EP1083217A2 - Verdickungsmittel - Google Patents
Verdickungsmittel Download PDFInfo
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- EP1083217A2 EP1083217A2 EP00119067A EP00119067A EP1083217A2 EP 1083217 A2 EP1083217 A2 EP 1083217A2 EP 00119067 A EP00119067 A EP 00119067A EP 00119067 A EP00119067 A EP 00119067A EP 1083217 A2 EP1083217 A2 EP 1083217A2
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- European Patent Office
- Prior art keywords
- acid
- carbon atoms
- esters
- oil
- acids
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/667—Neutral esters, e.g. sorbitan esters
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
Definitions
- the invention relates to the use of polyol carboxylic acid esters as thickeners in surface-active Preparations.
- Surface-active preparations in particular those used in the field of detergents and cleaning agents and in personal care, usually contain anionic surfactants, such as, for example, alkyl ether sulfates.
- anionic surfactants such as, for example, alkyl ether sulfates.
- thickening agents are usually added to these surfactant solutions [ Seifen- ⁇ le-Fette-Wwachs, 116 , 60 (1990) ].
- a large number of inorganic and organic compounds which are used to increase the viscosity of surface-active preparations, such as, for example, solutions containing anionic surfactants, are already known to the person skilled in the art.
- Water-soluble electrolyte salts are generally used as inorganic thickeners [ soap-oil-fat waxes, 113 , 135 (1987) ].
- organic thickeners are fatty acid alkanolamides, polyethylene glycol difatty acid esters and a number of water-soluble polymers.
- organic thickeners In most cases it is at most possible to use large amounts to adjust the desired viscosity of the surfactant solution simply by using inorganic electrolyte salts. It is therefore generally the way to use organic thickeners in addition to the inorganic salts, but some of them have a number of disadvantages. For example, those with polyethylene glycol fatty acid diesters [ DE 3541813 A1, DE 3551535 A1.
- thickened surfactant solutions often have inadequate viscosity stability during storage, while water-soluble polymers have an undesirable slimy flow behavior with a tendency to string in the thickened surfactant solutions.
- German patent applications DE 3730179 A1, EP 0343463 A2 and DE 3817415 A1 it is therefore proposed to use adducts of ethylene oxide and / or propylene oxide with fatty alcohols to thicken surfactant solutions.
- Glycerol trifatty acid esters [ Cosm. Toil., 103 , 99 (1988) ] and fatty acid alkanolamides are known as organic thickeners.
- the object of the present invention was to provide further organic thickeners with increased to provide thickening effect, which is already at lower concentrations in surface-active Preparations show effectiveness and deliver stable viscosities. Beyond that in addition to a refatting effect, they are free of ethylene oxide.
- the invention relates to the use of polyol carboxylic acid esters, which one by reaction of (I) polyols with 2 to 15 carbon atoms and 2 to 6 OH groups with (II) linear and / or branched, saturated and / or unsaturated fatty acids with 6 to 22 carbon atoms and (III) polyfunctional carboxylic acids with 2 to 8 carbon atoms and hydroxycarboxylic acids with 2 to 4 Receives carbon atoms as a thickener in surface-active preparations.
- the long-chain polyolcarboxylic esters mentioned thickened Possess properties. Their use as thickeners in surface-active preparations leads to stable mixtures with constant viscosities even at low concentrations when storing. It also has a synergistic effect in combination with low ethoxylated Fatty alcohols as well as found with other thickeners. Another advantage is that the Polyolcarboxylic acid esters according to the invention are free of ethylene oxide and are also lipid-replenishing Have properties.
- Polyol carboxylic acid esters which are obtained by reacting (I) polyols having 2 to 15 carbon atoms and 2 to 6 OH groups with (II) linear and / or branched, saturated and / or unsaturated fatty acids with 6 to 22 carbon atoms and (III) polyfunctional carboxylic acids with 2 up to 8 carbon atoms and hydroxycarboxylic acids with 2 to 4 carbon atoms are available.
- Typical examples of fatty acids which are considered as component (II) in the context of the invention are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, Linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid as well as their technical mixtures, which occur, for example, in the pressure splitting of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or the dimerization of unsaturated fatty acids.
- fatty acids with 12 to 18 carbon atoms such as coconut, palm, palm kernel or tallow fatty acid
- Corresponding C 2-8 dicarboxylic acids can also be used as polyfunctional carboxylic acids (III), so that succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid and dodecanedioic acid are also suitable.
- the preferred hydroxycarboxylic acids which can be used as component (III) in the context of the invention are citric acid, malic acid, tartaric acid, glycolic acid and / or lactic acid.
- the polyol carboxylic acid esters are obtained by first reacting the corresponding polyols in a manner known per se in the presence of acidic catalysts with the fatty acids to give corresponding partial esters and then in a further step using the polyfunctional carboxylic acids or hydroxy carboxylic acids to give the desired polyol carboxylic acid and / or polyol hydroxy carboxylic acid esters implements.
- the polyol carboxylic acid esters can preferably be used in combination with fatty alcohol ethoxylates of the formula (I) , in which R 1 is a linear or branched, saturated or unsaturated hydrocarbon radical having 10 to 18, preferably 12 to 14 carbon atoms and m is an average of 2 to 6; preferably 2 to 3 is used.
- R 1 is a linear or branched, saturated or unsaturated hydrocarbon radical having 10 to 18, preferably 12 to 14 carbon atoms and m is an average of 2 to 6; preferably 2 to 3 is used.
- Typical examples are add-on products from 2 to 6 ethylene oxide units to capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, elaelyl alcohol, elaelyl alcohol, elaalyl alcohol, elaol alcohol, alcohol , Behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, which are obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols.
- Technical fatty alcohols with 12 to 18 carbon atoms such as coconut, palm, palm kernel or tallow fatty
- the polyol carboxylic acid esters can preferably be used in combination with other suitable thickeners can be used in surface-active preparations.
- a thickener for example Aerosil types (hydrophilic silicas), polysaccharides, especially xanthan gum, Guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, further High molecular weight polyethylene glycol monoesters and diesters of fatty acids, polyacrylates, (e.g.
- Surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane or alkyl oligoglucosides
- electrolytes such as Cooking salt and ammonium chloride in question.
- the amount of thickener used - based on the sum of the thickeners in the surface-active Preparations - can be 0.1 to 6, usually 0.5 to 4 and preferably 2 to 3% by weight be.
- the polyol carboxylic acid esters according to the invention can be used to prepare surface-active preparations, such as detergents, dishwashing detergents and fabric softeners and cosmetic and / or pharmaceutical preparations for the care and cleaning of skin, hair, mouth and teeth, such as for example hair lotions, bubble baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat masses, stick preparations or ointments, preferably Hair shampoos, serve.
- surface-active preparations such as detergents, dishwashing detergents and fabric softeners and cosmetic and / or pharmaceutical preparations for the care and cleaning of skin, hair, mouth and teeth, such as for example hair lotions, bubble baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat masses, stick preparations or ointments, preferably Hair shampoos, serve.
- oils can also be used as further auxiliaries and additives, Oil bodies, superfatting agents, pearlescent waxes, consistency enhancers, polymers, silicone compounds, Fats, waxes, stabilizers, biogenic agents, deodorants, antiperspirants, antidandruff agents, Film formers, swelling agents, UV light protection factors, antioxidants, hydrotropes, preservatives, Insect repellents, self-tanners, solubilizers, perfume oils, dyes and the like.
- the surface-active preparations which generally have a non-aqueous content in the range from 1 to 99 and preferably 20 to 50% by weight, can contain nonionic, anionic, cationic and / or amphoteric surfactants.
- anionic surfactants are soaps, alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxymischog sulfate sulfate, hydroxymischogether sulfate sulfate, hydroxymischogether sulfate sulfates, , Mono
- 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 or especially glucoramic acid protein derivatives, and glucoronic acid protein derivatives Wheat base), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides.
- nonionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution.
- cationic surfactants are quaternary ammonium compounds, such as, for example, dimethyldistearylammonium chloride, and esterquats, 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.
- Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C 6 -C 22 fatty acids with linear C 6 -C 22 fatty alcohols, esters of branched C 6 -C 13 carboxylic acids are, for example, oil bodies with linear C 6 -C 22 -fatty alcohols, such as myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, myristyl, Myristylbehenat, Myristylerucat, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, stearyl oleate, stearyl behenate, Steary
- esters of linear C 6 -C 22 fatty acids with branched alcohols in particular 2-ethylhexanol
- esters of hydroxycarboxylic acids with linear or branched C 6 -C 22 fatty alcohols in particular dioctyl malates
- esters of linear and / or branched fatty acids are also suitable polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C 6 -C 10 fatty acids, liquid mono- / di- / triglyceride mixtures based on C 6 -C 18 fatty acids, esters of C 6 -C 22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C 2 -C 12 dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10 carbon atom
- Finsolv® TN linear or branched, symmetrical or unsymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic Hydrocarbons, such as, for example, squalane, squalene or dialkylcyclohexanes.
- 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.
- Pearlescent waxes that can be used are, for example: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids with fatty alcohols with 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
- Suitable consistency agents are primarily fatty alcohols or hydroxy fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and, in addition, 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 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, for example, amidomethicones, copolymers of adipic acid and dimethylaminetetrohydaminopoly (eg) aminomethyl trinoxydiamine (d
- Anionic, zwitterionic, amphoteric and nonionic polymers include, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornylacrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, uncrosslinked acrylamide acrylamide and non-crosslinked acrylamide acrylamide and polyethylenethacrylate acrylate and non-crosslinked acrylamide and polyamides with non-crosslinked acrylamide acrylamide and polyamides, non-crosslinked acrylamide acrylamide and with polyesters, uncrosslinked acrylamide acrylamide and non-crosslinked acrylamide and polyamides Copolymers, octylacrylamide / methyl methacrylate / tert.
- Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-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.
- a detailed overview of suitable volatile silicones can also be found by Todd et al. in Cosm.Toil. 91 , 27 (1976).
- fats are glycerides
- waxes include natural waxes, such as candelilla wax, carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, walnut, lanolin (wool wax), broom fat , 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, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beesw
- Metal salts of fatty acids such as magnesium, aluminum and / or zinc stearate or ricinoleate can be used as stabilizers .
- Cosmetic deodorants counteract, mask or eliminate body odors.
- Body odors arise from the action of skin bacteria on apocrine sweat, whereby unpleasant smelling breakdown products are formed. Accordingly, deodorants contain active ingredients which act as germ-inhibiting agents, enzyme inhibitors, odor absorbers or odor maskers.
- germ-inhibiting agents such as.
- Esterase inhibitors are suitable as enzyme inhibitors .
- These are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and in particular triethyl citrate (Hydagen® CAT, Henkel KGaA, Düsseldorf / FRG).
- the substances inhibit enzyme activity and thereby reduce odor.
- esterase inhibitors include sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesteric, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, such as, for example, glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, Monoethyl adipate, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or tartaric acid diethyl ester, and zinc glycinate.
- sterol sulfates or phosphates such as, for example, lanosterol, cholesterol, campesteric, stigmasterol and sitosterol sulfate or phosphate
- dicarboxylic acids and their esters such as, for example, glutaric acid
- Suitable odor absorbers are substances that absorb odor-forming compounds and can retain them to a large extent. They lower the partial pressure of the individual components and thus also reduce their speed of propagation. It is important that perfumes remain unaffected. Odor absorbers are not effective against bacteria. They contain, for example, a complex zinc salt of ricinoleic acid or special, largely odorless fragrances, which are known to the person skilled in the art as "fixators", such as, for example, the main component. B. extracts of Labdanum or Styrax or certain abietic acid derivatives. Fragrance agents or perfume oils act as odor maskers, which, in addition to their function as odor maskers, give the deodorants their respective fragrance.
- Perfume oils are, for example, mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peels, roots, woods, herbs and grasses, needles and branches as well as resins and balms. 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, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
- the ethers include, for example, benzyl ethyl ether
- the aldehydes include, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
- the ketones include, for example, the jonones and methylcedryl ketone
- the alcohols are anethole, citronellellone Eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol
- the hydrocarbons mainly include the terpenes and balsams.
- bergamot oil dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, ⁇ -hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, Cyclovertal, lavandin oil, muscatel Sage oil, ⁇ -damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evernyl, Iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilate, iroty
- water-soluble additives are e.g. Preservatives, water-soluble fragrances, pH value adjusting agents, e.g. Buffer mixtures, water soluble thickeners, e.g. water soluble natural or synthetic polymers such as Xanthan gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high molecular weight polyethylene oxides.
- 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.
- UV-A filters -4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds as described in DE 19712033 A1 (BASF).
- the UV-A and UV-B filters can of course also be used in mixtures.
- insoluble light protection pigments namely finely dispersed metal oxides or salts, are also suitable for this purpose.
- 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 the 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 a 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. Further suitable UV light protection filters can be found in the overview by P.Finkel in S ⁇ FW-Journal 122, 543 (1996) .
- secondary light stabilizers of the antioxidant type can also be used, which 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. ansetin).
- Carotenoids e.g.
- ⁇ -carotene, ⁇ -carotene, lycopene and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiotes (e.g.
- 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 , Distearylthiodipropionate, 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-, heptathioninsulfoximine
- noticeable 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
- stilbenes and their derivatives e.g. stilbene oxide, trans-stilbene oxide
- derivatives suitable according to the invention salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids
- Hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used to improve the flow behavior.
- Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the other classes of substances listed in Appendix 6, Parts A and B of the Cosmetics Regulation.
- N, N-diethyl-m-toluamide, 1,2-pentanediol or ethyl butylacetylaminopropionate are suitable as insect repellents
- dihydroxyacetone is suitable as a self-tanning agent .
- 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 balms (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, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexylpropylatepylatepylatepylatepionate, stally.
- the ethers include, for example, benzyl ethyl ether
- the aldehydes include, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
- the ketones include, for example, the jonones, ⁇ -isomethylionone and methylcedrenyl ketone Anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol
- the hydrocarbons mainly include the terpenes and balsams.
- fragrance oils which are mostly used as aroma components, are also suitable as perfume oils, e.g. 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 lavandin oil.
- bergamot oil dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, ⁇ -hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, Cyclovertal, lavandin oil, muscatel Sage oil, ⁇ -damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evernyl, Iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilliate, irot
- 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 . 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 on the middle - amount.
- the agents can be produced by customary cold or hot processes; the phase inversion temperature method is preferably used.
- Tables 1 and 2 provide an overview of the possible surface-active preparations in which polyol carboxylic acid esters can be used.
- the glycerol monostearate malate used in the following detergent (Tab. 1: Ex. 1-15) or cosmetic preparations (Tab. 2: Ex. 1-28) can be obtained by reacting glycerol with stearic acid and maleic acid.
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Abstract
Description
Dem Fachmann sind bereits eine Vielzahl von anorganischen und organischen Verbindungen bekannt, die zur Erhöhung der Viskosität oberflächenaktiver Zubereitungen, wie beispielsweise aniontensidhaltiger Lösungen, eingesetzt werden. Als anorganische Verdickungsmittel [Seifen-Öle-Fette-Wachse, 113, 135 (1987)] werden in der Regel wasserlösliche Elektrolytsalze, üblicherweise Kochsalz, eingesetzt. Beispiele für organische Verdickungsmittel sind Fettsäurealkanolamide, Polyethylenglykoldifettsäureester sowie eine Reihe wasserlöslicher Polymere. In den meisten Fällen ist es höchstens unter Einsatz großer Mengen möglich, alleine durch Verwendung anorganischer Elektrolytsalze die gewünschte Viskosität der Tensidlösung einzustellen. Man geht daher in der Regel den Weg, zusätzlich zu den anorganischen Salzen organische Verdickungsmittel einzusetzen, die aber teilweise mit einer Reihe von Nachteilen behaftet sind. So weisen die mit Polyethylenglykolfettsäurediestern [DE 3541813 A1, DE 3551535 A1. DE 3600263 A1] verdickte Tensidlösungen oft eine unzureichende Viskositätsstabilität bei Lagerung auf, während wasserlösliche Polymere ein unerwünschtes schleimiges Fließverhalten mit Neigung zum Fädenziehen in den verdickten Tensidlösungen zeigen. In den deutschen Patentanmeldungen DE 3730179 A1, EP 0343463 A2 und DE 3817415 A1 wird daher vorgeschlagen, zur Verdickung von Tensidlösungen Anlagerungsprodukte von Ethylenoxid und/oder Propylenoxid an Fettalkohole zu verwenden. Weiterhin sind Glycerintrifettsäureester [Cosm. Toil., 103, 99 (1988)] sowie Fettsäurealkanolamide als organische Verdickungsmittel bekannt.
- Glycerin;
- Alkylenglycole, wie beispielsweise Ethylenglycol, Diethylenglycol, Propylenglycol, Butylenglycol, 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.-%;
- Methyolverbindungen, wie insbesondere Trimethylolethan, Trimethylolpropan, Tnmethylolbutan, Pentaerythrit und Dipentaerythrit;
- 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,
- Zucker mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Glucose oder Saccharose,
- Aminozucker, wie beispielsweise Glucamin und
- Dialkoholamine, wie Diethanolamin oder 2-Amino-1,3-propandiol.
Als polyfunktionelle Carbonsäuren (III) können auch entsprechende C2-8-Dicarbonsäuren eingesetzt werden, so daß ebenfalls Bernsteinsäure, Maleinsäure, Fumarsäure, Glutarsäure, Adipinsäure und Dodecandisäure in Frage kommen. Als Hydroxycarbonsäuren, die im Sinne der Erfindung als Komponente (III) in Betracht kommen, werden vorzugsweise Citronensäure, Apfelsäure, Weinsäure, Glykolsäure und/oder Milchsäure eingesetzt.
Die Polyolcarbonsäureester werden erhalten, indem man zunächst die entsprechenden Polyole in an sich bekannter Weise in Gegenwart saurer Katalysatoren mit den Fettsäuren zu entsprechenden Partialestern umsetzt und diese dann in einem weiteren Schritt mit den polyfunktionellen Carbonsäuren bzw. Hydroxycarbonsäuren zu den gewünschten Polyolcarbonsäure- und/oder Polyolhydroxycarbonsäureestern umsetzt.
Typische Beispiele sind Anlagerungsprodukte 2 bis 6 Ethylenoxid-Einheiten an Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen, die z.B. bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und Ölen oder Aldehyden aus der Roelen'schen Oxosynthese sowie als Monomerfraktion bei der Dimerisierung von ungesättigten Fettalkoholen anfallen. Bevorzugt sind technische Fettalkohole mit 12 bis 18 Kohlenstoffatomen, wie beispielsweise Kokos-, Palm-, Palmkern- oder Talgfettalkohol.
Daneben können in Antitranspirantien übliche öllösliche und wasserlösliche Hilfsmittel in geringeren Mengen enthalten sein. Solche öllöslichen Hilfsmittel können z.B. sein:
Claims (7)
- Verwendung von Polyolcarbonsäureestern, erhältlich durch Umsetzung von (I) Polyolen mit 2 bis 15 Kohlenstoffatomen und 2 bis 6 OH-Gruppen mit (II) linearen und/oder verzweigten, gesättigten und/oder ungesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen und (III) polyfunktionellen Carbonsäuren mit 2 bis 8 Kohlenstoffatomen und Hydroxycarbonsäuren mit 2 bis 4 Kohlenstoffatomen, als Verdickungsmittel in oberflächenaktiven Zubereitungen.
- Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß man Polyolcarbonsäureester einsetzt, die durch Umsetzung von Polyolen (I) erhältlich sind, die ausgewählt sind aus der Gruppe, die gebildet wird von Trimethylolpropan, Pentaerythrit, Propylenglykol, Sorbitol und/oder Glycerin.
- Verwendung nach den Ansprüchen 1 und/oder 2, dadurch gekennzeichnet, daß man Polyolcarbonsäureester einsetzt, die durch Umsetzung von linearen und/oder verzweigten, gesättigten und/oder ungesättigten Fettsäuren mit 12 bis 18 Kohlenstoffatomen (III) erhältlich sind.
- Verwendung nach mindestens einem der Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß man Polyolcarbonsäureester einsetzt, die durch Umsetzung von Hydroxycarbonsäuren (III) erhalten werden, die ausgewählt sind aus der Gruppe, die gebildet wird von Citronensäure, Apfelsäure, Weinsäure Glykolsäure und/oder Milchsäure.
- Verwendung nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Polyolcarbonsäureester in Mengen von 0,1 bis 6 Gew.-% - bezogen auf die Endkonzentration der oberflächenaktiven Zubereitungen - einsetzt.
- Verwendung nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Polyolcarbonsäureester in Kombination mit Fettalkoholethoxylaten der Formel (I) einsetzt, in der R1 für einen linearen oder verzweigten, gesättigten oder ungesättigten Kohlenwasserstoffrest mit 10 bis 18 Kohlenstoffatomen und m für Zahlen von durchschnittlich 2 bis 6 steht.
- Verwendung nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man die Polyolcarbonsäureester in Kombination mit weiteren Verdickungsmitteln einsetzt.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19943586 | 1999-09-11 | ||
DE1999143586 DE19943586A1 (de) | 1999-09-11 | 1999-09-11 | Verdickungsmittel |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1083217A2 true EP1083217A2 (de) | 2001-03-14 |
EP1083217A3 EP1083217A3 (de) | 2001-04-04 |
Family
ID=7921688
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00119067A Withdrawn EP1083217A3 (de) | 1999-09-11 | 2000-09-02 | Verdickungsmittel |
Country Status (2)
Country | Link |
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EP (1) | EP1083217A3 (de) |
DE (1) | DE19943586A1 (de) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1207193A1 (de) * | 2000-11-09 | 2002-05-22 | Cognis Deutschland GmbH & Co. KG | Verwendung von Tensidgemischen zur Herstellung von Wasch- und Reinigungsmitteln |
WO2003015742A1 (de) * | 2001-08-16 | 2003-02-27 | Cognis Deutschland Gmbh & Co. Kg | Fettsäurehaltige reinigungsmittel |
CN112794953A (zh) * | 2020-12-31 | 2021-05-14 | 中国石油大学(华东) | 一种支化聚合物型酸液稠化剂的制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3541813A1 (de) * | 1985-11-27 | 1987-06-04 | Akzo Gmbh | Verdickungsmittel fuer tensidhaltige zubereitungen auf basis polyaetherderivate |
DE4236109A1 (de) * | 1992-10-26 | 1994-04-28 | Henkel Kgaa | Flüssiges Waschmittel |
US5424469A (en) * | 1992-07-16 | 1995-06-13 | Solvay Fluor Und Derivate Gmbh | Process for preparing polyglycerol fatty acid ester mixtures and use in cosmetic, pharmeceutical and chemical preparations |
DE19512411A1 (de) * | 1995-04-03 | 1996-10-10 | Henkel Kgaa | Verfahren zur Herstellung viskoser Zuckertenside |
US5576451A (en) * | 1991-11-13 | 1996-11-19 | Henkel Kommanditgesellschaft Auf Aktien | Esters of fatty acids with ethoxylated polyols |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19802206A1 (de) * | 1998-01-22 | 1999-07-29 | Beiersdorf Ag | Lipidreduzierte, fließfähige Zubereitungen |
-
1999
- 1999-09-11 DE DE1999143586 patent/DE19943586A1/de not_active Withdrawn
-
2000
- 2000-09-02 EP EP00119067A patent/EP1083217A3/de not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3541813A1 (de) * | 1985-11-27 | 1987-06-04 | Akzo Gmbh | Verdickungsmittel fuer tensidhaltige zubereitungen auf basis polyaetherderivate |
US5576451A (en) * | 1991-11-13 | 1996-11-19 | Henkel Kommanditgesellschaft Auf Aktien | Esters of fatty acids with ethoxylated polyols |
US5424469A (en) * | 1992-07-16 | 1995-06-13 | Solvay Fluor Und Derivate Gmbh | Process for preparing polyglycerol fatty acid ester mixtures and use in cosmetic, pharmeceutical and chemical preparations |
DE4236109A1 (de) * | 1992-10-26 | 1994-04-28 | Henkel Kgaa | Flüssiges Waschmittel |
DE19512411A1 (de) * | 1995-04-03 | 1996-10-10 | Henkel Kgaa | Verfahren zur Herstellung viskoser Zuckertenside |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1207193A1 (de) * | 2000-11-09 | 2002-05-22 | Cognis Deutschland GmbH & Co. KG | Verwendung von Tensidgemischen zur Herstellung von Wasch- und Reinigungsmitteln |
WO2003015742A1 (de) * | 2001-08-16 | 2003-02-27 | Cognis Deutschland Gmbh & Co. Kg | Fettsäurehaltige reinigungsmittel |
CN112794953A (zh) * | 2020-12-31 | 2021-05-14 | 中国石油大学(华东) | 一种支化聚合物型酸液稠化剂的制备方法 |
Also Published As
Publication number | Publication date |
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DE19943586A1 (de) | 2001-03-15 |
EP1083217A3 (de) | 2001-04-04 |
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