydagen ® HSP
  • R 1 CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms
  • R 2 is hydrogen or methyl
  • R 3 is linear or branched alkyl radicals having 1 to 4 carbon atoms
  • w is a number from 1 to 20 stands
  • Hydroxymix ethers as described for example in DE-OS 19738866, Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,
  • R 4 is an alkyl or alkenyl radical having 4 to 22 carbon atoms
  • G is a sugar radical having 5 or 6 carbon atoms
  • p is a number from 1 to 10.
  • the alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • the index number p in the general formula (E4-II) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10.
  • the value p for a certain alkyloligoglycoside is an analytically determined arithmetical variable, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred.
  • the alkyl or alkenyl radical R 4 can be derived from primary alcohols having 4 to 1 1, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, as they are For example, be obtained in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from the Roelen oxo synthesis.
  • the alkyl or alkenyl radical R 15 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms.
  • Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above.
  • R 5 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 6 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their preparation, reference is made to US Pat. Nos.
  • the fatty acid N-alkylpolyhydroxyalkylamides are derived from reducing sugars with 5 or 6 Carbon atoms, in particular from the glucose.
  • the preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (E4-IV):
  • the fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (E4-IV) in which R 8 is hydrogen or an alkyl group and R 7 is CO for the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures.
  • R 8 is hydrogen or an alkyl group
  • R 7 is CO for the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid
  • fatty acid N-alkylglucamides of the formula (E4-IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C 12/14 coconut fatty acid or a corresponding derivative.
  • the polyhydroxyalkylamides can also be derived from maltose and palatinose.
  • the preferred nonionic surfactants are the alkylene oxide addition products of saturated linear fatty alcohols and fatty acids having in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations having excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants.
  • the alkyl radical R contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals.
  • Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl.
  • oxo-alcohols compounds with an odd number of carbon atoms in the alkyl chain predominate.
  • very particularly preferred nonionic surfactants are the sugar surfactants. These may preferably be present in the agents used according to the invention in amounts of from 0.1 to 20% by weight, based on the total agent. Amounts of 0.5-15% by weight are preferred, and most preferred are amounts of 0.5-7.5% by weight.
  • the compounds used as surfactant with alkyl groups may each be uniform substances. However, it is usually preferred to start from the production of these substances from native plant or animal raw materials, so as to obtain substance mixtures with different, depending on the particular raw material alkyl chain lengths.
  • both products with a "normal” homolog distribution and those with a narrow homolog distribution can be used.
  • normal homolog distribution are meant mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with narrow homolog distribution may be preferred.
  • the surfactants (E) are used in amounts of 0.1-45% by weight, preferably 0.5-30% by weight and very particularly preferably 0.5-25% by weight, based on the total agent used according to the invention ,
  • cationic surfactants (E5) of the quaternary ammonium compound type are also usable according to the invention.
  • Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, Dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g.
  • cetyltrimethylammonium chloride stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium 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 18 carbon atoms.
  • Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element.
  • Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines.
  • Such products are marketed under the trade names Stepantex® ®, ® and Dehyquart® Armocare® ®.
  • alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines.
  • the cationic surfactants (E5) are contained in the agents used according to the invention preferably in amounts of 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.
  • anionic, nonionic, zwitterionic and / or amphoteric surfactants and mixtures thereof may be preferred according to the invention.
  • the action of the active ingredient complex according to the invention can be increased by emulsifiers (F).
  • Emulsifiers effect at the phase interface the formation of water- or oil-stable adsorption layers, which protect the dispersed droplets against coalescence and thus stabilize the emulsion.
  • Emulsifiers are therefore constructed like surfactants from a hydrophobic and a hydrophilic part of the molecule. Hydrophilic emulsifiers preferably form O / W emulsions and hydrophobic emulsifiers preferably form W / O emulsions.
  • An emulsion is to be understood as meaning a droplet-like distribution (dispersion) of a liquid in another liquid under the expense of energy in order to create stabilizing phase interfaces by means of surfactants.
  • the selection of these emulsifying surfactants or emulsifiers depends on the substances to be dispersed and the respective outer phase and the fineness of the emulsion. Further definitions and properties of emulsifiers can be found in "H. -D. Dörfler, Grenz perennial- and Kolloidchemie, VCH Verlagsgesellschaft mbH., Weinheim, 1994".
  • Emulsifiers which can be used according to the invention are, for example
  • Glucosides mixtures of alkyl (oligo) and fatty alcohols for example, the commercially available product ® Montanov 68,
  • Sterols Partial esters of polyols having 3-6 carbon atoms with saturated fatty acids having 8 to 22 carbon atoms.
  • Sterols are understood to mean a group of steroids which have a hydroxyl group on C-atom 3 of the steroid skeleton and are isolated both from animal tissue (zoosterols) and from vegetable fats (phytosterols). Examples of zoosterols are cholesterol and lanosterol. Examples of suitable phytosterols are ergosterol, stigmasterol and sitosterol. Mushrooms and yeasts are also used to isolate sterols, the so-called mycosterols. Phospholipids.
  • glucose phospholipids which are obtained, for example, as lecithins or phosphatidylcholines from, for example, egg yolks or plant seeds (for example soybeans).
  • Fatty acid ester of sugars and sugar alcohols such as sorbitol, polyglycerols and polyglycerol derivatives such as polyglycerol poly-12-hy- droxystearat (Dehymuls ® PGPH commercial product)
  • Linear and branched fatty acids with 8 to 30 C atoms and their Na, K, ammonium, Ca, Mg and Zn salts.
  • the agents according to the invention preferably contain the emulsifiers in amounts of 0.1-25% by weight, in particular 0.5-15% by weight, based on the total agent.
  • compositions according to the invention may preferably contain at least one nonionic emulsifier having an HLB value of 8 to 18, according to the methods described in the Römpp Lexikon Chemie (Hrg. J. Falbe, M. Regitz), 10th edition, Georg Thieme Verlag Stuttgart, New York, (1997), page 1764, listed definitions.
  • Nonionic emulsifiers having an HLB value of 10 to 15 may be particularly preferred according to the invention.
  • polymers (G) can support the action of the active substance complex according to the invention.
  • polymers are added to the compositions used according to the invention, both cationic, anionic, amphoteric and nonionic polymers having proven effective.
  • particularly preferred polymers are described.
  • the distinction of the polymers which can be used according to the invention can be made on the basis of the charges of the polymers and / or because of their particularly pronounced properties in terms of their application.
  • the term "particularly distinctive features" reflects the fact that polymers generally combine several properties in one molecule, but often one of the properties is particularly prominent and is decisive for the selection of this particular polymer.
  • Cationic polymers are to be understood as meaning polymers which have a group in the main and / or side chain which may be “temporary” or “permanent” cationic.
  • "permanently cationic” refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group.
  • Preferred cationic groups are quaternary ammonium groups.
  • those polymers in which the quaternary ammonium group is bonded via a C 1-4 hydrocarbon group to a polymer main chain constructed from acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.
  • cationic polymers according to the invention are the so-called “temporary cationic" polymers, which usually contain an amino group which, at certain pH values, is present as a quaternary ammonium group and thus cationically.
  • the cationic polymers according to the invention can be both firming and / or film-forming and / or antistatic and / or scavenging polymers as well as polymers with conditioning and / or thickening properties.
  • the suitable cationic polymers are preferably hair-setting and / or hair-conditioning polymers.
  • polymers are both natural and synthetic polymers which may be cationic or amphoteric charged.
  • the cationic charge density is preferably 1 to 7 meq / g.
  • the cationic polymers may be homopolymers or copolymers wherein the quaternary nitrogen groups are contained either in the polymer chain or preferably as a substituent on one or more of the monomers.
  • the ammonium group-containing monomers may be copolymerized with non-cationic monomers.
  • Suitable cationic monomers are unsaturated, free-radically polymerizable compounds which carry at least one cationic group, in particular ammonium-substituted vinyl monomers, for example trialkylmethacryloxyalkylammonium, trialkylacryloxyalkylammonium,
  • Dialkyl diallyl ammonium and quaternary vinyl ammonium monomers with cyclic, cationic nitrogen-containing groups such as pyridinium, imidazolium or quaternary pyrrolidones, e.g. Alkylvinylimidazolium, Alkylvinylpyridinium, or Alyklvinylpyrrolidon salts.
  • the alkyl groups of these monomers are preferably lower alkyl groups such as C1 to C7 alkyl groups, more preferably C1 to C3 alkyl groups.
  • the ammonium group-containing monomers may be copolymerized with non-cationic monomers.
  • Suitable comonomers are, for example, acrylamide, methacrylamide; Alkyl and dialkylacrylamide, alkyl and dialkylmethacrylamide, alkyl acrylate, alkyl methacrylate, vinylcaprolactone, vinylcaprolactam, vinylpyrrolidone, vinyl esters, for example vinyl acetate, vinyl alcohol, propylene glycol or ethylene glycol, wherein the alkyl groups of these monomers preferably C1 to C7 alkyl groups, particularly preferably C1 to C3 Alkyl groups are.
  • Suitable polymers having quaternary amine groups are, for example, the polymers described in the CTFA Cosmetic Ingredient Dictionary under the names Polyquaternium, such as methylvinylimidazolium chloride A / inylpyrrolidone copolymer (Polyquaternium-16) or quaternized
  • Vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer (Polyquaternium 1 1) and quaternary silicone polymers or oligomers such as silicone polymers with quaternary end groups (Quaternium-80).
  • cationic polymers for example vinylpyrrolidone / dimethylaminoethyl copolymer available under the trade names Gafquat ® 755 N and Gafquat ® 734, United States is marketed by Gaf Co. and of which the Gafquat ® 734 is particularly preferred suitable.
  • cationic polymers are, for example, Germany, marketed by the company BASF under the tradename Luviquat ® HM 550 copolymer of polyvinyl pyrrolidone and imidazolimine which ® by the company Calgon / USA under the trade name Merquat Plus 3300 sold terpolymer of dimethyldiallylammonium chloride, sodium acrylate and acrylamide and sold by the company ISP under the trade name Gafquat ® HS 100 vinylpyrrolidone / methacrylamidopropyltrimethylammonium chloride copolymer.
  • R -H or -CH 3
  • R, R and R are independently selected from C 1-4 alkyl, alkenyl or hydroxyalkyl groups
  • m 1, 2, 3 or 4
  • n is a natural number
  • X is a physiologically acceptable organic or inorganic anion and copolymers consisting essentially of the monomer units listed in formula (G1-I) and nonionic monomer units are particularly preferred cationic polymers.
  • R 1 is a methyl group
  • R 2 , R 3 and R 4 are methyl groups - m is 2.
  • Suitable physiologically acceptable counter ions X include halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Preferred are halide ions, particularly chloride.
  • a particularly suitable homopolymer is, if desired, crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37.
  • poly methacryloyloxyethyltrimethylammonium chloride
  • Rheocare ® CTH Cosmetic Rheologies
  • Synthalen® ® CR 3V Sigma
  • the crosslinking can be carried out with the aid of poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ethers, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose.
  • Methylenebisacrylamide is a preferred crosslinking agent.
  • the homopolymer is preferably used in the form of a nonaqueous polymer dispersion which should not have a polymer content of less than 30% by weight.
  • Such polymer dispersions are (under the names Salcare ® SC 95 about 50% polymer content, additional components: mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1 trideceth-6) ) and Salcare ® SC 96 (about 50% polymer content, other components: mixture of Diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: Propylene Glycol Dicaprylate / Dicaprate) and tridecyl polyoxypropylenepolyoxyethylene ether (INCI name: PPG-1-Trideceth-6)) commercially available.
  • Copolymers with monomer units of the formula (G1-I) contain as nonionic monomer units preferably acrylamide, methacrylamide, acrylic acid-C- M- alkyl esters and methacrylic acid-D- 4- alkyl esters. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above in the case of the homopolymers. A copolymer preferred according to the invention is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, are commercially available as approximately 50% non-aqueous polymer dispersion 92 under the name Salcare ® SC.
  • Suitable cationic silicone compounds preferably have either at least one amino group or at least one ammonium group.
  • Suitable silicone polymers with amino groups are known under the INCI name Amodimethicone. These are polydimethylsiloxanes with aminoalkyl groups. The aminoalkyl groups may be side or terminal.
  • the N-containing silicone cationic polymer of the present invention may preferably be selected from the group comprising siloxane polymers having at least one amino group, siloxane polymers having at least one terminal amino group, amodimethicone, trimethylsilylamodimethicone, and / or aminoethylaminopropylsiloxane-dimethylsiloxane copolymer.
  • Suitable silicone polymers having two terminal quaternary ammonium groups are known by the INCI name Quaternium-80. These are dimethylsiloxanes having two terminal aminoalkyl groups.
  • Preferred according to the invention is the use of an aminosiloxane according to the following general formula (G 1-11),
  • R OH or CH 3
  • Emulsions which can preferably be used according to the invention are Dow Corning® 949, which is a cationic emulsion comprising amodimethicone, cetrimonium chloride and trideceth-12; Dow Corning® 939, which is an emulsion containing amodimethicone, cetrimonium chloride and trideceth-12; Dow Corning® 929, which is a cationic emulsion containing amodimethicone, talc trimonium chloride and nonoxynol-10; Dow Corning® 7224 or 1401 based on trimethylsilylamodimethicone, octoxynol-40, isolaureth-6 and glycol; Dow Corning® 2-8194 microemulsion (26%) based on an amine-functionalized silicone polymer; Dow Corning® 2-8177 microemulsion (12%) based on
  • the molecular weight of the aminosilicones is preferably between 500 and 100,000.
  • the amine content (meq / g) is preferably in the range from 0.05 to 2.3, more preferably from 01 to 0.5.
  • the silicone as a cationic polymer according to the invention is used in an amount of 0.01 to 20% by weight, based on the total agent, preferably in amounts of 0.05 to 15% by weight and very particularly preferably in amounts of 0.05 to 10% by weight .% used.
  • Suitable cationic polymers derived from natural polymers are cationic derivatives of polysaccharides, for example cationic derivatives of
  • Cellulose, starch or guar are also suitable.
  • chitosan and chitosan derivatives are also suitable.
  • Cationic polysaccharides have the general formula (G1-III) GOB-N + R a R b R c X "
  • G is an anhydroglucose residue, for example starch or cellulose anhydroglucose
  • B is a divalent linking group, for example alkylene, oxyalkylene,
  • R 3 , Rb and R c are independently alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl or alkoxyaryl each having up to 18 C atoms, wherein the total number of C atoms in
  • R 3 , Rb and R c is preferably at most 20;
  • X " is a common counteranion and is preferably chloride.
  • a cationic cellulose is sold under the name Polymer JR 400 from Amerchol ® and has the INCI designation Polyquaternium-10 degrees.
  • Another cationic cellulose bears the INCI name Polyquaternium-24 and is sold under the trade name Polymer LM-200 by Amerchol.
  • Other commercial products are the compounds Celquat ® H 100, Celquat ® L and 200. The commercial products mentioned are preferred cationic celluloses.
  • Suitable cationic guar derivatives are marketed under the trade name Jaguar ® and have the INCI name guar hydroxypropyltrimonium chloride. Further particularly suitable cationic guar derivatives are also used by the company. Hercules under the name N-Hance ® commercially. Other cationic guar derivatives are marketed by the company. Cognis under the name Cosmedia® ®. A preferred cationic guar derivative is the commercial product AquaCat® ® from. Hercules. This raw material is an already pre-dissolved cationic guar derivative.
  • hydrocolloids of the chitosan type are partially deacetylated chitins of different molecular weight, which contain the - idealized - monomer unit (I): CH 2 OBI HO NH 2
  • chitosans are cationic biopolymers under these conditions.
  • the positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products as a film former.
  • the chitosans are also quaternized, alkylated and / or hydroxyalkylated derivatives, optionally also in microcrystalline form into consideration.
  • the insert can also be in the form of aqueous gels having a solids content in the range of 1 to 5 wt .-%.
  • chitosans For the production of chitosans is based on chitin, preferably the shell remains of crustaceans, which are available as inexpensive raw materials in large quantities.
  • the chitin is usually first deproteinized by the addition of bases, demineralized by the addition of mineral acids and finally deacetylated by the addition of strong bases, wherein the molecular weights can be distributed over a broad spectrum.
  • the chitosans to be used according to the invention are completely or partially deacetylated chitins.
  • the molecular weight of the chitosan can be distributed over a broad spectrum, for example from 20,000 to about 5 million g / mol.
  • a low molecular weight chitosan having a molecular weight of from 30,000 to 70,000 g / mol is suitable.
  • the molecular weight is above 100,000 g / mol, more preferably from 200,000 to 700,000 g / mol.
  • the degree of deacetylation is preferably 10 to 99%, more preferably 60 to 99%.
  • the chitosans or chitosan derivatives are preferably in neutralized or partially neutralized form.
  • the degree of neutralization of the chitosan or the chitosan derivative is preferably at least 50%, more preferably between 70 and 100%, based on the number of free base groups.
  • a neutralizing agent it is possible in principle to use all cosmetically acceptable inorganic or organic acids such as, for example, formic acid, tartaric acid, malic acid, lactic acid, citric acid, pyrrolidonecarboxylic acid, hydrochloric acid and the like, of which the pyrrolidonecarboxylic acid is particularly preferred.
  • a suitable chitosan is sold, for example, by Kyowa Oil & Fat, Japan under the trade name Flonac ®. It has a molecular weight of 300,000 to 700,000 g / mol and is deacetylated to 70 to 80%.
  • a preferred chitosan is chitosoniumpyrrolidone is, for example, sold under the name Kytamer ® PC by Amerchol, USA. The contained chitosan has a molecular weight of about 200,000 to 300,000 g / mol and is deacetylated to 70 to 85%.
  • chitosan derivatives come quaternized, alkylated or hydroxyalkylated derivatives, for example hydroxyethyl or hydroxybutyl chitosan into consideration.
  • Further chitosan derivatives are Hydagen® ® CMF, Hydagen® ® HCMF and Chitolam ® NB / 101 freely available under the trade names in the trade.
  • quaternized cellulose derivatives such as are available under the names of Celquat ® and Polymer JR ® commercially.
  • the compounds Celquat ® H 100, Celquat ® L 200 and Polymer JR ® 400 are preferred quaternized cellulose derivatives, cationic alkyl polyglycosides according to DE-PS 44 13 686, cationized honey, for example the commercial product Honeyquat ® 50, cationic guar derivatives, such as in particular the products sold under the trade names Cosme- dia ® guar and Jaguar ® products, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid.
  • Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers.
  • Such compounds are available under the names Gafquat ® 734 and Gafquat ® 755 commercially, vinylpyrrolidone-vinyl imidazolium copolymers, such as those offered under the names Luviquat ® FC 370, FC 550, FC 905 and HM 552, quaternized polyvinyl alcohol, as well as the under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 known polymers with quaternary nitrogen atoms in the polymer main chain,
  • Vinylpyrrolidone-vinylcaprolactam-acrylate terpolymers such as those offered with acrylic acid esters and acrylamides as the third monomer building commercially, for example, under the name Aquaflex ® SF 40.
  • Can be used as cationic polymers are sold under the names Polyquaternium-24 (commercial product z. B. Quatrisoft ® LM 200), known polymers.
  • copolymers of vinylpyrrolidone such as the commercial products Copolymer 845 (manufactured by ISP), Gaffix ® VC 713 (manufactured by ISP), Gafquat ® ASCP 101 1, Gafquat ® HS 1 10, Luviquat ® 8155 and Luviquat ® MS 370 are available.
  • cationic polymers which can be used in the compositions according to the invention are the so-called "temporary cationic" polymers. These polymers usually contain an amino group which, at certain pH values, is present as quaternary ammonium group and thus cationic.
  • temporary cationic polymers usually contain an amino group which, at certain pH values, is present as quaternary ammonium group and thus cationic.
  • chitosan and its derivatives are preferred as Hydagen CMF ®, Hydagen HCMF ®, Kytamer ® PC and Chitolam ® NB / 101 are freely available commercially, for example under the trade names.
  • preferred cationic polymers are cationic cellulose derivatives and chitosan and its derivatives, in particular the commercial products Polymer ® JR 400, Hydagen ® HCMF and Kytamer ® PC, cationic guar derivatives, cationic honey derivatives, in particular the commercial product Honeyquat ® 50, cationic Alkylpolyglycodside according to DE-PS 44 13 686 and polymers of the type Polyquaternium-37.
  • cationized protein hydrolyzates are to be counted among the cationic polymers, wherein the underlying protein hydrolyzate from the animal, for example from collagen, milk or keratin, from the plant, for example from wheat, corn, rice, potatoes, soy or almonds, marine life forms, for example from fish collagen or algae, or biotechnologically derived protein hydrolysates.
  • the protein hydrolyzates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acid hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis.
  • cationic protein hydrolyzates are to be understood as meaning quaternized amino acids and mixtures thereof. Quaternization of the protein hydrolyzates or amino acids is often carried out using quaternary ammonium salts such as N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides.
  • the cationic protein hydrolysates may also be further derivatized.
  • the cationic protein hydrolysates and derivatives according to the invention those mentioned under the INCI names in the "International Cosmetic Ingredient Dictionary and Handbook", (seventh edition 1997, The Cosmetic, Toiletry and Fragrance Association 1 101 17 th Street, NW, Suite 300, Washington, DC 20036-4702) and commercially available products called: Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Hydroxypropyl Arginine Lauryl / My
  • the cationic polymers are preferably contained in the agents according to the invention in amounts of from 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.
  • amphoteric polymers can be used as polymers.
  • amphoteric polymers both those polymers which contain both free amino groups and free -COOH or SO ß H groups in the molecule and are capable of forming inner salts, but also zwitterionic polymers containing quaternary ammonium groups in the molecule and -COO contain " - or -SO ß ' groups, and summarized those polymers containing -COOH or SO 3 H groups and quaternary ammonium groups.
  • Amphoteric polymers like the cationic polymers, are most preferred polymers.
  • amphopolymer suitable is the acrylic resin commercially available as Amphomer ®, ethyl methacrylate, a copolymer of tert-butylamino, N- (1, 1, 3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group Acrylic acid, methacrylic acid and their simple esters.
  • amphoteric polymers are those polymers which are composed essentially
  • R 1 -CH CR 2 -CO-Z- (C n H 2n ) -N (+)
  • R 1 and R 2 independently of one another are hydrogen or a methyl group and R 3 , R 4 and R 5 independently of one another are alkyl groups having 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer from 2 to 5 and A H is the anion of an organic or inorganic acid, and
  • R 6 and R 7 are independently hydrogen or methyl groups.
  • These compounds can be used both directly and in salt form, which is obtained by neutralization of the polymers, for example with an alkali metal hydroxide, according to the invention.
  • Very particular preference is given to those polymers in which monomers of the type (a) are used in which R 3 , R 4 and R 5 are methyl groups, Z is an NH group and A H is a halide, methoxysulfate or ethoxysulfate ion ;
  • Acrylamidopropyl trimethyl ammonium chloride is a particularly preferred monomer (a).
  • Acrylic acid is preferably used as monomer (b) for the stated polymers.
  • Suitable starting monomers are, for. Dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, dimethylaminopropylacrylamide,
  • the monomers containing a tertiary amino group are then quaternized in a known manner, methyl chloride, dimethyl sulfate or diethyl sulfate being particularly suitable as alkylating reagents.
  • the quaternization reaction can be carried out in aqueous solution or in the solvent.
  • those monomers of the formula (G3-I) are used which are derivatives of acrylamide or methacrylamide. Preference is furthermore given to those monomers which contain halide, methoxysulfate or ethoxysulfate ions as counterions. Also preferred are those monomers of formula (G3-I) wherein R3, R4 and R5 are methyl groups.
  • the acrylamidopropyltrimethylammonium chloride is a most preferred monomer of the formula (G3-I).
  • Suitable monomeric carboxylic acids of the formula (G3-II) are acrylic acid, methacrylic acid, crotonic acid and 2-methylcrotonic acid. Preference is given to using acrylic or methacrylic acid, in particular acrylic acid.
  • the zwitterionic polymers which can be used according to the invention are prepared from monomers of the formulas (G3-I) and (G3-II) by polymerization processes known per se. Further details of the polymerization process can be found in the relevant specialist literature.
  • Such polymers have been found in which the monomers of the formula (G3-I) were present in excess over the monomers of formula (G3-II). It is therefore preferred according to the invention to use those polymers which consist of monomers of the formula (G3-I) and the monomers of the formula (G3-II) in a molar ratio of 60:40 to 95: 5, in particular 75:25 to 95 : 5, persist.
  • the amphoteric polymers are preferably contained in the agents according to the invention in amounts of from 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.
  • amphoteric polymers which can be used according to the invention are the compounds mentioned in British Patent Application 2,104,091, European Patent Application 47,714, European Offenlegungsschrift 217,274, European Offenlegungsschrift 283,817 and German Offenlegungsschrift 28 17 369.
  • Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copoly- mers (AMERCHOL) are commercially available under the name Amersette® ®.
  • the cationic and amphoteric polymers share a potentially cationic charge. Both cationic and amphoteric or zwitterionic polymers can therefore be characterized by their cationic charge density.
  • the polymers of the invention are characterized by a charge density of at least 1 to 7 meq / g. A charge density of at least 2 to 7 meq / g is preferred. Particularly preferred is a charge density of at least equal to 3meq / g to 7 meq / g.
  • cationic and amphoteric polymers are their molecular weight.
  • the molecular weight of the particular polymer is understood to mean the molecular weight which the manufacturer indicates in the corresponding data sheets by its method.
  • a molecular weight of at least 50,000 g / u has proven to be suitable according to the invention.
  • Polymers with a molecular weight of more than 100,000 g / u have proven to be particularly suitable.
  • Polymers with a molecular weight of more than 1,000,000 g / u are particularly suitable.
  • the deposition of polymers of surfactant solutions on the surface of keratinic fibers is an adsorption process. This adsorption process is not fully understood until today. The previously described selection of suitable polymers already takes place in the prior art according to the criteria presented above the charge density or the molecular weight. These criteria are often not effective. The deposition of polymers on keratinic fibers is physically an adsorption process.
  • Suitable cationic and amphoteric polymers have a value of greater than 100,000 for the product of cationic charge density and molecular weight. Particularly suitable are polymers which have a value of at least 200,000 for this product. Especially suitable are those polymers in which this product has a value greater than 250,000. Most suitable are those polymers in which this product has a value of at least 1,000,000.
  • anionic polymers can advantageously also be used complexly with the active ingredient.
  • the anionic polymers (G2) are anionic polymers which have carboxylate and / or sulfonate groups.
  • anionic monomers from which such polymers may consist are acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid.
  • the acidic groups may be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt.
  • Preferred monomers are 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.
  • An anionic polymers have proven to be particularly effective, containing as sole or co-monomer 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group may be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt.
  • the homopolymer of 2-acrylamido-2-methylpropanesulfonic acid is, which is 1 1-80 commercially available, for example under the name Rheothik ®.
  • copolymers of at least one anionic monomer and at least one nonionic monomer are preferable to use copolymers of at least one anionic monomer and at least one nonionic monomer.
  • anionic monomers reference is made to the substances listed above.
  • Preferred nonionic monomers are acrylamide, methacrylamide, acrylic esters, methacrylic esters, vinylpyrrolidone, vinyl ethers and vinyl esters.
  • Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with sulfonic acid-containing monomers.
  • a particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group is wholly or partly in the form of sodium, potassium, ammonium, mono- or triethanolammonium Salt is present.
  • This copolymer may also be crosslinked, with crosslinking agents preferably polyolefinically unsaturated compounds such as tetraallyloxyethane, allylsucrose, allylpentaerythritol and methylene-bisacrylamide are used.
  • crosslinking agents preferably polyolefinically unsaturated compounds such as tetraallyloxyethane, allylsucrose, allylpentaerythritol and methylene-bisacrylamide are used.
  • crosslinking agents preferably polyolefinically unsaturated compounds such as tetraallyloxyethane, allylsucrose, allylpentaerythritol and methylene-bisacrylamide are used.
  • Such a polymer is contained in the commercial product Sepigel ® 305 from SEPPIC.
  • Simulgel ® 600 as a compound with isohexadecane and polysorbate-80 Natriumacryloyldimethyltaurat copolymers have proved to be particularly effective according to the invention.
  • preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be preferred crosslinking agents. Such compounds are for example available under the trademark Carbopol ® commercially.
  • Copolymers of maleic anhydride and methyl vinyl ether, especially those with crosslinks, are also color-retaining polymers.
  • a 1, 9-decadiene cross-linked methyl vinyl ether-maleic acid copolymer is available under the name ® Stabileze QM.
  • the anionic polymers are preferably contained in the agents according to the invention in amounts of from 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.
  • polyurethanes consist of at least two different monomer types, a compound (V1) having at least 2 active hydrogen atoms per molecule and a di- or polyisocyanate (V2).
  • the compounds (V1) may be, for example, diols, triols, diamines, triamines, polyetherols and polyesterols.
  • the compounds having more than 2 active hydrogen atoms are usually used only in small amounts in combination with a large excess of compounds having 2 active hydrogen atoms.
  • Examples of compounds (V1) are ethylene glycol, 1, 2 and 1, 3-propylene glycol, butylene glycols, di-, tri-, tetra- and poly-ethylene and -Propylenglykole, copolymers of lower alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, Ethylenediamine, propylenediamine, diamines based on?,? 1, 4-diaminobutane, hexamethylenediamine and long-chain alkanes or polyalkylene oxides.
  • Polyurethanes in which the compounds (V1) are diols, triols and polyetherols may be preferred according to the invention.
  • polyethylene glycols and polypropylene glycols having molecular weights between 200 and 3000, in particular between 1600 and 2500, have proven to be particularly suitable in individual cases.
  • Polyesterols are usually obtained by modifying the compound (V1) with dicarboxylic acids such as phthalic acid, isophthalic acid and adipic acid.
  • polyurethanes used in the invention may contain other building blocks such as diamines as chain extenders and hydroxycarboxylic acids.
  • Dialkylolcarboxylic acids such as dimethylolpropionic acid are particularly suitable hydroxycarboxylic acids.
  • further building blocks there is no fundamental restriction as to whether they are nonionic, anionic or cationic building blocks.
  • compositions according to the invention when the polyurethanes were not mixed directly with the other components, but introduced in the form of aqueous dispersions.
  • aqueous dispersions usually have a solids content of about 20-50%, in particular about 35-45% and are also commercially available.
  • the agents according to the invention may contain nonionic polymers (G4).
  • Suitable nonionic polymers are, for example:
  • VinylpyrrolidonA ynyl ester copolymers such as for example, under the trade name Luviskol ® (BASF) /.
  • Luviskol ® VA 64 and Luviskol ® VA 73, each VinylpyrrolidonA / inylacetat copolymers, are also preferred nonionic polymers.
  • Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and hydroxypropylcellulose Methylhy-, as sold for example under the trademark Culminal® ® and Benecel ® (AQUALON) and Natrosol ® grades (Hercules).
  • Siloxanes These siloxanes can be both water-soluble and water-insoluble. Both volatile and nonvolatile siloxanes are suitable, nonvolatile siloxanes being understood as meaning those compounds whose boiling point is above 200 ° C. under normal pressure.
  • Preferred siloxanes are polydi- Alkylsiloxanes, such as polydimethylsiloxane, Polyalkylarylsiloxane, such as polyphenylmethylsiloxane, ethoxylated polydialkylsiloxanes and polydialkylsiloxanes containing amine and / or hydroxyl groups. Glycosidically substituted silicones.
  • the nonionic polymers are preferably contained in the agents according to the invention in amounts of from 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.
  • the term polymer also means special preparations of polymers, such as spherical polymer powders.
  • Various methods are known for producing such microspheres from different monomers, for example by special polymerization processes or by dissolving the polymer in a solvent and spraying it into a medium in which the solvent can evaporate or diffuse out of the particles.
  • Suitable polymers are, for example, polycarbonates, polyurethanes, polyacrylates, polyolefins, polyesters or polyamides.
  • Particularly suitable are those spherical polymer powders whose primary particle diameter is less than 1 micron.
  • Such products based on a polymethacrylate copolymer are, for example, under the trade name Polytrap ® Q5-6603 (Dow Corning) in the trade.
  • Other polymer powders for example based on polyamides (nylon 6, nylon 12) having a particle size of 2 - (10 microns (90%) and a specific surface area of about 10 m 2 / g under the trade name Orgasol ® 2002 DU Nat Cos Atochem SA, Paris).
  • spherical polymer powders which are suitable for the purpose according to the invention are, for example, the polymethacrylates (Micropearl M) from SEPPIC or (Plastic Powder A) from NIKKOL, the styrene-divinylbenzene copolymers (Plastic Powder FP) from NIKKOL, the polyethylene and polypropylene AKZO powder (ACCUREL EP 400) or silicone polymers (Silicone Powder X2-1605) from Dow Corning or even spherical cellulose powders.
  • the polymer powders described above are preferably contained in the agents according to the invention in amounts of from 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.
  • Polymers regardless of their chemical structure and charge, can also be characterized by their function in cosmetic agents.
  • the description of the polymers according to their function in the agents according to the invention does not necessarily correspond to a rating or significance of these polymers. Rather, all polymers are in principle to be regarded as equivalent for use in the compositions according to the invention, although some of these polymers may also be preferred.
  • some polymers can be found in several descriptions with different effects. Polymers which can bring about several desired effects are accordingly particularly preferred for use in the agents according to the invention.
  • a film-forming cationic or amphoteric polymer is particularly preferably selected if the composition is to be used as a styling agent or setting agent.
  • film-forming polymers are meant those polymers which on drying produce a continuous film on the skin, hair or nails leave.
  • film formers can be used in a wide variety of cosmetic products, such as for example face masks, make-up, hair fixatives, hair sprays, hair gels, hair waxes, hair treatments, shampoos or nail varnishes.
  • Particular preference is given to those polymers which have sufficient solubility in alcohol or water / alcohol mixtures to be present in completely completely dissolved form in the composition according to the invention. Because of their pronounced film formation properties, these polymers are very particularly preferred in the compositions of the invention. The use of at least one of these polymers is therefore also very particularly preferred according to the invention.
  • the film-forming polymers may be of synthetic or natural origin.
  • film-forming polymers are also understood to mean those polymers which, when used in 0.01 to 20% strength aqueous, alcoholic or aqueous-alcoholic solution, are capable of depositing a transparent polymer film on the hair.
  • the film-forming polymers may be anionic, amphoteric, nonionic, permanent cationic or temporarily cationically charged.
  • Suitable synthetic, film-forming, hair-setting polymers are homopolymers or copolymers made up of at least one of the following monomers: vinylpyrrolidone, vinylcaprolactam, vinyl esters, e.g. Vinyl acetate, vinyl alcohol, acrylamide, methacrylamide, alkyl and dialkylacrylamide, alkyl and dialkylmethacrylamide, alkyl acrylate, alkyl methacrylate, propylene glycol or ethylene glycol, wherein the alkyl groups of these monomers are preferably C1 to C7 alkyl groups, particularly preferably C1 to C3 alkyl groups.
  • Suitable examples are homopolymers of vinylcaprolactam, vinylpyrrolidone or N-vinylformamide.
  • Further suitable synthetic film-forming, hair-fixing polymers are copolymers of vinyl pyrrolidone and vinyl acetate, terpolymers of vinylpyrrolidone, vinyl acetate and vinyl propionate, polyacrylamides, for example, under the trade designations Akypomine ® P 191 by the company CHEM-Y, Emmerich or Sepigel ® 305 by the company Seppic be distributed; Polyvinyl alcohols, which are marketed under the trade names Elvanol.RTM ® from DuPont or Vinol ® 523/540 by Air Products as well as polyethylene glycol / polypropylene glycol copolymers, for example, sold under the trade names Ucon® Union Carbide. Particularly preferred are polyvinylpyrrolidone and polyvinylpyrrolidone / vinyl acetate copolymers.
  • Suitable natural film-forming polymers include cellulose derivatives, eg. B. hydroxypropyl cellulose having a molecular weight of 30,000 to 50,000 g / mol, which is sold, for example, under the trade name Nisso Sl ® from Lehmann & Voss, Hamburg.
  • Examples of common film formers are Abies Balsamea (Balsam Canada) Resin, Acetylenediurea / Formaldehyde / Tosylamide Crosspolymer, Acrylamide / Ammonium Acrylate Copolymer, Acrylamide Copolymer, Acrylamide / DMAPA Acrylates / Methoxy PEG Methacrylate Copolymer, Acrylamide / Sodium Acrylate Copolymer, Acrylamidopropyltrimonium Chloride / Acrylamide Copolymer , Acrylamidopropyltrimonium Chloride / Acrylates Copolymer, Acrylates / Acetoacetoxyethyl Methacrylate Copolymer, Acrylates / Acrylamide Copolymer, Acrylates / Ammonium Methacrylate Copolymer, Acrylates / Behenyl Methacrylates / Dimethicone Methacrylate Copolymer, Acrylates /
  • Dimethicone / Vinyltrimethylsiloxysilicate Crosspolymer Dimethiconol / IPDI Copolymer, Dimethylamine / Ethylene Diamine / Epichlorohydrin Copolymer, Dioctyldecyl IPDI, Dioctyldodecyl IPDI, Di-PPG-3 Myristyl Ether Adipate, Divinyl Dimethicone / Dimethicone Copolymer, Divinyl Dimethicone / Dimethicone Crosspolymer, DMAPA Acrylates / Acrylic Acid / Acrylonitrogen Copolymer , Dodecanedioic Acid / Cetearyl Alcohol / Glycol Copolymer, Ethyl Cellulose, Ethylene / Acrylic Acid Copolymer, Ethylene / Acrylic Acid / VA Copolymer, Ethylene / Calcium Acrylate Copolymer, Ethylene
  • Polymethacrylic acid polymethyl acrylates, polymethylglutamates, polymethyl methacrylates, polyoxyisobutylenes / methylene urea copolymer, polyoxymethylenes Melamine, Polypentaerythrityl Terephthalate, Polypentene,
  • Polyphosphorylcholines glycol acrylates polyquaternium-1, polyquaternium-2, polyquaternium-4, polyquaternium-5, polyquaternium-6, polyquaternium-7,
  • Film-forming polymers and gums are therefore generally typical substances for hair treatment agents such as hair fixatives, hair foams, hair waxes, hair sprays or leave-on conditioners. As such, they are preferably used in the compositions of the present invention when used in such compositions. Substances which further impart hydrophobic properties to the hair are preferred because they reduce the tendency of the hair to absorb moisture, that is, water. As a result, the limp drooping of the strands of hair is reduced and thus a long-lasting hairstyle structure and preservation is guaranteed. The test method for this is often the so-called curl retention test applied.
  • Examples of common film-forming, setting polymers are: Acrylamide / Ammonium Acrylate Copolymer, Acrylamide / DMAPA Acrylate / Methoxy PEG Methacrylate Copolymer, Acrylamidopropyltrimonium Chloride / Acrylamide Copolymer, Acrylamidopropyltrimonium Chloride / Acrylate Copolymer,
  • Amodimethicone Copolymer Acrylates / Stearyl Acrylates / Ethylamine Oxides Methacrylate Copolymer, Acrylates / VA Copolymer, Acrylates / VP Copolymer, Adipic Acid / Diethylenetriamine Copolymer, Adipic Acid / Dimethylaminohydroxypropyl Diethylenetriamine Copolymer, Adipic Acid / Epoxypropyl Diethylenetriamine Copolymer, Adipic Acid / Isophthalic Acid / Neopentyl Glycol / Trimethylolpropane Copolymer, Allyl Stearate / VA Copolymer, Aminoethyl Acrylate Phosphate / Acrylate Copolymer, Aminoethylpropanediol Acrylate / Acrylamide Copolymer, Aminoethyl Propanediol AMPD Acrylate / Diacetone Acrylamide Copolymer
  • Polyperfluoroperhydrophenanthrenes Polyquaternium-1, Polyquaternium-2, Polyquaternium-4, Polyquaternium-5, Polyquaternium-6, Polyquaternium-7,
  • the film-forming and / or setting polymer is preferably present in the composition according to the invention in an amount of from 0.01 to 40% by weight, particularly preferably from 0.1 to 30% by weight, very particularly preferably in an amount of from 0.1 to 10% by weight ,
  • film-forming and / or solid polymers may also be present in the composition according to the invention.
  • These film-forming and / or setting polymers may be both permanent and temporary cationic, anionic, nonionic or amphoteric.
  • the present invention also encompasses the recognition that, when using at least two film-forming and / or setting polymers, these can of course have different charges.
  • an ionic film-forming and / or setting polymer with an amphoteric and / or nonionic film-forming and / or setting polymer is shared.
  • the use of at least two oppositely charged film-forming and / or setting polymers is also preferred.
  • a particular embodiment may in turn additionally contain at least one further amphoteric and / or nonionic film-forming and / or setting polymer.
  • the antistatic effect of polymers is another essential function for cosmetic agents.
  • the surfaces of the cosmetically treated substrates skin, nails and keratinic fibers are influenced in their electrical potential.
  • this effect reduces the effect known as "fly-away effect” and is based on the electrostatic repulsion of the hair fibers, but it also affects the skin surface on the skin surface, and some of these polymers have their optimum effect
  • preference is given from this group of polymers to those which at the same time belong to at least one of the groups of fixing and / or film-forming polymers It is, however, preferred to select the polymers such that at least one of the polymers has at least two of the desired properties Accordingly, when the polymer further satisfies another property in addition to the three most important properties of strengthening, fixation and film formation.
  • antistatic polymers examples include:
  • the emulsion-stabilizing polymers are also among the polymers preferred according to the invention. These are understood to mean polymers which essentially support the structure and the stabilization of emulsions (O / W and W / O as well as multiple emulsions). Surfactants and emulsifiers are of course the essential ingredients, but the stabilizing polymers contribute to a reduction in the coalescence of the emulsified droplets by positively affecting the continuous or disperse phase.
  • This positive influence may be due to an electrical repulsion, an increase in viscosity or a film formation on the surface of the droplets.
  • These properties of the polymers in question can also be used to particular advantage in the compositions according to the invention in order to dissolve the powdery compositions according to the invention before and / or during the application of the powder in water.
  • Examples of such polymers are Acrylamide / Sodium Acryloyl Dimethyl Taurate Copolymer, Acrylates / Amino Acrylates / C10-30 Alkyl PEG-20 Itaconate Copolymer, Acrylates / C10-30 Alkyl Acrylate Crosspolymer, Acrylates / Stearyl Methacrylate Copolymer, Acrylates / Vinyl Isodecanoate Crosspolymer, Alcaligenes Polysaccharides, AIIyI Methacrylate Crosspolymer, Ammonium Acryloyldimethyltaurate / Beheneth-25 Methacrylate Crosspolymer, Ammonium Acryloyldimethyltaurate / Vinyl Formamide Copolymer, Ammonium Alginate, Ammonium Phosphatidyl Rapeseedate, Ammonium Polyacrylate, Ammonium Polyacryloyldimethyl Taurate, Ammonium Shellacate, Arachidyl Alcohol, Astragalus Gummifer
  • Cerifera Fruit Wax, Octadecene / MA Copolymer, Oleic / Linoleic / Linolenic Polyglycerides, Ozokerite, Pectin, PEG-350, PEG-400, PEG-500, PEG-12 Carnauba, PEG-12 Dimethicone Crosspolymer, PEG-22 / Dodecyl Glycol Copolymer, PEG-45 / Dodecyl Glycol Copolymer, PEG-6 Hydrogenated Palmamide, PEG-100 / IPDI Copolymer, PEG-2M, PEG-5M, PEG-7M, PEG-9M, PEG-14M, PEG-20M, PEG-23M, PEG-25M, PEG-45M, PEG-65M, PEG-90M, PEG-1 15M, PEG-160M, PEG / PPG-20/23 dimethicones, PEG / PPG-23/6 dimethicones,
  • Polymers can increase the viscosity of aqueous and non-aqueous phases in cosmetic preparations.
  • aqueous phases their viscosity-increasing function is based on their solubility in water or their hydrophilic nature. They are used in both surfactant and emulsion systems. This property of the polymers is also advantageous in the powders according to the invention before and / or during use.
  • Acrylamide Copolymer Acrylamide / Sodium Acrylate Copolymer, Acrylamide / Sodium Acryloyl Dimethyl Taurate Copolymer, Acrylates / Acetoacetoxyethyl Methacrylate Copolymer, Acrylates / Beheneth-25 Methacrylate Copolymer, Acrylates / CI O-30 Alkyl Acrylate Crosspolymer, Acrylates / Ceteth-20 Itaconate Copolymer, Acrylates / Ceteth -20 Methacrylate Copolymer, Acrylates / Laureth-25 Methacrylate Copolymer, Acrylates / Palmeth-25 Acrylate Copolymer, Acrylates / Palmeth-25 Itaconate Copolymer, Acrylates / Steareth-50 Acrylate Copolymer, Acrylates / Steareth-20 Itaconate Copolymer, Acrylates / Steareth-20 Methacrylate copolymer, acrylates /
  • Another way to increase the viscosity of cosmetic products is the thickening of the non-aqueous phase, the lipid phase of the cosmetic products.
  • polymers which are not water-soluble but compatible with lipids. They are also used for the gelation of cosmetic products with high lipid levels. This also contributes significantly to the excellent application of the powders according to the invention. With these polymers, the viscosity of the composition which forms on dissolution is excellently controlled.
  • Divinyl Dimethicone / Dimethicone Crosspolymer Dodecanedioic Acid / Cetearyl Alcohol / Glycol Copolymer, Ethyl Cellulose, Ethylene / Acrylic Acid Copolymer, Ethylene / Acrylic Acid / VA Copolymer, Ethylenediamine / Dimer Tallate Copolymer Bis-Hydrogenated Tallow Amide, Ethylene Diamine / Stearyl Dimer Dilinoleate Copolymer, Ethylene Diamine / Stearyl Dimer Tallate Copolymer, Ethylene / Octene Copolymer, Ethylene / Propylene Copolymer, Ethylene / Propylene / Styrene Copolymer, Euphorbia Cerifera (Candelilla) Wax, Hydrogenated Butylene / Ethylene / Styrene Copolymer, Hydrogenated Ethylene / Propy
  • Styrene / Methacrylamide / Acrylates Copolymer Synthetic Beeswax, Synthetic Candelilla Wax, Synthetic Carnauba, Synthetic Japan Wax, Synthetic Wax, TDI Oxidized Microcrystalline Wax, Tricontanyl PVP, Trifluoropropyl Dimethicone Crosspolymer, Trifluoropropyl Dimethicone / Trifluoropropyl Divinyl Dimethicone Crosspolymer, Trifluoropropyl Dimethicone / Vinyl Trifluoropropyl Dimethicone / Silsesquioxane Crosspolymer, Trimethylpentanediol / Isophthalic Acid / Trimellitic Anhydride Copolymer, Trimethylsiloxysilicate / Dimethiconol Crosspolymer, Vinyl Dimethicone / Lauryl Dimethicone Crosspolymer, Vinyl Dimethicone / Methicone Silsesqui
  • microparticles filled or unfilled may also be used in the composition of the invention both to achieve certain effects, such as the release of an active agent from the capsules or the achievement of particular visual, esthetic effects of the overall formulation.
  • Suspension aids facilitate the distribution of solids in Liquids.
  • the polymers occupy the surface of the solid particles by adsorption and thereby change the surface properties of the solids. The following are examples of these polymers:
  • Phosphonobutanetricarboxylic Acid Polyacrylamidomethylpropanes, Sulfonic Acid, Polycaprolactones, Polyethylacrylates, Polyhydroxystearic Acid,
  • the preparations used contain a plurality of, in particular two different polymers of the same charge and / or in each case an ionic and an amphoteric and / or nonionic polymer.
  • polymers are all polymers in the "International Cosmetic Ingredient Dictionary and Handbook” (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1 101 17 th Street, NW, Suite 300, Washington, DC 20036- 4702) as Polymers are referred to in one of the chapters on polymers such as "film formers” or “hair fixatives” and are commercially available, reference is made to this document and the sections cited therefrom.
  • the polymer (G) according to the invention may be both a consolidating and / or film-forming polymer and a polymer having conditioning or avivating and / or thickening properties.
  • the polymers (G) are contained in the agents used according to the invention preferably in amounts of 0.01 to 30 wt .-%, based on the total agent. Amounts of from 0.01 to 25, in particular from 0.01 to 15 wt .-%, are particularly preferred.
  • the active ingredient complex according to the invention has the property of itself to minimize adverse effects on the skin and hair due to UV light, it may still be advantageous to use further UV filters in the compositions according to the invention.
  • the effect of the active substance complex by UV filter (I) can be increased.
  • the UV filters to be used according to the invention are not subject to any general restrictions with regard to their structure and their physical properties. On the contrary, all UV filters which can be used in the cosmetics sector and whose absorption maximum lies in the UVA (315-400 nm), in the UVB (280-315 nm) or in the UVC ( ⁇ 280 nm) range are suitable. UV filters with an absorption maximum in the UVB range, in particular in the range from about 280 to about 300 nm, are particularly preferred.
  • the UV filters used according to the invention can be selected, for example, from substituted benzophenones, p-aminobenzoic acid esters, diphenylacrylic acid esters, cinnamic acid esters, salicylic acid esters, benzimidazoles and o-aminobenzoic acid esters.
  • UV filters which can be used according to the invention are 4-aminobenzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) aniline methylsulfate, 3,3,5-trimethylcyclohexyl salicylate (homosalates), 2-hydroxy-4-methoxy-benzophenone (Benzophenone- 3; Uvinul ® M 40, Uvasorb MET ®, ® Neo Heliopan BB, Eusolex ® 4360), 2-Phenylbenzimida- zol-5-sulfonic acid and potassium, sodium and triethanolamine (Phenylben- zimidazole sulfonic acid; Parsol ® HS; Neo Heliopan Hydro ®), 3,3 '- (1, 4-Phenylendime- Thylen) -bis (7,7-dimethyl-2-oxo-bicyclo [2.2.
  • water-insoluble UV filters are those which dissolve in water at not more than 1% by weight, in particular not more than 0.1% by weight, at 20 ° C. Furthermore, these compounds should be soluble in the usual cosmetic oil components at room temperature to at least 0.1, in particular at least 1 wt .-%). The use of water-insoluble UV filters may therefore be preferred according to the invention.
  • UV filters which have a cationic group, in particular a quaternary ammonium group.
  • UV filters have the general structure U - Q.
  • the structural part U stands for a UV-absorbing group.
  • This group can in principle be derived from the known UV filters which can be used in the cosmetics sector, in which a group, generally a hydrogen atom, of the UV filter is replaced by a cationic group Q, in particular having a quaternary amino function ,
  • Structural parts U which are derived from cinnamic acid amide or from N, N-dimethylaminobenzoic acid amide, are preferred according to the invention.
  • the structural parts U can in principle be chosen such that the absorption maximum of the UV filters can be in both the UVA (315-400 nm) and in the UVB (280-315 nm) or in the UVC ( ⁇ 280 nm) range. UV filters with an absorption maximum in the UVB range, in particular in the range from about 280 to about 300 nm, are particularly preferred.
  • the structural part U also as a function of structural part Q, is preferably selected so that the molar extinction coefficient of the UV filter at the absorption maximum is above 15,000, in particular above 20,000.
  • the structural part Q preferably contains, as a cationic group, a quaternary ammonium group.
  • This quaternary ammonium group can in principle be connected directly to the structural part U, so that the structural part U represents one of the four substituents of the positively charged nitrogen atom.
  • one of the four substituents on the positively charged nitrogen atom is a group, especially an alkylene group having 2 to 6 carbon atoms, which functions as a compound between the structural part U and the positively charged nitrogen atom.
  • the group Q has the general structure - (CH 2 ) X -N + R 1 R 2 R 3 X " , in which x is an integer from 1 to 4, R 1 and R 2 are independently of one another 4 alkyl groups, R 3 is a Ci -22- alkyl group or a benzyl group and X "is a physiologically acceptable anion.
  • x preferably represents the number 3
  • R 1 and R 2 each represent a methyl group and R 3 either for a methyl group or a saturated or unsaturated, linear or branched hydrocarbon chain having 8 to 22, in particular 10 to 18, carbon atoms.
  • Physiologically acceptable anions are, for example, inorganic anions such as halides, in particular chloride, bromide and fluoride, sulfate ions and phosphate ions and organic anions such as lactate, citrate, acetate, tartrate, methosulfate and tosylate.
  • inorganic anions such as halides, in particular chloride, bromide and fluoride, sulfate ions and phosphate ions and organic anions such as lactate, citrate, acetate, tartrate, methosulfate and tosylate.
  • UV filters with cationic groups the commercially available compounds cinnamic acid-trimethylammonium chloride are (Incro- quat ® UV-283) and dodecyl tosylate (Escalol ® HP 610).
  • the teaching of the invention also includes the use of a combination of several UV filters.
  • the combination of at least one water-insoluble UV filter with at least one UV filter with a cationic group is preferred.
  • the UV filters (I) are contained in the compositions according to the invention usually in amounts of 0.1-5 wt .-%, based on the total agent. Levels of 0.4-2.5 wt .-% are preferred.
  • short-chain carboxylic acids can additionally support the active ingredient in a complex manner.
  • Short-chain carboxylic acids and their derivatives in the context of the invention are understood to mean carboxylic acids which may be saturated or unsaturated and / or straight-chain or branched or cyclic and / or aromatic and / or heterocyclic and have a molecular weight of less than 750.
  • preference may be given to saturated or unsaturated straight-chain or branched carboxylic acids having a chain length of from 1 to 16 C atoms in the chain, very particular preference being given to those having a chain length of from 1 to 12 C atoms in the chain.
  • the short-chain carboxylic acids according to the invention may have one, two, three or more carboxy groups.
  • Preferred within the meaning of the invention are carboxylic acids having a plurality of carboxy groups, in particular di- and tricarboxylic acids.
  • the carboxy groups may be wholly or partly present as esters, acid anhydride, lactone, amide, imidic acid, lactam, lactim, dicarboximide, carbohydrazide, hydrazone, hydroxam, hydroxime, amidine, amidoxime, nitrile, phosphonic or phosphate ester.
  • the carboxylic acids according to the invention may of course be substituted along the carbon chain or the ring skeleton.
  • the substituents of the carboxylic acids according to the invention are, for example, C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, aryl, aralkyl and aralkenyl, hydroxymethyl, C 2 -C 8 -hydroxyalkyl, C 2 -C 8 -hydroxyalkenyl, Aminomethyl, C 2 -C 8 -aminoalkyl, cyano, formyl, oxo, thioxo, hydroxy, mercapto, amino, carboxy or imino groups.
  • Preferred substituents are C 1 -C 8 alkyl, hydroxymethyl, hydroxy, amino and carboxy groups. Particularly preferred are substituents in a - position.
  • substituents are hydroxy, alkoxy and amino groups, where the amino function may optionally be further substituted by alkyl, aryl, aralkyl and / or alkenyl radicals.
  • preferred carboxylic acid derivatives are the phosphonic and phosphate esters.
  • carboxylic acids examples include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, suberic acid, sebacic acid, propiolic acid, crotonic acid, isocrotonic acid , elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, Toluoylklare, hydratropic acid, atropic acid, cinnamic acid, isonicotinic acid, nicotinic acid, Bicarbaminklare, 4,4 '-Dicyano- 6, 6
  • Propanetricarboxylic acid a dicarboxylic acid selected from the group formed by compounds of general formula (NI), (NI) Z- () (C n H 2n ) - COOH
  • n is a number from 4 to 12 and one of the two groups X and Y is a COOH group and the other is hydrogen or a methyl or Ethyl radical
  • dicarboxylic acids of the general formula (NI) which additionally carry 1 to 3 methyl or ethyl substituents on the cyclohexene ring and dicarboxylic acids formed formally from the dicarboxylic acids according to formula (NI) by addition of a molecule of water to the double bond in the cyclohexene ring.
  • German Patent 22 50 055 discloses the use of these dicarboxylic acids in liquid soap masses.
  • German Offenlegungsschrift 28 33 291 discloses deodorizing agents which contain zinc or magnesium salts of these dicarboxylic acids.
  • German Patent Application 35 03 618 means for washing and rinsing the hair are known in which by adding these dicarboxylic acids a noticeably improved hair cosmetic effect of the water-soluble ionic polymers contained in the means is obtained.
  • German Patent Application 197 54 053 means for hair treatment are known which have nourishing effects.
  • the dicarboxylic acids of the formula (NI) can be prepared, for example, by reacting polyunsaturated dicarboxylic acids with unsaturated monocarboxylic acids in the form of a Diels-Alder cyclization. Usually one will assume a polyunsaturated fatty acid as the dicarboxylic acid component. Preferred is the linoleic acid obtainable from natural fats and oils. When Monocarboxylic acid component are in particular acrylic acid, but also, for example, methacrylic acid and crotonic acid are preferred. Normally, in the case of reactions according to Diels-Alder, mixtures of isomers are formed in which one component is present in excess. These isomer mixtures can be used according to the invention as well as the pure compounds.
  • those dicarboxylic acids which differ from the compounds according to formula (NI) by 1 to 3 methyl or ethyl substituents on the cyclohexyl ring or formally from these compounds by addition of one molecule of water are also usable according to the invention be formed on the double formation of the cyclohexene ring.
  • the dicarboxylic acid (mixture), which is obtained by reacting linoleic acid with acrylic acid, has proved to be particularly effective according to the invention. It is a mixture of 5- and 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid.
  • Such compounds are commercially available under the designations Westvaco Diacid 1550 Westvaco Diacid ® ® 1595 (manufacturer: Westvaco).
  • carboxylic acids of the invention listed above by way of example, their physiologically tolerable salts can also be used according to the invention.
  • examples of such salts are the alkali metal salts, alkaline earth metal salts, zinc salts and ammonium salts, which in the context of the present application also includes the mono-, di- and trimethyl-, -ethyl- and -hydroxyethyl ammonium salts.
  • neutralized acids can very particularly preferably be used with alkaline-reacting amino acids, such as, for example, arginine, lysine, ornithine and histidine.
  • hydroxycarboxylic acids and here again in particular the dihydroxy, trihydroxy and polyhydroxycarboxylic acids and the dihydroxy, trihydroxy and polyhydroxy di-, tri- and polycarboxylic acids use together with the active ingredient complex. It has been found that in addition to the hydroxycarboxylic acids, the hydroxycarboxylic acid esters and the mixtures of hydroxycarboxylic acids and their esters as well as polymeric hydroxycarboxylic acids and their esters can be very particularly preferred.
  • Preferred hydroxycarboxylic acid esters are, for example, full esters of glycolic acid, lactic acid, malic acid, tartaric acid or citric acid.
  • hydroxycarboxylic acid esters are esters of ⁇ -hydroxypropionic acid, tartronic acid, D-gluconic acid, sugar acid, mucic acid or glucuronic acid.
  • Suitable alcohol components of these esters are primary, linear or branched aliphatic alcohols having 8-22 C atoms, ie, for example, fatty alcohols or synthetic fatty alcohols.
  • the esters of C12-C15 fatty alcohols are particularly preferred. Esters of this type are commercially available, eg under the trademark Cosmacol® ® EniChem, Augusta Industriale. Especially preferred
  • Polyhydroxypolycarboxylic acids are polylactic acid and polyuric acid and their esters.
  • protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins).
  • protein hydrolyzates also means total hydrolyzates as well as individual amino acids and their derivatives as well as mixtures of different amino acids.
  • polymers made up of amino acids and amino acid derivatives are understood by the term protein hydrolyzates. The latter include, for example, polyalanine, polyasparagine, polyserine, etc.
  • compounds which can be used according to the invention are L-alanyl-L-proline, polyglycine, glycyl-L-glutamine or D / L-methionine-S-
  • Methylsulfoniumchlorid ⁇ -amino acids and their derivatives such as ⁇ -alanine, anthranilic acid or hippuric acid can also be used.
  • the molecular weight of the protein hydrolysates which can be used according to the invention is between 75, the molecular weight for glycine, and 200,000 the molecular weight is 75 to 50,000 and most preferably 75 to 20,000 daltons.
  • Another inventive synergistic active ingredient with the active ingredient according to the invention is therefore complex protein hydrolyzates and / or its derivatives (P).
  • Proteins and / or protein hydrolysates are able to significantly restructure the internal structure of fibers, especially keratinic fibers.
  • Structural strengthening that is to say restructuring in the context of the invention, is to be understood as meaning a reduction in the damage of keratinic fibers which has arisen due to the most diverse influences.
  • the restoration of natural strength plays an essential role.
  • Restructured fibers are distinguished, for example, by an improved gloss or by an improved grip or by easier combing.
  • they have an optimized strength and elasticity.
  • a successful restructuring can be physically detected as a melting point increase compared to the damaged fiber. The higher the melting point of the hair, the firmer the structure of the fiber.
  • composition according to the invention is further increased by the simultaneous use of polymers and / or penetration and swelling aids.
  • polymers and / or penetration and swelling aids even after the application of the particular composition significantly more protein hydrolyzate or its derivative remains on the surface of the hair, resulting in an improved effect.
  • the hair is thus significantly strengthened and smoothed in its structure.
  • This effect is also clearly detectable with objective proofs of effectiveness such as, for example, the measurement of the combing forces of wet and dry hair, the measurement of the breaking forces or the measurement of the torsion angle on the skin. A confirmation of these results can also be found in the results of the consumer tests.
  • Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins).
  • the term protein hydrolyzates also means total hydrolyzates as well as individual amino acids and their derivatives as well as mixtures of different amino acids.
  • polymers made up of amino acids and amino acid derivatives are understood by the term protein hydrolyzates. The latter include, for example, polyalanine, polyasparagine, polyserine, etc.
  • Further examples of compounds which can be used according to the invention are L-alanyl-L-proline, polyglycine, glycyl-L-glutamine or D / L-methionine-S-
  • Methylsulfoniumchlorid ⁇ -amino acids and their derivatives such as ⁇ -alanine, anthranilic acid or hippuric acid can also be used.
  • the molecular weight of the protein hydrolyzates which can be used according to the invention is between 75, the molecular weight for glycine, and 200,000, preferably the molecular weight is 75 to 50,000 and most preferably 75 to 20,000 Dalton.
  • the present teaching according to the invention also encompasses that in the case of the amino acids, these may be present in the form of derivatives, such as, for example, the N-acyl derivatives, the N-alkyl or the O-esters.
  • the acyl group is a formyl radical, an acetyl radical, a propionyl radical, a butyryl radical or the radical of a straight-chain, branched or unbranched, saturated or unsaturated fatty acid having a chain length of 8 to 30 carbon atoms.
  • the alkyl group may be linear, branched, saturated or unsaturated and has a C chain length of 1 to 30 carbon atoms.
  • the alcohols on which the esterification is based are methanol, ethanol, isopropanol, propanol, butanol, isobutanol, pentanol, neopentanol, isopentanol, hexanols, heptanols, caprylic or caproic alcohol, octanols, nonanols, decanols, dodecanols, lauranols, in particular saturated or unsaturated, linear or branched alcohols having a C chain length of 1 to 30 carbon atoms.
  • the amino acids can be simultaneously derivatized both at the N atom and at the O atom.
  • the amino acids can also be used in salt form, in particular as mixed salts together with edible acids. This may be preferred according to the invention.
  • amino acids and their derivatives as protein hydrolysates according to the invention are: alanine, arginine, carnitine, creatine, cystathionine, cysteine, cystine, cystic acid, glycine, histidine, homocysteine, homoserine, isoleucine, lanthionine, leucine, lysine, methionine, norleucine, norvaline , Ornithine, phenylalanine, proline, hydroxyproline, sarcosine, serine, threonine, tryptophan, thyronine, tyrosine, VaNn, aspartic acid, asparagine, glutamic acid and glutamine.
  • Preferred amino acids are alanine, arginine, glycine, histidine, lanthionine, leucine, lysine, proline, hydroxyproline serine and asparagine.
  • Alanine, glycine, histidine, lysine, serine and arginine are very particularly preferably used. Most preferably, glycine, histidine, lysine and serine are used.
  • protein hydrolysates of both vegetable and animal or marine or synthetic origin can be used.
  • Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts.
  • Such products are, for example, under the trademarks Dehylan ® (Cognis), Promois® ® (Interorgana) Collapuron ® (Cognis), Nutrilan® ® (Cognis), Gelita-Sol ® (German Gelatinefabriken Stoess & Co), Lexein ® (Inolex) and kerasol tm ® (Croda) sold.
  • Moringa growths have been known since ancient times. Better known are plants of this species under their common name "Wunderbaum.” They are preferably native to tropical areas.The various parts of this genus of plants have been used since ancient times, especially for medical purposes.
  • This protein has a molecular weight of 500 to 50,000 daltons
  • Preferred is a protein extract with a molecular weight of 3,000 to 30,000 daltons, most preferably from 5,000 to 15,000 daltons
  • the most preferred extract is obtained from the plant Moringa oleifera
  • the extract according to the invention naturally contains water and glycerol on the basis of the extraction
  • the content of extracted protein in the extract is 0.01 to 20% by weight
  • a content of protein of 0.01 to 10% by weight is preferred.
  • Particularly preferred is an extract with a protein content of 0.01 to 5 wt.%.
  • at least 30% by weight of glycerol are contained in the extract.
  • water is contained in the extract according to the invention.
  • the above-described protein extract from the seeds of the Moringa growths is contained in an amount of at least 0.01 to 20% by weight.
  • amounts of the extract of 0.01 to 10 wt.%, Very particularly preferably amounts of 0.01 to 5 wt.% Based on the total cosmetic composition used.
  • Further preferred vegetable protein hydrolysates according to the invention are, for example, soya, almond, pea, potato and wheat protein hydrolysates.
  • Such products are, for example, under the trademarks Gluadin ® (Cognis), diamine ® (Diamalt) ® (Inolex), Hydrosoy ® (Croda), hydro Lupine ® (Croda), hydro Sesame ® (Croda), Hydro tritium ® (Croda) and Crotein ® (Croda) available.
  • protein hydrolysates according to the invention are of maritime origin. These include, for example, collagen hydrolyzates of fish or algae as well as protein hydrolysates of mussels or pearl hydrolyzates.
  • Beads of mussels consist essentially of inorganic and organic calcium salts, trace elements and proteins. Pearls can be easily obtained from cultivated mussels. The cultivation of the mussels can be done in fresh water as well as in sea water. This can affect the ingredients of the beads. According to the invention, preference is given to a pearl extract which originates from shells cultivated in marine or salt water. The pearls consist to a large extent of aragonite (calcium carbonate), conchiolin and an albuminoid. The latter components are proteins. Also included in beads are magnesium and sodium salts, inorganic silicon compounds, and phosphates.
  • the beads are pulverized. Thereafter, the pulverized beads are extracted by the usual methods.
  • extraction agent for Preparation of the pearl extracts can be used water, alcohols and mixtures thereof. Underwater are understood to mean both demineralized water and seawater.
  • the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as glycerol, diglycerol, triglycerol, polyglycerol, ethylene glycol, propylene glycol and butylene glycol, both as sole extractant and in admixture with demineralized water or sea water, preferably.
  • Pearl extracts based on water / glycerine mixtures have proven to be particularly suitable.
  • the pearl proteins can be largely in the native state or already partially or largely present as protein hydrolysates. Preference is given to a pearl extract in which conchiolin and albuminoid are already partially hydrolyzed.
  • the essential amino acids of these proteins are glutamic acid, serine, alanine, glycine aspartic acid and phenylalanine.
  • the bead extract is additionally enriched with at least one or more of these amino acids these amino acids.
  • the pearl extract is enriched with glutamic acid, serine and leucine.
  • a preferred extract contains organic and / or inorganic calcium salts as well as magnesium and sodium salts, inorganic silicon compounds and / or phosphates.
  • a most preferred pearl extract contains at least 75%, preferably 85%, more preferably 90% and most preferably 95% of all ingredients of the naturally occurring pearls.
  • pearl extracts according to the invention are the commercial products Pearl Protein Extract BG ® or Crodarom ® Pearl.
  • one of the above-described pearl extracts is contained in an amount of at least 0.01 to 20% by weight.
  • amounts of the extract of 0.01 to 10 wt.%, Very particularly preferably amounts of 0.01 to 5 wt.% Based on the total cosmetic composition used.
  • protein hydrolysates Although the use of the protein hydrolysates is preferred as such, amino acid mixtures otherwise obtained may be used in their place, if appropriate. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products. Such products are sold, for example, under the names Lamepon® ® (Cognis), Lexein ® (Inolex), Crolastin ® (Croda) or crotein ® (Croda).
  • the protein hydrolysates (P) are present in the compositions in concentrations of 0.001% by weight to 20% by weight, preferably from 0.05% by weight to 15% by weight and most preferably in amounts of 0.05% by weight. up to 5% by weight.
  • vitamins are vitamins, provitamins or vitamin precursors.
  • Vitamins, pro-vitamins and vitamin precursors are particularly preferred, which are assigned to the groups A, B, C, E, F and H.
  • the skin which naturally also includes the scalp, leaves behind the treatment with these very particularly preferred components a much better-looking, more vital, stronger impression with significantly improved gloss and a very good grip both in the wet and in the dry state.
  • this drug affects the regeneration and restructuring of the affected skin and damaged hair, leads to a regulation of the fat balance, so that the thus treated skin and hair greases more slowly and not prone to over-greasing.
  • this ingredient has an anti-inflammatory and skin-calming effect.
  • the split hair is regenerated and repaired by these agents again. These ingredients are able to penetrate the hair and strengthen and repair the hair from the inside out. This "repair effect" can be demonstrated objectively by means of DSC measurements, for example, these effects can also be verified subjectively in the consumer test.
  • vitamin A includes retinol (vitamin A 1 ) and 3,4-didehydroretinol (vitamin A 2 ).
  • the ß-carotene is the provitamin of retinol.
  • vitamin A component according to the invention for example, vitamin A acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters such as the palmitate and the acetate into consideration.
  • the agents according to the invention preferably contain the vitamin A component in amounts of 0.05-1% by weight, based on the total preparation.
  • the vitamin B group or the vitamin B complex include u. a.
  • Vitamin B 2 (riboflavin)
  • Vitamin B 3 the compounds nicotinic acid and nicotinamide (niacinamide) are often performed.
  • Preferred according to the invention is the nicotinic acid amide which is contained in the agents used according to the invention preferably in amounts of from 0.05 to 1% by weight, based on the total agent.
  • Vitamin B 5 pantothenic acid, panthenol and pantolactone. Panthenol and / or pantolactone are preferably used in the context of this group.
  • Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and also cationically derivatized panthenols.
  • panthenol triacetate the panthenol monoethyl ether and its monoacetate and the cationic disclosed in WO 92/13829 Panthenol.
  • the said compounds of the vitamin B 5 type are preferably contained in the agents according to the invention in amounts of 0.05-10% by weight, based on the total agent. Amounts of 0.1-5 wt .-% are particularly preferred.
  • Vitamin B 6 pyridoxine and pyridoxamine and pyridoxal.
  • Vitamin C (ascorbic acid). Vitamin C is used in the agents according to the invention preferably in amounts of 0.1 to 3 wt .-%, based on the total agent. Use in the form of palmitic acid ester, glucosides or phosphates may be preferred. The use in combination with tocopherols may also be preferred.
  • Vitamin E tocopherols, especially ⁇ -tocopherol.
  • Tocopherol and its derivatives including in particular the esters such as the acetate, the nicotinate, the phosphate and the succinate, are preferably present in the agents according to the invention in amounts of 0.05-1% by weight, based on the total agent.
  • Vitamin F is usually understood as meaning essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid.
  • Vitamin H is the compound (3aS, 4S, 6aR) -2-oxohexahydrothienol [3,4-d] imidazole-4-valeric acid, for which, however, the trivial name biotin has meanwhile become established.
  • Biotin is preferably present in the compositions according to the invention in amounts of from 0.0001 to 1.0% by weight, in particular in amounts of from 0.001 to 0.01% by weight.
  • the agents according to the invention preferably contain vitamins, provitamins and vitamin precursors from groups A, B, E and H. Panthenol, pantolactone, pyridoxine and its derivatives as well as nicotinic acid amide and biotin are particularly preferred.
  • compositions according to the invention additionally contain antimicrobial compounds.
  • Suitable antimicrobial compounds are, for.
  • B. cationic surfactants such. Cetyltrimethylammonium bromide, Benzethonium chloride, cetylpyridinium chloride or tris- (2-hydroxyethyl) amine known as fluoride N, N, IST-N '-octadecyl-1, 3-diaminopropane dihydrofluoride. Good are also the antimicrobial biguanide compounds such.
  • the polyhexamethylene biguanide (Vantocil® IB, ICI) or the 1, 1 ' hexamethylene bis (4-chlorophenyl) biguanide (“chlorhexidine”) in the form of a water-soluble, compatible salt, e.g. In the form of the acetate or gluconate.
  • the antimicrobial 5-amino-hexahydropyrimidines, z. B. 1, 3-bis (2-ethylhexyl) -5-methyl-5-amino-hexahydropyrimidine ("hexetidine”).
  • suitable antimicrobial agents are the non-cationic, phenolic, antimicrobial substances, in particular the halogenated phenols and diphenyl ethers.
  • Particularly suitable antimicrobial compounds of this type are z.
  • the 6,6 '- methylene-bis- (2-bromo-4-chlorophenol) ( “bromochlorophene”) and 2,4,4' -Trichlor- 2 '-hydroxy-diphenyl ether "triclosan”
  • antimicrobial substances are the p-hydroxybenzoic acid esters and sesquiterpene alcohols such.
  • p-hydroxybenzoic acid esters such as the bisabolol, farnesol, Santalol or Nerolidol.
  • plant extracts (L) in the compositions according to the invention gives rise to further synergistic advantages. Therefore, the use of these substances is particularly advantageous.
  • Such combinations cause a pleasant fragrance of both the cosmetic composition, as well as the treated skin and the treated hair.
  • this active ingredient according to the invention also has a favorable influence on the moisture balance of the skin and the hair.
  • it shows an anti-inflammatory and skin-calming effect when, for example, chamomile or valerian are used.
  • Nettle, hops, birch and burdock roots, for example, show particularly good hair-related effects.
  • these extracts are produced by extraction of the whole plant. However, in individual cases it may also be preferred to prepare the extracts exclusively from flowers and / or leaves of the plant.
  • composition according to the invention are the extracts of green tea, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi and melon.
  • alcohols and mixtures thereof can be used as extraction agent for the preparation of said plant extracts water.
  • the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric Alcohols such as ethylene glycol and propylene glycol, both as the sole extractant and in admixture with water, are preferred.
  • Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable.
  • the plant extracts can be used according to the invention both in pure and in diluted form. If they are used in diluted form, they usually contain about 2 to 80 wt .-% of active substance and as a solvent used in their extraction agent or extractant mixture.
  • compositions according to the invention mixtures of several, especially two, different plant extracts.
  • rock crystal extract In addition to the plant extracts, a rock crystal extract has also recently been used in cosmetic compositions.
  • Rock crystal is a modification of silica.
  • Silica itself is also included in many other clays and earths as a companion material.
  • quartz is found in bentonite. Quartz in the form of various silicates is also used, for example, in homeopathic remedies, for example sodium aluminum silicate for the reduction of heartburn or also in the medicine of Ayurveda.
  • Sand which can be contaminated with quartz, finds use in cleansing cosmetic products as exfoliating body.
  • quartz has a mystical meaning. So the rock crystal is considered something special.
  • Contaminants are not understood to mean the traces of other elements embedded in them, which contribute to the color of the rose quartz, for example.
  • the term "quartz” understood silicates, phyllosilicates, talcs, spades, etc.
  • Finely ground quartz and an extract of finely ground quartz is used in cosmetic compositions to give the skin and hair a velvety, soft, pleasant feeling. Furthermore, the gloss of skin and hair is remarkably increased significantly. However, there is no undesirable stress on the skin and hair. Also on the hair subsequent treatments such as cold wave or dyeing processes are not only not adversely affected but there is no impairment.
  • the finely ground quartz, the quartz powder is obtained by conventional methods for comminution and grinding of rocks. Quartz powder is used especially in particle sizes from 0.5 ⁇ m up to 500 ⁇ m. Particular preference is given to particle sizes of from 0.5 to 250 ⁇ m, very particularly preferably from 10 ⁇ m to 200 ⁇ m.
  • the finely-milled quartz is extracted by means of protic solvents and the resulting quartz extract is used in the cosmetic compositions.
  • quartz, tridymite, cristobalite, keatite, coesite, stishovite, rock crystal, smoky quartz, amethyst, chrysoprase, citrine, morion, rose quartz, opal and its varieties agate, chalcedony, onyx, carnelian, heliotrope, jasper or flint are used as starting materials used for the production of a flour and the subsequent extraction to the "quartz extract".
  • quartz, smoky quartz, Rock crystal, rose quartz and agate Very particular preference is given to using smoke quartz, rose quartz and rock crystal. Most preferred is rock crystal.
  • extraction agent for the preparation of said quartz extracts water, alcohols and mixtures thereof can be used.
  • Underwater are to be understood here as demineralized water, as well as seawater and mineral water.
  • alcohols are lower alcohols such as ethanol, isopropanol, butanol, iso-butanol, tert.
  • the invention also includes the teaching that, of course, a plurality of alcohols and / or polyhydric alcohols can be used as extractant in admixture with water.
  • a plurality of alcohols and / or polyhydric alcohols can be used as extractant in admixture with water.
  • the mineral waters include Evian, SpA, Leau de Vichy, etc.
  • any known methods such as hot extraction or other methods may be used.
  • a quartz extract thus obtained usually contains at least 1 to 100,000 ppm of silicon.
  • Preferred is an extract with a minimum amount of silicon of 10 ppm.
  • Particularly preferred is an extract with a content of silicon of at least 50 ppm.
  • an extract with a content of at least 100 ppm. Most preferred is a content of at least 200 ppm silicon.
  • the amount of silicon in the extract is determined by flame spectrometry in distilled water.
  • the quartz extract may optionally be adjusted with water glass to a constant minimum content of silicon. If water glass is used to adjust the silicon content, it may still be necessary to Adjust the pH of the quartz extract.
  • the quartz extract usually has a pH of from 4 to 11, preferably from 6 to 11, more preferably from 7 to 10, and most preferably from 7.5 to 9.5.
  • the pH value will be adjusted with mineral acids such as aqueous solutions of hydrogen halides, sulfuric acid and its salts, sulphurous acid and its salts, phosphorous acid and its salts, phosphoric acid and salts thereof or with organic acids Acids and their salts such as iminodisuccinic acid, etidronic acid, tartaric acid or citric acid made.
  • acids which also have complex-forming properties, may be preferred. These include, for example, phosphoric acid, iminodisuccinic acid, etidronic acid, tartaric acid or citric acid and their salts. Very particular preference is given to using phosphoric acid in the case of a necessary pH adjustment.
  • An example of a commercially available quartz extract is available under the name Crodarom ® rock crystal by Croda free in the trade.
  • compositions according to the invention contain penetration aids and / or swelling agents (M).
  • M penetration aids and / or swelling agents
  • These excipients provide better penetration of active ingredients into the keratin fiber or help swell the keratin fiber.
  • compositions according to the invention are particularly well suited to deposit perfume oils or perfumes on the skin and hair in an increased amount. At the same time the perfume oils and fragrances remain much longer on the skin or the hair adhere. this leads to to an increased acceptance of such compositions in the consumer. These results are particularly relevant to compositions such as shampoos, shower baths, cures, spa wraps, conditioners, leave-on hair treatments, styling agents, and hair fixative and firming agents.
  • compositions of the invention are perfumes.
  • perfumes are perfumes.
  • the excellent and completely surprising positive results of compositions containing the active compounds and perfumes according to the invention has already been described in detail above.
  • perfume means perfume oils, fragrances and fragrances. As perfume oils are called mixtures of natural and synthetic fragrances.
  • Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (macis, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme, chamomile ), Needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax).
  • animal raw materials come into question, such as civet and Castoreum.
  • Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, cyclohexylsalicylate, floramate, melusate, jasmecyclate and benzylsalicylate.
  • the ethers include, for example, benzyl ethyl ether and ambroxane, to the aldehydes such as the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, ° ⁇ -lsomethylionon and methylcedryl ketone to the alcohols anethole, citronellol, eugenol, isoeugenol, geraniol, linalool , Phenyl ethyl alcohol and terpineol, the hydrocarbons include mainly the terpenes and balsams such as limonene and pinene.
  • the aldehydes such as the linear alkanals having 8 to 18 carbon atoms, citral, citronella
  • fragrance oils which are most commonly used as aroma components, are useful as perfume oils, e.g. Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil.
  • fragrances which may be present in the compositions according to the invention are found, for example, in US Pat. In S. Arctander, Perfume and Flavor Materials, Vol. I and II, Montclair, NJ, 1969, Dverlag or K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 3 rd . Ed., Wiley-VCH, Weinheim 1997.
  • a fragrance In order to be perceptible, a fragrance must be volatile, with molecular weight also playing an important role in addition to the nature of the functional groups and the structure of the chemical compound. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception.
  • fragrances Due to the different volatility of fragrances, the smell of a perfume composed of several fragrances or Perfume during evaporation, wherein the odor impressions in top note, middle note or body and "base note” (end note or dry out) divided is based to a large extent on the odor intensity, is the top note of a perfume or fragrance not only from volatile compounds, while the base note for the most part consists of less volatile, ie adherent fragrances.
  • Adhesive-resistant fragrances which are advantageously usable in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, Arnica blossom oil, basil oil, bay oil, bergamot oil, Champacablütenöl, Edeltannenöl, Edeltannenzapfenapfen, Elemiöl, eucalyptus oil, fennel oil, spruce oil, galbanum oil, geranium oil, gingergrass oil , Guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copa ⁇ va balsam oil, coriander oil, spearmint oil, cumin oil, cumin oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil , Musk Grain
  • fragrances can be used in the context of the present invention advantageously as adherent fragrances or fragrance mixtures, ie fragrances.
  • These compounds include the following compounds and mixtures thereof: ambrettolide, amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol, Bornyl acetate, bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol,
  • the lower-boiling fragrances include natural or synthetic origin, which can be used alone or in mixtures.
  • Examples of more readily volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
  • boiling points of the individual fragrances are substantially below 300 ° C.
  • a preferred embodiment of the invention wherein preferably at least 50% of the fragrances contained have a boiling point below 300 ° C., advantageously at least 60%, more preferably at least 70%. , in an even more advantageous manner at least 80%, in an extremely advantageous manner at least 90%, in particular even 100%.
  • Boiling points below 300 ° C. are advantageous because the fragrances in question would have too low a volatility at higher boiling points.
  • a certain volatility of the fragrances is advantageous.
  • Unstable fragrances for the purposes of this invention can be identified by incorporating a perfume composition comprising at least 6 fragrances into activated / dehydrated zeolite X and storing the resulting sample for 24 hours at room temperature. Then the fragrances are extracted with acetone and analyzed by gas chromatography to determine the stability.
  • a fragrance is considered to be unstable in the context of this invention, if at least 50 wt .-%, preferably at least 65 wt .-%, advantageously at least 80 wt .-%, in particular at least 95 wt .-% of this perfume decomposed into degradation products, and in the extraction can not be provided again.
  • the unstable perfume in particular the group of allyl alcohol esters, esters of secondary alcohols, esters of tertiary alcohols, allylic ketones, condensation products of amines and aldehydes, Acetals, ketals and mixtures of the foregoing.
  • perfume adsorbed in / on the particle ad / at least 4 advantageously at least 5, in a further advantageous manner at least 6, more preferably at least 7, even more preferably at least 8, preferably at least 9, in particular at least Contains 10 different fragrances, so is a preferred embodiment of the invention.
  • the logP value of the perfume components adsorbed in / on the particle ad / is substantially at least 2, preferably at least 3 or greater, so that at least 40%, advantageously at least 50%, more preferably at least 60%, more preferably at least 70%, preferably at least 80%, in particular 90% of the perfume components fulfill this log requirement, then a preferred embodiment of the invention is present.
  • the logP value is a measure of the hydrophobicity of the perfume components. It is the decadic logarithm of the partition coefficient between n-octanol and water.
  • the octanol / water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentrations in water and octanol.
  • a perfume ingredient with higher partition coefficient P is more hydrophobic.
  • the logP value of many perfume ingredients is given in the literature; For example, the Pomona 92 database, available from Daylight Chemical Information Systems, Inc. (Daylog CIS) of Irvine, California, contains many such values along with references to the original literature.
  • the logP values can also be calculated, for example with the "CLOG P" program named company Daylight CIS. Calculated logP values are usually referred to as ClogP values.
  • the term logP values also includes the Clog P values.
  • Clog-P values should then be used for hydrophobicity estimation if there are no experimental logP values for certain perfume constituents.
  • the perfume can also be combined with a perfume fixative. It is believed that perfume fixatives can slow the exhalation of higher volatile fractions of perfume.
  • the perfume which is adsorbed in / on the carrier material comprises a perfume fixative, preferably in the form of diethyl phthalates, musk (derivatives) and mixtures thereof, the fixative amount preferably being from 1 to 55% by weight. , Advantageously, 2 to 50 wt .-%, more preferably 10 to 45 wt .-%, in particular 20 to 40 wt .-% of the total amount of perfume.
  • the particles contain a viscosity of liquids, in particular perfume-increasing agent, preferably PEG (polyethylene glycol), advantageously having a molecular weight of 400 to 2000, wherein the viscosity increasing agent in a preferred manner in amounts of 0.1 to 20 wt .-%, advantageously from 0.15 to 10 wt .-%, more preferably from 0.2 to 5 wt .-%, in particular from 0.25 to 3 wt .-% is contained, based on the particles.
  • PEG polyethylene glycol
  • the viscosity-increasing agents are preferably polyethylene glycols (PEG for short) which can be described by the general formula I:
  • n of about 5 to> 100,000 corresponding to molecular weights of 200 to 5,000,000 gmol-1, may vary.
  • the products with molecular weights below 25,000 g / mol are referred to as actual polyethylene glycols, while higher molecular weight products are often referred to in the literature as polyethylene oxides (PEOX for short).
  • the polyethylene glycols preferably used may have a linear or branched structure, with particular preference being given to linear polyethylene glycols and end-capped.
  • the particularly preferred polyethylene glycols include those having molecular weights between 400 and 2000. It can be used in particular also polyethylene glycols, which are present in a liquid state at room temperature and a pressure of 1 bar; Here is mainly of polyethylene glycol with a molecular weight of 200, 400 and 600 the speech.
  • the perfumes are generally added in an amount of 0.05 to 5 wt .-%, preferably from 0.1 to 2.5 wt .-%, particularly preferably from 0.2 to 1.5 wt .-%, based on the total composition, of the total composition.
  • the perfumes may be added to the compositions in liquid form, neat or diluted with a solvent for perfuming.
  • Suitable solvents for this purpose are, for.
  • ethanol isopropanol
  • diethylene glycol monoethyl ether glycerol
  • propylene glycol 1, 2-butylene glycol
  • dipropylene glycol diethyl phthalate
  • triethyl citrate isopropyl myristate
  • the perfumes for the compositions of the present invention may be adsorbed to a carrier which provides both a fine distribution of the fragrances in the product and a controlled release in use.
  • Such carriers can be porous inorganic materials such as light sulfate, silica gels, zeolites, gypsum, clays, clay granules, aerated concrete, etc., or organic materials such as woods and cellulosic based materials.
  • perfume oils for the compositions according to the invention can also be microencapsulated, spray-dried, present as inclusion complexes or as extruded products and added in this form to the compositions to be perfumed.
  • the properties of the perfume oils modified in this way can be further optimized by so-called “coating” with suitable materials with a view to a more targeted release of fragrance, for which purpose preferably wax-like plastics, such as, for example, As polyvinyl alcohol can be used.
  • suitable materials such as, for example, As polyvinyl alcohol can be used.
  • compositions according to the invention may associate the composition of the invention with a stimulant such as confectionery or beverages.
  • a stimulant such as confectionery or beverages.
  • the compositions according to the invention contain a bitter substance in order to prevent swallowing or accidental ingestion.
  • Bitter substances which are soluble in water at 20 ° C. to at least 5 g / l are preferred according to the invention.
  • the ionogenic bitter substances have proved to be superior to the nonionic, lonogenic bitter substances, preferably consisting of organic cation (s) and organic anion (s), are therefore preferred for the preparations according to the invention ,
  • Quaternary ammonium compounds which contain an aromatic group both in the cation and in the anion are outstandingly suitable as bitter substances.
  • One such compound is the ammonium benzoate commercially for example under the trademark Bitrex ® and Indige-stin ® available benzyldiethyl ((2,6 Xylylcarbamoyl) methyl). This compound is also known by the name Denatonium Benzoate.
  • the bittering agent is contained in the compositions according to the invention in amounts of 0.0005 to 0.1 wt .-%, based on the total composition. Particular preference is given to amounts of from 0.001 to 0.05% by weight.
  • polyhydroxy compounds are used as active ingredient with the other components according to the invention.
  • polyhydroxy compounds are understood as meaning all substances which fulfill the definition in Römpp 's Lexikon der Chemie, 1999 edition, published by Georg Thieme. Accordingly, polyhydroxy compounds are understood as meaning organic compounds having at least two hydroxyl groups.
  • Polyols having at least two hydroxy groups such as
  • Carbohydrates, sugar alcohols and sugars and their salts in particular monosaccharides, disaccharides, trisaccharides and oligosaccharides, these also being in the form of aldoses, ketoses and / or lactoses, as well as protected by customary and known in the literature -OH and -NH-protecting groups, such as, for example, the triflate group, the trimethylsilyl group or acyl groups and furthermore in the form of the methyl ethers and as phosphate esters,
  • monosaccharides having 3 to 8 C atoms such as, for example, trioses, tetroses, pentoses, hexoses, heptoses and octoses, these also being protected in the form of aldoses, ketoses and / or lactoses and by conventional and known in the literature -OH and -NH - protecting groups, such as the triflate group, the trimethylsilyl group or acyl groups, and furthermore in the form of the methyl ethers and as phosphate esters.
  • oligosaccharides having up to 50 monomer units, these also being protected in the form of aldoses, ketoses and / or lactoses and protected by customary and known in the literature -OH and -NH protecting groups, such as the triflate, trimethylsilyl or acyl groups and furthermore in the form of the methyl ethers and as phosphate esters.
  • polyols according to the invention examples include sorbitol, inositol, mannitol, tetrite, pentite, hexite, threitol, erythritol, adonite, arabitol, xyNt, dulcite, erythrose, threose, arabinose, ribose, xylose, lyxose, glucose, galactose, mannose, allose , Altrose, gulose, idose, talose, fructose, sorbose, psicose, tegatose, deoxyribose, glucosamine, galactosamine, rhamnose, digitoxose, thioglucose, sucrose, lactose, trehalose, maltose, cellobiose, melibiose, gestiobiose, rut
  • Preferred polyhydroxy compounds are sorbitol, inositol, mannitol, threitol, erythrose, erythrose, threose, arabinose, ribose, xylose, glucose, galactose, mannose, allose, fructose, sorbose, deoxyribose, glucosamine, galactosamine, sucrose, lactose, trehalose, maltose and cellobiose , Particular preference is given to using glucose, galactose, mannose, fructose, deoxyribose, glucosamine, sucrose, lactose, maltose and cellobiose. However, the use of glucose, galactose, mannose, fructose, sucrose, lactose, maltose or cellobiose is very particularly preferred
  • the active ingredient is at least one polyhydroxy compound having at least 2 OH groups.
  • these compounds those having 2 to 12 OH groups, and especially those having 2, 3, 4, 5, 6 or 10 OH groups are preferred.
  • the (n, n + 1) or (n, n + 2) diols with non-terminal OH groups can also be used.
  • polyhydroxy compounds having 2 OH groups are also the polyethylene and polypropylene glycols.
  • glycerin is of outstanding importance.
  • compositions according to the invention are preferred in which the polyhydroxy compound is selected from ethylene glycol, propylene glycol, Polyethylene glycol, polypropylene glycol, glycerol, glucose, fructose, pentaerythritol, sorbitol, mannitol, XyNt and their mixtures.
  • agents according to the invention are preferred which, based on the weight of the composition, contain 0.01 to 5% by weight, preferably 0.05 to 4% by weight, particularly preferably 0.05 to 3.5% by weight and in particular 0.1 to 2.5% by weight of polyhydroxy compound (s).
  • agents according to the invention may additionally comprise polyethylene glycol ethers of the formula (IV)
  • k is a number between 1 and 18, with particular preference given to the values 0, 10, 12, 16 and 18 and n is a number between 2 and 20 with particular preference given to the values 2, 4, 5, 6, 7, 8, 9 , 10, 12 and 14 means.
  • Preferred among these are the alkyl derivatives of diethylene glycol, triethylene glycol, tetraethylene glycol, pentahylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, dodecaethylene glycol and tetradecaethylene glycol, and the alkyl derivatives of dipropylene glycol, tripropylene glycol, tetrapropylene glycol, of pentapropylene glycol, hexapropylene glycol, heptapropylene glycol, octapropylene glycol, nonapropylene glycol, decapropylene glycol, dodecapropylene glycol and tetradecaprop
  • Short chain polyalkylene glycol ethers with such "long chain” polyalkylene glycol ethers have advantages.
  • Short or long chain refers in this context to the degree of polymerization of the polyalkylene glycol.
  • Particularly preferred are mixtures of polyalkylene glycol ethers having a degree of oligomerization of 5 or less with polyalkylene glycol ethers having a degree of oligomerization of 7 or more.
  • Particularly preferred agents according to the invention are characterized in that they contain at least one polyalkylene glycol ether (IV a) of the formula (IV) in which n is the number 2, 3, 4 or 5 and at least one polyalkylene glycol ether (IV b) of the formula (IV) in which n represents the numbers 10, 12, 14 or 16, wherein the weight ratio (IV b) to (IV a) 10: 1 to 1:10, preferably 7.5: 1 to 1: 5 and in particular 5 : 1 to 1: 1.
  • Very particularly preferred polyols of the present invention are polyols having 2 to 12 C atoms in the molecular skeleton. These polyols can be straight-chain, branched, cyclic and / or unsaturated. The hydroxyl groups are very particularly preferably terminally adjacent or terminally separated from one another by the remainder of the chain.
  • polystyrene resin examples include polyethylene glycol up to a molecular weight of up to 1000 daltons, neopentyl glycol, partial glycerol ethers having a molecular weight of up to 1000 daltons, 1, 2-propanediol, 1, 3-propanediol, glycerol, 1, 2-butanediol , 1, 3-butanediol, 1, 4-butanediol, 1, 2,3-butanetriol, 1, 2,4-butanetriol, pentanediols, for example 1, 2-pentanediol, 1, 5-pentanediol, hexanediols, 1, 2- Hexanediol, 1,6-hexanediol, 1, 2,6-hexanetriol, 1,4-cyclohexanediol, 1,2-cyclohexanediol, heptanediol
  • the polyhydroxy compounds according to the invention are present in the compositions in concentrations of 0.01% by weight up to 20% by weight, preferably from 0.05% by weight up to 15% by weight and very particularly preferably in amounts of 0.1% by weight. up to 10% by weight.
  • Preservatives used are the substance classes listed in Appendix 6, Parts A and B of the European Cosmetics Regulation. Particularly preferred is mild preservation, ideally without the addition of typical preservatives. In general, the following substances and their mixtures are used:
  • aromatic alcohols such as, for example, phenoxyethanol, benzyl alcohol, phenethyl alcohol, phenoxyisopropanol,
  • Aldehydes such as formaldehyde solution and paraformaldehyde, glutaraldehyde
  • Parabens for example methylparaben, ethylparaben, propylparaben, butylparaben, isobutylparaben
  • 1, 2-alkanediols having 5 to 22 carbon atoms in the carbon chain such as 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-heptanediol, 1, 2-decanediol, 1, 2-dodecanediol, 1, 2 -Hexadekandiol,
  • Formaldehyde-releasing compounds such as DMDM hydantoin
  • Halogenated compounds such as isothiazolinones, such as
  • Inorganic compounds such as sulfites, boric acid and borates,
  • Cationic substances such as quaternium-15, benzalkonium chloride,
  • Citric acid lactic acid, acetic acid, benzoic acid, sorbic acid, salicylic acid,
  • Active ingredients with additional effects such as zinc pyrithione,
  • Antioxidants such as BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, t-butylhydroquinone,
  • the water activity in the compositions according to the invention can also be reduced to the extent that growth of microorganisms can no longer take place.
  • glycerol and sorbitol are used for this purpose.
  • compositions according to the invention contribute to the preservation being possible in an outstanding manner with the mild preservative additives. But the complete abandonment of preservatives is possible and preferred according to the invention.
  • the amounts of preservative are from 0 to 5 wt.%, Preferably from 0 to 2 wt.%, Particularly preferably from 0 to 1 wt.% And most preferably from 0 to 0.8 wt.% Based on the total amount of the composition ,
  • compositions of the invention are Deowirk für.
  • Deodorants can not only be used in deodorants to prevent underarm sweating. They can also be used in skin care products to influence sweat on other skin areas. This includes, for example, the scalp.
  • inventive compositions significantly increase analytically detectable the deposition of deodorant substances on the skin and hair. In the panel test, this is also noticeable through a significantly prolonged effect.
  • Deowirkstoffe esterase inhibitors can be added. These are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and in particular triethyl citrate (Hydagen® CAT, COGNIS).
  • the substances inhibit the enzyme activity and thereby reduce odors.
  • the cleavage of the citric acid ester is likely to release the free acid, which lowers the pH on the skin to the extent that it inhibits the enzymes.
  • esterase inhibitors are dicarboxylic acids and their esters, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, diethyl adipate, malonic acid and diethyl malonate,
  • dicarboxylic acids and their esters for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, diethyl adipate, malonic acid and diethyl malonate,
  • Hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or diethyl tartrate.
  • Antibacterial agents that affect the bacterial flora and kill sweat-degrading bacteria or inhibit their growth may also be included in the stick formulations. Examples of these are chitosan, phenoxyethanol and chlorhexidine gluconate. 5-chloro-2- (2,4-dichlorophenoxy) phenol, which is marketed under the trade name Irgasan® by Ciba-Geigy, Basel / CH, has also proved to be particularly effective. In addition, it may prove advantageous and further increase the synergistic effects of the compositions according to the invention, if penetration aids and / or swelling agents (M) are included.
  • These substances can bring about a better penetration of active ingredients into the skin to be treated or the hair to be treated.
  • active ingredients include, for example, urea and urea derivatives, guanidine and its derivatives, arginine and derivatives thereof, water glass, imidazole and its derivatives, histidine and its derivatives, benzyl alcohol, glycerol, glycol and glycol ethers, propylene glycol and propylene glycol ethers, for example propylene glycol monoethyl ether, carbonates, hydroxides.
  • gencarbonates diols and triols, and in particular 1, 2-diols and 1, 3-diols such as 1, 2-propanediol, 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-dodecanediol, 1, 3-propanediol , 1, 6-hexanediol, 1, 5-pentanediol, 1, 4-butanediol.
  • 1, 2-diols and 1, 3-diols such as 1, 2-propanediol, 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-dodecanediol, 1, 3-propanediol , 1, 6-hexanediol, 1, 5-pentanediol, 1, 4-butanediol.
  • the substances suitable and approved for cosmetic purposes can be used, as compiled, for example, in the publication "Kosmetician Anlagenrbesch" of the Farbstoffkommission of the Irish Anlagenstician, Verlag Chemie, Weinheim, 1984, pp. 81-106. These dyes are usually used in concentrations of 0.001 to 0.1 wt .-%, based on the total mixture.
  • the pH of the preparations according to the invention can in principle be between 2 and 11.
  • the pH is selected and adjusted very selectively depending on the purpose and use of the composition according to the invention.
  • colorants for example, it is preferably between 5 and 11, with values of 6 to 10 being particularly preferred.
  • cleaning compositions it is for example between 4 and 7.5, preferably between 4 and 6.
  • any acid or base that can be used for cosmetic purposes can be used.
  • Preferred bases are ammonia, alkali hydroxides, monoethanolamine, triethanolamine and N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine.
  • acids are used as acids.
  • By-acids are understood to mean those acids which are absorbed as part of the usual food intake and have positive effects on the human organism.
  • Eat acids are, for example, acetic acid, lactic acid, tartaric acid, citric acid, malic acid, ascorbic acid and gluconic acid.
  • citric acid and lactic acid is particularly preferred.
  • the action of the active ingredient according to the invention in the compositions according to the invention can be further increased in combination with substances which contain primary or secondary amino groups.
  • amino compounds include ammonia, monoethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-propanediol and basic amino acids such as lysine, arginine or histidine.
  • these amines can also be used in the form of the corresponding salts with inorganic and / or organic acids, such as, for example, ammonium carbonate, ammonium citrate, ammonium oxalate, ammonium tartrate or lysine hydrochloride.
  • the amines are used together with the active compound according to the invention in ratios of from 1:10 to 10: 1, preferably from 3: 1 to 1: 3, and very particularly preferably in stoichiometric amounts.
  • Protic solvents such as, for example, water, and alcohols can also be present in the compositions according to the invention.
  • the alcohols used are all physiologically unsuitable alcohols, for example methanol, ethanol, isopropanol, propanol, butanol, isobutanol, glycol, glycerol and mixtures thereof with one another.
  • the proportion of protic solvents in each case complements the composition according to the invention to 100 parts by weight.
  • At least 30% by weight of protic solvents, particularly preferably at least 50% by weight and very particularly preferably at least 75% by weight, and most preferably at least 85% by weight, protic solvents are preferably present in the cosmetic compositions. If the active ingredient according to the invention is used in a complex manner in colorants, dye precursors and / or dyes are furthermore present in the compositions. These are described in detail below.
  • developer-type oxidation dye precursors (B1) are usually primary aromatic amines having a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4, 5,6-tetraaminopyrimidine and its derivatives used.
  • Suitable developer components are, for example, p-phenylenediamine, p-toluenediamine, p-aminophenol, o-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis (2-hydroxy-ethyl) -p -phenylenediamine, 2- (2,5-diaminophenoxy) ethanol, 4-amino-3-methylphenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy -2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-dia- minopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2-hydroxymethylamino-4-aminophenol, bis- (4- aminophenyl) amine, 4-amino-3-fluorophenol, 2-aminomethyl-4-aminophenol,
  • Particularly advantageous developer components are p-phenylenediamine, p-toluenediamine, p-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2 , 4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine.
  • coupler type oxidation dye precursors (B2) m-phenylenediamine derivatives, naphthols, resorcin and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are usually used.
  • coupler components are m-aminophenol and its derivatives such as 5-amino-2-methylphenol, 5- (3-hydroxypropylamino) -2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4 - aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5 - (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylamino) -benzene, 3- (ethylamino) -4 -methylphenol and 2,4-dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as,
  • Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3 , 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine, naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8- Dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxyna
  • coupler components are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.
  • Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.
  • Particularly suitable substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds as well as 1, 4-bis- ( ⁇ - hydroxyethyl) amino-2-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitro-toluidine, picramic acid, 2-amino- 6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.
  • Directly acting dyes found in nature include, for example, henna red, henna neutral, chamomile flower, sandalwood, black tea, buckthorn bark, sage, sawnwood, madder root, catechu, sedre and alkana root.
  • oxidation dye precursors or the direct dyes each represent uniform compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, in minor amounts, other components may be included, as far as they do not adversely affect the dyeing result or for other reasons, eg. As toxicological, must be excluded.
  • indoles and indolines and their physiologically acceptable salts are used as precursors of naturally-analogous dyes.
  • These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group.
  • Particularly advantageous properties have 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline and also 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N- Propyl 5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.
  • N-methyl-5,6-dihydroxyindoline N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxy-indoline and in particular the 5,6-dihydroxyindoline and N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5, 6-dihydroxyindole.
  • indoline and indole derivatives in the colorants used in the process according to the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, eg. As the Hydrochlori- de, sulfates and hydrobromides, are used.
  • amino acids are aminocarboxylic acids, in particular ⁇ -aminocarboxylic acids and ⁇ -aminocarboxylic acids.
  • ⁇ -aminocarboxylic acids are arginine, lysine, ornithine and histidine particularly preferred.
  • a very particularly preferred amino acid is arginine, especially in free form, but also used as the hydrochloride.
  • Both the oxidation dye precursors and the substantive dyes and the precursors of naturally-analogous dyes are preferably present in the compositions according to the invention in amounts of from 0.01 to 20% by weight, preferably 0.1 to 5% by weight, based in each case on the entire composition, contain.
  • Hair dyes especially if the dyeing is oxidative, be it with atmospheric oxygen or other oxidizing agents such as hydrogen peroxide, are usually weakly acidic to alkaline, d. H. adjusted to pH values in the range of about 5 to 1 1.
  • the colorants contain alkalizing agents, usually alkali metal or alkaline earth metal hydroxides, ammonia or organic amines.
  • Preferred alkalizing agents are monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino 2-methylbutanol and triethanolamine and alkali and alkaline earth metal hydroxides.
  • monoethanolamine, triethanolamine and 2-amino-2-methyl-propanol and 2-amino-2-methyl-1, 3-propanediol are preferred in the context of this group.
  • the use of ⁇ -amino acids such as ⁇ -aminocaproic acid as alkalizing agent is also possible.
  • oxidizing agents in particular hydrogen peroxide or its addition products of urea, melamine or sodium borate
  • oxidation with atmospheric oxygen as the sole oxidant may be preferred.
  • enzymes which enzymes are used both for the production of oxidizing per-compounds and for the enhancement of the action of a small amount of existing oxidizing agents, or enzymes are used, the electrons from suitable developer components (reducing agent) transferred to atmospheric oxygen.
  • Oxidases such as tyrosinase, ascorbate oxidase and laccase but also glucose oxidase, uricase or pyruvate oxidase are preferred. Continue to be the procedure to increase the effect of small amounts (eg 1% and less, based on the total agent) of hydrogen peroxide by peroxidases.
  • the preparation of the oxidizing agent is then mixed with the preparation with the dye precursors immediately prior to dyeing the hair.
  • the resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 10. Particularly preferred is the use of the hair dye in a weakly alkaline medium.
  • the application temperatures may range between 15 and 40 ° C., preferably at the temperature of the scalp.
  • the hair dye is removed by rinsing of the hair to be dyed.
  • the washing with a shampoo is eliminated if a strong surfactant-containing carrier, eg. As a dyeing shampoo was used.
  • the preparation with the dye precursors can be applied to the hair without prior mixing with the oxidation component.
  • the oxidation component is then applied, if appropriate after an intermediate rinse.
  • the product is then rinsed and, if desired, shampooed again.
  • the corresponding agent is adjusted to a pH of about 4 to 7.
  • an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10.
  • the use of acidified peroxydisulfate solutions may be preferred as the oxidizing agent.
  • the formation of the coloration can be supported and increased by adding certain metal ions to the agent.
  • metal ions are, for example, Zn 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2+ , Mn 4+ , Li + , Mg 2+ , Ca 2+ and Al 3+ .
  • Particularly suitable are Zn 2+ , Cu 2+ and Mn 2+ .
  • the metal ions can in principle in the form be used of any physiologically acceptable salt.
  • Preferred salts are the acetates, sulfates, halides, lactates and tartrates.
  • Another object of the present invention is a method for hair treatment, in which the composition of the invention is incorporated into the wet hair, and the composition is rinsed after a contact time of a few seconds to 5 minutes with cold up to about 40 0 C warm water , optionally, drying the hair with a towel, then incorporating another conditioning and conditioning composition B into the towel, dry to wet hair, this composition remaining on the hair for a few seconds to 30 minutes followed by rinsing out the hair again with a towel, optionally followed by a foehning step to completely dry the hair, and finally a styling and styling composition C is added to the hair and preferably is not rinsed out again.
  • both the composition B as conditioning and conditioning composition and the composition C may in turn contain the active ingredient complex according to the invention. It is preferred if at least composition B also contains the active ingredient complex according to the invention.
  • the method according to the invention also includes that the first step of shampooing may optionally be repeated.
  • the active substance complex according to the invention can in principle be added directly to the colorant, the corrugation medium or the fixation.
  • the application of the active substance complex to the keratinic fiber can also take place in a separate step, either before or after the actual dyeing or corrugating process. Separate treatments, optionally also days or weeks before or after the hair treatment, for example by dyeing or waves, are encompassed by the teaching according to the invention.
  • the application of the Compound according to the invention take place after the corresponding hair treatment such as dyeing or waves in particular in the corresponding hair treatment agents.
  • dyeing process comprises all processes known to those skilled in the art, in which a colorant is applied to the hair, which may have been moistened, and left on the hair either for a period of a few minutes to about 45 minutes and then with water or a surfactant-containing agent is rinsed or left completely on the hair. It is in this context explicitly on the known monographs, z. B. K. H. Schrader, bases and formulations of cosmetics, 2nd edition, Wegig book Verlag, Heidelberg, 1989, referenced that reflect the corresponding knowledge of the expert.
  • corrugating process encompasses all processes known to those skilled in the art in which a corrugating agent is applied to the hair, which may have been moistened and wound on winder, and left on the hair either for a period of a few minutes to about 45 minutes and then with water or a surfactant-containing agent is rinsed out, then a permanent wave fixation is applied to the hair and this left for a time between a few minutes and about 45 minutes on the hair and then rinsed with water or a surfactant-containing agent. It is in this context explicitly on the known monographs, z. B. K. H. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book Verlag, Heidelberg, 1989, referenced that reflect the relevant knowledge of the expert.
  • the active ingredient complex according to the invention is applied to the keratinic fiber, in particular human hair
  • emulsions such as W / O, O / W
  • PIT emulsions known as phase inversion emulsions, PIT
  • microemulsions and multiple emulsions gels, Sprays, aerosols and foam aerosols suitable.
  • the pH of these preparations can in principle be between 2 and 11. It is preferably between 5 and 11, with values of 6 to 10 being particularly preferred.
  • any acid or base that can be used for cosmetic purposes can be used.
  • Preferred bases are ammonia, alkali hydroxides, monoethanolamine, triethanolamine and N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine.
  • Preparations remaining on the hair have proven to be effective and can therefore represent preferred embodiments of the teaching according to the invention.
  • hair remaining according to the invention are understood such preparations that are not rinsed out of the hair within the scope of treatment after a period of a few seconds to one hour with the aid of water or an aqueous solution. Rather, the preparations remain until the next shampooing, i. usually more than 12 hours, on the hair.
  • these preparations are formulated as a hair conditioner or hair conditioner.
  • the preparations of the invention according to this embodiment can be rinsed with water or an at least predominantly aqueous agent after this exposure time; however, they may be left on the hair as stated above. It may be preferred to apply the preparation according to the invention to the hair before the application of a cleansing agent, a waving agent or other hair treatment agents. In this case, the preparation according to the invention serves as a structural protection for the following applications.
  • the agents according to the invention may also be, for example, cleansing agents such as shampoos, nourishing agents such as rinses, firming agents such as hair fixatives, mousses, styling gels and hair drier, permanent shaping agents such as perming and fixing agents and in particular in the context of a perming process or dyeing process used pre-treatment or rinsing act.
  • cleansing agents such as shampoos
  • nourishing agents such as rinses
  • firming agents such as hair fixatives, mousses, styling gels and hair drier
  • permanent shaping agents such as perming and fixing agents and in particular in the context of a perming process or dyeing process used pre-treatment or rinsing act.
  • these preparations may in principle contain all other known to those skilled in such cosmetic means components.
  • auxiliaries and additives are, for example, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins, paraffin oils, vegetable oils, eg. Sunflower oil, orange oil, almond oil, wheat germ oil and peach kernel oil, dimethyl isosorbide and cyclodextrins,
  • hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins, paraffin oils, vegetable oils, eg. Sunflower oil, orange oil, almond oil, wheat germ oil and peach kernel oil, dimethyl isosorbide and cyclodextrins,
  • Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
  • Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers, pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate, pigments,
  • Reducing agents such as B. thioglycolic acid and its derivatives, thiolactic acid, cysteamine, thiomalic acid and ⁇ -mercaptoethanesulfonic acid,
  • Propellants such as propane-butane mixtures, N 2 O, dimethyl ether, CO 2 and air,
  • the active ingredient complex may be preferable to incorporate directly into a dyeing or tinting agent, that is to use the active ingredient according to the invention complexly in combination with dyes and / or dye precursors.
  • oxidation dye precursors of the developer (B1) and coupler type (B2), natural and synthetic direct dyes (C) and precursors of naturally occurring dyes, such as indole and indoline derivatives, and mixtures of representatives of one or more of these groups it is possible to use oxidation dye precursors of the developer (B1) and coupler type (B2), natural and synthetic direct dyes (C) and precursors of naturally occurring dyes, such as indole and indoline derivatives, and mixtures of representatives of one or more of these groups ,
  • packaging for the cosmetic compositions of the present invention in principle, all known in the art packaging can be used. In particular, these are crucibles, tubes, bottles, sachets. In this case, different embodiments with respect to the shape and the color are possible. However, it is preferred if the packaging has at least a transparent portion of at least 15% of the outer packaging surface. Even better suited to enhance the aesthetic appearance is at least 30% of the transparent surface, but especially of 50%, but this is at least 75% and in a very outstanding way at least 85% transparent.
  • Another object of the invention are cosmetic compositions containing: a. the active substance complex b. and a compound selected from the group of surfactants (E) and / or polymers (G).
  • a final object of the invention is a method for the treatment of skin or hair in which an agent with the active ingredient complex according to the invention as claimed in any one of claims 1 to 6 is applied to the fibers, the agent optionally after an exposure time of 1 to 45 Is rinsed out again for a few minutes.

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Abstract

L'invention concerne des préparations cosmétiques pour le traitement de la peau et des cheveux, contenant un complexe de substances actives à action synergique comprenant de la soie naturelle et/ou ses dérivés et au moins un métal ou son sel sélectionné parmi les éléments du premier et/ou du huitième sous-groupe de la classification périodique des éléments.
EP07822560A 2006-12-27 2007-11-13 Combinaison synergique de protéines de soie et de métaux sélectionnés Withdrawn EP2099411A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200610061555 DE102006061555A1 (de) 2006-12-27 2006-12-27 Synergistische Kombination von Seidenproteinen und ausgewählten Metallen
PCT/EP2007/062291 WO2008080682A2 (fr) 2006-12-27 2007-11-13 Combinaison synergique de protéines de soie et de métaux sélectionnés

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