WO2003096998A1 - Anti-dandruff shampoos - Google Patents

Anti-dandruff shampoos Download PDF

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Publication number
WO2003096998A1
WO2003096998A1 PCT/EP2003/004776 EP0304776W WO03096998A1 WO 2003096998 A1 WO2003096998 A1 WO 2003096998A1 EP 0304776 W EP0304776 W EP 0304776W WO 03096998 A1 WO03096998 A1 WO 03096998A1
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Prior art keywords
acid
weight
extracts
surfactants
active ingredients
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PCT/EP2003/004776
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German (de)
French (fr)
Inventor
Sybille Buchwald-Werner
Ute Griesbach
Original Assignee
Cognis Deutschland Gmbh & Co. Kg
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Priority to AU2003227728A priority Critical patent/AU2003227728A1/en
Publication of WO2003096998A1 publication Critical patent/WO2003096998A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/006Antidandruff preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35Ketones, e.g. benzophenone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • A61K8/375Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A61K8/498Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783Angiosperms [Magnoliophyta]
    • A61K8/9789Magnoliopsida [dicotyledons]
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair

Definitions

  • the invention is in the field of hair treatment compositions and relates to new antidandruff shampoos with an effective content of special plant extracts or their active ingredients, and their use for the preparation of the compositions.
  • dandruff By the term dandruff, more precisely: dandruff, the cosmetic chemist understands parts of the horny layer of the skin that are rejected as part of the constant renewal of the skin layers. They are particularly well visible on the hairy head due to their sticking to tall aggregates due to sebum and sweat. A cosmetically disruptive scaling is counteracted by treating the scalp with anti-dandruff agents, which are usually applied in special hair treatment agents, so-called anti-dandruff shampoos.
  • Selenium disulfide, pyrethione salts, shale oils and other microbicides are used as active ingredients, which have in common that they have skin-irritating properties, have an undesirable intrinsic odor and / or are difficult to incorporate into the formulations.
  • the object of the present invention was therefore to provide new antidandruff shampoos which are free from the disadvantages mentioned at the outset.
  • the active ingredients should be of a vegetable nature and should not be further derivatized chemically, should not cause irritation, be free from unpleasant odors and be easy to formulate, and of course reliably prevent the undesirable formation of dandruff or reduce it to a level that is no longer disruptive.
  • the invention relates to antidandruff shampoos containing an effective amount of extracts of Camellia sinensis or their active substances of the catechin and / or flavonoid type.
  • compositions which contain extracts of Camellia sinensis or their active principles (polyphenols, in particular catechins and or flavonoids) as active ingredients reliably prevent dandruff formation on the scalp to such an extent that it is no longer a problem.
  • the active ingredients are of natural origin, are not chemically modified, are odorless and can be easily incorporated into the formulations.
  • Camellia sinensis is green tea which, as active ingredients ("tea tannins), contains essentially polyphenols, namely epicatechin, epigallocatechin, epigallocatechingallate, epigallocatechin gallate, theaflavin, theaflavin monogallate A or B and theaflavindigallate find themselves enriched in the extracts.
  • the freshly dried tea leaves have catechin contents of 20 to 25% by weight, of which the epigallocatechin gallate alone makes up about 50 to 70% by weight.
  • agents are preferred which have this active ingredient in particularly high concentrations.
  • the extracts can be prepared in a manner known per se, ie for example by aqueous, alcoholic or aqueous-alcoholic extraction of the plants or parts of plants or of the leaves or fruits. All conventional extraction methods such as maceration, remaceration, digestion, movement maceration, vortex extraction, ultrasound extraction, countercurrent extraction, percolation, repercolation, evacolation (extraction under reduced pressure), diacolation or solid-liquid extraction with continuous reflux are suitable.
  • the percolation method is advantageous for large-scale use. Fresh plants or parts of plants can be used as the starting material, but usually dried plants and / or parts of plants are used, which can be mechanically comminuted before extraction.
  • Organic solvents water (preferably hot water at a temperature of above 80 ° C. and in particular above 95 ° C.) or mixtures of organic solvents and water, in particular low molecular weight alcohols with more or less high water contents, can be used as solvents for carrying out the extractions become. Extraction with methanol, ethanol, pentane, hexane, heptane, acetone, propylene glycols, polyethylene glycols and ethyl acetate as well as mixtures thereof and their aqueous mixtures is particularly preferred.
  • the extraction is usually carried out at 20 to 100 ° C, preferably at 30 to 90 ° C, in particular at 60 to 80 ° C.
  • the extraction takes place under an inert gas atmosphere to avoid oxidation of the active ingredients of the extract. This is particularly important for extractions at temperatures above 40 ° C.
  • the extraction times are determined by the person skilled in the art depending on the starting material. rial, the extraction process, the extraction temperature, the ratio of solvent to raw material, among others.
  • the crude extracts obtained can optionally be subjected to further customary steps, such as purification, concentration and / or decolorization. If desired, the extracts produced in this way can, for example, be subjected to a selective separation of individual undesirable ingredients.
  • the extraction can take place to any degree of extraction, but is usually carried out to exhaustion.
  • the present invention encompasses the knowledge that the extraction conditions and the yields of the final extracts can be selected by the person skilled in the art depending on the desired field of use.
  • the extracts can also serve as starting materials for the production of the above-mentioned pure active ingredients, provided that these cannot be produced more easily and inexpensively by synthetic means. Accordingly, the active substance content in the extracts can be 5 to 100, preferably 50 to 98% by weight.
  • the extracts themselves can be present as aqueous and / or preparations dissolved in organic solvents and as spray-dried or freeze-dried, anhydrous solids. Examples of suitable organic solvents in this context are the aliphatic alcohols having 1 to 6 carbon atoms (eg ethanol), ketones (eg acetone), halogenated hydrocarbons (eg chloroform or methylene chloride), lower esters or polyols (eg glycerol or glycols).
  • the agents according to the invention typically have a content of extracts of Camellia sinensis or its active ingredients in amounts of 0.01 to 15, preferably 0.1 to 5 and in particular 0.5 to 1% by weight, based on the agents.
  • the antidandruff agents can contain further active ingredients known for this purpose than, for example, are: piroctone olamine (1-hydroxy-4-methyl-6- (2,4,4-trimythylpentyl) -2- (1H) - pyridinone monoethanolamine salt), Baypival® (climazole), Ketoconazol®, (4-acetyl-l - ⁇ - 4- [2- (2.4-dichlorophenyl)) r-2- (lH-imidazol-l-ylmethyl) - 1,3 -dioxylan-c-4-ylmethoxyphenyl ⁇ piperazine, elubiol, selenium disulfide, sulfur colloidal, sulfur polyethylene glycol sorbit
  • the preparations can furthermore - preferably - contain mild anionic, nonionic, amphoteric and / or zwitterionic and / or cationic surfactants.
  • Typical examples are soaps, sulfonates alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether, glycerol ether, ⁇ -methyl ester sulfonates, sulfofatty acids, alkyl sulfates, alkylene ether sulfates, Glycerol ether, Fettklareethersulfate, Hydroxymischethersulfate, Mo noglycerid (ether) sulfates, fatty acid amide (ether) sulfates, mono and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps,
  • anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides, protein fatty acids, and glucuric acid hydrochloride acids, or glucuric acid hydrochloride acids and glucuric acid silicate acids or glucuric acid silicate acid derivatives, especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides.
  • nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • cationic surfactants are quaternary ammonium compounds, such as, for example, dimethyldistearylammonium chloride, and ester quats, in particular quaternized fatty acid trialkanolamine ester salts.
  • amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds.
  • Typical examples of particularly suitable mild, that is to say particularly skin-compatible, surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, ⁇ -olefin sulfonates or alkyl carboxylates, alkyl carboxylates, alkyl carboxylates, alkyl carboxamides, the latter preferably based on wheat proteins.
  • the antidandruff agents contain
  • Another object of the invention relates to the use of effective amounts of extracts of Camellia sinensis or of phenols, in particular catechins and / or flavoid as antidandruff agents.
  • the substances can be used in amounts of 0.01 to 15, preferably 0.1 to 3% by weight.
  • oil bodies In addition to the surfactants, oil bodies, emulsifiers, pearlescent waxes, consistency enhancers, thickeners, superfatting agents, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, UN light protection factors, biogenic agents, antioxidants, these agents can also be used as further auxiliaries and additives , contain additional other anti-dandruff agents, film formers, hydrotropes, solubilizers, preservatives, perfume oils, dyes and the like. Olthetic
  • esters of linear C 6 -C 22 fatty acids with linear or branched C 6 -C 2 fatty alcohols or esters of branched C 6 come as oil bodies, for example -C 3 - carboxylic acids with linear or branched C 6 -C 2 fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl stylate stearate Cetylerucat, leat Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, Stearylo-, stearyl palmitate
  • esters of linear C 6 -C 2 fatty acids with branched alcohols in particular 2-ethylhexanol
  • esters of C 8 -C 38 alkyl hydroxy carboxylic acids with linear or branched C 6 -C 2 fatty alcohols see.
  • dioctyl malates especially dioctyl malates, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C 6 -Crj fatty acids, liquid mono-, di- / triglyceride mixtures based of C 6 -C 8 fatty acids, esters of C 6 -C fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C -C 2 dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 up to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C 6 -C 22 fatty alcohol carbonates, such as, for example, dic ap
  • Suitable emulsifiers are nonionic surfactants from at least one of the following groups:> Adducts of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms Atoms, on alkylphenols with 8 to 15 carbon atoms in the alkyl group and alkylamines with 8 to 22 carbon atoms in the alkyl radical; Alkyl and / or alkenyl oligoglycosides with 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs; Addition products of 1 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;
  • glucosides e.g. cellulose
  • linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 mol ethylene oxide; > Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol.
  • the adducts of ethylene oxide and or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are mixtures of homologs, the average degree of alkoxylation of which is the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out.
  • C 12/18 - fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known as refatting agents for cosmetic preparations.
  • Alkyl and / or alkenyl oligoglycosides their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms.
  • the glycoside residue both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to about 8 are suitable.
  • the degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.
  • Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride. Hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid moglyceride, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linoleic acid monoglyceride, erolene acid monoglyceride
  • Sorbitantrieracat Sorbitanmonoricinoleat, Sorbitansesquiricinoleat, Sorbitandiricinoleat, Sorbitantriricinoleat, Sorbitanmonohydroxystearat, Sorbitansesquihydroxystearat, sorbitan tandihydroxystearat, Sorbitantrihydroxystearat, Sorbitanmonotartrat, sesqui- tartrate, Sorbitanditartrat, Sorbitantritartrat, Sorbitanmonocitrat, Sorbitansesquicitrat, sorting bitandicitrat, sorbitan, sorbitan, sorbitan, sorbitan dimaleate, sorbitan and their technical mixtures. Addition products of 1 to 30, preferably 5 to 10, mol of ethylene oxide onto the sorbitan esters mentioned are also suitable.
  • polyglycerol esters are polyglyceryl-2 dipolyhydroxystearate (Dehymuls® PGPH), polyglycerol-3-diisostearate (Lameform® TGI), polyglyceryl-4 isostearate (Isolan® GI 34), polyglyceryl-3 oleate, diisostearoyl polyglycerol ryl-3 Diisostearate (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether ( Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimer
  • Polyol esters are the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like which are optionally reacted with 1 to 30 mol of ethylene oxide.
  • Typical anionic emulsifiers are aliphatic fatty acids with 12 to 22 carbon atoms, such as, for example, palmitic acid, stearic acid or behenic acid, and dicarboxylic acids with 12 to 22 carbon atoms, such as, for example, azelaic acid or sebacic acid.
  • Amphoteric and cationic emulsifiers are aliphatic fatty acids with 12 to 22 carbon atoms, such as, for example, palmitic acid, stearic acid or behenic acid, and dicarboxylic acids with 12 to 22 carbon atoms, such as, for example, azelaic acid or sebacic acid.
  • Zwitterionic surfactants can also be used as emulsifiers.
  • Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl-3 -carboxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethyl carboxymethylglycinate.
  • betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example
  • Suitable emulsifiers are ampholytic surfactants.
  • Ampholytic surfactants are surface-active compounds which, in addition to a C 8/18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO 3 H group in the molecule and are capable of forming internal salts .
  • suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylamino-butyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylamino acetic acids each about 8 to 18 carbon atoms in the alkyl group ..
  • ampholytic surfactants are the N-coconut alkylaminopropionate, the coconut acylaminoethylaminopropionate and the C ⁇ / ⁇ 8 acyl sarcosine.
  • cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.
  • Typical examples of fats are glycerides, that is to say solid or liquid vegetable or animal products which essentially consist of mixed glycerol esters of higher fatty acids, and waxes include natural waxes, such as candelilla wax, carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax and sugar cane wax , Ouricury wax, montan wax, beeswax, shellac wax, walrus, lanolin (wool wax), pretzel fat, ceresin, ozokerite (earth wax), petrolatum, paraffin waxes, micro waxes; chemically modified waxes (hard waxes), such as montan ester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as polyalkylene waxes and polyethylene glycol waxes.
  • natural waxes such as candelilla wax, carnauba wax, Japanese wax, espart
  • lecithins In addition to fats, fat-like sub- punch like lecithins and phospholipids.
  • lecithins are those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification.
  • Lecithins are therefore often used in the professional world as phosphatidylcholines (PC).
  • PC phosphatidylcholines
  • Examples of natural lecithins are the cephalins, which are also referred to as phosphatidic acids and are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids.
  • phospholipids are usually understood to be mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally classed as fats.
  • glycerol phosphates glycerol phosphates
  • sphingosines or sphingolipids are also suitable.
  • Pearlescent waxes that can be used are, for example: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid di ethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to
  • Suitable consistency agents are primarily fatty alcohols or hydroxy fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides, fatty acids or hydroxy fatty acids. A combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred.
  • Suitable thickeners are, for example, aerosil types (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl and hydroxypropyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, Polyacrylates, (e.g. Carbopole® and Pemulen types from Goodrich; Synthalene® from Sigma; Keltrol types from Kelco; Sepigel types from Seppic; Salcare types from Allied Colloids), polyacrylamides, polymers, polyvinyl alcohol and polyvinyl pyrrolidone.
  • aerosil types hydrophilic silicas
  • polysaccharides in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl and hydroxypropyl
  • Bentone® Gel VS-5PC which is a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate
  • Surfactants such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as, for example, pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyloligoglucosides and electrolytes such as sodium chloride and ammonium chloride are also suitable.
  • Bentone® Gel VS-5PC which is a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate
  • Surfactants such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as, for example, pentaerythritol or trimethylolpropane,
  • Substances such as, for example, lanolin and lecithin and polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers.
  • Metal salts of fatty acids such as e.g. Magnesium, aluminum and / or zinc stearate or ricinoleate are used.
  • Suitable cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose, which is available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such as, for example, Luviquat® (BASF) , Condensation products of polyglycols and amines, quaternized collagen polypeptides, such as, for example, lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as amodimethicone, copolymers of adiphylohydroxy acid and dimethylaminodiaminethyl (dimethyl) Cartaretine® / Sandoz),
  • Anionic, zwitterionic, amphoteric and nonionic polymers include, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and polyesters and their esters, uncrosslinked polyols - amidopropyltrimethylarnmoniumchlorid / acrylate copolymers, octylacrylamide / acrylate Methylmeth- / tert.Butylaminoethylmethacrylat / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / Ninylacetat copolymers, Nmylpyrrolidon / dimethylamino-ethylmethacrylatNinylcaprol
  • Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyf-modified silicone compounds which can be both liquid and resinous at room temperature.
  • Simethicones which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates, are also suitable.
  • UV light protection factors are understood to mean, for example, organic substances (light protection filters) which are liquid or crystalline at room temperature and which are able to absorb ultraviolet rays and absorb the energy absorbed in the form of longer-wave radiation, e.g. To give off heat again.
  • UVB filters can be oil-soluble or water-soluble. As oil-soluble substances e.g. to call:
  • 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives e.g. 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate;
  • esters of cinnamic acid preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester 2-cyano-3, 3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); > Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester;
  • benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
  • Esters of benzalmalonic acid preferably 4-methoxybenzmalonic acid di-2-ethylhexyl ester;
  • Triazine derivatives e.g.
  • benzoylmethane such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl
  • benzoylmethane such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl
  • the UV-A and UV-B filters can of course also be used in mixtures.
  • Particularly favorable combinations consist of the derivatives of benzoylmethane, e.g.
  • insoluble light protection pigments namely finely dispersed metal oxides or salts
  • suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • Silicates (talc), barium sulfate or zinc stearate can be used as salts.
  • the oxides and salts are used in the form of pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm.
  • the pigments can also be surface-treated, ie hydrophilized or hydrophobicized.
  • Typical examples are coated titanium dioxides such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. So-called micro- or nanopigments are preferably used in sunscreens. Micronized zinc oxide is preferably used.
  • biogenic active ingredients are tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy) ribonucleic acid and its fragmentation products, ⁇ -glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudo-ceramides, penal ceramides, Plant extracts, such as To understand prunus extract, bambanus extract and vitamin complexes.
  • Antioxidants interrupt the photochemical reaction chain, which is triggered when UV radiation penetrates the skin.
  • Typical examples are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g.
  • Carotenoids eg ⁇ -carotene, ⁇ -carotene, lycopene
  • carbotenoids eg ⁇ -carotene, ⁇ -carotene, lycopene
  • chlorogenic acid and their derivatives lipoic acid and their derivatives (eg dihydroliponic acid)
  • aurothioglucose propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine , Cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, ⁇ -linoleyl, cholesteryl and glyceryl esters) and their Salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (
  • buthioninsulfoximines homocysteine sulfoximine, butioninsulfones, penta-, hexa-, himinathion
  • very low in compatible dosages e.g. pmol to ⁇ mol / kg
  • metal chelators e.g. ⁇ -hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin
  • ⁇ -hydroxy acids e.g. citric acid, lactic acid, malic acid
  • humic acid bile acid, bile extracts, bilirubin, Biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g.
  • ⁇ -linolenic acid linoleic acid, oleic acid
  • folic acid and their derivatives ubiquinone and ubiquinol and their derivatives
  • vitamin C and derivatives e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate
  • tocopherols and derivatives e.g.
  • vitamin E acetate
  • vitamin A and derivatives vitamin A palmitate
  • Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds.
  • Montmorillonites, clay minerals, pemulene and alkyl-modified carbopol types can serve as swelling agents for aqueous phases. Further suitable polymers or swelling agents can be found in the overview by R. Lochhead in Cosm.Toil. 108, 95 (1993).
  • Hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used to improve the flow behavior.
  • Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups.
  • the polyols can also contain further functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are
  • glycerol > Alkylene glycols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons; technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;
  • Methyl compounds such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
  • Lower alkyl glucosides especially those with 1 to 8 carbons in the alkyl radical, such as methyl and butyl glucoside; > Sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or mannitol,
  • Dialcohol amines such as diethanolamine or 2-amino-1, 3-propanediol.
  • Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid as well as the silver complexes known under the name Surfacine® and the other substance classes listed in Appendix 6, Parts A and B of the Cosmetics Ordinance.
  • Perfume oils include 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 (anise, coriander, cumin, juniper), fruit peel (bergamot, lemon, Oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme) ), Needles and twigs (spruce, fir, pine, mountain pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax).
  • Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, lylpropionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, ⁇ -isomethylionone and methylcedryl ketone, and the alcohols Anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpinol, the hydrocarbons mainly include terpenes and balms.
  • fragrance oils of lower volatility which are mostly used as aroma components, are also suitable as perfume oils, for example sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavolanum oil.
  • Suitable flavors are, for example, peppermint oil, spearmint oil, anise oil, star anise oil, caraway oil, eucalyptus oil, fennel oil, lemon oil, winter green oil, clove oil, menthol and the like.
  • the dyes which can be used are those substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes” by the Dye Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106. Examples are culinary red A (CI 16255), patent blue V (CI42051), indigotine (CI73015), chlorophyllin (CI75810), quinoline yellow (CI47005), titanium dioxide (CI77891), indanthrene blue RS (CI 69800) and madder varnish (CI 58000). Luminol may also be present as the luminescent dye. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.
  • the total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40,% by weight, based on the composition.
  • the agents can be produced by customary cold or hot processes; the phase inversion temperature method is preferably used. Examples
  • the following table shows a number of formulation examples for antidandruff shampoos. The quantities are understood as% by weight.

Abstract

The invention relates to anti-dandruff shampoos containing an effective quantity of extracts of Camellia sinensis or of their active substances of the polyphenol type, particularly of the catechin and/or flavonoid type.

Description

Antischuppenshampoos Anti-dandruff shampoos
Gebiet der ErfindungField of the Invention
Die Erfindung befindet sich auf dem Gebiet der Haarbehandlungsmittel und betrifft neue Antischuppenshampoos mit einem wirksamen Gehalt an speziellen Pflanzenextrakten bzw. an deren Wirkstoffen sowie deren Verwendung zur Herstellung der Mittel.The invention is in the field of hair treatment compositions and relates to new antidandruff shampoos with an effective content of special plant extracts or their active ingredients, and their use for the preparation of the compositions.
Stand der TechnikState of the art
Unter der Bezeichnung Schuppen, genauer: Kopfschuppen, versteht der Kosmetikchemiker Teile der Hornschicht der Haut, die im Rahmen der ständigen Erneuerung der Hautschichten abgestoßen werden. Am behaarten Kopf sind sie infolge ihrer Nerklebung durch Talg und Schweiß zu größeren Aggregaten besonders gut sichtbar. Einer kosmetisch störenden Schuppung wird durch Behandlung der Kopfhaut mit Antischuppenmitteln entgegengewirkt, die üblicherweise in speziellen Haarbehandlungsmitteln, sogenannten Antischuppenshampoos appliziert werden. Als Wirkstoffe gelangen dabei beispielsweise Selendisulfid, Pyrethionsal- ze, Schieferöle und andere Mikrobizide zum Einsatz, denen gemeinsam ist, dass sie hautrei- zende Eigenschaften verfügen, einen unerwünschten Eigengeruch besitzen und/oder nur schwer in die Formulierungen einzuarbeiten sind.By the term dandruff, more precisely: dandruff, the cosmetic chemist understands parts of the horny layer of the skin that are rejected as part of the constant renewal of the skin layers. They are particularly well visible on the hairy head due to their sticking to tall aggregates due to sebum and sweat. A cosmetically disruptive scaling is counteracted by treating the scalp with anti-dandruff agents, which are usually applied in special hair treatment agents, so-called anti-dandruff shampoos. Selenium disulfide, pyrethione salts, shale oils and other microbicides are used as active ingredients, which have in common that they have skin-irritating properties, have an undesirable intrinsic odor and / or are difficult to incorporate into the formulations.
Die Aufgabe der vorliegenden Erfindung hat daher darin bestanden, neue Antischuppenshampoos zur Verfügung zu stellen, die frei von den eingangs genannten Nachteilen sind. Insbe- sondere sollten die Wirkstoffe pflanzlicher Natur und chemisch nicht weiter derivatisiert sein, keine Irritationen hervorrufen, frei von störenden Eigengerüchen und leicht formulierbar sein und dabei selbstverständlich die uneπvünschte Schuppenbildung zuverlässig verhindern bzw. auf ein nicht länger störendes Maß reduzieren. Beschreibung der ErfindungThe object of the present invention was therefore to provide new antidandruff shampoos which are free from the disadvantages mentioned at the outset. In particular, the active ingredients should be of a vegetable nature and should not be further derivatized chemically, should not cause irritation, be free from unpleasant odors and be easy to formulate, and of course reliably prevent the undesirable formation of dandruff or reduce it to a level that is no longer disruptive. Description of the invention
Gegenstand der Erfindung sind Antischuppenshampoos, enthaltend eine wirksame Menge von Extrakten der Camellia sinensis bzw. an deren Wirkstoffen vom Typ der Catechine und/oder Flavonoide.The invention relates to antidandruff shampoos containing an effective amount of extracts of Camellia sinensis or their active substances of the catechin and / or flavonoid type.
Überraschenderweise wurde gefunden, dass Zubereitungen, die als Wirkstoffe Extrakte der Camellia sinensis bzw. deren aktive Prinzipien (Polyphenole, insbesondere Catechine und oder Flavonoide) enthalten, die Schuppenbildung auf der Kopfhaut so weit zuverlässig unterbinden, dass es nicht länger störend ist. Die Wirkstoffe sind natürlicher Herkunft, nicht weiter chemisch verändert, geruchsfrei und lassen sich problemlos in die Formulierungen einarbeiten.Surprisingly, it was found that preparations which contain extracts of Camellia sinensis or their active principles (polyphenols, in particular catechins and or flavonoids) as active ingredients reliably prevent dandruff formation on the scalp to such an extent that it is no longer a problem. The active ingredients are of natural origin, are not chemically modified, are odorless and can be easily incorporated into the formulations.
Extrakte von Camellia sinensisExtracts from Camellia sinensis
Bei der Camellia sinensis handelt es sich um den Grünen Tee, der als Wirkstoffe ("Tee- Tannine), im wesentlichen Polyphenole, nämlich Epicatechin, Epigallocatechin, Epigallocate- chingallat, Epigallocatechingallat, Theaflavin, Theaflavinmonogallat A oder B und Theafla- vindigallat enthält, die sich angereichert in den Extrakten finden.Camellia sinensis is green tea which, as active ingredients ("tea tannins), contains essentially polyphenols, namely epicatechin, epigallocatechin, epigallocatechingallate, epigallocatechin gallate, theaflavin, theaflavin monogallate A or B and theaflavindigallate find themselves enriched in the extracts.
Figure imgf000003_0001
Figure imgf000003_0001
Catechine Flavonoide
Figure imgf000004_0001
Catechine flavonoids
Figure imgf000004_0001
In der Regel weisen die frisch getrockneten Teeblätter Catechingehalte von 20 bis 25 Gew.-% auf, von denen allein das Epigallocatechingallat etwa 50 bis 70 Gew.-% ausmacht. Somit sind solche Mittel bevorzugt, die diesen Wirkstoff in besonders hohen Konzentrationen aufweisen.As a rule, the freshly dried tea leaves have catechin contents of 20 to 25% by weight, of which the epigallocatechin gallate alone makes up about 50 to 70% by weight. Thus, agents are preferred which have this active ingredient in particularly high concentrations.
Die Herstellung der Extrakte kann in an sich bekannter Weise erfolgen, d.h. beispielsweise durch wässrigen, alkoholischen oder wässrig-alkoholischen Auszug der Pflanzen bzw. Pflan- zenteile bzw. der Blätter oder Früchte. Geeignet sind alle herkömmlichen Extraktionsverfahren wie z.B. Mazeration, Remazeration, Digestion, Bewegungsmazeration, Wirbelextraktion, Ultraschallextraktion, Gegenstromextraktion, Perkolation, Reperkolation, Evakolation (Extraktion unter vermindertem Druck), Diakolation oder Festflüssig-Extraktion unter kontinuierlichem Rückfluss. Für den großtechnischen Einsatz vorteilhaft ist die Perkolationsmethode. Als Ausgangsmaterial können frische Pflanzen oder Pflanzenteile eingesetzt werden, üblicherweise wird jedoch von getrockneten Pflanzen und/oder Pflanzenteilen ausgegangen, die vor der Extraktion mechanisch zerkleinert werden können. Hierbei eignen sich alle dem Fachmann bekannten Zerkleinerungsmethoden, als Beispiel sei die Gefriermahlung genannt. Als Lösungsmittel für die Durchführung der Extraktionen können organische Lösungsmittel, Wasser (vorzugsweise heißes Wasser einer Temperatur von über 80 °C und insbesondere von über 95 °C) oder Gemische aus organischen Lösungsmitteln und Wasser, insbesondere niedermolekulare Alkohole mit mehr oder weniger hohen Wassergehalten, verwendet werden. Besonders bevorzugt ist die Extraktion mit Methanol, Ethanol, Pentan, Hexan, Heptan, Ace- ton, Propylenglykolen, Polyethylenglykolen sowie Ethylacetat sowie Mischungen hieraus sowie deren wässrige Gemische. Die Extraktion erfolgt in der Regel bei 20 bis 100 °C, bevorzugt bei 30 bis 90 °C, insbesondere bei 60 bis 80 °C. In einer bevorzugten Ausfuhrungsform erfolgt die Extraktion unter Inertgasatmosphäre zur Vermeidung der Oxidation der Wirkstoffe des Extraktes. Dies ist insbesondere bei Extraktionen bei Temperaturen über 40 °C von Bedeutung. Die Extraktionszeiten werden vom Fachmann in Abhängigkeit vom Ausgangsmate- rial, dem Extraktionsverfahren, der Extraktionstemperatur, vom Verhältnis Lösungsmittel zu Rohstoff u.a. eingestellt. Nach der Extraktion können die erhaltenen Rohextrakte gegebenenfalls weiteren üblichen Schritten, wie beispielsweise Aufreinigung, Konzentration und/oder Entfärbung unterzogen werden. Falls wünschenswert, können die so hergestellten Extrakte beispielsweise einer selektiven Abtrennung einzelner unerwünschter Inhaltsstoffe, unterzogen werden. Die Extraktion kann bis zu jedem beliebigen Extraktionsgrad erfolgen, wird aber gewöhnlich bis zur Erschöpfung durchgeführt. Typische Ausbeuten (= Trockensubstanzmenge des Extraktes bezogen auf eingesetzte Rohstoffmenge) bei der Extraktion getrockneter Blätter liegen im Bereich von 1 bis 25, insbesondere 2 bis 22 Gew.-%. Die vorliegenden Erfindung umfasst die Erkenntnis, dass die Extraktionsbedingungen sowie die Ausbeuten der Endextrakte vom Fachmann ja nach gewünschtem Einsatzgebiet gewählt werden können. Diese Extrakte, die in der Regel Aktivsubstanzgehalte (= Feststoffgehalte) im Bereich von 0,5 bis 25 Gew.-% aufweisen, können als solche eingesetzt werden, es ist jedoch ebenfalls möglich, das Lösungsmittel durch Trocknung, insbesondere durch Sprüh- oder Gefriertrocknung vollstän- dig zu entfernen, wobei ein intensiv rot gefärbter Feststoff zurückbleibt. Die Extrakte können auch als Ausgangsstoffe für die Gewinnung der oben genannten reinen Wirkstoffe dienen, sofern diese nicht auf synthetischem Wege einfacher und kostengünstiger hergestellt werden können. Demzufolge kann der Wirkstoffgehalt in den Extrakten 5 bis 100, vorzugsweise 50 bis 98 Gew.-% betragen. Die Extrakte selbst können als wässrige und/oder in organischen Solventien gelöste Zubereitungen sowie als sprüh- bzw. gefriergetrocknete, wasserfreie Feststoffe vorliegen. Als organische Lösungsmittel kommen in diesem Zusammenhang beispielsweise die aliphatischen Alkohole mit 1 bis 6 Kohlenstoffatomen (z.B. Ethanol), Ketone (z.B. Aceton), Halogenkohlenwasserstoffe (z.B. Chloroform oder Methylenchlorid), niedere Ester oder Polyole (z.B. Glycerin oder Glycole) in Frage.The extracts can be prepared in a manner known per se, ie for example by aqueous, alcoholic or aqueous-alcoholic extraction of the plants or parts of plants or of the leaves or fruits. All conventional extraction methods such as maceration, remaceration, digestion, movement maceration, vortex extraction, ultrasound extraction, countercurrent extraction, percolation, repercolation, evacolation (extraction under reduced pressure), diacolation or solid-liquid extraction with continuous reflux are suitable. The percolation method is advantageous for large-scale use. Fresh plants or parts of plants can be used as the starting material, but usually dried plants and / or parts of plants are used, which can be mechanically comminuted before extraction. All comminution methods known to the person skilled in the art are suitable here, freeze grinding being mentioned as an example. Organic solvents, water (preferably hot water at a temperature of above 80 ° C. and in particular above 95 ° C.) or mixtures of organic solvents and water, in particular low molecular weight alcohols with more or less high water contents, can be used as solvents for carrying out the extractions become. Extraction with methanol, ethanol, pentane, hexane, heptane, acetone, propylene glycols, polyethylene glycols and ethyl acetate as well as mixtures thereof and their aqueous mixtures is particularly preferred. The extraction is usually carried out at 20 to 100 ° C, preferably at 30 to 90 ° C, in particular at 60 to 80 ° C. In a preferred embodiment, the extraction takes place under an inert gas atmosphere to avoid oxidation of the active ingredients of the extract. This is particularly important for extractions at temperatures above 40 ° C. The extraction times are determined by the person skilled in the art depending on the starting material. rial, the extraction process, the extraction temperature, the ratio of solvent to raw material, among others. After the extraction, the crude extracts obtained can optionally be subjected to further customary steps, such as purification, concentration and / or decolorization. If desired, the extracts produced in this way can, for example, be subjected to a selective separation of individual undesirable ingredients. The extraction can take place to any degree of extraction, but is usually carried out to exhaustion. Typical yields ( = dry matter amount of the extract based on the amount of raw material used) in the extraction of dried leaves are in the range from 1 to 25, in particular 2 to 22,% by weight. The present invention encompasses the knowledge that the extraction conditions and the yields of the final extracts can be selected by the person skilled in the art depending on the desired field of use. These extracts, which as a rule have active substance contents (= solids contents) in the range from 0.5 to 25% by weight, can be used as such, but it is also possible to complete the solvent by drying, in particular by spray or freeze drying - Dig to remove, leaving an intense red solid. The extracts can also serve as starting materials for the production of the above-mentioned pure active ingredients, provided that these cannot be produced more easily and inexpensively by synthetic means. Accordingly, the active substance content in the extracts can be 5 to 100, preferably 50 to 98% by weight. The extracts themselves can be present as aqueous and / or preparations dissolved in organic solvents and as spray-dried or freeze-dried, anhydrous solids. Examples of suitable organic solvents in this context are the aliphatic alcohols having 1 to 6 carbon atoms (eg ethanol), ketones (eg acetone), halogenated hydrocarbons (eg chloroform or methylene chloride), lower esters or polyols (eg glycerol or glycols).
AntischuppenmittelAnti-dandruff agents
Typischerweise besitzen die erfindungsgemäßen Mittel einen Gehalt an Extrakten der Camel- lia sinensis oder deren Wirkstoffe in Mengen von 0,01 bis 15, vorzugsweise 0,1 bis 5 und insbesondere 0,5 bis 1 Gew.-% - bezogen auf die Mittel. In einer besonderen Ausführungsform der Erfindung können die Antischuppenmittel weitere für diesen Anwendungszweck bekannte Wirkstoffe enthalten als da beispielsweise sind : Pirocton Olamin (l-Hydroxy-4- methyl-6-(2,4,4-trimythylpentyl)-2-(lH)-pyridinonmonoethanolaminsalz), Baypival® (Clim- bazole), Ketoconazol®, (4-Acetyl-l-{-4-[2-(2.4-dichlorphenyI) r-2-(lH-imidazol-l-ylmethyl)- l,3-dioxylan-c-4-ylmethoxyphenyl}piperazin, Elubiol, Selendisulfid, Schwefel kolloidal, Schwefelpolyethylenglykolsorbitanmonooleat, Schwefelrizinolpolyethtoxylat, Schwefelteer- Destillate, Salicylsäure (bzw. in Kombination mit Hexachlorophen), Undexylensäure- monoethanolamid Sulfosuccinat Na-Salz, Lamepon® UD (Protein-Undecylensäurekon- densat), Zinkpyrithion, Aluminiumpyrithion und Magnesiumpyrithion / Dipyrithion- Magnesiumsulfat. Die Extrakte bzw. deren Wirkstoffe und die weiteren Antischuppenmittel können im Gewichtsverhältnis 90 : 10 bis 10 : 90, vorzugsweise 75 : 25 bis 25 : 75 und insbe- sondere 60 : 40 bis 40 : 60 in den Mitteln enthalten sein.The agents according to the invention typically have a content of extracts of Camellia sinensis or its active ingredients in amounts of 0.01 to 15, preferably 0.1 to 5 and in particular 0.5 to 1% by weight, based on the agents. In a particular embodiment of the invention, the antidandruff agents can contain further active ingredients known for this purpose than, for example, are: piroctone olamine (1-hydroxy-4-methyl-6- (2,4,4-trimythylpentyl) -2- (1H) - pyridinone monoethanolamine salt), Baypival® (climazole), Ketoconazol®, (4-acetyl-l - {- 4- [2- (2.4-dichlorophenyl)) r-2- (lH-imidazol-l-ylmethyl) - 1,3 -dioxylan-c-4-ylmethoxyphenyl} piperazine, elubiol, selenium disulfide, sulfur colloidal, sulfur polyethylene glycol sorbitan monooleate, sulfuric ricinole polyethoxylate, sulfuric tar distillates, salicylic acid (or in combination with hexachlorophene), undexylenic acid - monoethanolamide sulfosuccinate sodium salt, Lamepon® UD (protein undecylenic acid condensate), zinc pyrithione, aluminum pyrithione and magnesium pyrithione / dipyrithione magnesium sulfate. The extracts or their active ingredients and the further antidandruff agents can be contained in the compositions in a weight ratio of 90:10 to 10:90, preferably 75:25 to 25:75 and in particular 60:40 to 40:60.
Daneben können die Zubereitungen weiterhin - vorzugsweise - milde anionische, nichtionische, amphotere und/oder zwitterionische und/oder kationische Tenside enthalten. Typische Beispiele sind Seifen, Alkylbenzolsulfonate, Alkansulfonate, Olefmsulfonate, Alkylethersul- fonate, Glycerinethersulfonate, α-Methylestersulfonate, Sulfofettsäuren, Alkylsulfate, Alky- lethersulfate, Glycerinethersulfate, Fettsäureethersulfate, Hydroxymischethersulfate, Mo- noglycerid(ether) sulfate, Fettsäureamid(ether)sulfate, Mono- und Dialkylsulfosuccinate, Mono- und Dialkylsulfosuccinamate, Sulfotriglyceride, Amidseifen, Ethercarbonsäuren und deren Salze, Fettsäureisethionate, Fettsäuresarcosinate, Fettsäuretauride, N-Acylaminosäuren, wie beispielsweise Acyllactylate, Acyltartrate, Acylglutamate und Acylaspartate, Alkyloligogluco- sidsulfate, Proteinfettsäurekondensate (insbesondere pflanzliche Produkte auf Weizenbasis) und Alkyl(ether)phosphate. Sofern die anionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen. Typische Beispiele für nichtionische Tenside sind Fettalkoholpolyglycolether, Al- kylphenolpolyglycolether, Fettsäurepolyglycolester, Fettsäureamidpolyglycolether, Fettamin- polyglycolether, alkoxylierte Triglyceride, Mischether bzw. Mischformale, gegebenenfalls partiell oxidierte Alk(en)yloligoglykoside bzw. Glucoronsäurederivate, Fettsäure-N-alkylglu- camide, Proteinhydrolysate (insbesondere pflanzliche Produkte auf Weizenbasis), Polyolfett- säureester, Zuckerester, Sorbitanester, Polysorbate und Aminoxide. Sofern die nichtionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen. Typische Beispiele für kationische Tenside sind quartäre Ammoniumverbindungen, wie beispielsweise das Dimethyldisteary- lammoniumchlorid, und Esterquats, insbesondere quaternierte Fettsäuretrialkanolamin- estersalze. Typische Beispiele für amphotere bzw. zwitterionische Tenside sind Alkylbetaine, Alkylamidobetaine, Aminopropionate, Aminoglycinate, Imidazoliniumbetaine und Sulfobe- taine. Bei den genannten Tensiden handelt es sich ausschließlich um bekannte Verbindungen. Typische Beispiele für besonders geeignete milde, d.h. besonders hautverträgliche Tenside sind Fettalkoholpolyglycolethersulfate, Monoglyceridsulfate, Mono- und oder Dialkylsulfosuccinate, Fettsäureisethionate, Fettsäuresarcosinate, Fettsäuretauride, Fettsäureglutama- te, α-Olefinsulfonate, Ethercarbonsäuren, Alkyloligoglucoside, Fettsäureglucamide, Alkylamidobetaine, Amphoacetale und/oder Proteinfettsäurekondensate, letztere vorzugsweise auf Basis von Weizenproteinen. In einer bevorzugten Ausführungsform der Erfindung enthalten die AntischuppenmittelIn addition, the preparations can furthermore - preferably - contain mild anionic, nonionic, amphoteric and / or zwitterionic and / or cationic surfactants. Typical examples are soaps, sulfonates alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether, glycerol ether, α-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, alkylene ether sulfates, Glycerol ether, Fettsäureethersulfate, Hydroxymischethersulfate, Mo noglycerid (ether) sulfates, fatty acid amide (ether) sulfates, mono and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids, such as, for example, acyl lactate, wheat acylate glate fatty acids, acyl glucosate fatty acid based on acyl glucosate fats and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides, protein fatty acids, and glucuric acid hydrochloride acids, or glucuric acid hydrochloride acids and glucuric acid silicate acids or glucuric acid silicate acid derivatives, especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds, such as, for example, dimethyldistearylammonium chloride, and ester quats, in particular quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds. Typical examples of particularly suitable mild, that is to say particularly skin-compatible, surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, α-olefin sulfonates or alkyl carboxylates, alkyl carboxylates, alkyl carboxylates, alkyl carboxamides, the latter preferably based on wheat proteins. In a preferred embodiment of the invention, the antidandruff agents contain
(a) 10 bis 50, vorzugsweise 20 bis 40 Gew.-% Tenside und(a) 10 to 50, preferably 20 to 40 wt .-% surfactants and
(b) 0,1 bis 5, vorzugsweise 0,5 bis 1 Gew.-% Extrakte der Camellia sinensis oder deren Wirkstoffe(b) 0.1 to 5, preferably 0.5 to 1 wt .-% extracts of Camellia sinensis or its active substances
mit der Maßgabe, dass sich die Mengenangaben mit Wasser und gegebenenfalls weiteren Hilfs- und Zusatzstoffen zu 100 Gew.-% ergänzen. Besonders bevorzugt sind Mittel, enthaltendwith the proviso that the amounts given with water and possibly other auxiliary substances and additives are 100% by weight. Agents containing are particularly preferred
(al) 20 bis 30, vorzugsweise 22 bis 28 Gew.-% anionische Tenside,(al) 20 to 30, preferably 22 to 28% by weight of anionic surfactants,
(a2) 5 bis 10, vorzugsweise 6 bis 9 Gew.-% nichtionische Tenside,(a2) 5 to 10, preferably 6 to 9% by weight of nonionic surfactants,
(a3) 1 bis 5, vorzugsweise 2 bis 4 Gew.-% amphotere und/oder zwitterionische Tenside,(a3) 1 to 5, preferably 2 to 4% by weight of amphoteric and / or zwitterionic surfactants,
(b) 0,1 bis 5, vorzugsweise 0,5 bis 1 Gew.-% Extrakte der Camellia sinensis oder deren Wirkstoffe und(b) 0.1 to 5, preferably 0.5 to 1 wt .-% extracts of Camellia sinensis or its active ingredients and
(c) 0 bis 5, vorzugsweise 0,1 bis 1 Gew.-% weitere Antischuppenwirkstoffe,(c) 0 to 5, preferably 0.1 to 1% by weight of further antidandruff active ingredients,
ebenfalls mit der Maßgabe, dass sich die Mengenangaben mit Wasser und gegebenenfalls weiteren Hilfs- und Zusatzstoffen zu 100 Gew.-% ergänzen.also with the proviso that the amounts given with water and possibly other auxiliary substances and additives are 100% by weight.
Gewerbliche AnwendbarkeitIndustrial applicability
Ein weiterer Gegenstand der Erfindung betrifft die Verwendung von wirksamen Mengen an Extrakten der Camellia sinensis bzw. von Phenolen, insbesondere Catechinen und/oder Fla- vonoiden als Antischuppenmittel. Die Stoffe können - bezogen auf die Endprodukte - in Mengen von 0,01 bis 15, vorzugsweise 0,1 bis 3 Gew.-% - eingesetzt werden.Another object of the invention relates to the use of effective amounts of extracts of Camellia sinensis or of phenols, in particular catechins and / or flavoid as antidandruff agents. Based on the end products, the substances can be used in amounts of 0.01 to 15, preferably 0.1 to 3% by weight.
Diese Mittel können ferner als weitere Hilfs- und Zusatzstoffe neben den bereits genannten Tensiden, Olkörper, Emulgatoren, Perlglanzwachse, Konsistenzgeber, Verdickungsmittel, Überfettungsmittel, Stabilisatoren, Polymere, Siliconverbindungen, Fette, Wachse, Lecithine, Phospholipide, UN-Lichtschutzfaktoren, biogene Wirkstoffe, Antioxidantien, zusätzliche andere Antischuppenmittel, Filmbildner, Hydrotrope, Solubilisatoren, Konservierungsmittel, Parfümöle, Farbstoffe und dergleichen enthalten. OlkörperIn addition to the surfactants, oil bodies, emulsifiers, pearlescent waxes, consistency enhancers, thickeners, superfatting agents, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, UN light protection factors, biogenic agents, antioxidants, these agents can also be used as further auxiliaries and additives , contain additional other anti-dandruff agents, film formers, hydrotropes, solubilizers, preservatives, perfume oils, dyes and the like. Olkörper
Als Olkörper kommen beispielsweise Guerbetalkohole auf Basis von Fettalkoholen mit 6 bis 18, vorzugsweise 8 bis 10 Kohlenstoffatomen, Ester von linearen C6-C22-Fettsäuren mit li- nearen oder verzweigten C6-C2 -Fettalkoholen bzw. Ester von verzweigten C6-C-3- Carbonsäuren mit linearen oder verzweigten C6-C 2-Fettalkoholen, wie z.B. Myristylmyristat, Myristylpalmitat, Myristylstearat, Myristylisostearat, Myristyloleat, Myristylbehenat, My- ristylerucat, Cetylmyristat, Cetylpalmitat, Cetylstearat, Cetylisostearat, Cetyloleat, Cetylbehe- nat, Cetylerucat, Stearylmyristat, Stearylpalmitat, Stearylstearat, Stearylisostearat, Stearylo- leat, Stearylbehenat, Stearylerucat, Isostearylmyristat, Isostearylpalmitat, Isostearylstearat, Isostearylisostearat, Isostearyloleat, Isostearylbehenat, Isostearyloleat, Oleylmyristat, Oleyl- palmitat, Oleylstearat, Oleylisostearat, Oleyloleat, Oleylbehenat, Oleylerucat, Behenylmy- ristat, Behenylpalmitat, Behenylstearat, Behenylisostearat, Behenyloleat, Behenylbehenat, Behenylerucat, Erucylmyristat, Erucylpalmitat, Erucylstearat, Erucylisostearat, Erucyloleat, Erucylbehenat und Erucylerucat. Daneben eignen sich Ester von linearen C6-C 2-Fettsäuren mit verzweigten Alkoholen, insbesondere 2-Ethylhexanol, Ester von Cι8-C38-Alkylhy- droxycarbonsäuren mit linearen oder verzweigten C6-C 2-Fettalkoholen (vgl. DE 19756377 AI), insbesondere Dioctyl Malate, Ester von linearen und/oder verzweigten Fettsäuren mit mehrwertigen Alkoholen (wie z.B. Propylengfycol, Dimerdiol oder Trimertriol) und/oder Guerbetalkoholen, Triglyceride auf Basis C6-Cιrj-Fettsäuren, flüssige Mono- Di- /Triglyceridmischungen auf Basis von C6-Cι8-Fettsäuren, Ester von C6-C -Fettalkoholen und/oder Guerbetalkoholen mit aromatischen Carbonsäuren, insbesondere Benzoesäure, Ester von C -Cι2-Dicarbonsäuren mit linearen oder verzweigten Alkoholen mit 1 bis 22 Kohlenstoffatomen oder Polyolen mit 2 bis 10 Kohlenstoffatomen und 2 bis 6 Hydroxylgruppen, pflanzliche Öle, verzweigte primäre Alkohole, substituierte Cyclohexane, lineare und verzweigte C6-C22-Fettalkoholcarbonate, wie z.B. Dicaprylyl Carbonate (Cetiol® CC), Guer- betcarbonate auf Basis von Fettalkoholen mit 6 bis 18, vorzugsweise 8 bis IO C Atomen, Ester der Benzoesäure mit linearen und/oder verzweigten C6-C22- Alkoholen (z.B. Finsolv® TN), lineare oder verzweigte, symmetrische oder unsymmetrische Dialkylether mit 6 bis 22 Koh- lenstoffatomen pro Alkylgruppe, wie z.B. Dicaprylyl Ether (Cetiol® OE), Ringöffhungspro- dukte von epoxidierten Fettsäureestern mit Polyolen, Siliconöle (Cyclomethicone, Silicium- methicontypen u.a.) und/oder aliphatische bzw. naphthenische Kohlenwasserstoffe, wie z.B. wie Squalan, Squalen oder Dialkylcyclohexane in Betracht. EmulgatorenGuerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C 6 -C 22 fatty acids with linear or branched C 6 -C 2 fatty alcohols or esters of branched C 6 come as oil bodies, for example -C 3 - carboxylic acids with linear or branched C 6 -C 2 fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl stylate stearate Cetylerucat, leat Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, Stearylo-, stearyl palmitate, Stearylerucat, isostearyl, isostearyl palmitate, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, oleyl myristate, oleyl, oleyl stearate, oleyl isostearate, oleyl oleate, Oleylbehenat, oleyl erucate, Behenylmy- ristat, behenyl palmitate, behenyl stearate, behenyl isostearate, Behe nyloleate, behenyl behenate, behenylerucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. In addition, esters of linear C 6 -C 2 fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C 8 -C 38 alkyl hydroxy carboxylic acids with linear or branched C 6 -C 2 fatty alcohols (see. DE 19756377 AI ), especially dioctyl malates, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C 6 -Crj fatty acids, liquid mono-, di- / triglyceride mixtures based of C 6 -C 8 fatty acids, esters of C 6 -C fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C -C 2 dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 up to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C 6 -C 22 fatty alcohol carbonates, such as, for example, dic aprylyl carbonates (Cetiol® CC), Guerbet carbonates based on fatty alcohols with 6 to 18, preferably 8 to 10 C atoms, esters of benzoic acid with linear and / or branched C 6 -C 22 alcohols (eg Finsolv® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, such as dicaprylyl ether (Cetiol® OE), ring opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicon methicone types etc.) and / or aliphatic or naphthenic hydrocarbons, such as, for example, squalane, squalene or dialkylcyclohexanes. emulsifiers
Als Emulgatoren kommen beispielsweise nichtionogene Tenside aus mindestens einer der folgenden Gruppen in Frage: > Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/ oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C- Atomen, an Fettsäuren mit 12 bis 22 C-Atomen, an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe sowie Alkylamine mit 8 bis 22 Kohlenstoffatomen im Alkylrest; Alkyl- und/oder Alkenyloligoglykoside mit 8 bis 22 Kohlenstoffatomen im Alk(en)ylrest und deren ethoxylierte Analoga; Anlagerungsprodukte von 1 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:> Adducts of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms Atoms, on alkylphenols with 8 to 15 carbon atoms in the alkyl group and alkylamines with 8 to 22 carbon atoms in the alkyl radical; Alkyl and / or alkenyl oligoglycosides with 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs; Addition products of 1 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;
> Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl; > Partialester von Glycerin und/oder Sorbitan mit ungesättigten, linearen oder gesättigten, verzweigten Fettsäuren mit 12 bis 22 Kohlenstoffatomen und/oder Hydroxycarbonsäuren mit 3 bis 18 Kohlenstoffatomen sowie deren Addukte mit 1 bis 30 Mol Ethylenoxid; Partialester von Polyglycerin (durchschnittlicher Eigenkondensationsgrad 2 bis 8), Polye- thylenglycol (Molekulargewicht 400 bis 5000), Trimethylolpropan, Pentaerythrit, Zucker- alkoholen (z.B. Sorbit), Alkylglucosiden (z.B. Methylglucosid, Butylglucosid, Laurylglu- cosid) sowie Polyglucosiden (z.B. Cellulose) mit gesättigten und/oder ungesättigten, linearen oder verzweigten Fettsäuren mit 12 bis 22 Kohlenstoffatomen und/oder Hydroxycarbonsäuren mit 3 bis 18 Kohlenstoffatomen sowie deren Addukte mit 1 bis 30 Mol Ethylenoxid; > Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, Methylglucose und Polyolen, vorzugsweise Glycerin oder Polyglycerin. Mono-, Di- und Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEG-alkylphosphate und deren Salze; > Wollwachsalkohole; Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate; Block-Copolymere z.B. Polyethylenglycol-30 Dipolyhydroxystearate; Polymeremulgatoren, z.B. Pemulen-Typen (TR-l,TR-2) von Goodrich; Polyalkylenglycole sowie > Glycerincarbonat. Ethylenoxidanlagerungsprodukte> Adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil; > Partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated, branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide; Partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose) with saturated and / or unsaturated, linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 mol ethylene oxide; > Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol. Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts; > Wool wax alcohols; Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives; Block copolymers, for example polyethylene glycol 30 dipolyhydroxystearate; Polymer emulsifiers, for example Pemulen types (TR-1, TR-2) from Goodrich; Polyalkylene glycols and> glycerine carbonate. Ethylene Oxide
Die Anlagerungsprodukte von Ethylenoxid und oder von Propylenoxid an Fettalkohole, Fettsäuren, Alkylphenole oder an Ricinusöl stellen bekannte, im Handel erhältliche Produkte dar. Es handelt sich dabei um Homologengemische, deren mittlerer Alkoxy- lierungsgrad dem Verhältnis der Stoffmengen von Ethylenoxid und/ oder Propylenoxid und Substrat, mit denen die Anlagerungsreaktion durchgeführt wird, entspricht. C12/18- Fettsäuremono- und -diester von Anlagerungsprodukten von Ethylenoxid an Glycerin sind als Rückfettungsmittel für kosmetische Zubereitungen bekannt.The adducts of ethylene oxide and or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are mixtures of homologs, the average degree of alkoxylation of which is the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. C 12/18 - fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known as refatting agents for cosmetic preparations.
Alkyl- und/oder AlkenyloligoglykosideAlkyl and / or alkenyl oligoglycosides
Alkyl- und/oder Alkenyloligoglycoside, ihre Herstellung und ihre Verwendung sind aus dem Stand der Technik bekannt. Ihre Herstellung erfolgt insbesondere durch Umsetzung von Glucose oder Oligosacchariden mit primären Alkoholen mit 8 bis 18 Kohlenstoffatomen. Bezüglich des Glycosidrestes gilt, daß sowohl Monoglycoside, bei denen ein cyclischer Zuckerrest glycosidisch an den Fettalkohol gebunden ist, als auch oligomere Glycoside mit einem Oligomerisationsgrad bis vorzugsweise etwa 8 geeignet sind. Der Oligomerisierungsgrad ist dabei ein statistischer Mittelwert, dem eine für solche technischen Produkte übliche Homologenverteilung zugrunde liegt.Alkyl and / or alkenyl oligoglycosides, their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. Regarding the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.
Partialglyceridepartial glycerides
Typische Beispiele für geeignete Partialglyceride sind Hydroxystearinsäuremonoglycerid. Hydroxystearinsäurediglycerid, Isostearinsäuremonoglycerid, Isostearinsäurediglycerid, Ölsäuremonoglycerid, Ölsäurediglycerid, Ricinolsäuremoglycerid, Ricinolsäurediglyce- rid, Linolsäuremonoglycerid, Linolsäurediglycerid, Linolensäuremonoglycerid, Linolen- säurediglycerid, Erucasäuremonogfycerid, Erucasäurediglycerid, Weinsäuremonoglycerid,Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride. Hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid moglyceride, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linoleic acid monoglyceride, erolene acid monoglyceride
Weinsäurediglycerid, Citronensäuremonoglycerid, Citronendiglycerid, Äpfelsäuremo- noglycerid, Äpfelsäurediglycerid sowie deren technische Gemische, die untergeordnet aus dem Herstellungsprozeß noch geringe Mengen an Triglycerid enthalten können. Ebenfalls geeignet sind Anlagerungsprodukte von 1 bis 30, vorzugsweise 5 bis 10 Mol Ethylenoxid an die genannten Partialglyceride. > SorbitanesterTartaric acid diglyceride, citric acid monoglyceride, citric diglyceride, malic acid monoglyceride, malic acid diglyceride as well as their technical mixtures, which may still contain small amounts of triglyceride from the manufacturing process. Addition products of 1 to 30, preferably 5 to 10, mol of ethylene oxide onto the partial glycerides mentioned are also suitable. > Sorbitan esters
Als Sorbitanester kommen Sorbitanmonoisostearat, Sorbitansesquiisostearat, Sorbitan- diisostearat, Sorbitantriisostearat, Sorbitanmonooleat, Sorbitansesquioleat, Sorbitan- dioleat, Sorbitantrioleat, Sorbitanmonoerucat, Sorbitansesquierucat, Sorbitandierucat,Sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sorbitan sorbierucate, sorbitan esters
Sorbitantrieracat, Sorbitanmonoricinoleat, Sorbitansesquiricinoleat, Sorbitandiricinoleat, Sorbitantriricinoleat, Sorbitanmonohydroxystearat, Sorbitansesquihydroxystearat, Sorbi- tandihydroxystearat, Sorbitantrihydroxystearat, Sorbitanmonotartrat, Sorbitansesqui- tartrat, Sorbitanditartrat, Sorbitantritartrat, Sorbitanmonocitrat, Sorbitansesquicitrat, Sor- bitandicitrat, Sorbitantricitrat, Sorbitanmonomaleat, Sorbitansesquimaleat, Sorbitan- dimaleat, Sorbitantrimaleat sowie deren technische Gemische. Ebenfalls geeignet sind Anlagerungsprodukte von 1 bis 30, vorzugsweise 5 bis 10 Mol Ethylenoxid an die genannten Sorbitanester.Sorbitantrieracat, Sorbitanmonoricinoleat, Sorbitansesquiricinoleat, Sorbitandiricinoleat, Sorbitantriricinoleat, Sorbitanmonohydroxystearat, Sorbitansesquihydroxystearat, sorbitan tandihydroxystearat, Sorbitantrihydroxystearat, Sorbitanmonotartrat, sesqui- tartrate, Sorbitanditartrat, Sorbitantritartrat, Sorbitanmonocitrat, Sorbitansesquicitrat, sorting bitandicitrat, sorbitan, sorbitan, sorbitan, sorbitan dimaleate, sorbitan and their technical mixtures. Addition products of 1 to 30, preferably 5 to 10, mol of ethylene oxide onto the sorbitan esters mentioned are also suitable.
> Polyglycerinester> Polyglycerol esters
Typische Beispiele für geeignete Polyglycerinester sind Polygfyceryl-2 Dipolyhydro- xystearate (Dehymuls® PGPH), Polyglycerin-3-Diisostearate (Lameform® TGI), Po- lyglyceryl-4 Isostearate (Isolan® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyce- ryl-3 Diisostearate (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) und Polyglyceryl Polyricinoleate (Admul® WOL 1403) Po- lyglyceryl Dimerate Isostearate sowie deren Gemische. Beispiele für weitere geeigneteTypical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearate (Dehymuls® PGPH), polyglycerol-3-diisostearate (Lameform® TGI), polyglyceryl-4 isostearate (Isolan® GI 34), polyglyceryl-3 oleate, diisostearoyl polyglycerol ryl-3 Diisostearate (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether ( Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate Isostearate and their mixtures. Examples of other suitable ones
Polyolester sind die gegebenenfalls mit 1 bis 30 Mol Ethylenoxid umgesetzten Mono-, Di- und Triester von Trimethylolpropan oder Pentaerythrit mit Laurinsäure, Kokosfettsäure, Taigfettsäure, Palmitinsäure, Stearinsäure, Ölsäure, Behensäure und dergleichen.Polyol esters are the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like which are optionally reacted with 1 to 30 mol of ethylene oxide.
> Anionische Emulgatoren> Anionic emulsifiers
Typische anionische Emulgatoren sind aliphatische Fettsäuren mit 12 bis 22 Kohlenstoffatomen, wie beispielsweise Palmitinsäure, Stearinsäure oder Behensäure, sowie Dicar- bonsäuren mit 12 bis 22 Kohlenstoffatomen, wie beispielsweise Azelainsäure oder Seba- cinsäure. Amphotere und kationische EmulgatorenTypical anionic emulsifiers are aliphatic fatty acids with 12 to 22 carbon atoms, such as, for example, palmitic acid, stearic acid or behenic acid, and dicarboxylic acids with 12 to 22 carbon atoms, such as, for example, azelaic acid or sebacic acid. Amphoteric and cationic emulsifiers
Weiterhin können als Emulgatoren zwitterionische Tenside verwendet werden. Als zwitterionische Tenside werden solche oberflächenaktiven Verbindungen bezeichnet, die im Molekül mindestens eine quartäre Ammoniumgruppe und mindestens eine Carboxylat- und eine Sulfonatgruppe tragen. Besonders geeignete zwitterionische Tenside sind die sogenannten Betaine wie die N-Alkyl-N,N-dimethylammoniumglycinate, beispielsweise das Kokosalkyldimethylammoniumgfycinat, N-Acylaminopropyl-N,N-dimethylammo- niumgly-cinate, beispielsweise das Kokosacylaminopropyldimethyl-ammoniumglycinat, und 2-Alkyl-3-carboxylmethyl-3-hydroxyethylimidazoline mit jeweils 8 bis 18 C-Atomen in der Alkyl- oder Acylgruppe sowie das Kokosacylaminoethylhydroxyethyl- carboxymethylglycinat. Besonders bevorzugt ist das unter der CTFA-Bezeichnung Coca- midopropyl Betaine bekannte Fettsäureamid-Derivat. Ebenfalls geeignete Emulgatoren sind ampholytische Tenside. Unter ampholytischen Tensiden werden solche oberflächen- aktiven Verbindungen verstanden, die außer einer C8/18- Alkyl- oder Acylgruppe im Molekül mindestens eine freie Aminogruppe und mindestens eine -COOH- oder -SO3H- Gruppe enthalten und zur Ausbildung innerer Salze befähigt sind. Beispiele für geeignete ampholytische Tenside sind N-Alkylglycine, N-Alkylpropionsäuren, N-Alkylamino- buttersäuren, N-Alkyliminodipropionsäuren, N-Hydroxyethyl-N-alkylamidopropylg- lycine, N-Alkyltaurine, N-Alkylsarcosine, 2-Alkylaminopropionsäuren und Alkylami- noessigsäuren mit jeweils etwa 8 bis 18 C-Atomen in der Alkylgruppe.. Besonders bevorzugte ampholytische Tenside sind das N-Kokosalkylaminopropionat, das Kokosacylami- noethylaminopropionat und das Cι /ι8-Acylsarcosin. Schließlich kommen auch Kation- tenside als Emulgatoren in Betracht, wobei solche vom Typ der Esterquats, vorzugsweise methylquaternierte Difettsäuretriethanolaminester-Salze, besonders bevorzugt sind.Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl-3 -carboxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethyl carboxymethylglycinate. The fatty acid amide derivative known under the CTFA name cocamidopropyl betaine is particularly preferred. Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C 8/18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO 3 H group in the molecule and are capable of forming internal salts , Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylamino-butyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylamino acetic acids each about 8 to 18 carbon atoms in the alkyl group .. Particularly preferred ampholytic surfactants are the N-coconut alkylaminopropionate, the coconut acylaminoethylaminopropionate and the Cι / ι 8 acyl sarcosine. Finally, cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.
Fette und WachseFats and waxes
Typische Beispiele für Fette sind Glyceride, d.h. feste oder flüssige pflanzliche oder tierische Produkte, die im wesentlichen aus gemischten Glycerinestern höherer Fettsäuren bestehen, als Wachse kommen u.a. natürliche Wachse, wie z.B. Candelillawachs, Carnaübawachs, Japanwachs, Espartograswachs, Korkwachs, Guarumawachs, Reiskeimölwachs, Zuckerrohrwachs, Ouricurywachs, Montanwachs, Bienenwachs, Schellackwachs, Walrat, Lanolin (Wollwachs), Bürzelfett, Ceresin, Ozokerit (Erdwachs), Petrolatum, Paraffinwachse, Mikrowachse; chemisch modifizierte Wachse (Hartwachse), wie z.B. Montanesterwachse, Sasolwachse, hydrierte Jojobawachse sowie synthetische Wachse, wie z.B. Polyalkylenwachse und Polyethy- lenglycolwachse in Frage. Neben den Fetten kommen als Zusatzstoffe auch fettähnliche Sub- stanzen, wie Lecithine und Phospholipide in Frage. Unter der Bezeichnung Lecithine versteht der Fachmann diejenigen Glycero-Phospholipide, die sich aus Fettsäuren, Glycerin, Phosphorsäure und Cholin durch Veresterung bilden. Lecithine werden in der Fachwelt daher auch häufig als Phosphatidylcholine (PC). Als Beispiele für natürliche Lecithine seien die Kephaline genannt, die auch als Phosphatidsäuren bezeichnet werden und Derivate der 1,2-Diacyl-sn- glycerin-3 -phosphorsäuren darstellen. Dem gegenüber versteht man unter Phospholipiden gewöhnlich Mono- und vorzugsweise Diester der Phosphorsäure mit Glycerin (Glycerinphos- phate), die allgemein zu den Fetten gerechnet werden. Daneben kommen auch Sphingosine bzw. Sphingolipide in Frage.Typical examples of fats are glycerides, that is to say solid or liquid vegetable or animal products which essentially consist of mixed glycerol esters of higher fatty acids, and waxes include natural waxes, such as candelilla wax, carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax and sugar cane wax , Ouricury wax, montan wax, beeswax, shellac wax, walrus, lanolin (wool wax), pretzel fat, ceresin, ozokerite (earth wax), petrolatum, paraffin waxes, micro waxes; chemically modified waxes (hard waxes), such as montan ester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as polyalkylene waxes and polyethylene glycol waxes. In addition to fats, fat-like sub- punch like lecithins and phospholipids. The person skilled in the art understands the term lecithins as those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Lecithins are therefore often used in the professional world as phosphatidylcholines (PC). Examples of natural lecithins are the cephalins, which are also referred to as phosphatidic acids and are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. In contrast, phospholipids are usually understood to be mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally classed as fats. In addition, sphingosines or sphingolipids are also suitable.
Perlglanzwachsepearlescent
Als Perlglanzwachse kommen beispielsweise in Frage: Alkylenglycolester, speziell Ethy- lenglycoldistearat; Fettsäurealkanolamide, speziell Kokosfettsäuredi ethanolamid; Partialglyceride, speziell Stearinsäuremonoglycerid; Ester von mehrwertigen, gegebenenfalls hydroxy- sübstituierte Carbonsäuren mit Fettalkoholen mit 6 bis 22 Kohlenstoffatomen, speziell lang- kettige Ester der Weinsäure; Fettstoffe, wie beispielsweise Fettalkohole, Fettketone, Fettaldehyde, Fettether und Fettcarbonate, die in Summe mindestens 24 Kohlenstoffatome aufweisen, speziell Lauron und Distearylether; Fettsäuren wie Stearinsäure, Hydroxystearinsäure oder Behensäure, Ringöffnungsprodukte von Olefinepoxiden mit 12 bis 22 Kohlenstoffatomen mit Fettalkoholen mit 12 bis 22 Kohlenstoffatomen und/oder Polyolen mit 2 bis 15 Kohlenstoffatomen und 2 bis 10 Hydroxylgruppen sowie deren Mischungen.Pearlescent waxes that can be used are, for example: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid di ethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.
Konsistenzgeber und VerdickungsmittelConsistency agents and thickeners
Als Konsistenzgeber kommen in erster Linie Fettalkohole oder Hydroxyfettalkohole mit 12 bis 22 und vorzugsweise 16 bis 18 Kohlenstoffatomen und daneben Partialglyceride, Fettsäu- ren oder Hydroxyfettsäuren in Betracht. Bevorzugt ist eine Kombination dieser Stoffe mit Alkyloligoglucosiden und/oder Fettsäure-N-methylglucamiden gleicher Kettenlänge und/oder Polyglycerinpoly-12-hydroxystearaten. Geeignete Verdickungsmittel sind beispielsweise Ae- rosil-Typen (hydrophile Kieselsäuren), Polysaccharide, insbesondere Xanthan-Gum, Guar- Guar, Agar-Agar, Alginate und Tylosen, Carboxymethylcellulose und Hydroxyethyl- und Hydroxypropylcellulose, ferner höhermolekulare Polyethylenglycolmono- und -diester von Fettsäuren, Polyacrylate, (z.B. Carbopole® und Pemulen-Typen von Goodrich; Synthalene® von Sigma; Keltrol-Typen von Kelco; Sepigel-Typen von Seppic; Salcare-Typen von Allied Colloids), Polyacrylamide, Polymere, Polyvinylalkohol und Polyvinylpyrrolidon. Als beson- ders wirkungsvoll haben sich auch Bentonite, wie z.B. Bentone® Gel VS-5PC (Rheox) erwiesen, bei dem es sich um eine Mischung aus Cyclopentasiloxan, Disteardimonium Hectorit und Propylencarbonat handelt. Weiter in Frage kommen Tenside, wie beispielsweise ethoxylierte Fettsäureglyceride, Ester von Fettsäuren mit Polyolen wie beispielsweise Pentaerythrit oder Trimethylolpropan, Fettalkoholethoxylate mit eingeengter Homologenverteilung oder Alkylo- ligoglucoside sowie Elektrolyte wie Kochsalz und Ammoniumchlorid. ÜberfetτungsmittelSuitable consistency agents are primarily fatty alcohols or hydroxy fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides, fatty acids or hydroxy fatty acids. A combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred. Suitable thickeners are, for example, aerosil types (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl and hydroxypropyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, Polyacrylates, (e.g. Carbopole® and Pemulen types from Goodrich; Synthalene® from Sigma; Keltrol types from Kelco; Sepigel types from Seppic; Salcare types from Allied Colloids), polyacrylamides, polymers, polyvinyl alcohol and polyvinyl pyrrolidone. As a special Bentonites such as Bentone® Gel VS-5PC (Rheox), which is a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate, have also proven to be effective. Surfactants such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as, for example, pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyloligoglucosides and electrolytes such as sodium chloride and ammonium chloride are also suitable. Überfetτungsmittel
Als Überfettungsmittel können Substanzen wie beispielsweise Lanolin und Lecithin sowie polyethoxylierte oder acylierte Lanolin- und Lecithinderivate, Polyolfettsäureester, Monogly- ceride und Fettsäurealkanolamide verwendet werden, wobei die letzteren gleichzeitig als Schaumstabilisatoren dienen.Substances such as, for example, lanolin and lecithin and polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers.
Stabilisatorenstabilizers
Als Stabilisatoren können Metallsalze von Fettsäuren, wie z.B. Magnesium-, Aluminium- und/oder Zinkstearat bzw. -ricinoleat eingesetzt werden.Metal salts of fatty acids, such as e.g. Magnesium, aluminum and / or zinc stearate or ricinoleate are used.
Polymerepolymers
Geeignete kationische Polymere sind beispielsweise kationische Cellulosederivate, wie z.B. eine quaternierte Hydroxyethylcellulose, die unter der Bezeichnung Polymer JR 400® von Amerchol erhältlich ist, kationische Stärke, Copolymere von Diallylammoniumsalzen und Acrylamiden, quaternierte Vinylpyrrolidon/Vinylimidazol-Polymere, wie z.B. Luviquat® (BASF), Kondensationsprodukte von Polyglycolen und Aminen, quaternierte Kollagenpoly- peptide, wie beispielsweise Lauryldimonium Hydroxypropyl Hydrolyzed Collagen (Lame- quat®L/Grünau), quaternierte Weizenpolypeptide, Polyethylenimin, kationische Sili- conpolymere, wie z.B. Amodimethicone, Copolymere der Adipinsäure und Dimethyla- minohydroxypropyldiethylentriamin (Cartaretine®/Sandoz), Copolymere der Acrylsäure mit Dimethyl-diallylammoniumchlorid (Merquat® 550/Chemviron), Polyaminopolyamide sowie deren vernetzte wasserlöslichen Polymere, kationische Chitinderivate wie beispielsweise quaterniertes Chitosan, gegebenenfalls mikrokristallin verteilt, Kondensationsprodukte aus Dihalogenalkylen, wie z.B. Dibrombutan mit Bisdialkylaminen, wie z.B. Bis-Dimethylamino- 1,3-propan, kationischer Guar-Gum, wie z.B. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 der Firma Celanese, quaternierte Ammoniumsalz-Polymere, wie z.B. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 der Firma Miranol. Als anionische, zwitterionische, amphotere und nichtionische Polymere kommen beispielsweise Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Ninylacrylat-Copolymere, Ni- nylacetat/Butylmaleat/ Isobornylacrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid- Copolymere und deren Ester, unvemetzte und mit Polyolen vernetzte Polyacrylsäuren, Acryl- amidopropyltrimethylarnmoniumchlorid/ Acrylat-Copolymere, Octylacrylamid/Methylmeth- acrylat/tert.Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere, Polyvi- nylpyrrolidon, Vinylpyrrolidon/Ninylacetat-Copolymere, Nmylpyrrolidon/ Dimethylamino- ethylmethacrylatNinylcaprolactam-Terpolymere sowie gegebenenfalls derivatisierte Cellulo- seether und Silicone in Frage.Suitable cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose, which is available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such as, for example, Luviquat® (BASF) , Condensation products of polyglycols and amines, quaternized collagen polypeptides, such as, for example, lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as amodimethicone, copolymers of adiphylohydroxy acid and dimethylaminodiaminethyl (dimethyl) Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides and their cross-linked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally microcrystalline distributed, condensation products from dihaloalkylene, such as dibromobutane with bisdialkylamines, such as bis-dimethylamino-1,3-propane, cationic guar gum, such as Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers, such as Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol. Anionic, zwitterionic, amphoteric and nonionic polymers include, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and polyesters and their esters, uncrosslinked polyols - amidopropyltrimethylarnmoniumchlorid / acrylate copolymers, octylacrylamide / acrylate Methylmeth- / tert.Butylaminoethylmethacrylat / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / Ninylacetat copolymers, Nmylpyrrolidon / dimethylamino-ethylmethacrylatNinylcaprolactam terpolymers and optionally derivatized cellulose and silicones seether ,
Siliconverbindungensilicone compounds
Geeignete Siliconverbindungen sind beispielsweise Dimethylpolysiloxane, Methylphenylpo- lysiloxane, cyclische Silicone sowie amino-, fettsäure-, alkohol-, polyether-, epoxy-, fluor-, glykosid- und/oder alkyfmodifizierte Siliconverbindungen, die bei Raumtemperatur sowohl flüssig als auch harzförmig vorliegen können. Weiterhin geeignet sind Simethicone, bei denen es sich um Mischungen aus Dimethiconen mit einer durchschnittlichen Kettenlänge von 200 bis 300 Dimethylsiloxan-Einheiten und hydrierten Silicaten handelt.Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyf-modified silicone compounds which can be both liquid and resinous at room temperature. Simethicones, which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates, are also suitable.
UN-LichtschutzfilterUN sunscreen
Unter UV-Lichtschutzfaktoren sind beispielsweise bei Raumtemperatur flüssig oder kristallin vorliegende organische Substanzen (Lichtschutzfilter) zu verstehen, die in der Lage sind, ultraviolette Strahlen zu absorbieren und die aufgenommene Energie in Form längerwelliger Strahlung, z.B. Wärme wieder abzugeben. UVB-Filter können öllöslich oder wasserlöslich sein. Als öllösliche Substanzen sind z.B. zu nennen:UV light protection factors are understood to mean, for example, organic substances (light protection filters) which are liquid or crystalline at room temperature and which are able to absorb ultraviolet rays and absorb the energy absorbed in the form of longer-wave radiation, e.g. To give off heat again. UVB filters can be oil-soluble or water-soluble. As oil-soluble substances e.g. to call:
3-Benzylidencampher bzw. 3-Benzylidennorcampher und dessen Derivate, z.B. 3-(4- Methylbenzyliden)campher beschrieben; 4-Aminobenzoesäurederivate, vorzugsweise 4-(Dimethylamino)benzoesäure-2-ethyl- hexylester, 4-(Dimethylamino)benzoesäure-2-octylester und 4-(Dimethylamino)benzoe- säureamylester;3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, e.g. 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate;
> Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure-2-ethylhexylester, 4-Methoxy- zimtsäurepropylester, 4-Methoxyzimtsäureisoamylester 2-Cyano-3 ,3 -phenylzimtsäure-2- ethylhexylester (Octocrylene); > Ester der Salicylsäure, vorzugsweise Salicylsäure-2-ethylhexylester, Salicylsäure-4-iso- propylbenzylester, S alicylsäurehomomenthylester;> Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester 2-cyano-3, 3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); > Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester;
> Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2- Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon; Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzmalonsäuredi-2-ethylhexyl- ester; Triazinderivate, wie z.B. 2,4,6-Trianilino-(p-carbo-2'-ethyl-l'-hexyloxy)-l,3,5-triazin und Octyl Triazon oder Dioctyl Butamido Triazone (Uvasorb® HEB); Propan-l,3-dione, wie z.B. l-(4-tert.Butylphenyl)-3-(4'methoxyphenyl)propan-l,3-dion; > Ketotricyclo(5.2.1.0)decan-Derivate.> Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably 4-methoxybenzmalonic acid di-2-ethylhexyl ester; Triazine derivatives, e.g. 2,4,6-trianilino- (p-carbo-2'-ethyl-l'-hexyloxy) -l, 3,5-triazine and octyl triazone or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-dione, e.g. l- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-l, 3-dione; > Ketotricyclo (5.2.1.0) decane derivatives.
Als wasserlösliche Substanzen kommen in Frage:Possible water-soluble substances are:
> 2-Phenylbenzimidazol-5-sulfonsäure und deren Alkali-, Erdalkali-, Ammonium-, Alky- lammoniu -, Alkanolammonium- und Glucammoniumsalze; Sulfonsäurederivate von Benzophenonen, vorzugsweise 2-Hydroxy-4-methoxybenzo- phenon-5-sulfonsäure und ihre Salze; Sulfonsäurederivate des 3-Benzylidencamphers, wie z.B. 4-(2-Oxo-3-bornylidenme- thyl)benzolsulfonsäure und 2-Methyl-5-(2-oxo-3-bornyliden)sulfonsäure und deren Salze.> 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-benzylidene camphor, e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.
Als typische UV-A-Filter kommen insbesondere Derivate des Benzoylmethans in Frage, wie beispielsweise l-(4'-tert.Butylphenyl)-3-(4'-methoxyphenyl)propan-l ,3-dion, 4-tert.-Butyl-4'- methoxydibenzoylmethan (Parsol® 1789), l-Phenyl-3-(4'-isopropylphenyl)-propan-l,3-dion sowie Enaminverbindungen. Die UV-A und UV-B-Filter können selbstverständlich auch in Mischungen eingesetzt werden. Besonders günstige Kombinationen bestehen aus den Derivate des Benzoylmethans,, z.B. 4-tert.-Butyl-4'-methoxydibenzoylmethan (Parsol® 1789) und 2- Cyano-3,3-phenylzimtsäure-2-ethyl-hexylester (Octocrylene) in Kombination mit Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure-2-ethylhexylester und/oder 4-Methoxyzimt- säurepropylester und/oder 4-Methoxyzimtsäureisoamylester. Vorteilhaft werden deartige Kombinationen mit wasserlöslichen Filtern wie z.B. 2-Phenylbenzimidazol-5-sulfonsäure und deren Alkali-, Erdalkali-, Ammonium-, Alkylammonium-, Alkanolammonium- und Glucammoniumsalze kombiniert.Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl, are particularly suitable as typical UV-A filters -4'- methoxydibenzoylmethane (Parsol® 1789), l-phenyl-3- (4'-isopropylphenyl) propane-l, 3-dione and enamine compounds. The UV-A and UV-B filters can of course also be used in mixtures. Particularly favorable combinations consist of the derivatives of benzoylmethane, e.g. 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol® 1789) and 2-cyano-3,3-phenylcinnamic acid-2-ethyl-hexyl ester (octocrylene) in combination with ester of cinnamic acid, preferably 4-methoxycinnamic acid-2-ethylhexyl ester and / or propyl 4-methoxycinnamate and / or isoamyl 4-methoxycinnamate. Such combinations with water-soluble filters such as e.g. 2-Phenylbenzimidazole-5-sulfonic acid and their alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts combined.
Neben den genannten löslichen Stoffen kommen für diesen Zweck auch unlösliche Licht- schutzpigmente, nämlich feindisperse Metalloxide bzw. Salze in Frage. Beispiele für geeignete Metalloxide sind insbesondere Zinkoxid und Titandioxid und daneben Oxide des Eisens, Zirkoniums, Siliciums, Mangans, Aluminiums und Cers sowie deren Gemische. Als Salze können Silicate (Talk), Bariumsulfat oder Zinkstearat eingesetzt werden. Die Oxide und Salze werden in Form der Pigmente für hautpflegende und hautschützende Emulsionen und dekorative Kosmetik verwendet. Die Partikel sollten dabei einen mittleren Durchmesser von weniger als 100 nm, vorzugsweise zwischen 5 und 50 nm und insbesondere zwischen 15 und 30 nm aufweisen. Sie können eine sphärische Form aufweisen, es können jedoch auch solche Partikel zum Einsatz kommen, die eine ellipsoide oder in sonstiger Weise von der sphärischen Gestalt abweichende Form besitzen. Die Pigmente können auch oberflächenbehandelt, d.h. hydrophi- lisiert oder hydrophobiert vorliegen. Typische Beispiele sind gecoatete Titandioxide, wie z.B. Titandioxid T 805 (Degussa) oder Eusolex® T2000 (Merck). Als hydrophobe Coatingmittel kommen dabei vor allem Silicone und dabei speziell Trialkoxyoctylsilane oder Simethicone in Frage. In Sonnenschutzmitteln werden bevorzugt sogenannte Mikro- oder Nanopigmente eingesetzt. Vorzugsweise wird mikronisiertes Zinkoxid verwendet.In addition to the soluble substances mentioned, insoluble light protection pigments, namely finely dispersed metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The oxides and salts are used in the form of pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or shape which differs from the spherical shape in some other way. The pigments can also be surface-treated, ie hydrophilized or hydrophobicized. Typical examples are coated titanium dioxides such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. So-called micro- or nanopigments are preferably used in sunscreens. Micronized zinc oxide is preferably used.
Biogene Wirkstoffe und AntioxidantienBiogenic agents and antioxidants
Unter biogenen Wirkstoffen sind beispielsweise Tocopherol, Tocopherolacetat, Tocopherol- palmitat, Ascorbinsäure, (Desoxy)Ribonucleinsäure und deren Fragmentierungsprodukte, ß- Glucane, Retinol, Bisabolol, Allantoin, Phytantriol, Panthenol, AHA-Säuren, Aminosäuren, Ceramide, Pseudoceramide, essentielle Öle, Pflanzenextrakte, wie z.B. Prunusextrakt, Bamba- ranussextrakt und Vitaminkomplexe zu verstehen.Examples of biogenic active ingredients are tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy) ribonucleic acid and its fragmentation products, β-glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudo-ceramides, essentielle ceramides, Plant extracts, such as To understand prunus extract, bambanus extract and vitamin complexes.
Antioxidantien unterbrechen die photochemische Reaktionskette, welche ausgelöst wird, wenn UV-Strahlung in die Haut eindringt. Typische Beispiele hierfür sind Aminosäuren (z.B. Glycin, Histidin, Tyrosin, Tryptophan) und deren Derivate, Imidazole (z.B. Urocaninsäure) und deren Derivate, Peptide wie D,L-Carnosin, D-Carnosin, L-Carnosin und deren Derivate (z.B. Anserin), Carotinoide, Carotine (z.B. α-Carotin, ß-Carotin, Lycopin) und deren Derivate, Chloro gensäure und deren Derivate, Liponsäure und deren Derivate (z.B. Dihydroliponsäu- re), Aurothioglucose, Propylthiouracil und andere Thiole (z.B. Thioredoxin, Glutathion, Cystein, Cystin, Cystamin und deren Glycosyl-, N-Acetyl-, Methyl-, Ethyl-, Propyl-, Amyl-, Butyl- und Lauryl-, Palmitoyl-, Oleyl-, γ-Linoleyl-, Cholesteryl- und Glycerylester) sowie deren Salze, Dilaurylthiodipropionat, Distearylthiodipropionat, Thiodipropionsäure und deren Derivate (Ester, Ether, Peptide, Lipide, Nukleotide, Nukleoside und Salze) sowie Sulfoximin- verbindungen (z.B. Buthioninsulfoximine, Homocysteinsulfoximin, Butioninsulfone, Penta-, Hexa-, Heptathioninsulfoximin) in sehr geringen verträglichen Dosierungen (z.B. pmol bis μmol/kg), ferner (Metall)-Chelatoren (z.B. α-Hydroxyfettsäuren, Palmitinsäure, Phytinsäure, Lactoferrin), α-Hydroxysäuren (z.B. Citronensäure, Milchsäure, Äpfelsäure), Huminsäure, Gallensäure, Gallenextrakte, Bilirubin, Biliverdin, EDTA, EGTA und deren Derivate, ungesättigte Fettsäuren und deren Derivate (z.B. γ-Linolensäure, Linolsäure, Ölsäure), Folsäure und deren Derivate, Ubichinon und Ubichinol und deren Derivate, Vitamin C und Derivate (z.B. Ascorbylpalmitat, Mg-Ascorbylphosphat, Ascorbylacetat), Tocopherole und Derivate (z.B. Vitamin-E-acetat), Vitamin A und Derivate (Vitamin-A-palmitat) sowie Koniferylben- zoat des Benzoeharzes, Rutinsäure und deren Derivate, α-Glycosylrutin, Ferulasäure, Furfu- rylidenglucitol, Carnosin, Butymydroxytoluol, Butylhydroxyamsol, Nordihydroguajak- harzsäure, Nordihydroguajaretsäure, Trihydroxybutyrophenon, Harnsäure und deren Derivate, Mannose und deren Derivate, Superoxid-Dismutase, Zink und dessen Derivate (z.B. ZnO, ZnSO4) Selen und dessen Derivate (z.B. Selen-Methionin), Stilbene und deren Derivate (z.B. Stilbenoxid, trans-Stilbenoxid) und die erfindungsgemäß geeigneten Derivate (Salze, Ester, Ether, Zucker, Nukleotide, Nukleoside, Peptide und Lipide) dieser genannten Wirkstoffe.Antioxidants interrupt the photochemical reaction chain, which is triggered when UV radiation penetrates the skin. Typical examples are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine) , Carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (eg dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine , Cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their Salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. buthioninsulfoximines, homocysteine sulfoximine, butioninsulfones, penta-, hexa-, himinathion), very low in compatible dosages (e.g. pmol to μmol / kg), (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, Biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and their derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) as well Koniferyl benzoate of benzoin, rutinic acid and its derivatives, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butymydroxytoluene, butylhydroxyamsol, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutylbenzate and its derivatives, superficial derivatives, and its derivatives, urea dehydrobenzate, derivatives and their derivatives, superficial dehydrobenzene and its derivatives and its derivatives (for example ZnO, ZnSO 4 ) selenium and its derivatives (for example selenium-methionine), stilbenes and their derivatives (for example stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides , Peptides and lipids) of these active ingredients.
Filmbildnerfilm formers
Gebräuchliche Filmbildner sind beispielsweise Chitosan, mikrokristallines Chitosan, quater- niertes Chitosan, Polyvinylpyrrolidon, Vinylpyrrolidon-Vinylacetat-Copolymerisate, Polymere der Acrylsäurereihe, quaternäre Cellulose-Derivate, Kollagen, Hyaluronsäure bzw. deren Salze und ähnliche Verbindungen.Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds.
OuellmittelOuellmittel
Als Quellmittel für wäßrige Phasen können Montmorillonite, Clay Mineralstoffe, Pemulen sowie alkylmodifizierte Carbopoltypen (Goodrich) dienen. Weitere geeignete Polymere bzw. Quellmittel können der Übersicht von R.Lochhead in Cosm.Toil. 108, 95 (1993) entnommen werden.Montmorillonites, clay minerals, pemulene and alkyl-modified carbopol types (Goodrich) can serve as swelling agents for aqueous phases. Further suitable polymers or swelling agents can be found in the overview by R. Lochhead in Cosm.Toil. 108, 95 (1993).
Hydrotropehydrotropes
Zur Verbesserung des Fließverhaltens können ferner Hydrotrope, wie beispielsweise Ethanol, Isopropylalkohol, oder Polyole eingesetzt werden. Polyole, die hier in Betracht kommen, besitzen vorzugsweise 2 bis 15 Kohlenstoffatome und mindestens zwei Hydroxylgruppen. Die Polyole können noch weitere fttnktionelle Gruppen, insbesondere Aminogruppen, enthalten bzw. mit Stickstoff modifiziert sein. Typische Beispiele sindHydrotropes such as ethanol, isopropyl alcohol or polyols can also be used to improve the flow behavior. Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols can also contain further functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are
Glycerin; > Alkylenglycole, wie beispielsweise Ethylenglycol, Diethylenglycol, Propylenglycol, Bu- tylenglycol, Hexylenglycol sowie Polyethylenglycole mit einem durchschnittlichen Molekulargewicht von 100 bis 1.000 Dalton; technische Oligoglyceringemische mit einem Eigenkondensationsgrad von 1,5 bis 10 wie etwa technische Diglyceringemische mit einem Diglyceringehalt von 40 bis 50 Gew.-%;glycerol; > Alkylene glycols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons; technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;
> Methyolverbindungen, wie insbesondere Trimethylolethan, Trimethylolpropan, Tri- methylolbutan, Pentaerythrit und Dipentaerythrit;> Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
> Niedrigalkylglucoside, insbesondere solche mit 1 bis 8 Kohlenstoffen im Alkylrest, wie beispielsweise Methyl- und Butylglucosid; > Zuckeralkohole mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Sorbit oder Mannit,> Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical, such as methyl and butyl glucoside; > Sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or mannitol,
> Zucker mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Glucose oder Saccharose; Aminozucker, wie beispielsweise Glucamin;> Sugar with 5 to 12 carbon atoms, such as glucose or sucrose; Aminosugars such as glucamine;
> Dialkoholamine, wie Diethanolamin oder 2-Amino- 1 ,3-propandiol.> Dialcohol amines, such as diethanolamine or 2-amino-1, 3-propanediol.
Konservierungsmittelpreservative
Als Konservierungsmittel eignen sich beispielsweise Phenoxyethanol, Formaldehydlösung, Parabene, Pentandiol oder Sorbinsäure sowie die unter der Bezeichnung Surfacine® bekann- ten Silberkomplexe und die in Anlage 6, Teil A und B der Kosmetikverordnung aufgeführten weiteren Stoffklassen.Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid as well as the silver complexes known under the name Surfacine® and the other substance classes listed in Appendix 6, Parts A and B of the Cosmetics Ordinance.
Parfümöle und AromenPerfume oils and flavors
Als Parfümöle seien genannt Gemische aus natürlichen und synthetischen Riechstoffen. Natürliche Riechstoffe sind Extrakte von Blüten (Lilie, Lavendel, Rosen, Jasmin, Neroli, Ylang- Ylang), Stengeln und Blättern (Geranium, Patchouli, Petitgrain), Früchten (Anis, Koriander, Kümmel, Wacholder), Fruchtschalen (Bergamotte, Zitrone, Orangen), Wurzeln (Macis, An- gelica, Sellerie, Kardamon, Costus, Iris, Calmus), Hölzern (Pinien-, Sandel-, Guajak-, Zedern- , Rosenholz), Kräutern und Gräsern (Estragon, Lemongras, Salbei, Thymian), Nadeln und Zweigen (Fichte, Tanne, Kiefer, Latschen), Harzen und Balsamen (Galbanum, Elemi, Benzoe, Myrrhe, Olibanum, Opoponax). Weiterhin kommen tierische Rohstoffe in Frage, wie beispielsweise Zibet und Castoreum. Typische synthetische Riechstoffverbindungen sind Pro- dukte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe. Riechstoffverbindungen vom Typ der Ester sind z.B. Benzylacetat, Phenoxyethylisobutyrat, p-tert.- Butylcyclohexylacetat, Linalylacetat, Dimethylbenzylcarbinylacetat, Phenylethylacetat, Lina- lylbenzoat, Benzylformiat, Ethylmethylphenylglycinat, Allylcyclohexylpropionat, Styral- lylpropionat imd Benzylsalicylat. Zu den Ethem zählen beispielsweise Benzylethylether, zu den Aldehyden z.B. die linearen Alkanale mit 8 bis 18 Kohlenstoffatomen, Citral, Citronellal, Citronellyloxyacetaldehyd, Cyclamenaldehyd, Hydroxycitronellal, Lilial und Bourgeonal, zu den Ketonen z.B. die Jonone, α-Isomethylionon und Methylcedrylketon, zu den Alkoholen Anethol, Citronellol, Eugenol, Isoeugenol, Geraniol, Linalool, Phenylethylalkohol und Terpi- neol, zu den Kohlenwasserstoffen gehören hauptsächlich die Terpene und Balsame. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Auch ätherische Öle geringerer Flüchtigkeit, die meist als Aromakomponenten verwendet werden, eignen sich als Parfumöle, z.B. Salbeiöl, Kamillenöl, Nelkenöl, Melissenöl, Minzenöl, Zimtblätteröl, Lindenblütenöl, Wacholderbeerenöl, Vetive- röl, Olibanöl, Galbanumöl, Labolanumöl und Lavandinöl. Vorzugsweise werden Bergamotte- öl, Dihydromyrcenol, Lilial, Lyral, Citronellol, Phenylethylalkohol, α-Hexylzimtaldehyd, Geraniol, Benzylaceton, Cyclamenaldehyd, Linalool, Boisambrene Forte, Ambroxan, Indol, He- dione, Sandelice, Citronenöl, Mandarinenöl, Orangenöl, Allylamylglycolat, Cyclovertal, La- vandinöl, Muskateller Salbeiöl, ß-Damascone, Geraniumöl Bourbon, Cyclohexylsalicylat, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evemyl, Iraldein gamma, Phenylessigsäure, Gera- nylacetat, Benzylacetat, Rosenoxid, Romilllat, Irotyl und Floramat allein oder in Mischungen, eingesetzt. Als Aromen kommen beispielsweise Pfefferminzöl, Krauseminzöl, Anisöl, Stern- anisöl, Kümmelöl, Eukalyptusöl, Fenchelöl, Citronenöl, Wintergrünöl, Nelkenöl, Menthol und dergleichen in Frage.Perfume oils include 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 (anise, coriander, cumin, juniper), fruit peel (bergamot, lemon, Oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme) ), Needles and twigs (spruce, fir, pine, mountain pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, such as civet and castoreum, are also suitable. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, lylpropionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, α-isomethylionone and methylcedryl ketone, and the alcohols Anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpinol, the hydrocarbons mainly include terpenes and balms. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Essential oils of lower volatility, which are mostly used as aroma components, are also suitable as perfume oils, for example sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavolanum oil. Bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, mandarin oil, allyl glycolate, allyl glycolate, allyl glycolate, orangelyl oil, orol , Lavandin oil, Muscatel sage oil, ß-Damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evemyl, Iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllate, irotyl and floram or in mixtures. Suitable flavors are, for example, peppermint oil, spearmint oil, anise oil, star anise oil, caraway oil, eucalyptus oil, fennel oil, lemon oil, winter green oil, clove oil, menthol and the like.
Farbstoffedyes
Als Farbstoffe können die für kosmetische Zwecke geeigneten und zugelassenen Substanzen verwendet werden, wie sie beispielsweise in der Publikation "Kosmetische Färbemittel" der Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, S.81-106 zusammengestellt sind. Beispiele sind Kochenillerot A (C.I. 16255), Patentblau V (C.I.42051), lndigotin (C.I.73015), Chlorophyllin (C.I.75810), Chinolingelb (C.I.47005), Titandioxid (C.I.77891), Indanthrenblau RS (C.I. 69800) und Krapplack (C.I.58000). Als Lumineszenzfarbstoff kann auch Luminol enthalten sein. Diese Farbstoffe werden üblicherweise in Konzentrationen von 0,001 bis 0,1 Gew.-%, bezogen auf die gesamte Mischung, eingesetzt.The dyes which can be used are those substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes" by the Dye Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106. Examples are culinary red A (CI 16255), patent blue V (CI42051), indigotine (CI73015), chlorophyllin (CI75810), quinoline yellow (CI47005), titanium dioxide (CI77891), indanthrene blue RS (CI 69800) and madder varnish (CI 58000). Luminol may also be present as the luminescent dye. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.
Der Gesamtanteil der Hilfs- und Zusatzstoffe kann 1 bis 50, vorzugsweise 5 bis 40 Gew.-% - bezogen auf die Mittel - betragen. Die Herstellung der Mittel kann durch übliche Kalt - oder Heißprozesse erfolgen; vorzugsweise arbeitet man nach der Phaseninversionstemperatur- Methode. BeispieleThe total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40,% by weight, based on the composition. The agents can be produced by customary cold or hot processes; the phase inversion temperature method is preferably used. Examples
In der folgenden Tabelle sind eine Reihe von Formulierungsbeispiele für Antischuppensham- poos wiedergegeben. Die Mengenangaben verstehen sich als Gew.-%.The following table shows a number of formulation examples for antidandruff shampoos. The quantities are understood as% by weight.
Tabelle 1 AntischuppenshampoosTable 1 Antidandruff shampoos
Figure imgf000021_0001
Figure imgf000021_0001

Claims

Patentansprüche claims
1. Antischuppenshampoos, enthaltend eine wirksame Menge von Extrakten der Camellia sinensis.1. Antidandruff shampoos containing an effective amount of Camellia sinensis extracts.
2. Antischuppenshampoos, enthaltend eine wirksame Menge von Polyphenolen, insbesondere Catechinen und/oder Flavonoiden.2. Antidandruff shampoos containing an effective amount of polyphenols, especially catechins and / or flavonoids.
3. Mittel nach den Ansprüchen 1 und/oder 2, dadurch gekennzeichnet, dass sie Wirkstoffe enthalten, die ausgewählt sind aus der Gruppe, die gebildet wird von Epicatechin, E- pigallocatechin, Epigallocatechingallat, Epigallocatechingallat, Theaflavin, Theaflavinmonogallat A oder B und Theaflavindigallat.3. Composition according to claims 1 and / or 2, characterized in that they contain active ingredients which are selected from the group formed by epicatechin, e-pigallocatechin, epigallocatechin gallate, epigallocatechin gallate, theaflavin, theaflavin monogallate A or B and theaflavine digallate.
4. Mittel nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass sie Extrakte der Camellia sinensis oder deren Wirkstoffe in Mengen von 0,01 bis 15 Gew.-% - bezogen auf die Mittel - enthalten.4. Agent according to at least one of claims 1 to 3, characterized in that it contains extracts of Camellia sinensis or their active ingredients in amounts of 0.01 to 15 wt .-% - based on the agent.
5. Mittel nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass sie weiterhin zusätzliche Antischuppenwirkstoffe enthalten, die ausgewählt sind aus der5. Composition according to at least one of claims 1 to 4, characterized in that they further contain additional anti-dandruff active substances which are selected from the
Gruppe, die gebildet wird von Pirocton Olamin, Climbazole, Ketoconazol, Elubiol, Se- lendisulfid, Schwefel kolloidal, Schwefelpolyethylenglykolsorbitanmonooleat, Schwefel- rizinolpolyehtoxylat, Schwefelteer-Destillaten, Salicylsäure, Undexylensäure- monoethanolamid Sulfosuccinat Na-Salz, Protein-Undecylensäurekondensat, Zinkpy- rithion, Aluminiumpyrithion und Magnesiumpyrithion / Dipyrithion-Magnesiumsulfat.Group formed by piroctone olamine, climbazole, ketoconazole, elubiol, selenium disulphide, sulfur colloidal, sulfur polyethylene glycol sorbitan monooleate, sulfuric ricinole polyoxide, sulfuric tar distillates, salicylic acid, undexylenic acid, monoethynateylsulfonate, monoethynateyl sulfate, Aluminum pyrithione and magnesium pyrithione / dipyrithione magnesium sulfate.
6. Mittel nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass sie weiterhin milde anionische, nichtionische, amphotere und/oder zwitterionische und/oder kationische Tenside enthalten.6. Composition according to at least one of claims 1 to 5, characterized in that they further contain mild anionic, nonionic, amphoteric and / or zwitterionic and / or cationic surfactants.
7. Mittel nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass sie7. Composition according to at least one of claims 1 to 6, characterized in that it
(a) 10 bis 50 Gew.-% Tenside und (b) 0,1 bis 5 Gew.-% Extrakte der Camellia sinensis oder deren Wirkstoffe(a) 10 to 50% by weight of surfactants and (b) 0.1 to 5% by weight of extracts of Camellia sinensis or its active ingredients
mit der Maßgabe enthalten, dass sich die Mengenangaben mit Wasser und gegebenenfalls weiteren Hilfs- und Zusatzstoffen zu 100 Gew.-% ergänzen. with the proviso that the amounts given with water and possibly other auxiliary substances and additives are 100% by weight.
8. Mittel nach Anspruch nach mindestens einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie8. Composition according to claim according to at least one of claims 1 to 7, characterized in that it
(al) 20 bis 30 Gew.-% anionische Tenside,(al) 20 to 30% by weight of anionic surfactants,
(a2) 5 bis 10 Gew.-% nichtionische Tenside,(a2) 5 to 10% by weight of nonionic surfactants,
(a3) 1 bis 5 Gew.-% amphotere und/oder zwitterionische Tenside,(a3) 1 to 5% by weight of amphoteric and / or zwitterionic surfactants,
(b) 0,1 bis 5 Gew.-% Extrakte der Camellia sinensis oder deren Wirkstoffe und(b) 0.1 to 5% by weight of extracts of Camellia sinensis or its active ingredients and
(c) 0 bis 5 Gew.-% weitere Antischuppenwirkstoffe(c) 0 to 5% by weight of other antidandruff agents
mit der Maßgabe enthalten, dass sich die Mengenangaben mit Wasser und gegebenenfalls weiteren Hilfs- und Zusatzstoffen zu 100 Gew.-% ergänzen.with the proviso that the amounts given with water and possibly other auxiliary substances and additives are 100% by weight.
9. Verwendung von wirksamen Mengen an Extrakten der Camellia sinensis als Antischup- penmittel.9. Use of effective amounts of Camellia sinensis extracts as an anti-dandruff agent.
10. Verwendung von wirksamen Mengen von Polyphenolen, insbesondere Catechinen und/oder Flavonoiden als Antischuppenmittel.10. Use of effective amounts of polyphenols, especially catechins and / or flavonoids as anti-dandruff agents.
11. Verwendung nach den Ansprüchen 9 und/oder 10, dadurch gekennzeichnet, dass man die Extrakte bzw. Wirkstoffe in Mengen von 0,01 bis 15 Gew.-% - bezogen auf die Endprodukte einsetzt. 11. Use according to claims 9 and / or 10, characterized in that the extracts or active ingredients are used in amounts of 0.01 to 15% by weight, based on the end products.
PCT/EP2003/004776 2002-05-16 2003-05-07 Anti-dandruff shampoos WO2003096998A1 (en)

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WO2011048011A3 (en) * 2009-10-23 2011-06-16 Basf Se Benzotropolone derivatives as antimicrobial agents
US8574561B1 (en) 2012-12-21 2013-11-05 L'oreal Compositions containing anti-dandruff agents
CN104721065A (en) * 2013-12-18 2015-06-24 武汉海鹏医药科技有限公司 Neticonazole shampoo and formula and production method thereof
WO2018069045A1 (en) * 2016-10-13 2018-04-19 Unilever Plc Anti-dandruff composition
CN109568181A (en) * 2018-12-14 2019-04-05 江西绿海油脂有限公司 A kind of tea oil hand lotion
CN113081927A (en) * 2021-04-27 2021-07-09 福建俪萃缘生物科技有限公司 Tea polyphenol shampoo and preparation method thereof
US11197809B2 (en) 2016-03-24 2021-12-14 The Procter And Gamble Company Hair care compositions comprising malodor reduction compositions
US11679065B2 (en) 2020-02-27 2023-06-20 The Procter & Gamble Company Compositions with sulfur having enhanced efficacy and aesthetics
US11771635B2 (en) 2021-05-14 2023-10-03 The Procter & Gamble Company Shampoo composition
US11819474B2 (en) 2020-12-04 2023-11-21 The Procter & Gamble Company Hair care compositions comprising malodor reduction materials
US11904036B2 (en) 2017-10-10 2024-02-20 The Procter & Gamble Company Sulfate free clear personal cleansing composition comprising low inorganic salt

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FR2956807B1 (en) * 2010-03-01 2012-05-25 Oreal COSMETIC COMPOSITION BASED ON ELLAGIC ACID OR ONE OF ITS DERIVATIVES AND A PARTICULAR MIXTURE OF ANIONIC SURFACTANTS.
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011048011A3 (en) * 2009-10-23 2011-06-16 Basf Se Benzotropolone derivatives as antimicrobial agents
US8574561B1 (en) 2012-12-21 2013-11-05 L'oreal Compositions containing anti-dandruff agents
EP4241758A2 (en) 2012-12-21 2023-09-13 L'oreal Anti-dandruff composition
CN104721065A (en) * 2013-12-18 2015-06-24 武汉海鹏医药科技有限公司 Neticonazole shampoo and formula and production method thereof
US11197809B2 (en) 2016-03-24 2021-12-14 The Procter And Gamble Company Hair care compositions comprising malodor reduction compositions
US11197810B2 (en) 2016-03-24 2021-12-14 The Procter And Gamble Company Hair care compositions comprising malodor reduction compositions
WO2018069045A1 (en) * 2016-10-13 2018-04-19 Unilever Plc Anti-dandruff composition
EA038875B1 (en) * 2016-10-13 2021-11-01 ЮНИЛЕВЕР АйПи ХОЛДИНГС Б.В. Anti-dandruff composition
US11904036B2 (en) 2017-10-10 2024-02-20 The Procter & Gamble Company Sulfate free clear personal cleansing composition comprising low inorganic salt
CN109568181B (en) * 2018-12-14 2021-09-21 江西绿海油脂有限公司 Tea oil hand cream
CN109568181A (en) * 2018-12-14 2019-04-05 江西绿海油脂有限公司 A kind of tea oil hand lotion
US11679065B2 (en) 2020-02-27 2023-06-20 The Procter & Gamble Company Compositions with sulfur having enhanced efficacy and aesthetics
US11819474B2 (en) 2020-12-04 2023-11-21 The Procter & Gamble Company Hair care compositions comprising malodor reduction materials
CN113081927A (en) * 2021-04-27 2021-07-09 福建俪萃缘生物科技有限公司 Tea polyphenol shampoo and preparation method thereof
US11771635B2 (en) 2021-05-14 2023-10-03 The Procter & Gamble Company Shampoo composition

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