EP1449911A1 - Aqueous compositions containing microencapsulated active components - Google Patents

Aqueous compositions containing microencapsulated active components Download PDF

Info

Publication number
EP1449911A1
EP1449911A1 EP03003176A EP03003176A EP1449911A1 EP 1449911 A1 EP1449911 A1 EP 1449911A1 EP 03003176 A EP03003176 A EP 03003176A EP 03003176 A EP03003176 A EP 03003176A EP 1449911 A1 EP1449911 A1 EP 1449911A1
Authority
EP
European Patent Office
Prior art keywords
acid
matrix
active ingredients
preparations according
alcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP03003176A
Other languages
German (de)
French (fr)
Other versions
EP1449911B1 (en
Inventor
Nuria Dr. Bonastre Gilabert
Agustin Sanchez
Maria Dr. De Moragas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cognis IP Management GmbH
Original Assignee
Cognis Iberia SL
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cognis Iberia SL filed Critical Cognis Iberia SL
Priority to AT03003176T priority Critical patent/ATE364681T1/en
Priority to ES03003176T priority patent/ES2286341T3/en
Priority to DE50307461T priority patent/DE50307461D1/en
Priority to EP03003176A priority patent/EP1449911B1/en
Publication of EP1449911A1 publication Critical patent/EP1449911A1/en
Application granted granted Critical
Publication of EP1449911B1 publication Critical patent/EP1449911B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/12Processes in which the treating agent is incorporated in microcapsules
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions
    • C11D3/0015Softening compositions liquid
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/18Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3749Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/02Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/20Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease

Definitions

  • the invention is in the field of laundry treatment agents and relates to new preparations with microencapsulated active ingredients that improve ironing behavior, a process for the treatment of textiles and the use of special microencapsulated Active ingredients for laundry equipment.
  • the object of the present invention was therefore to provide new aqueous preparations with which textiles can be finished in such a way that easy ironing is possible ( " easy ironing effect") without the disadvantages of the prior art being associated therewith are.
  • the active ingredients should be easy to incorporate and the resulting aqueous preparations should be stable on storage. Another wish was still to use such active substances that have additional positive effects in connection with the textile finish.
  • the invention relates to aqueous preparations, for example fabric softener, Liquid detergent or laundry detergent, with microencapsulated active ingredients, which are characterized by the fact that the active substances are substances which Improve the ironing behavior of textiles.
  • the preparations according to the invention contain the known active ingredients now included used in microencapsulated form.
  • the microcapsules additional dyes, for example transparent preparations are possible, which Active substances in the form of clearly visible, for example blue or red colored spherical Forms contain what may be desired for aesthetic reasons, because it is Consumers immediately notice the presence of active auxiliary substances.
  • the microencapsulated Active substances are drawn onto the fibers; when ironed, the capsules become mechanical broken open and then release the active ingredient spontaneously.
  • microencapsulated active ingredients are used in which the shell consists entirely or at least predominantly of chitosan. Chitosan also owns the tendency to pull on fibers. Since it has nourishing and antibacterial properties, is the desired additional with the use of chitosan microcapsules Benefits achieved.
  • the main active ingredients that improve the ironing behavior of textiles are silicone compounds, Paraffin waxes, polyolefin waxes and their mixtures in question.
  • Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones as well as amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl modified silicone compounds, the 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.
  • paraffin waxes saturated hydrocarbons are sufficient To understand carbon chain length that only at temperatures above soften or melt at 50, preferably above 60 ° C.
  • the paraffin waxes can also be partially oxidized, i.e. have free carboxyl groups.
  • polyolefin waxes are polyethylene waxes, polypropylene waxes and to understand their mixtures. Suitable representatives are those who are only at Soften temperatures above 50, preferably above 60 ° C or melt. Polyolefin waxes, such as e.g. the Adalin® product K (Cognis Deutschland GmbH & Co. KG)
  • Both the silicone compounds and the waxes can be in the form of aqueous emulsions or dispersions are used, the active substance content in the range of 1 can be up to 25% by weight. Small amounts of suitable ones can be used as further constituents Emulsifiers can also be used.
  • microcapsule is understood by the person skilled in the art to mean spherical aggregates with a diameter in the range from approximately 0.0001 to approximately 5 mm, which contain at least one solid or liquid core which is enclosed by at least one continuous shell. More precisely, it involves finely dispersed liquid or solid phases coated with film-forming polymers, in the production of which the polymers precipitate on the material to be encased after emulsification and coacervation or interfacial polymerization. According to another method, melted waxes are taken up in a matrix ( " microsponge"), which as microparticles can additionally be coated with film-forming polymers.
  • the microscopic capsules, also called nanocapsules can be dried like powder.
  • multinuclear aggregates also called microspheres
  • Single or multi-core microcapsules can also be enclosed by an additional second, third, etc. shell.
  • the shell can consist of natural, semi-synthetic or synthetic materials.
  • wrapping materials are, for example, gum arabic, agar agar, agarose, maltodextrins, alginic acid or its salts, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or Dextran, polypeptides, protein hydrolyzates, sucrose and waxes.
  • Semi-synthetic casing materials include chemically modified celluloses, in particular cellulose esters and ethers, for example cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose, and starch derivatives, in particular starch ethers and esters.
  • Synthetic covering materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinyl pyrrolidone.
  • microcapsules of the prior art are the following commercial products (the shell material is given in brackets) : Hallcrest microcapsules (gelatin, gum arabic), Coletica Thalaspheres (maritime collagen), Lipotec millicapsules (alginic acid, agar agar), Induchem Unispheres (lactose , microcrystalline cellulose, hydroxypropylmethyl cellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar agar) and Kuhs Probiol Nanospheres (phospholipids) as well as Primaspheres and Primasponges (Chitosan, Alysol phosphates ) and Alginate ,
  • such substances are preferably considered as gel formers drawn, which show the property in aqueous solution at temperatures above of 40 ° C to form gels.
  • Typical examples are heteropolysaccharides and proteins.
  • Agaroses are preferably used as thermogelating heteropolysaccharides in question, which together in the form of the agar agar to be obtained from red algae with up to 30% by weight of non-gel-forming agaropectins.
  • the main constituent of the agaroses are linear polysaccharides from D-galactose and 3,6-anhydro-L-galactose, which are linked alternately ⁇ -1,3- and ⁇ -1,4-glycosidically.
  • the heteropolysaccharides preferably have a molecular weight in the range from 110,000 to 160,000 and are both colorless and tasteless.
  • Pectins, xanthans (also xanthan gum) and mixtures thereof can be used. Those types which are still in 1% by weight aqueous solution are also preferred Form gels that do not melt below 80 ° C and are already above of 40 ° C solidify again. From the group of thermogeling proteins the different types of gelatin are mentioned as examples.
  • Chitosans are biopolymers and belong to the group of hydrocolloids. From a chemical point of view, these are partially deacetylated chitins of different molecular weights that contain the following - idealized - monomer unit: In contrast to most hydrocolloids, which are negatively charged in the range of biological pH values, chitosans are cationic biopolymers under these conditions. The positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products as well as pharmaceuticals Preparations used. The production of chitosans is based on chitin, preferably the shell remains of crustaceans, which are available in large quantities as cheap raw materials.
  • the chitin is used in a process that was first developed by Hackmann et al. has been described, usually first deproteinized by adding bases, demineralized by adding mineral acids and finally deacetylated by adding strong bases, it being possible for the molecular weights to be distributed over a broad spectrum.
  • Those types are preferably used which have an average molecular weight of 10,000 to 500,000 or 800,000 to 1,200,000 Daltons and / or a Brookfield viscosity (1% by weight in glycolic acid) below 5000 mPas, a degree of deacetylation in the range have from 80 to 88% and an ash content of less than 0.3% by weight.
  • the chitosans are generally used in the form of their salts, preferably as glycolates.
  • the matrix can optionally be dispersed in an oil phase before the membrane is formed.
  • Suitable oils for this purpose are, for example, 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 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, 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 squalane, squalene or dialkylcyclohexanes.
  • the anionic polymers have the task of forming membranes with the chitosans. Salts of alginic acid are preferably suitable for this purpose.
  • Alginic acid is a mixture of carboxyl-containing polysaccharides with the following idealized monomer unit:
  • the average molecular weight of the alginic acids or alginates is in the range from 150,000 to 250,000.
  • Salts of alginic acid are to be understood to mean both their complete and their partial neutralization products, in particular the alkali metal salts and preferably the sodium alginate ( “ algin”) and the ammonium and alkaline earth metal salts.
  • Mixed alginates such as sodium / magnesium or sodium / calcium alginates, are particularly preferred.
  • anionic chitosan derivatives such as carboxylation and especially succinylation products, are also suitable for this purpose.
  • poly (meth) acrylates with average molecular weights in the range from 5,000 to 50,000 daltons and the various carboxymethyl celluloses are also suitable.
  • anionic polymers anionic surfactants or low molecular weight inorganic salts, such as, for example, pyrophosphates, can also be used for the formation of the envelope membrane.
  • the microcapsules are usually prepared in a 1 to 10, preferably 2 to 5 % By weight aqueous solution of the gel former, preferably the agar, and heated this under reflux. At boiling point, preferably at 80 to 100 ° C, a second added aqueous solution containing the chitosan in amounts of 0.1 to 2, preferably 0.25 up to 0.5% by weight and the active compounds in amounts of 0.1 to 25 and in particular 0.25 to 10 % By weight; this mixture is called the matrix.
  • the loading of the microcapsules with active ingredients can therefore also 0.1 to 25 wt .-% based on the capsule weight be.
  • water-insoluble ones can also be used at this time to adjust the viscosity Components, for example inorganic pigments, are added, where they are usually added in the form of aqueous or aqueous / alcoholic dispersions.
  • inorganic pigments for example inorganic pigments
  • the Matrix of gelling agent, chitosan and active ingredients the matrix can optionally in an oil phase be dispersed very finely under strong shear in order to be encapsulated in the following to produce the smallest possible particles.
  • the resulting aqueous Preparations generally have a microcapsule content in the range from 1 to 10% by weight on.
  • the solution of the polymers is further Contains ingredients, such as emulsifiers or preservatives.
  • emulsifiers or preservatives After filtration microcapsules are obtained which preferably have an average diameter in the range of have about 1 mm. It is advisable to sift the capsules to get one if possible ensure even size distribution.
  • the microcapsules obtained in this way can manufacturing-related frames have any shape, but they are preferably approximate spherical.
  • the anionic polymers can also be used to prepare the Insert the matrix and encapsulate it with the chitosans.
  • an O / W emulsion is first prepared, which in addition to the oil body, water and Active ingredients contain an effective amount of emulsifier. This is used to manufacture the matrix Preparation with vigorous stirring with an appropriate amount of an aqueous anion polymer solution added.
  • Polysaccharides in particular Xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and Hydroxyethylcellulose, higher molecular weight polyethylene glycol mono- and diesters of fatty acids, Polyacrylates, polyacrylamides and the like can still be supported. Finally the microcapsules are removed from the aqueous phase, for example by decanting, Filter or centrifuge separated.
  • the preparations can usually contain microencapsulated active ingredients in amounts of 0.1 up to 10, preferably 1 to 8 and in particular 2 to 5% by weight, based on the composition.
  • the agents are aqueous solutions that are only which contain microcapsules and, if appropriate, suitable thickeners. This is for example in the case of laundry treatment agents of the ironing aid type which the laundry is treated immediately before ironing.
  • the preparations can be used all still anionic, nonionic, cationic and / or amphoteric or zwitterionic Contain surfactants.
  • anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, Olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, Alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, Monoglyceride (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-
  • anionic surfactants polyglycol ether chains contain, these can be a conventional, but preferably a narrow homolog distribution exhibit.
  • Alkylbenzenesulfonates, alkylsulfates, soaps, Alkane sulfonates, olefin sulfonates, methyl ester sulfonates and mixtures thereof are used.
  • Preferred alkylbenzenesulfonates follow the formula (I) R 1 -Ph-SO 3 X in which R 1 is a branched but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • R 1 is a branched but preferably linear alkyl radical having 10 to 18 carbon atoms
  • Ph is a phenyl radical
  • X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are particularly suitable
  • Alkyl and / or alkenyl sulfates which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary and / or secondary alcohols, which preferably follow the formula (II) R 2 O-SO 3 X in which R 2 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali metal and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aryl selenyl alcohol, elaidyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
  • the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts.
  • Alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred.
  • these are oxo alcohols, as are obtainable, for example, by converting carbon monoxide and hydrogen to alpha-containing olefins using the shop process.
  • Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®.
  • oxo alcohols such as those obtained by the classic Enichema or Condea oxo process by adding carbon monoxide and hydrogen to olefins.
  • These alcohol mixtures are a mixture of strongly branched alcohols.
  • Such alcohol mixtures are commercially available under the trade name Lial®.
  • Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.
  • Soaps are to be understood as meaning fatty acid salts of the formula (III) R 3 CO-OX in which R 3 CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and again X represents alkali and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium.
  • Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of 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, elaoleic acid, petoleic acid, linoleic acid, petoleic acid, linoleic acid, petoleic acid, linoleic acid, linoleic acid, Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
  • coconut or palm kernel fatty acid is preferably used in the form of its sodium or potassium salts.
  • nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, Fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine polyglycol ether, alkoxylated triglycerides, mixed ethers or mixed formals, alk (en) yl oligoglycosides, Fatty acid-N-alkylglucamides, protein hydrolyzates (especially vegetable products based on wheat), Polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides.
  • nonionic surfactants contain polyglycol ether chains, these can be a conventional, but preferably have a narrow homolog distribution. Preferably become fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides used.
  • the preferred fatty alcohol polyglycol ethers follow the formula (IV) R 4 O (CH 2 CHR 5 O) n1 H in which R 4 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 5 represents hydrogen or methyl and n1 represents numbers from 1 to 20.
  • Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, isostyl alcohol , Petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Addition products of 3, 5 or 7 moles of ethylene oxide onto technical coconut oil alcohols are particularly preferred.
  • Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V) R 6 CO- (OCH 2 CHR 7 ) n2 OR 8 in which R 6 CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R 7 is hydrogen or methyl, R 8 is a linear or branched alkyl radical having 1 to 4 carbon atoms and n2 is a number from 1 to 20 stands.
  • Typical examples are the formal insert products of on average 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of 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, arachidic acid, gadoleic acid, behenic acid and technical grade and erucas.
  • the products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Reaction products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.
  • Alkyl and alkenyl oligoglycosides which are also preferred nonionic surfactants, usually follow the formula (VI), R 9 O- [G] p in which R 8 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligo glucosides.
  • Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4.
  • the alkyl or alkenyl radical R 9 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms.
  • Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 9 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.
  • cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyldistearylammonium chloride or hydroxyethyl hydroxycetyldimmonium chloride (Dehyquart E), or else esterquats, which are typically a constituent of finishing agents.
  • tetraalkylammonium compounds such as, for example, dimethyldistearylammonium chloride or hydroxyethyl hydroxycetyldimmonium chloride (Dehyquart E), or else esterquats, which are typically a constituent of finishing agents.
  • R 10 CO for an acyl radical with 6 to 22 carbon atoms
  • R 11 and R 12 independently of one another for hydrogen or R 10 CO
  • R 11 for an alkyl radical with 1 to 4 carbon atoms or a (CH 2 CH 2 O) m4 H- Group
  • m1, m2 and m3 in total for 0 or numbers from 1 to 12
  • m4 for numbers from 1 to 12 and Y for halide
  • ester quats that can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils.
  • Technical C 12/18 coconut fatty acids and in particular partially hardened C 16/18 tallow or palm fatty acids as well as C 16/18 fatty acid cuts rich in elaidic acid are preferably used.
  • the fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters.
  • an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
  • the preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C 16/18 - tallow or palm fatty acid (iodine number 0 to 40).
  • quaternized fatty acid triethanolamine ester salts of the formula (VII) have proven to be particularly advantageous in which R 10 CO for an acyl radical having 16 to 18 carbon atoms, R 11 for R 10 CO, R 12 for hydrogen, R 13 for a methyl group, m1 , m2 and m3 stands for 0 and Y for methyl sulfate.
  • quaternized ester salts of fatty acids with diethanolalkylamines of the formula (VIII) may also be used as ester quats.
  • R 14 CO for an acyl radical with 6 to 22 carbon atoms
  • R 15 for hydrogen or R 14 CO
  • R 16 and R 17 independently of one another for alkyl radicals with 1 to 4 carbon atoms
  • m5 and m6 in total for 0 or numbers from 1 to 12
  • Y again represents halide, alkyl sulfate or alkyl phosphate.
  • ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (IX) should be mentioned as a further group of suitable ester quats, in which R 18 CO for an acyl radical with 6 to 22 carbon atoms, R 19 for hydrogen or R 18 CO, R 20 , R 21 and R 22 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m7 and m8 in total for 0 or numbers from 1 to 12 and X again represents halide, alkyl sulfate or alkyl phosphate.
  • suitable esterquats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (X) based on diethylenetriamine, in which R 23 CO represents an acyl radical having 6 to 22 carbon atoms, R 24 represents hydrogen or R 23 CO, R 25 and R 26 independently of one another represent alkyl radicals having 1 to 4 carbon atoms and Y again represents halide, alkyl sulfate or alkyl phosphate.
  • Such amide ester quats are available on the market, for example, under the Incroquat® (Croda) brand.
  • alkyl betaines examples include alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
  • alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XI) in which R 27 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R 28 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 29 for alkyl radicals with 1 to 4 carbon atoms, q1 for numbers from 1 to 6 and Z for a Alkali and / or alkaline earth metal or ammonium.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C 12/14 -Kokosalkyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearyl, oleyl, C 16/18 tallow alkyl dimethyl amine and technical mixtures thereof.
  • Carboxyalkylation products of amidoamines which follow the formula (XII) are also suitable, in which R 30 CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R 31 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 32 for alkyl radicals with 1 to 4 carbon atoms, q2 for numbers from 1 to 6, q3 for numbers from 1 to 3 and Z again represents an alkali and / or alkaline earth metal or ammonium.
  • Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate.
  • condensation product of C 8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.
  • Imidazolinium betaines are also suitable. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as, for example, aminoethyl ethanolamine (AEEA) or diethylene triamine.
  • AEEA aminoethyl ethanolamine
  • the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
  • Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C 12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
  • the preparations impart such a high viscosity that the microcapsules remain stably dispersed, i.e. do not sediment over time.
  • the term increased viscosity is therefore a to understand such rheology which stabilizes the microcapsules in the aqueous (surfactant) phase ensures.
  • Such viscosities are usually (determined according to Brookfield, RVT viscometer, 20 ° C, spindle 1, 10 rpm) above 100 and preferably above 500 mPas, preferably in the range from 200 to 2,000 and in particular 500 to 1,000 mPas.
  • Suitable thickeners are all the substances that make up the formulations give correspondingly high viscosity.
  • polymeric Compounds are preferably polymeric Compounds, since these are able to form a three-dimensional in the aqueous preparations To build a network in which the microcapsules are stabilized.
  • Typical examples are Aerosil types (hydrophilic silicas), polysaccharides, especially xanthan gum, Guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl and Hydroxypropyl cellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, (e.g.
  • Bentonites such as Bentone® Gel VS-5PC (Rheox) proven to be a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate.
  • the proportion of these thickeners in the aqueous preparations can be 0.1 to 5, preferably 0.5 to 3 and in particular 1 to 2% by weight.
  • Two other objects of the present invention relate to a method for improvement the ironing behavior of textiles, in which the fibers, yarns or textile fabrics are used with microencapsulated active ingredients selected from the group which is formed by silicone compounds, paraffin waxes and polyolefin waxes as well the use of microencapsulated silicone compounds, paraffin waxes and / or Polyolefin waxes for the production of laundry treatment agents.
  • microencapsulated active ingredients selected from the group which is formed by silicone compounds, paraffin waxes and polyolefin waxes as well the use of microencapsulated silicone compounds, paraffin waxes and / or Polyolefin waxes for the production of laundry treatment agents.

Abstract

Aqueous composition containing microencapsulated active compounds (I) that improve the ironing properties of textiles. An independent claim is also included for a method for improving the ironing properties of textiles by finishing the fibers, yarn or fabrics with microencapsulated silicone compounds or paraffin or polyolefin waxes.

Description

Gebiet der ErfindungField of the Invention

Die Erfindung befindet sich auf dem Gebiet Wäschebehandlungsmittel und betrifft neue Zubereitungen mit mikroverkapselten Wirkstoffen, die das Bügelverhalten verbessern, ein Verfahren zur Behandlung von Textilien sowie die Verwendung von speziellen mikroverkapselten Wirkstoffen zur Wäscheausrüstung.The invention is in the field of laundry treatment agents and relates to new preparations with microencapsulated active ingredients that improve ironing behavior, a process for the treatment of textiles and the use of special microencapsulated Active ingredients for laundry equipment.

Stand der TechnikState of the art

Sowohl synthetische als auch natürliche Fasern zeigen die Tendenz, infolge statischer Aufladung zu verketten. Im textilen Bereich wird dies vom Verbraucher durch mangelnden Weichgriff und schlechte Bügelbarkeit wahrgenommen. Aus diesem Grunde befinden sich schon seit langem Wäscheweichspülmittel auf dem Markt, die auch als Avivagemittel oder kurz Softener bezeichnet werden. Ihnen gemeinsam ist ein Gehalt an kationischen Tensiden, vorzugsweise Tetraalkylammoniumsalzen oder insbesondere Esterquats, die die statische Aufladung herabsetzen und der Wäsche einen verbesserten Weichgriff verleihen. Auch für das Problem der mangelnden Bügelbarkeit, die sich insbesondere dadurch bemerkbar macht, dass Falten nur durch mehrfaches Bügeln geglättet werden können, sind Hilfsstoffe bekannt, mit denen Textilien bei der Wäschevor- oder -nachbehandlung ausgerüstet werden können. Es handelt sich dabei insbesondere um Silikonverbindungen, Paraffin- und Polyolefinwachse. Nachteilig bei diesen Stoffen ist jedoch, dass sie sich nur mit Schwierigkeiten homogen und lagerstabil in entsprechende wässrige Zubereitungen einarbeiten lassen. Sowohl die Silikonverbindungen als auch die genannten Wachse zeigen vielmehr die Tendenz zu separieren, was dazu führt, dass die Zubereitungen vor der Anwendung erst einmal wieder durch Schütteln intensiv gemischt werden müssen. Abgesehen davon, dass Verbraucher solchen zusätzlichen Aufwand nicht durch besonderes Kaufinteresse honorieren, sind die entmischten Zubereitungen im besten Fall trüb; die im Markt gewünschten klaren, transparenten Mittel lassen sich so nicht oder nicht lagerstabil herstellen. Both synthetic and natural fibers show a tendency due to static electricity to chain. In the textile sector, this is due to the lack of softness by the consumer and perceived poor ironability. For this reason, have been around since long fabric softener on the market, also as a finishing agent or short softener be designated. Common to them is a content of cationic surfactants, preferably Tetraalkylammonium salts or in particular ester quats, which reduce the static charge and give the laundry an improved soft feel. Even for the problem of lack of ironability, which is particularly noticeable in the fact that wrinkles only Auxiliaries with which textiles can be smoothed by multiple ironing are known can be equipped for pre- or post-treatment of laundry. It is about especially silicone compounds, paraffin and polyolefin waxes. A disadvantage of However, these substances are difficult to homogeneous and stable in storage have the appropriate aqueous preparations incorporated. Both the silicone compounds as well as the waxes mentioned rather show the tendency to separate, which leads to that the preparations are mixed thoroughly by shaking before use Need to become. Aside from that, consumers have such extra effort the unmixed preparations are not rewarded by special buying interest at best cloudy; the clear, transparent means desired in the market cannot be so or not produce stable storage.

Die Aufgabe der vorliegenden Erfindung hat somit darin bestanden, neue wässrige Zubereitungen zur Verfügung zu stellen, mit denen Textilien so ausgerüstet werden können, dass ein leichtes Bügeln möglich wird ("easy ironing Effekt"), ohne dass damit die Nachteile des Stands der Technik verbunden sind. Insbesondere sollten die Wirkstoffe leicht einzuarbeiten und die resultierenden wässrigen Zubereitungen lagerstabil sein. Ein weiterer Wunsch bestand weiterhin, solche aktiven Substanzen einzusetzen, die über zusätzliche positive Effekte im Zusammenhang mit der textilen Ausrüstung verfügen.The object of the present invention was therefore to provide new aqueous preparations with which textiles can be finished in such a way that easy ironing is possible ( " easy ironing effect") without the disadvantages of the prior art being associated therewith are. In particular, the active ingredients should be easy to incorporate and the resulting aqueous preparations should be stable on storage. Another wish was still to use such active substances that have additional positive effects in connection with the textile finish.

Beschreibung der ErfindungDescription of the invention

Gegenstand der Erfindung sind wässrige Zubereitungen, beispielsweise Wäscheweichspülmittel, Flüssigwaschmittel oder Wäschenachbehandlungsmittel, mit mikroverkapselten Wirkstoffen, welche sich dadurch auszeichnen, dass die Wirkstoffe Substanzen darstellen, welche das Bügelverhalten von Textilien verbessern.The invention relates to aqueous preparations, for example fabric softener, Liquid detergent or laundry detergent, with microencapsulated active ingredients, which are characterized by the fact that the active substances are substances which Improve the ironing behavior of textiles.

Das Problem der mangelnden Formulierbarkeit und der geringen Lagerbeständigkeit konnte dadurch gelöst werden, dass die erfindungsgemäßen Zubereitungen die bekannten Wirkstoffe nunmehr in mikroverkapselter Form eingesetzt enthalten. Auf diese Weise lassen sich transparente und über einen langen Zeitraum stabile Mittel herstellen. Enthalten die Mikrokapseln noch zusätzlich Farbstoffe, sind beispielsweise transparente Zubereitungen möglich, die die Wirkstoffe in Form von deutlich sichtbaren, beispielsweise blau oder rot gefärbten sphärischen Gebilden enthalten, was aus ästhetischen Gründen gewünscht sein kann, weil es dem Verbraucher die Präsenz der aktiven Hilfsstoffe unmittelbar vor Augen führt. Die mikroverkapselten Wirkstoffe ziehen auf die Fasern auf; beim Bügeln werden die Kapseln mechanisch aufgebrochen und setzen den Wirkstoff dann spontan frei. In einer bevorzugten Ausführungsform der vorliegenden Erfindung werden mikroverkapselte Wirkstoffe eingesetzt, bei denen die Hülle ganz oder wenigstens überwiegend aus Chitosan besteht. Chitosan besitzt ebenfalls die Tendenz, auf Fasern aufzuziehen. Da es pflegende und antibakterielle Eigenschaften besitzt, ist mit der Verwendung von Chitosanmikrokapseln zudem der gewünschte zusätzliche Nutzen erreicht.The problem of poor formulation and poor shelf life could can be solved in that the preparations according to the invention contain the known active ingredients now included used in microencapsulated form. In this way, transparent and produce stable agents over a long period of time. Contain the microcapsules additional dyes, for example transparent preparations are possible, which Active substances in the form of clearly visible, for example blue or red colored spherical Forms contain what may be desired for aesthetic reasons, because it is Consumers immediately notice the presence of active auxiliary substances. The microencapsulated Active substances are drawn onto the fibers; when ironed, the capsules become mechanical broken open and then release the active ingredient spontaneously. In a preferred embodiment In the present invention, microencapsulated active ingredients are used in which the shell consists entirely or at least predominantly of chitosan. Chitosan also owns the tendency to pull on fibers. Since it has nourishing and antibacterial properties, is the desired additional with the use of chitosan microcapsules Benefits achieved.

Wirkstoffedrugs

Als Wirkstoffe, die das Bügelverhalten von Textilien verbessern, kommen in erster Linie Silikonverbindungen, Paraffinwachse, Polyolefinwachse und deren Gemische in Frage. The main active ingredients that improve the ironing behavior of textiles are silicone compounds, Paraffin waxes, polyolefin waxes and their mixtures in question.

Silikonverbindungen Silicon compounds

Geeignete Silikonverbindungen sind beispielsweise Dimethylpolysiloxane, Methylphenylpolysiloxane, cyclische Silikone sowie amino-, fettsäure-, alkohol-, polyether-, epoxy-, fluor-, glykosid- und/oder alkylmodifizierte 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 as well as amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl modified silicone compounds, the can be both liquid and resinous at room temperature. Farther suitable are simethicones, which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates.

Paraffinwachse paraffin waxes

Unter der Bezeichnung Paraffinwachse sind gesättigte Kohlenwasserstoffe einer hinreichenden Kohlenstoffkettenlänge zu verstehen, die erst bei Temperaturen oberhalb von 50, vorzugsweise oberhalb von 60 °C erweichen bzw. schmelzen. Die Paraffinwachse können auch teilweise oxidiert vorliegen, d.h. über freie Carboxylgruppen verfügen.Under the name paraffin waxes, saturated hydrocarbons are sufficient To understand carbon chain length that only at temperatures above soften or melt at 50, preferably above 60 ° C. The paraffin waxes can also be partially oxidized, i.e. have free carboxyl groups.

Polyolefinwachse polyolefin waxes

Unter der Bezeichnung Polyolefinwachse sind Polyethylenwachse, Polypropylenwachse sowie deren Gemische zu verstehen. Geeignete Vertreter sind solche, die erst bei Temperaturen oberhalb von 50, vorzugsweise oberhalb von 60 °C erweichen bzw. schmelzen. Besonders bevorzugt sind Polyolefinwachse, wie z.B. das Produkt Adalin® K (Cognis Deutschland GmbH & Co. KG)Under the name polyolefin waxes are polyethylene waxes, polypropylene waxes and to understand their mixtures. Suitable representatives are those who are only at Soften temperatures above 50, preferably above 60 ° C or melt. Polyolefin waxes, such as e.g. the Adalin® product K (Cognis Deutschland GmbH & Co. KG)

Sowohl die Silikonverbindungen als auch die Wachse können in Form von wässrigen Emulsionen bzw. Dispersionen eingesetzt werden, wobei der Aktivsubstanzgehalt im Bereich von 1 bis 25 Gew.-% liegen kann. Als weitere Bestandteile können geringe Mengen an geeigneten Emulgatoren mitverwendet werden.Both the silicone compounds and the waxes can be in the form of aqueous emulsions or dispersions are used, the active substance content in the range of 1 can be up to 25% by weight. Small amounts of suitable ones can be used as further constituents Emulsifiers can also be used.

Mikrokapselnmicrocapsules

Unter dem Begriff "Mikrokapsel" werden vom Fachmann sphärische Aggregate mit einem Durchmesser im Bereich von etwa 0,0001 bis etwa 5 mm verstanden, die mindestens einen festen oder flüssigen Kern enthalten, der von mindestens einer kontinuierlichen Hülle umschlossen ist. Genauer gesagt handelt es sich um mit filmbildenden Polymeren umhüllte feindisperse flüssige oder feste Phasen, bei deren Herstellung sich die Polymere nach Emulgierung und Koazervation oder Grenzflächenpolymerisation auf dem einzuhüllenden Material niederschlagen. Nach einem anderen Verfahren werden geschmolzene Wachse in einer Matrix aufgenommen ("microsponge"), die als Mikropartikel zusätzlich mit filmbildenden Polymeren umhüllt sein können. Die mikroskopisch kleinen Kapseln, auch Nanokapseln genannt, lassen sich wie Pulver trocknen. Neben einkernigen Mikrokapseln sind auch mehrkernige Aggregate, auch Mikrosphären genannt, bekannt, die zwei oder mehr Kerne im kontinuierlichen Hüllmaterial verteilt enthalten. Ein- oder mehrkernige Mikrokapseln können zudem von einer zusätzlichen zweiten, dritten etc. Hülle umschlossen sein. Die Hülle kann aus natürlichen, halbsynthetischen oder synthetischen Materialien bestehen. Natürlich Hüllmaterialien sind beispielsweise Gummi Arabicum, Agar-Agar, Agarose, Maltodextrine, Alginsäure bzw. ihre Salze, z.B. Natrium- oder Calciumalginat, Fette und Fettsäuren, Cetylalkohol, Collagen, Chitosan, Lecithine, Gelatine, Albumin, Schellack, Polysaccharide, wie Stärke oder Dextran, Polypeptide, Proteinhydrolysate, Sucrose und Wachse. Halbsynthetische Hüllmaterialien sind unter anderem chemisch modifizierte Cellulosen, insbesondere Celluloseester und -ether, z.B. Celluloseacetat, Ethylcellulose, Hydroxypropylcellulose, Hydroxypropylmethylcellulose und Carboxymethylcellulose, sowie Stärkederivate, insbesondere Stärkeether und -ester. Synthetische Hüllmaterialien sind beispielsweise Polymere wie Polyacrylate, Polyamide, Polyvinylalkohol oder Polyvinylpyrrolidon.The term “microcapsule” is understood by the person skilled in the art to mean spherical aggregates with a diameter in the range from approximately 0.0001 to approximately 5 mm, which contain at least one solid or liquid core which is enclosed by at least one continuous shell. More precisely, it involves finely dispersed liquid or solid phases coated with film-forming polymers, in the production of which the polymers precipitate on the material to be encased after emulsification and coacervation or interfacial polymerization. According to another method, melted waxes are taken up in a matrix ( " microsponge"), which as microparticles can additionally be coated with film-forming polymers. The microscopic capsules, also called nanocapsules, can be dried like powder. In addition to mononuclear microcapsules, multinuclear aggregates, also called microspheres, are known which contain two or more nuclei distributed in the continuous shell material. Single or multi-core microcapsules can also be enclosed by an additional second, third, etc. shell. The shell can consist of natural, semi-synthetic or synthetic materials. Of course, wrapping materials are, for example, gum arabic, agar agar, agarose, maltodextrins, alginic acid or its salts, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or Dextran, polypeptides, protein hydrolyzates, sucrose and waxes. Semi-synthetic casing materials include chemically modified celluloses, in particular cellulose esters and ethers, for example cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose, and starch derivatives, in particular starch ethers and esters. Synthetic covering materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinyl pyrrolidone.

Beispiele für Mikrokapseln des Stands der Technik sind folgende Handelsprodukte (in Klammern angegeben ist jeweils das Hüllmaterial) : Hallcrest Microcapsules (Gelatine, Gummi Arabicum), Coletica Thalaspheres (maritimes Collagen), Lipotec Millicapseln (Alginsäure, Agar-Agar), Induchem Unispheres (Lactose, mikrokristalline Cellulose, Hydroxypropylmethylcellulose); Unicerin C30 (Lactose, mikrokristalline Cellulose, Hydroxypropylmethylcellulose), Kobo Glycospheres (modifizierte Stärke, Fettsäureester, Phospholipide), Softspheres (modifiziertes Agar-Agar) und Kuhs Probiol Nanospheres (Phospholipide) sowie Primaspheres und Primasponges (Chitosan, Alginate) und Primasys (Phospholipide).Examples of microcapsules of the prior art are the following commercial products (the shell material is given in brackets) : Hallcrest microcapsules (gelatin, gum arabic), Coletica Thalaspheres (maritime collagen), Lipotec millicapsules (alginic acid, agar agar), Induchem Unispheres (lactose , microcrystalline cellulose, hydroxypropylmethyl cellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar agar) and Kuhs Probiol Nanospheres (phospholipids) as well as Primaspheres and Primasponges (Chitosan, Alysol phosphates ) and Alginate ,

Wie schon erläutert, besteht ein besonderer Nutzen darin, mikroverkapselte Wirkstoffe einzusetzen, deren Hülle wenigstens anteilig von Chitosan gebildet wird. Chitosanmikrokapseln und Verfahren zu ihrer Herstellung sind Gegenstand früherer Patenanmeldungen der Patentanmelderin [WO 01/01926, WO 01/01927, WO 01/01928, WO 01/01929]. Mikrokapseln mit mittleren Durchmessern im Bereich von 0,0001 bis 5, vorzugsweise 0,001 bis 0,5 und insbesondere 0,005 bis 0,1 mm, bestehend aus einer Hüllmembran und einer die Wirkstoffe enthaltenden Matrix, können beispielsweise erhalten werden, indem man

  • (a1) aus Gelbildnern, Chitosanen und Wirkstoffen eine Matrix zubereitet,
  • (a2) gegebenenfalls die Matrix in einer Ölphase dispergiert,
  • (a3) die dispergierte Matrix mit wässrigen Lösungen anionischer Polymere behandelt und gegebenenfalls dabei die Ölphase entfernt.
  • oder
  • (b1) aus Gelbildnern, anionischen Polymeren und Wirkstoffen eine Matrix zubereitet,
  • (b2) gegebenenfalls die Matrix in einer Ölphase dispergiert,
  • (b3) die dispergierte Matrix mit wässrigen Chitosanlösungen behandelt und gegebenenfalls dabei die Ölphase entfernt.
  • oder
  • (c1) wässrige Wirkstoffzubereitungen mit Ölkörpern in Gegenwart von Emulgatoren zu O/W-Emulsionen verarbeitet,
  • (c2) die so erhaltenen Emulsionen mit wässrigen Lösungen anionischer Polymere behandelt,
  • (c3) die so erhaltene Matrix mit wässrigen Chitosanlösungen in Kontakt bringt und
  • (c4) die so erhaltenen Verkapselungsprodukte von der wässrigen Phase abtrennt.
  • As already explained, there is a particular benefit in using microencapsulated active ingredients, the shell of which is at least partially formed by chitosan. Chitosan microcapsules and processes for their preparation are the subject of earlier patent applications by the applicant [WO 01/01926, WO 01/01927, WO 01/01928, WO 01/01929]. Microcapsules with average diameters in the range from 0.0001 to 5, preferably 0.001 to 0.5 and in particular 0.005 to 0.1 mm, consisting of a shell membrane and a matrix containing the active substances, can be obtained, for example, by
  • (a1) a matrix is prepared from gel formers, chitosans and active ingredients,
  • (a2) optionally dispersing the matrix in an oil phase,
  • (a3) the dispersed matrix is treated with aqueous solutions of anionic polymers and, if appropriate, the oil phase is removed in the process.
  • or
  • (b1) a matrix is prepared from gel formers, anionic polymers and active ingredients,
  • (b2) optionally dispersing the matrix in an oil phase,
  • (b3) the dispersed matrix is treated with aqueous chitosan solutions and, if appropriate, the oil phase is removed in the process.
  • or
  • (c1) processed aqueous active substance preparations with oil bodies in the presence of emulsifiers to form O / W emulsions,
  • (c2) treating the emulsions thus obtained with aqueous solutions of anionic polymers,
  • (c3) brings the matrix thus obtained into contact with aqueous chitosan solutions and
  • (c4) the encapsulation products thus obtained are separated from the aqueous phase.
  • Gelbildner gelling agent

    Im Sinne der Erfindung werden als Gelbildner vorzugsweise solche Stoffe in Betracht gezogen, welche die Eigenschaft zeigen in wässriger Lösung bei Temperaturen oberhalb von 40 °C Gele zu bilden. Typische Beispiele hierfür sind Heteropolysaccharide und Proteine. Als thermogelierende Heteropolysaccharide kommen vorzugsweise Agarosen in Frage, welche in Form des aus Rotalgen zu gewinnenden Agar-Agar auch zusammen mit bis zu 30 Gew.-% nicht-gelbildenden Agaropektinen vorliegen können. Hauptbestandteil der Agarosen sind lineare Polysaccharide aus D-Galaktose und 3,6-Anhydro-L-galaktose, die alternierend β-1,3- und β-1,4-glykosidisch verknüpft sind. Die Heteropolysaccharide besitzen vorzugsweise ein Molekulargewicht im Bereich von 110.000 bis 160.000 und sind sowohl farb- als auch geschmacklos. Als Alternativen kommen Pektine, Xanthane (auch Xanthan Gum) sowie deren Mischungen in Frage. Es sind weiterhin solche Typen bevorzugt, die noch in 1-Gew.-%iger wässriger Lösung Gele bilden, die nicht unterhalb von 80 °C schmelzen und sich bereits oberhalb von 40 °C wieder verfestigen. Aus der Gruppe der thermogelierenden Proteine seien exemplarisch die verschiedenen Gelatine-Typen genannt.For the purposes of the invention, such substances are preferably considered as gel formers drawn, which show the property in aqueous solution at temperatures above of 40 ° C to form gels. Typical examples are heteropolysaccharides and proteins. Agaroses are preferably used as thermogelating heteropolysaccharides in question, which together in the form of the agar agar to be obtained from red algae with up to 30% by weight of non-gel-forming agaropectins. The main constituent of the agaroses are linear polysaccharides from D-galactose and 3,6-anhydro-L-galactose, which are linked alternately β-1,3- and β-1,4-glycosidically. The heteropolysaccharides preferably have a molecular weight in the range from 110,000 to 160,000 and are both colorless and tasteless. As alternatives Pectins, xanthans (also xanthan gum) and mixtures thereof can be used. Those types which are still in 1% by weight aqueous solution are also preferred Form gels that do not melt below 80 ° C and are already above of 40 ° C solidify again. From the group of thermogeling proteins the different types of gelatin are mentioned as examples.

    Chitosane Chitosans

    Chitosane stellen Biopolymere dar und werden zur Gruppe der Hydrokolloide gezählt. Chemisch betrachtet handelt es sich um partiell deacetylierte Chitine unterschiedlichen Molekulargewichtes, die den folgenden - idealisierten - Monomerbaustein enthalten:

    Figure 00060001
    Im Gegensatz zu den meisten Hydrokolloiden, die im Bereich biologischer pH-Werte negativ geladen sind, stellen Chitosane unter diesen Bedingungen kationische Biopolymere dar. Die positiv geladenen Chitosane können mit entgegengesetzt geladenen Oberflächen in Wechselwirkung treten und werden daher in kosmetischen Haar- und Körperpflegemitteln sowie pharmazeutischen Zubereitungen eingesetzt. Zur Herstellung der Chitosane geht man von Chitin, vorzugsweise den Schalenresten von Krustentieren aus, die als billige Rohstoffe in großen Mengen zur Verfügung stehen. Das Chitin wird dabei in einem Verfahren, das erstmals von Hackmann et al. beschrieben worden ist, üblicherweise zunächst durch Zusatz von Basen deproteiniert, durch Zugabe von Mineralsäuren demineralisiert und schließlich durch Zugabe von starken Basen deacetyliert, wobei die Molekulargewichte über ein breites Spektrum verteilt sein können. Vorzugsweise werden solche Typen eingesetzt, wie die ein durchschnittliches Molekulargewicht von 10.000 bis 500.000 bzw. 800.000 bis 1.200.000 Dalton aufweisen und/oder eine Viskosität nach Brookfield (1 Gew.-%ig in Glycolsäure) unterhalb von 5000 mPas, einen Deacetylierungsgrad im Bereich von 80 bis 88 % und einem Aschegehalt von weniger als 0,3 Gew.-% besitzen. Aus Gründen der besseren Wasserlöslichkeit werden die Chitosane in der Regel in Form ihrer Salze, vorzugsweise als Glycolate eingesetzt.Chitosans are biopolymers and belong to the group of hydrocolloids. From a chemical point of view, these are partially deacetylated chitins of different molecular weights that contain the following - idealized - monomer unit:
    Figure 00060001
    In contrast to most hydrocolloids, which are negatively charged in the range of biological pH values, chitosans are cationic biopolymers under these conditions. The positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products as well as pharmaceuticals Preparations used. The production of chitosans is based on chitin, preferably the shell remains of crustaceans, which are available in large quantities as cheap raw materials. The chitin is used in a process that was first developed by Hackmann et al. has been described, usually first deproteinized by adding bases, demineralized by adding mineral acids and finally deacetylated by adding strong bases, it being possible for the molecular weights to be distributed over a broad spectrum. Those types are preferably used which have an average molecular weight of 10,000 to 500,000 or 800,000 to 1,200,000 Daltons and / or a Brookfield viscosity (1% by weight in glycolic acid) below 5000 mPas, a degree of deacetylation in the range have from 80 to 88% and an ash content of less than 0.3% by weight. For reasons of better water solubility, the chitosans are generally used in the form of their salts, preferably as glycolates.

    Ölphase oil phase

    Die Matrix kann vor der Bildung der Membran optional in einer Ölphase dispergiert werden. Als Öle kommen für diesen Zweck beispielsweise Guerbetalkohole auf Basis von Fettalkoholen mit 6 bis 18, vorzugsweise 8 bis 10 Kohlenstoffatomen, Ester von linearen C6-C22-Fettsäuren mit linearen C6-C22-Fettalkoholen, Ester von verzweigten C6-C13-Carbonsäuren mit linearen C6-C22-Fettalkoholen, wie z.B. Myristylmyristat, Myristylpalmitat, Myristylstearat, Myristylisostearat, Myristyloleat, Myristylbehenat, Myristylerucat, Cetylmyristat, Cetylpalmitat, Cetylstearat, Cetylisostearat, Cetyloleat, Cetylbehenat, Cetylerucat, Stearylmyristat, Stearylpalmitat, Stearylstearat, Stearylisostearat, Stearyloleat, Stearylbehenat, Stearylerucat, Isostearylmyristat, Isostearylpalmitat, Isostearylstearat, Isostearylisostearat, Isostearyloleat, Isostearylbehenat, Isostearyloleat, Oleylmyristat, Oleylpalmitat, Oleylstearat, Oleylisostearat, Oleyloleat, Oleylbehenat, Oleylerucat, Behenylmyristat, Behenylpalmitat, Behenylstearat, Behenylisostearat, Behenyloleat, Behenylbehenat, Behenylerucat, Erucylmyristat, Erucylpalmitat, Erucylstearat, Erucylisostearat, Erucyloleat, Erucylbehenat und Erucylerucat. Daneben eignen sich Ester von linearen C6-C22-Fettsäuren mit verzweigten Alkoholen, insbesondere 2-Ethylhexanol, Ester von Hydroxycarbonsäuren mit linearen oder verzweigten C6-C22-Fettalkoholen, insbesondere Dioctyl Malate, Ester von linearen und/oder verzweigten Fettsäuren mit mehrwertigen Alkoholen (wie z.B. Propylenglycol, Dimerdiol oder Trimertriol) und/oder Guerbetalkoholen, Triglyceride auf Basis C6-C10-Fettsäuren, flüssige Mono-/Di-/Triglyceridmischungen auf Basis von C6-C18-Fettsäuren, Ester von C6-C22-Fettalkoholen und/oder Guerbetalkoholen mit aromatischen Carbonsäuren, insbesondere Benzoesäure, Ester von C2-C12-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, Guerbetcarbonate, 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 Kohlenstoffatomen pro Alkylgruppe, Ringöffnungsprodukte von epoxidierten Fettsäureestern mit Polyolen, Siliconöle und/oder aliphatische bzw. naphthenische Kohlenwasserstoffe, wie z.B. wie Squalan, Squalen oder Dialkylcyclohexane in Betracht.The matrix can optionally be dispersed in an oil phase before the membrane is formed. Suitable oils for this purpose are, for example, 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 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, Stearylerucat, isostearyl, isostearyl palmitate, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, Oleylbehenat, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl, Behenylisostearat, behenyl oleate, behenyl behenate, Behenyleru cat, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucylerucate. In addition, 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 atoms and 2 to 6 hydroxyl groups, vegetable oils , branched primary alcohols, substituted cyclohexanes, linear and branched C 6 -C 22 fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with lin earen and / or branched C 6 -C 22 alcohols (e.g. 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 squalane, squalene or dialkylcyclohexanes.

    Anionpolymere anionic polymers

    Die anionische Polymere haben die Aufgabe, mit den Chitosanen Membranen zu bilden. Für diesen Zweck eignen sich vorzugsweise Salze der Alginsäure. Bei der Alginsäure handelt es sich um ein Gemisch carboxylgruppenhaltiger Polysaccharide mit folgendem idealisierten Monomerbaustein:

    Figure 00080001
    The anionic polymers have the task of forming membranes with the chitosans. Salts of alginic acid are preferably suitable for this purpose. Alginic acid is a mixture of carboxyl-containing polysaccharides with the following idealized monomer unit:
    Figure 00080001

    Das durchschnittliche Molekulargewicht der Alginsäuren bzw. der Alginate liegt im Bereich von 150.000 bis 250.000. Dabei sind als Salze der Alginsäure sowohl deren vollständige als auch deren partiellen Neutralisationsprodukte zu verstehen, insbesondere die Alkalisalze und hierunter vorzugsweise das Natriumalginat ("Algin") sowie die Ammonium- und Erdalkalisalze. besonders bevorzugt sind Mischalginate, wie z.B. Natrium/Magnesium- oder Natrium/Calciumalginate. In einer alternativen Ausführungsform der Erfindung kommen für diesen Zweck jedoch auch anionische Chitosanderivate, wie z.B. Carboxylierungs- und vor allem Succinylierungsprodukte in Frage. Alternativ kommen auch Poly(meth)acrylate mit durchschnittlichen Molekulargewichten im Bereich von 5.000 bis 50.000 Dalton sowie die verschiedenen Carboxymethylcellulosen in Frage. Anstelle der anionischen Polymeren können für die Ausbildung der Hüllmembran auch anionische Tenside oder niedermolekulare anorganische Salze, wie beispielsweise Pyrophosphate eingesetzt werden.The average molecular weight of the alginic acids or alginates is in the range from 150,000 to 250,000. Salts of alginic acid are to be understood to mean both their complete and their partial neutralization products, in particular the alkali metal salts and preferably the sodium alginate ( algin”) and the ammonium and alkaline earth metal salts. Mixed alginates, such as sodium / magnesium or sodium / calcium alginates, are particularly preferred. In an alternative embodiment of the invention, however, anionic chitosan derivatives, such as carboxylation and especially succinylation products, are also suitable for this purpose. Alternatively, poly (meth) acrylates with average molecular weights in the range from 5,000 to 50,000 daltons and the various carboxymethyl celluloses are also suitable. Instead of the anionic polymers, anionic surfactants or low molecular weight inorganic salts, such as, for example, pyrophosphates, can also be used for the formation of the envelope membrane.

    Emulgatoren 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;
    • 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), Polyethylenglycol (Molekulargewicht 400 bis 5000), Trimethylolpropan, Pentaerythrit, Zuckeralkoholen (z.B. Sorbit), Alkylglucosiden (z.B. Methylglucosid, Butylglucosid, Laurylglucosid) 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-PEGalkylphosphate und deren Salze;
    • Wollwachsalkohole;
    • Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;
    • Block-Copolymere z.B. Polyethylenglycol-30 Dipolyhydroxystearate;
    • Polymeremulgatoren, z.B. Pemulen-Typen (TR-1,TR-2) von Goodrich;
    • Polyalkylenglycole sowie
    • Glycerincarbonat.
    Suitable emulsifiers are, for example, nonionic surfactants from at least one of the following groups:
    • Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms, with 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;
    • Addition products 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 mol 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 polyglucosaturated (e.g. cellulose) or unsaturated (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 moles of 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 trialkylphosphates and mono-, di- and / or tri-PEGalkylphosphate and their salts;
    • Lanolin alcohol;
    • 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 as well
    • Glycerol carbonate.

    Zur Herstellung der Mikrokapseln stellt man üblicherweise eine 1 bis 10, vorzugsweise 2 bis 5 Gew.-%ige wässrige Lösung des Gelbildners, vorzugsweise des Agar-Agars her und erhitzt diese unter Rückfluss. In der Siedehitze, vorzugsweise bei 80 bis 100°C, wird eine zweite wässrige Lösung zugegeben, welche das Chitosan in Mengen von 0,1 bis 2, vorzugsweise 0,25 bis 0,5 Gew.-% und den Wirkstoffen in Mengen von 0,1 bis 25 und insbesondere 0,25 bis 10 Gew.-% enthält; diese Mischung wird als Matrix bezeichnet. Die Beladung der Mikrokapseln mit Wirkstoffen kann daher ebenfalls 0,1 bis 25 Gew.-% bezogen auf das Kapselgewicht betragen. Falls gewünscht, können zu diesem Zeitpunkt zur Viskositätseinstellung auch wasserunlösliche Bestandteile, beispielsweise anorganische Pigmente zugegeben werden, wobei man diese in der Regel in Form von wässrigen oder wässrig/alkoholischen Dispersionen zusetzt. Zur Emulgierung bzw. Dispergierung der Wirkstoffe kann es ferner von Nutzen sein, der Matrix Emulgatoren und/oder Lösungsvermittler hinzuzugeben. Nach der Herstellung der Matrix aus Gelbildner, Chitosan und Wirkstoffen kann die Matrix optional in einer Ölphase unter starker Scherung sehr fein dispergiert werden, um bei der nachfolgenden Verkapselung möglichst kleine Teilchen herzustellen. Dabei hat es sich als besonders vorteilhaft erwiesen, die Matrix auf Temperaturen im Bereich von 40 bis 60 °C zu erwärmen, während man die Ölphase auf 10 bis 20 °C kühlt. Im letzten, nun wieder obligatorischen Schritt erfolgt dann die eigentliche Verkapselung, d.h. die Ausbildung der Hüllmembran durch Inkontaktbringen des Chitosans in der Matrix mit den anionischen Polymeren. Hierzu empfiehlt es sich, die gegebenenfalls in der Ölphase dispergierte Matrix bei einer Temperatur im Bereich von 40 bis 100, vorzugsweise 50 bis 60 °C mit einer wässrigen, etwa 1 bis 50 und vorzugsweise 10 bis 15 Gew.-%ige wässrigen Lösung des Anionpolymers zu behandeln und dabei - falls erforderlich-gleichzeitig oder nachträglich die Ölphase zu entfernen. Die dabei resultierenden wässrigen Zubereitungen weisen in der Regel einen Mikrokapselgehalt im Bereich von 1 bis 10 Gew.-% auf. In manchen Fällen kann es dabei von Vorteil sein, wenn die Lösung der Polymeren weitere Inhaltsstoffe, beispielsweise Emulgatoren oder Konservierungsmittel enthält. Nach Filtration werden Mikrokapseln erhalten, welche im Mittel einen Durchmesser im Bereich von vorzugsweise etwa 1 mm aufweisen. Es empfiehlt sich, die Kapseln zu sieben, um eine möglichst gleichmäßige Größenverteilung sicherzustellen. Die so erhaltenen Mikrokapseln können im herstellungsbedingten Rahmen eine beliebige Form aufweisen, sie sind jedoch bevorzugt näherungsweise kugelförmig. Alternativ kann man die Anionpolymere auch zur Herstellung der Matrix einsetzen und die Verkapselung mit den Chitosanen durchführen.The microcapsules are usually prepared in a 1 to 10, preferably 2 to 5 % By weight aqueous solution of the gel former, preferably the agar, and heated this under reflux. At boiling point, preferably at 80 to 100 ° C, a second added aqueous solution containing the chitosan in amounts of 0.1 to 2, preferably 0.25 up to 0.5% by weight and the active compounds in amounts of 0.1 to 25 and in particular 0.25 to 10 % By weight; this mixture is called the matrix. The loading of the microcapsules with active ingredients can therefore also 0.1 to 25 wt .-% based on the capsule weight be. If desired, water-insoluble ones can also be used at this time to adjust the viscosity Components, for example inorganic pigments, are added, where they are usually added in the form of aqueous or aqueous / alcoholic dispersions. To emulsify or disperse the active ingredients, it may also be useful add emulsifiers and / or solubilizers to the matrix. After making the Matrix of gelling agent, chitosan and active ingredients, the matrix can optionally in an oil phase be dispersed very finely under strong shear in order to be encapsulated in the following to produce the smallest possible particles. It has proven to be particularly advantageous to heat the matrix to temperatures in the range of 40 to 60 ° C while the Cool the oil phase to 10 to 20 ° C. In the last step, which is now mandatory again, the actual encapsulation, i.e. the formation of the envelope membrane by bringing the Chitosans in the matrix with the anionic polymers. To do this, it is recommended that the matrix dispersed in the oil phase at a temperature in the range from 40 to 100, preferably 50 to 60 ° C with an aqueous, about 1 to 50 and preferably 10 to 15 To treat wt .-% aqueous solution of the anion polymer and - if necessary - simultaneously or to remove the oil phase afterwards. The resulting aqueous Preparations generally have a microcapsule content in the range from 1 to 10% by weight on. In some cases it can be advantageous if the solution of the polymers is further Contains ingredients, such as emulsifiers or preservatives. After filtration microcapsules are obtained which preferably have an average diameter in the range of have about 1 mm. It is advisable to sift the capsules to get one if possible ensure even size distribution. The microcapsules obtained in this way can manufacturing-related frames have any shape, but they are preferably approximate spherical. Alternatively, the anionic polymers can also be used to prepare the Insert the matrix and encapsulate it with the chitosans.

    In einem alternativen Verfahren wird zur Herstellung der erfindungsgemäßen Mikrokapseln wird zunächst eine O/W-Emulsion zubereitet, welche neben dem Ölkörper, Wasser und den Wirkstoffen eine wirksame Menge Emulgator enthält. Zur Herstellung der Matrix wird diese Zubereitung unter starkem Rühren mit einer entsprechenden Menge einer wässrigen Anionpolymerlösung versetzt. Die Membranbildung erfolgt durch Zugabe der Chitosanlösung. Der gesamte Vorgang findet vorzugsweise im schwach sauren Bereich bei pH = 3 bis 4 statt. Falls erforderlich erfolgt die pH-Einstellung durch Zugabe von Mineralsäure. Nach der Membranbildung wird der pH-Wert auf 5 bis 6 angehoben, beispielsweise durch Zugabe von Triethanolamin oder einer anderen Base. Hierbei kommt es zu einem Anstieg der Viskosität, die durch Zugabe von weiteren Verdickungsmitteln, wie z.B. Polysacchariden, insbesondere Xanthan-Gum, Guar-Guar, Agar-Agar, Alginaten und Tylosen, Carboxymethylcellulose und Hydroxyethylcellulose, höhermolekularen Polyethylenglycolmono- und -diesten von Fettsäuren, Polyacrylaten, Polyacrylamiden und dergleichen noch unterstützt werden kann. Abschließend werden die Mikrokapseln von der wässrigen Phase beispielsweise durch Dekantieren, Filtrieren oder Zentrifugieren abgetrennt. An alternative method is to produce the microcapsules according to the invention an O / W emulsion is first prepared, which in addition to the oil body, water and Active ingredients contain an effective amount of emulsifier. This is used to manufacture the matrix Preparation with vigorous stirring with an appropriate amount of an aqueous anion polymer solution added. The membrane is formed by adding the chitosan solution. The the entire process preferably takes place in the weakly acidic range at pH = 3 to 4. If the pH is adjusted by adding mineral acid. After membrane formation the pH is raised to 5 to 6, for example by adding triethanolamine or another base. This leads to an increase in viscosity by adding further thickeners, e.g. Polysaccharides, in particular Xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and Hydroxyethylcellulose, higher molecular weight polyethylene glycol mono- and diesters of fatty acids, Polyacrylates, polyacrylamides and the like can still be supported. Finally the microcapsules are removed from the aqueous phase, for example by decanting, Filter or centrifuge separated.

    Wässrige ZubereitungenAqueous preparations

    Üblicherweise können die Zubereitungen mikroverkapselten Wirkstoffe in Mengen von 0,1 bis 10, vorzugsweise 1 bis 8 und insbesondere 2 bis 5 Gew.-% - bezogen auf die Mittel - enthalten. Im einfachsten Fall handelt es sich bei den Mitteln um wässrige Lösungen, die lediglich die Mikrokapseln und gegebenenfalls geeignete Verdickungsmittel enthalten. Dies ist beispielsweise bei Wäschenachbehandlungsmitteln vom Typ der Bügelhilfen der Fall, bei denen die Wäsche unmittelbar vor dem Bügeln behandelt wird.The preparations can usually contain microencapsulated active ingredients in amounts of 0.1 up to 10, preferably 1 to 8 and in particular 2 to 5% by weight, based on the composition. In the simplest case, the agents are aqueous solutions that are only which contain microcapsules and, if appropriate, suitable thickeners. This is for example in the case of laundry treatment agents of the ironing aid type which the laundry is treated immediately before ironing.

    In anderen Fällen, also bei Avivage- oder Flüssigwaschmitteln, können die Zubereitungen vor allem noch anionische, nichtionische, kationische und/oder amphotere bzw. zwitterionische Tenside enthalten.In other cases, i.e. in the case of finishing or liquid detergents, the preparations can be used all still anionic, nonionic, cationic and / or amphoteric or zwitterionic Contain surfactants.

    Anionische TensideAnionic surfactants

    Typische Beispiele für anionische Tenside sind Seifen, Alkylbenzolsulfonate, Alkansulfonate, Olefinsulfonate, Alkylethersulfonate, Glycerinethersulfonate, α-Methylestersulfonate, Sulfofettsäuren, Alkylsulfate, Fettalkoholethersulfate, Glycerinethersulfate, Hydroxymischethersulfate, Monoglycerid(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, Alkyloligoglucosidsulfate, 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. Vorzugsweise werden Alkylbenzolsulfonate, Alkylsulfate, Seifen, Alkansulfonate, Olefinsulfonate, Methylestersulfonate sowie deren Gemische eingesetzt.Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, Olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, Alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, Monoglyceride (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 acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, Alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products Wheat base) and alkyl (ether) phosphates. If the anionic surfactants polyglycol ether chains contain, these can be a conventional, but preferably a narrow homolog distribution exhibit. Alkylbenzenesulfonates, alkylsulfates, soaps, Alkane sulfonates, olefin sulfonates, methyl ester sulfonates and mixtures thereof are used.

    Alkylbenzolsulfonate alkylbenzenesulfonates

    Bevorzugte Alkylbenzolsulfonate folgen der Formel (I), R1-Ph-SO3X in der R1 für einen verzweigten, vorzugsweise jedoch linearen Alkylrest mit 10 bis 18 Kohlenstoffatomen, Ph für einen Phenylrest und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Insbesondere von diesen geeignet sind Dodecylbenzolsulfonate, Tetradecylbenzolsulfonate, Hexadecylbenzolsulfonate sowie deren technische Gemische in Form der Natriumsalze.Preferred alkylbenzenesulfonates follow the formula (I) R 1 -Ph-SO 3 X in which R 1 is a branched but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Of these, dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are particularly suitable.

    Alkyl- und/oder Alkenylsulfate Alkyl and / or alkenyl sulfates

    Unter Alkyl- und/oder Alkenylsulfaten, die auch häufig als Fettalkoholsulfate bezeichnet werden, sind die Sulfatierungsprodukte primärer und/oder sekundärer Alkohole zu verstehen, die vorzugsweise der Formel (II) folgen, R2O-SO3X in der R2 für einen linearen oder verzweigten, aliphatischen Alkyl- und/oder Alkenylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen und X für ein Alkaliund/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Typische Beispiele für Alkylsulfate, die im Sinne der Erfindung Anwendung finden können, sind die Sulfatierungsprodukte von Capronalkohol, Caprylalkohol, Caprinalkohol, 2-Ethylhexylalkohol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol und Erucylalkohol sowie deren technischen Gemischen, die durch Hochdruckhydrierung technischer Methylesterfraktionen oder Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Die Sulfatierungsprodukte können vorzugsweise in Form ihrer Alkalisalze und insbesondere ihrer Natriumsalze eingesetzt werden. Besonders bevorzugt sind Alkylsulfate auf Basis von C16/18-Talg-Fettalkoholen bzw. pflanzliche Fettalkohole vergleichbarer C-Kettenverteilung in Form ihrer Natriumsalze. Im Falle von verzweigten primären Alkoholen handelt es sich um Oxoalkohole, wie sie z.B. durch Umsetzung von Kohlenmonoxid und Wasserstoff an alpha-ständige Olefine nach dem Shop-Verfahren zugänglich sind. Solche Alkoholmischungen sind im Handel unter dem Handelsnamen Dobanol® oder Neodol® erhältlich. Geeignete Alkoholmischungen sind Dobanol 91®, 23®, 25®, 45®. Eine weitere Möglichkeit sind Oxoalkohole, wie sie nach dem klassischen Oxoprozess der Enichema bzw. der Condea durch Anlagerung von Kohlenmonoxid und Wasserstoff an Olefine erhalten werden. Bei diesen Alkoholmischungen handelt es sich um eine Mischung aus stark verzweigten Alkoholen. Solche Alkoholmischungen sind im Handel unter dem Handelsnamen Lial® erhältlich. Geeignete Alkoholmischungen sind Lial 91®, 111®, 123®, 125®, 145®.Alkyl and / or alkenyl sulfates, which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary and / or secondary alcohols, which preferably follow the formula (II) R 2 O-SO 3 X in which R 2 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali metal and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aryl selenyl alcohol, elaidyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred. In the case of branched primary alcohols, these are oxo alcohols, as are obtainable, for example, by converting carbon monoxide and hydrogen to alpha-containing olefins using the shop process. Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®. Another possibility are oxo alcohols, such as those obtained by the classic Enichema or Condea oxo process by adding carbon monoxide and hydrogen to olefins. These alcohol mixtures are a mixture of strongly branched alcohols. Such alcohol mixtures are commercially available under the trade name Lial®. Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.

    Seifen soaps

    Unter Seifen sind Fettsäuresalze der Formel (III) zu verstehen, R3CO-OX in der R3CO für einen linearen oder verzweigten, gesättigten oder ungesättigten Acylrest mit 6 bis 22 und vorzugsweise 12 bis 18 Kohlenstoffatomen und wiederum X für Alkali- und/oder Erdalkali, Ammonium, Alkylammonium oder Alkanolammonium steht. Typische Beispiele sind die Natrium-, Kalium-, Magnesium-, Ammonium- und Triethanolammoniumsalze der Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen. Vorzugsweise werden Kokos- oder Palmkemfettsäure in Form ihrer Natrium- oder Kaliumsalze eingesetzt.Soaps are to be understood as meaning fatty acid salts of the formula (III) R 3 CO-OX in which R 3 CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and again X represents alkali and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium. Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of 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, elaoleic acid, petoleic acid, linoleic acid, petoleic acid, linoleic acid, petoleic acid, linoleic acid, linoleic acid, Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Coconut or palm kernel fatty acid is preferably used in the form of its sodium or potassium salts.

    Nichtionische TensideNonionic surfactants

    Typische Beispiele für nichtionische Tenside sind Fettalkoholpolyglycolether, Alkylphenolpolyglycolether, Fettsäurepolyglycolester, Fettsäureamidpolyglycolether, Fettaminpolyglycolether, alkoxylierte Triglyceride, Mischether bzw. Mischformale, Alk(en)yloligoglykoside, Fettsäure-N-alkylglucamide, Proteinhydrolysate (insbesondere pflanzliche Produkte auf Weizenbasis), Polyolfettsäureester, Zuckerester, Sorbitanester, Polysorbate und Aminoxide. Sofern die nichtionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen. Vorzugsweise werden Fettalkoholpolyglycolether, alkoxylierte Fettsäureniedrigalkylester oder Alkyloligoglucoside eingesetzt.Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, Fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine polyglycol ether, alkoxylated triglycerides, mixed ethers or mixed formals, alk (en) yl oligoglycosides, Fatty acid-N-alkylglucamides, protein hydrolyzates (especially vegetable products based on wheat), Polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. Provided the nonionic surfactants contain polyglycol ether chains, these can be a conventional, but preferably have a narrow homolog distribution. Preferably become fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides used.

    Fettalkoholpolyglycolether Fatty alcohol polyglycol ether

    Die bevorzugten Fettalkoholpolyglycolether folgen der Formel (IV), R4O(CH2CHR5O)n1H in der R4 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen, R5 für Wasserstoff oder Methyl und n1 für Zahlen von 1 bis 20 steht. Typische Beispiele sind die Anlagerungsprodukte von durchschnittlich 1 bis 20 und vorzugsweise 5 bis 10 Mol Ethylen- und/oder Propylenoxid 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. Besonders bevorzugt sind Anlagerungsprodukte von 3, 5 oder 7 Mol Ethylenoxid an technische Kokosfettalkohole.The preferred fatty alcohol polyglycol ethers follow the formula (IV) R 4 O (CH 2 CHR 5 O) n1 H in which R 4 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 5 represents hydrogen or methyl and n1 represents numbers from 1 to 20. Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, isostyl alcohol , Petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Addition products of 3, 5 or 7 moles of ethylene oxide onto technical coconut oil alcohols are particularly preferred.

    Alkoxylierte Fettsäureester Alkoxylated fatty acid esters

    Als alkoxylierte Fettsäureniedrigalkylester kommen Tenside der Formel (V) in Betracht, R6CO-(OCH2CHR7)n2OR8 in der R6CO für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen, R7 für Wasserstoff oder Methyl, R8 für lineare oder verzweigte Alkylreste mit 1 bis 4 Kohlenstoffatomen und n2 für Zahlen von 1 bis 20 steht. Typische Beispiele sind die formalen Einschubprodukte von durchschnittlich 1 bis 20 und vorzugsweise 5 bis 10 Mol Ethylen- und/oder Propylenoxid in die Methyl-, Ethyl-, Propyl-, Isopropyl-, Butyl- und tert.-Butylester von Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen. Üblicherweise erfolgt die Herstellung der Produkte durch Insertion der Alkylenoxide in die Carbonylesterbindung in Gegenwart spezieller Katalysatoren, wie z.B. calcinierter Hydrotalcit. Besonders bevorzugt sind Umsetzungsprodukte von durchschnittlich 5 bis 10 Mol Ethylenoxid in die Esterbindung von technischen Kokosfettsäuremethylestern. Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V) R 6 CO- (OCH 2 CHR 7 ) n2 OR 8 in which R 6 CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R 7 is hydrogen or methyl, R 8 is a linear or branched alkyl radical having 1 to 4 carbon atoms and n2 is a number from 1 to 20 stands. Typical examples are the formal insert products of on average 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of 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, arachidic acid, gadoleic acid, behenic acid and technical grade and erucas. The products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Reaction products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.

    Alkyl- und/oder Alkenyloligoglykoside alkyl and / or alkenyl oligoglycosides

    Alkyl- und Alkenyloligoglykoside, die ebenfalls bevorzugte nichtionische Tenside darstellen, folgen üblicherweise der Formel (VI), R9O-[G]p in der R8 für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht. Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden. Die Alkyl- und/oder Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ableiten. Die bevorzugten Alkyl- und/oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside. Die Indexzahl p in der allgemeinen Formel (VI) gibt den Oligomerisierungsgrad (DP), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muss und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl--und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt. Der Alkyl- bzw. Alkenylrest R9 kann sich von primären Alkoholen mit 4 bis 11, vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Bevorzugt sind Alkyloligoglucoside der Kettenlänge C8-C10 (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem C8-C18-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C12-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C9/11-Oxoalkohole (DP = 1 bis 3). Der Alkyl- bzw. Alkenylrest R9 kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidylalkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C12/14-Kokosalkohol mit einem DP von 1 bis 3.Alkyl and alkenyl oligoglycosides, which are also preferred nonionic surfactants, usually follow the formula (VI), R 9 O- [G] p in which R 8 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligo glucosides. The index number p in the general formula (VI) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound and especially here can assume the values p = 1 to 6, the value p for a specific alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4. The alkyl or alkenyl radical R 9 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C 8 -C 10 (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C 8 -C 18 coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C 12 - Alcohol can be contaminated and alkyl oligoglucosides based on technical C 9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R 9 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.

    Kationische TensideCationic surfactants

    Typische Beispiele für kationische Tenside sind insbesondere Tetraalkylammoniumverbindungen, wie beispielsweise Dimethyldistearylammoniumchlorid oder Hydroxyethyl Hydroxycetyl Dimmonium Chloride (Dehyquart E) oder aber Esterquats, die typischerweise Bestandteil von Avivagemitteln sind. Hierbei handelt es sich beispielsweise um quaternierte Fettsäuretriethanolaminestersalze der Formel (VII),

    Figure 00160001
    in der R10CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R11 und R12 unabhängig voneinander für Wasserstoff oder R10CO, R11 für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH2CH2O)m4H-Gruppe, m1, m2 und m3 in Summe für 0 oder Zahlen von 1 bis 12, m4 für Zahlen von 1 bis 12 und Y für Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C12/18-Kokosfettsäuren und insbesondere teilgehärtete C16/18-Talg- bzw. Palmfettsäuren sowie elaidinsäurereiche C16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quatemierten Ester können die Fettsäuren und das Triethanolamin im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C16/18- Talg- bzw. Palmfettsäure (Iodzahl 0 bis 40) ab. Aus anwendungstechnischer Sicht haben sich quaternierte Fettsäuretriethanolaminestersalze der Formel (VII) als besonders vorteilhaft erwiesen, in der R10CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R11 für R10CO, R12 für Wasserstoff, R13 für eine Methylgruppe, m1, m2 und m3 für 0 und Y für Methylsulfat steht.Typical examples of cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyldistearylammonium chloride or hydroxyethyl hydroxycetyldimmonium chloride (Dehyquart E), or else esterquats, which are typically a constituent of finishing agents. These are, for example, quaternized fatty acid triethanolamine ester salts of the formula (VII),
    Figure 00160001
    in which R 10 CO for an acyl radical with 6 to 22 carbon atoms, R 11 and R 12 independently of one another for hydrogen or R 10 CO, R 11 for an alkyl radical with 1 to 4 carbon atoms or a (CH 2 CH 2 O) m4 H- Group, m1, m2 and m3 in total for 0 or numbers from 1 to 12, m4 for numbers from 1 to 12 and Y for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats that can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils. Technical C 12/18 coconut fatty acids and in particular partially hardened C 16/18 tallow or palm fatty acids as well as C 16/18 fatty acid cuts rich in elaidic acid are preferably used. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C 16/18 - tallow or palm fatty acid (iodine number 0 to 40). From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (VII) have proven to be particularly advantageous in which R 10 CO for an acyl radical having 16 to 18 carbon atoms, R 11 for R 10 CO, R 12 for hydrogen, R 13 for a methyl group, m1 , m2 and m3 stands for 0 and Y for methyl sulfate.

    Neben den quatemierten Fettsäuretriethanolaminestersalzen kommen als Esterquats ferner auch quatemierte Estersalze von Fettsäuren mit Diethanolalkylaminen der Formel (VIII) in Betracht,

    Figure 00170001
    in der R14CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R15 für Wasserstoff oder R14CO, R16 und R17 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m5 und m6 in Summe für 0 oder Zahlen von 1 bis 12 und Y wieder für Halogenid, Alkylsulfat oder Alkylphosphat steht. Als weitere Gruppe geeigneter Esterquats sind schließlich die quatemierten Estersalze von Fettsäuren mit 1,2-Dihydroxypropyldialkylaminen der Formel (IX) zu nennen,
    Figure 00170002
    in der R18CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R19 für Wasserstoff oder R18CO, R20, R21 und R22 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m7 und m8 in Summe für 0 oder Zahlen von 1 bis 12 und X wieder für Halogenid, Alkylsulfat oder Alkylphosphat steht. Schließlich kommen als Esterquats noch Stoffe in Frage, bei denen die Ester- durch eine Amidbindung ersetzt ist und die vorzugsweise basierend auf Diethylentriamin der Formel (X) folgen,
    Figure 00170003
    in der R23CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R24 für Wasserstoff oder R23CO, R25 und R26 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen und Y wieder für Halogenid, Alkylsulfat oder Alkylphosphat steht. Derartige Amidesterquats sind beispielsweise unter der Marke Incroquat® (Croda) im Markt erhältlich.In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (VIII) may also be used as ester quats.
    Figure 00170001
    in which R 14 CO for an acyl radical with 6 to 22 carbon atoms, R 15 for hydrogen or R 14 CO, R 16 and R 17 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m5 and m6 in total for 0 or numbers from 1 to 12 and Y again represents halide, alkyl sulfate or alkyl phosphate. Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (IX) should be mentioned as a further group of suitable ester quats,
    Figure 00170002
    in which R 18 CO for an acyl radical with 6 to 22 carbon atoms, R 19 for hydrogen or R 18 CO, R 20 , R 21 and R 22 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m7 and m8 in total for 0 or numbers from 1 to 12 and X again represents halide, alkyl sulfate or alkyl phosphate. Finally, suitable esterquats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (X) based on diethylenetriamine,
    Figure 00170003
    in which R 23 CO represents an acyl radical having 6 to 22 carbon atoms, R 24 represents hydrogen or R 23 CO, R 25 and R 26 independently of one another represent alkyl radicals having 1 to 4 carbon atoms and Y again represents halide, alkyl sulfate or alkyl phosphate. Such amide ester quats are available on the market, for example, under the Incroquat® (Croda) brand.

    Amphotere bzw. zwitterionische TensideAmphoteric or zwitterionic surfactants

    Beispiele für geeignete amphotere bzw. zwitterionische Tenside sind Alkylbetaine, Alkylamidobetaine, Aminopropionate, Aminoglycinate, Imidazoliniumbetaine und Sulfobetaine. Beispiele für geeignete Alkylbetaine stellen die Carboxyalkylierungsprodukte von sekundären und insbesondere tertiären Aminen dar, die der Formel (XI) folgen,

    Figure 00180001
    in der R27 für Alkyl- und/oder Alkenylreste mit 6 bis 22 Kohlenstoffatomen, R28 für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R29 für Alkylreste mit 1 bis 4 Kohlenstoffatomen, q1 für Zahlen von 1 bis 6 und Z für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind die Carboxymethylierungsprodukte von Hexylmethylamin, Hexyldimethylamin, Octyldimethylamin, Decyldimethylamin, Dodecylmethylamin, Dodecyldimethylamin, Dodecylethylmethylamin, C12/14-Kokosalkyldimethylamin, Myristyldimethylamin, Cetyldimethylamin, Stearyldimethylamin, Stearylethylmethylamin, Oleyldimethylamin, C16/18-Talgalkyldimethylamin sowie deren technische Gemische. Weiterhin kommen auch Carboxyalkylierungsprodukte von Amidoaminen in Betracht, die der Formel (XII) folgen,
    Figure 00180002
    in der R30CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 oder 1 bis 3 Doppelbindungen, R31 für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R32 für Alkylreste mit 1 bis 4 Kohlenstoffatomen, q2 für Zahlen von 1 bis 6, q3 für Zahlen von 1 bis 3 und Z wieder für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind Umsetzungsprodukte von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, namentlich Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Gemische, mit N,N-Dimethylaminoethylamin, N,N-Dimethylaminopropylamin, N,N-Diethylaminoethylamin und N,N-Diethylaminopropylamin, die mit Natriumchloracetat kondensiert werden. Bevorzugt ist der Einsatz eines Kondensationsproduktes von C8/18-Kokosfettsäure-N,N-dime-thylaminopropylamid mit Natriumchloracetat. Weiterhin kommen auch Imidazoliniumbetaine in Betracht. Auch bei diesen Substanzen handelt es sich um bekannte Stoffe, die beispielsweise durch cyclisierende Kondensation von 1 oder 2 Mol Fettsäure mit mehrwertigen Aminen wie beispielsweise Aminöethylethanolamin (AEEA) oder Diethylentriamin erhalten werden können. Die entsprechenden Carboxyalkylierungsprodukte stellen Gemische unterschiedlicher offenkettiger Betaine dar. Typische Beispiele sind Kondensationsprodukte der oben genannten Fettsäuren mit AEEA, vorzugsweise Imidazoline auf Basis von Laurinsäure oder wiederum C12/14-Kokosfettsäure, die anschließend mit Natriumchloracetat betainisiert werden.Examples of suitable amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. Examples of suitable alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XI)
    Figure 00180001
    in which R 27 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R 28 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 29 for alkyl radicals with 1 to 4 carbon atoms, q1 for numbers from 1 to 6 and Z for a Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C 12/14 -Kokosalkyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearyl, oleyl, C 16/18 tallow alkyl dimethyl amine and technical mixtures thereof. Carboxyalkylation products of amidoamines which follow the formula (XII) are also suitable,
    Figure 00180002
    in which R 30 CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R 31 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 32 for alkyl radicals with 1 to 4 carbon atoms, q2 for numbers from 1 to 6, q3 for numbers from 1 to 3 and Z again represents an alkali and / or alkaline earth metal or ammonium. Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C 8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate. Imidazolinium betaines are also suitable. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as, for example, aminoethyl ethanolamine (AEEA) or diethylene triamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C 12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

    Verdickungsmittelthickener

    In einer bevorzugten Ausführungsform der Erfindung ist es gewünscht, den Zubereitungen eine solch hohe Viskosität zu verleihen, dass die Mikrokapseln stabil dispergiert bleiben, d.h. nicht im Laufe der Zeit sedimentieren. Unter dem Begriff erhöhter Viskosität ist somit eine solche Rheologie zu verstehen, die die Stabilisierung der Mikrokapseln in der wässrigen (Tensid-)phase sicherstellt. Üblicherweise liegen derartige Viskositäten (bestimmt nach Brookfield, RVT-Viskosimeter, 20 °C, Spindel 1, 10 Upm) oberhalb von 100 und vorzugsweise oberhalb von 500 mPas, vorzugsweise im Bereich von 200 bis 2.000 und insbesondere 500 bis 1.000 mPas. Geeignete Verdickungsmittel sind alle die Stoffe, die den Formulierungen eine entsprechend hohe Viskosität verleihen. Vorzugsweise handelt es sich jedoch um polymere Verbindungen, da diese in der Lage sind, in den wässrigen Zubereitungen ein dreidimensionales Netz aufzubauen, in welchem die Mikrokapseln stabilisiert werden. Typische Beispiele sind Aerosil-Typen (hydrophile Kieselsäuren), Polysaccharide, insbesondere Xanthan-Gum, Guar-Guar, Agar-Agar, Alginate und Tylosen, Carboxymethylcellulose und Hydroxyethylund 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 besonders 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. Der Anteil dieser Verdickungsmittel an den wässrigen Zubereitungen kann 0,1 bis 5, vorzugsweise 0,5 bis 3 und insbesondere 1 bis 2 Gew.-% betragen.In a preferred embodiment of the invention, it is desired to use the preparations impart such a high viscosity that the microcapsules remain stably dispersed, i.e. do not sediment over time. The term increased viscosity is therefore a to understand such rheology which stabilizes the microcapsules in the aqueous (surfactant) phase ensures. Such viscosities are usually (determined according to Brookfield, RVT viscometer, 20 ° C, spindle 1, 10 rpm) above 100 and preferably above 500 mPas, preferably in the range from 200 to 2,000 and in particular 500 to 1,000 mPas. Suitable thickeners are all the substances that make up the formulations give correspondingly high viscosity. However, they are preferably polymeric Compounds, since these are able to form a three-dimensional in the aqueous preparations To build a network in which the microcapsules are stabilized. Typical examples are Aerosil types (hydrophilic silicas), polysaccharides, especially xanthan gum, Guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl and Hydroxypropyl cellulose, 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; Seppic Sepigel types; Salcare types by Allied Colloids), polyacrylamides, polymers, polyvinyl alcohol and polyvinyl pyrrolidone. As Bentonites, such as Bentone® Gel VS-5PC (Rheox) proven to be a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate. The proportion of these thickeners in the aqueous preparations can be 0.1 to 5, preferably 0.5 to 3 and in particular 1 to 2% by weight.

    Gewerbliche AnwendbarkeitIndustrial applicability

    Zwei weitere Gegenstände der vorliegenden Erfindung betreffen ein Verfahren zur Verbesserung des Bügelverhaltens von Textilien, bei dem man die Fasern, Garne oder textilen Flächengebilde mit mikroverkapselten Wirkstoffen ausrüstet, die ausgewählt sind aus der Gruppe, die gebildet wird von Silikonverbindungen, Paraffinwachsen und Polyolefinwachsen sowie die Verwendung von mikroverkapselten Silikonverbindungen, Paraffinwachsen und/oder Polyolefinwachsen zur Herstellung von Wäschebehandlungsmitteln. Two other objects of the present invention relate to a method for improvement the ironing behavior of textiles, in which the fibers, yarns or textile fabrics are used with microencapsulated active ingredients selected from the group which is formed by silicone compounds, paraffin waxes and polyolefin waxes as well the use of microencapsulated silicone compounds, paraffin waxes and / or Polyolefin waxes for the production of laundry treatment agents.

    BeispieleExamples Beispiel 1example 1

    In einem 500-ml-Dreihalskolben mit Rührer und Rückflusskühler wurden in der Siedehitze 3 g Agar-Agar in 200 ml Wasser gelöst. Anschließend wurde die Mischung innerhalb von etwa 30 min unter starkem Rühren zunächst mit einer Lösung von 10 g Glycerin 90 ml Wasser und dann mit einer Zubereitung von 2,5 g Natriumalginat in Form einer 10 Gew.-%igen wässrigen Lösung, 1 g Dimethicone, 0,5 g Phenonip® und 0,5 g Polysorbat-20 (Tween® 20, ICI) in 64 g Wasser versetzt. Die erhaltene Matrix wurde filtriert, auf 60 °C erwärmt und in eine 1 Gew.-%ige Lösung von Chitosanglycolat in Wasser getropft. Zum Erhalt von Mikrokapseln gleichen Durchmessers wurden die Zubereitungen anschließend gesiebt.In a 500 ml three-necked flask with stirrer and reflux condenser, 3 g of agar-agar dissolved in 200 ml of water. Then the mixture was within about 30 min with vigorous stirring, first with a solution of 10 g glycerol, 90 ml water and then with a preparation of 2.5 g of sodium alginate in the form of a 10 wt .-% aqueous Solution, 1 g dimethicone, 0.5 g Phenonip® and 0.5 g polysorbate-20 (Tween® 20, ICI) in 64 g water added. The matrix obtained was filtered, heated to 60 ° C and in a 1 wt .-% Solution of chitosan glycolate dropped in water. Same to obtain microcapsules The preparations were then sieved in diameter.

    Beispiel 2Example 2

    In einem 500-ml-Dreihalskolben mit Rührer und Rückflusskühler wurden in der Siedehitze 3 g Agar-Agar in 200 ml Wasser gelöst. Anschließend wurde die Mischung innerhalb von etwa 30 min unter starkem Rühren zunächst mit einer Lösung von 10 g Glycerin 90 ml Wasser und dann mit einer Zubereitung von 2,5 g Natriumalginat in Form einer 10 Gew.-%igen wässrigen Lösung, 3 g einer wässrigen Paraffinwachsemulsion, 0,5 g Phenonip® und 0,5 g Polysorbat-20 (Tween® 20, ICI) in 64 g Wasser versetzt. Die erhaltene Matrix wurde filtriert, auf 60 °C erwärmt und in eine 1 Gew.-%ige Lösung von Chitosanglycolat in Wasser getropft. Zum Erhalt von Mikrokapseln gleichen Durchmessers wurden die Zubereitungen anschließend gesiebt.In a 500 ml three-necked flask with stirrer and reflux condenser, 3 g of agar-agar dissolved in 200 ml of water. Then the mixture was within about 30 min with vigorous stirring, first with a solution of 10 g glycerol, 90 ml water and then with a preparation of 2.5 g of sodium alginate in the form of a 10 wt .-% aqueous Solution, 3 g of an aqueous paraffin wax emulsion, 0.5 g Phenonip® and 0.5 g Polysorbat-20 (Tween® 20, ICI) in 64 g of water. The resulting matrix was filtered to 60 ° C warmed and dropped into a 1% by weight solution of chitosan glycolate in water. To receive the preparations were then sieved from microcapsules of the same diameter.

    Beispiel 3Example 3

    In einem 500-ml-Dreihalskolben mit Rührer und Rückflusskühler wurden in der Siedehitze 3 g Agar-Agar in 200 ml Wasser gelöst. Anschließend wurde die Mischung innerhalb von etwa 30 min unter starkem Rühren zunächst mit einer Lösung von 10 g Glycerin 90 ml Wasser und dann mit einer Zubereitung von 2,5 g Natriumalginat in Form einer 10 Gew.-%igen wässrigen Lösung, 5 g einer wässrigen Polyolefinwachsemulsion (Adalin® K), 0,5 g Phenonip® und 0,5 g Polysorbat-20 (Tween® 20, ICI) in 64 g Wasser versetzt. Die erhaltene Matrix wurde filtriert, auf 60 °C erwärmt und in eine 1 Gew.-%ige Lösung von Chitosanglycolat in Wasser getropft. Zum Erhalt von Mikrokapseln gleichen Durchmessers wurden die Zubereitungen anschließend gesiebt.In a 500 ml three-necked flask with stirrer and reflux condenser, 3 g of agar-agar dissolved in 200 ml of water. Then the mixture was within about 30 min with vigorous stirring, first with a solution of 10 g glycerol, 90 ml water and then with a preparation of 2.5 g of sodium alginate in the form of a 10 wt .-% aqueous Solution, 5 g of an aqueous polyolefin wax emulsion (Adalin® K), 0.5 g Phenonip® and 0.5 g of polysorbate-20 (Tween® 20, ICI) in 64 g of water. The matrix obtained was filtered heated to 60 ° C and in a 1 wt .-% solution of chitosan glycolate in water dripped. The preparations were used to obtain microcapsules of the same diameter then sieved.

    Die folgende Tabelle 1 enthält eine Reihe von Formulierungsbeispielen. Dabei bedeuten die Rezepturen folgendes:

  • 1,2) Flüssigwaschmittel
  • 3) Avivagemittel
  • 4) Bügelhilfe
  • Zusammensetzung wässriger Zubereitungen Zusammensetzung 1 2 3 4 C12/18-Kokosalkohol+5EO
    Dehydol® LT5
    25,0 25,0 - -
    C12/18-Kokosalkohol+7EO
    Dehydol® LT7
    10,0 - - -
    Mischether )
    Dehypon® KE 3447
    - 10,0 - -
    Dipalmoylmethylethoxymonium Methosulfate
    Dehyquart® AU 54
    - - 25,0 -
    Carbopol 0,49 0,49 0,49 Farbstoff 0,01 0,01 0,01 Mikrokapseln Bsp. 1 1,0 - - 1,0 Mikrokapseln Bsp. 2 - 1,0 - - Mikrokapseln Bsp. 3 - - 1,0 - Wasser          ad 100
    Table 1 below contains a number of formulation examples. The recipes mean the following:
  • 1,2) liquid detergent
  • 3) finishing agent
  • 4) Ironing aid
  • Composition of aqueous preparations composition 1 2 3 4 C 12/18 coconut alcohol + 5EO
    Dehydol® LT5
    25.0 25.0 - -
    C 12/18 coconut alcohol + 7EO
    Dehydol® LT7
    10.0 - - -
    mixed ethers )
    Dehypon® KE 3447
    - 10.0 - -
    Dipalmoylmethylethoxymonium methosulfate
    Dehyquart® AU 54
    - - 25.0 -
    Carbopol 0.49 0.49 0.49 dye 0.01 0.01 0.01 Microcapsules Ex. 1 1.0 - - 1.0 Microcapsules Ex. 2 - 1.0 - - Microcapsules Ex. 3 - - 1.0 - water ad 100

    Claims (14)

    Wässrige Zubereitungen mit mikroverkapselten Wirkstoffen, dadurch gekennzeichnet, dass die Wirkstoffe Substanzen darstellen, welche das Bügelverhalten von Textilien verbessern.Aqueous preparations with microencapsulated active ingredients, characterized in that the active ingredients are substances which improve the ironing behavior of textiles. Zubereitungen nach Anspruch 1, dadurch gekennzeichnet, dass es sich um Wäscheweichspülmittel handelt.Preparations according to claim 1, characterized in that it is fabric softener. Zubereitungen nach Anspruch 1, dadurch gekennzeichnet, dass es sich um Flüssigwaschmittel handelt.Preparations according to claim 1, characterized in that it is liquid detergent. Zubereitungen nach Anspruch 1, dadurch gekennzeichnet, dass es sich um Wäschenachbehandlungsmittel handelt.Preparations according to claim 1, characterized in that it is laundry aftertreatment. Zubereitungen nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Wirkstoffe ausgewählt sind aus der Gruppe, die gebildet wird von Silikonverbindungen, Paraffinwachsen und Polyolefinwachsen.Preparations according to at least one of claims 1 to 4, characterized in that the active ingredients are selected from the group formed by silicone compounds, paraffin waxes and polyolefin waxes. Zubereitungen nach Anspruch 5, dadurch gekennzeichnet, dass die Silikonverbindungen ausgewählt sind aus der Gruppe, die gebildet wird von Dimethylpolysiloxanen, Methylphenylpolysiloxanen, cyclischen Silikonen sowie amino-, fettsäure-, alkohol-, polyether-, epoxy-, fluor-, glykosid- und/oder alkylmodifizierten Silikonen.Preparations according to claim 5, characterized in that the silicone compounds are selected from the group formed by dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl modified silicones. Zubereitungen nach Anspruch 5, dadurch gekennzeichnet, dass die Polyolefinwachse Polyethylen- und/oder Polypropylenwachse darstellen.Preparations according to claim 5, characterized in that the polyolefin waxes are polyethylene and / or polypropylene waxes. Zubereitungen nach mindestens einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Wirkstoffe in einer wässrigen Emulsion oder Dispersion vorliegen.Preparations according to at least one of claims 1 to 7, characterized in that the active ingredients are present in an aqueous emulsion or dispersion. Zubereitungen nach mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass sie Mikrokapseln mit mittleren Durchmessern im Bereich von 0,0001 bis 5 mm, bestehend aus einer Hüllmembran und einer die Wirkstoffe enthaltenden Matrix enthalten, welche dadurch erhältlich sind, dass man (a1) aus Gelbildnem, Chitosanen und Wirkstoffen eine Matrix zubereitet, (a2) gegebenenfalls die Matrix in einer Ölphase dispergiert, (a3) die dispergierte Matrix mit wässrigen Lösungen anionischer Polymere behandelt und gegebenenfalls dabei die Ölphase entfernt. oder (b1) aus Gelbildnern, anionischen Polymeren und Wirkstoffen eine Matrix zubereitet, (b2) gegebenenfalls die Matrix in einer Ölphase dispergiert, (b3) die dispergierte Matrix mit wässrigen Chitosanlösungen behandelt und gegebenenfalls dabei die Ölphase entfernt. oder (c1) wässrige Wirkstoffzubereitungen mit Ölkörpern in Gegenwart von Emulgatoren zu O/W-Emulsionen verarbeitet, (c2) die so erhaltenen Emulsionen mit wässrigen Lösungen anionischer Polymere behandelt, (c3) die so erhaltene Matrix mit wässrigen Chitosanlösungen in Kontakt bringt und (c4) die so erhaltenen Verkapselungsprodukte von der wässrigen Phase abtrennt. Preparations according to at least one of claims 1 to 8, characterized in that they contain microcapsules with average diameters in the range from 0.0001 to 5 mm, consisting of an envelope membrane and a matrix containing the active ingredients, which are obtainable by (a1) a matrix is prepared from gel formers, chitosans and active ingredients, (a2) optionally dispersing the matrix in an oil phase, (a3) the dispersed matrix is treated with aqueous solutions of anionic polymers and, if appropriate, the oil phase is removed in the process. or (b1) a matrix is prepared from gel formers, anionic polymers and active ingredients, (b2) optionally dispersing the matrix in an oil phase, (b3) the dispersed matrix is treated with aqueous chitosan solutions and, if appropriate, the oil phase is removed in the process. or (c1) processed aqueous active substance preparations with oil bodies in the presence of emulsifiers to form O / W emulsions, (c2) treating the emulsions thus obtained with aqueous solutions of anionic polymers, (c3) brings the matrix thus obtained into contact with aqueous chitosan solutions and (c4) the encapsulation products thus obtained are separated from the aqueous phase. Zubereitungen nach mindestens einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass sie die mikroverkapselten Wirkstoffe in Mengen von 0,1 bis 10 Gew.-% - bezogen auf die Mittel - enthalten.Preparations according to at least one of Claims 1 to 9, characterized in that they contain the microencapsulated active ingredients in amounts of 0.1 to 10% by weight, based on the composition. Zubereitungen nach mindestens einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass sie weiterhin anionische, nichtionische, kationische und/oder amphotere bzw. zwitterionische Tenside enthalten.Preparations according to at least one of claims 1 to 10, characterized in that they further contain anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants. Zubereitungen nach mindestens einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass sie weiterhin Verdickungsmittel enthalten.Preparations according to at least one of claims 1 to 11, characterized in that they further contain thickeners. Verfahren zur Verbesserung des Bügelverhaltens von Textilien, bei dem man die Fasern, Garne oder textilen Flächengebilde mit mikroverkapselten Wirkstoffen ausrüstet, die ausgewählt sind aus der Gruppe, die gebildet wird von Silikonverbindungen, Paraffinwachsen und Polyolefinwachsen.Process for improving the ironing behavior of textiles, in which the fibers, Finishes yarn or textile fabrics with microencapsulated active ingredients, which are selected from the group consisting of silicone compounds, paraffin waxes and polyolefin waxes. Verwendung von mikroverkapselten Silikonverbindungen, Paraffinwachsen und/oder Polyolefinwachsen zur Herstellung von Wäschebehandlungsmitteln.Use of microencapsulated silicone compounds, paraffin waxes and / or Polyolefin waxes for the production of laundry treatment agents.
    EP03003176A 2003-02-18 2003-02-18 Aqueous compositions containing microencapsulated active components Expired - Lifetime EP1449911B1 (en)

    Priority Applications (4)

    Application Number Priority Date Filing Date Title
    AT03003176T ATE364681T1 (en) 2003-02-18 2003-02-18 AQUEOUS PREPARATIONS WITH MICRO-ENCAPSULED ACTIVE INGREDIENTS
    ES03003176T ES2286341T3 (en) 2003-02-18 2003-02-18 Aqueous PREPARATIONS WITH MICROENCASULATED ACTIVE PRODUCTS.
    DE50307461T DE50307461D1 (en) 2003-02-18 2003-02-18 Aqueous preparations with microencapsulated active ingredients
    EP03003176A EP1449911B1 (en) 2003-02-18 2003-02-18 Aqueous compositions containing microencapsulated active components

    Applications Claiming Priority (1)

    Application Number Priority Date Filing Date Title
    EP03003176A EP1449911B1 (en) 2003-02-18 2003-02-18 Aqueous compositions containing microencapsulated active components

    Publications (2)

    Publication Number Publication Date
    EP1449911A1 true EP1449911A1 (en) 2004-08-25
    EP1449911B1 EP1449911B1 (en) 2007-06-13

    Family

    ID=32731520

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP03003176A Expired - Lifetime EP1449911B1 (en) 2003-02-18 2003-02-18 Aqueous compositions containing microencapsulated active components

    Country Status (4)

    Country Link
    EP (1) EP1449911B1 (en)
    AT (1) ATE364681T1 (en)
    DE (1) DE50307461D1 (en)
    ES (1) ES2286341T3 (en)

    Cited By (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    FR2882765A1 (en) * 2005-03-07 2006-09-08 Rowenta Werke Gmbh Ges Mit Bes APPARATUS FOR IRONING OR IRISHING THE LAUNDRY COMPRISING AN ADDITIVE RESERVOIR
    CN103806285A (en) * 2013-10-11 2014-05-21 天津市中科健新材料技术有限公司 Method for manufacturing constant-temperature non-woven cloth for sanitary product
    EP2688996B1 (en) 2011-03-22 2015-05-06 Henkel AG&Co. KGAA Liquid laundry detergent comprising capsules

    Citations (7)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3632296A (en) * 1968-04-12 1972-01-04 Cluett Peabody & Co Inc Application of reactants and/or catalysts to textile fabrics in microencapsulated form
    DE2632318A1 (en) * 1975-07-21 1977-02-17 Procter & Gamble CAPSULES SUITABLE FOR USE IN LIQUID TEXTILE CONDITIONING AGENTS
    WO2001001927A1 (en) * 1999-07-02 2001-01-11 Primacare S.A. Microcapsules - i
    WO2001025385A1 (en) * 1999-10-05 2001-04-12 Ciba Specialty Chemicals Holding Inc. Fabric softener compositions
    WO2001062376A1 (en) * 2000-02-23 2001-08-30 Henkel Kommanditgesellschaft Auf Aktien Microcapsules and/or nanocapsules
    EP1201818A1 (en) * 2000-10-27 2002-05-02 The Procter & Gamble Company Process for the ironing of fabrics, and refill cartridge for irons
    WO2002064725A1 (en) * 2001-02-12 2002-08-22 The Procter & Gamble Company Delivery system having encapsulated porous carrier loaded with additives

    Patent Citations (7)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3632296A (en) * 1968-04-12 1972-01-04 Cluett Peabody & Co Inc Application of reactants and/or catalysts to textile fabrics in microencapsulated form
    DE2632318A1 (en) * 1975-07-21 1977-02-17 Procter & Gamble CAPSULES SUITABLE FOR USE IN LIQUID TEXTILE CONDITIONING AGENTS
    WO2001001927A1 (en) * 1999-07-02 2001-01-11 Primacare S.A. Microcapsules - i
    WO2001025385A1 (en) * 1999-10-05 2001-04-12 Ciba Specialty Chemicals Holding Inc. Fabric softener compositions
    WO2001062376A1 (en) * 2000-02-23 2001-08-30 Henkel Kommanditgesellschaft Auf Aktien Microcapsules and/or nanocapsules
    EP1201818A1 (en) * 2000-10-27 2002-05-02 The Procter & Gamble Company Process for the ironing of fabrics, and refill cartridge for irons
    WO2002064725A1 (en) * 2001-02-12 2002-08-22 The Procter & Gamble Company Delivery system having encapsulated porous carrier loaded with additives

    Cited By (7)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    FR2882765A1 (en) * 2005-03-07 2006-09-08 Rowenta Werke Gmbh Ges Mit Bes APPARATUS FOR IRONING OR IRISHING THE LAUNDRY COMPRISING AN ADDITIVE RESERVOIR
    WO2006095226A1 (en) * 2005-03-07 2006-09-14 Rowenta Werke Gmbh Appliance for ironing or steaming linen, comprising a container for additive
    US7661212B2 (en) 2005-03-07 2010-02-16 Rowenta Werke Gmbh Appliance for ironing or steaming linen, comprising a container for additive
    CN101133203B (en) * 2005-03-07 2011-05-04 罗文塔公司 Appliance for ironing or steaming linen, comprising a container for additive
    EP2688996B1 (en) 2011-03-22 2015-05-06 Henkel AG&Co. KGAA Liquid laundry detergent comprising capsules
    CN103806285A (en) * 2013-10-11 2014-05-21 天津市中科健新材料技术有限公司 Method for manufacturing constant-temperature non-woven cloth for sanitary product
    CN103806285B (en) * 2013-10-11 2016-05-11 天津市中科健新材料技术有限公司 A kind of constant temperature nonwoven preparation method for hygienic articles

    Also Published As

    Publication number Publication date
    ATE364681T1 (en) 2007-07-15
    ES2286341T3 (en) 2007-12-01
    EP1449911B1 (en) 2007-06-13
    DE50307461D1 (en) 2007-07-26

    Similar Documents

    Publication Publication Date Title
    EP1715834B1 (en) Microemulsions
    EP1359247B1 (en) Fibres and textile fabrics finished with microcapsules
    EP1449912B1 (en) Aqueous compositions containing microencapsulated active substances
    EP2694014A2 (en) Hair care agent
    EP3038590B1 (en) Cosmetic composition
    EP1359212B1 (en) Surfactant preparation comprising microencapsulated active ingredients
    EP1358872B1 (en) Use of mixtures of active compounds comprising azelaic acid and glycyrrhetic acid in the treatment of acne
    WO2002076604A1 (en) Microcapsules (viii)
    EP1449911B1 (en) Aqueous compositions containing microencapsulated active components
    EP1359213B1 (en) Aqueous Detergent Compositions
    EP1358876B1 (en) Microcapsules containing anti-acne agents
    DE10213031A1 (en) Use of extracts from the olive tree in detergents, dishwashing detergents and cleaning agents
    EP1378564A1 (en) Unit-dose liquid detergent compositions
    EP1167618A1 (en) Textile auxiliary
    WO2004009095A1 (en) Use of compositions comprising benzoyl peroxide and glycyrrhetinic acid for the treatment of acne
    EP1243322A1 (en) Microcapsules (X)
    DE10307389A1 (en) Anti-acne agents
    DE10329685A1 (en) Microcapsules for use in detergents, rinsing or cleansing compositions or in production of pharmaceuticals, cosmetics or food supplements contain neurotransmitters or their precursors
    EP1462013A1 (en) Microcapsules made of an hydroxytyrosol-containing matrix and an coating
    DE102004006405A1 (en) Microcapsule containing active ingredient for progressive release from textiles e.g. clothing
    DE10307388A1 (en) Glyzyrrhetinsäureester
    EP1657299A1 (en) Microcapsules
    EP1382342A1 (en) Use of compositiosn comprising glycyrrhetinic acid and salicylic acid for acne treatment
    DE10324473A1 (en) Textile finishes
    EP1338334A1 (en) Microcapsules - XVI

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    17P Request for examination filed

    Effective date: 20030218

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT SE SI SK TR

    AX Request for extension of the european patent

    Extension state: AL LT LV MK RO

    AKX Designation fees paid

    Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT SE SI SK TR

    RAP1 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: COGNIS IP MANAGEMENT GMBH

    17Q First examination report despatched

    Effective date: 20050513

    GRAP Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOSNIGR1

    GRAS Grant fee paid

    Free format text: ORIGINAL CODE: EPIDOSNIGR3

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT SE SI SK TR

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FG4D

    Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

    REF Corresponds to:

    Ref document number: 50307461

    Country of ref document: DE

    Date of ref document: 20070726

    Kind code of ref document: P

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20070913

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 20070905

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2286341

    Country of ref document: ES

    Kind code of ref document: T3

    NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
    ET Fr: translation filed
    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FD4D

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: NL

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20070613

    Ref country code: SI

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20070613

    Ref country code: CZ

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20070613

    Ref country code: IE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20070613

    Ref country code: BG

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20070913

    Ref country code: PT

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20071113

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: SK

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20070613

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DK

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20070613

    Ref country code: GR

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20070914

    26N No opposition filed

    Effective date: 20080314

    BERE Be: lapsed

    Owner name: COGNIS IP MANAGEMENT G.M.B.H.

    Effective date: 20080228

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: MC

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080228

    Ref country code: LI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080229

    Ref country code: CH

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080229

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: EE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20070613

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080228

    Ref country code: FI

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20070613

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080218

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: CY

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20070613

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: HU

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20071214

    Ref country code: LU

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080218

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: TR

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20070613

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 14

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 15

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 16

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20220222

    Year of fee payment: 20

    Ref country code: DE

    Payment date: 20220225

    Year of fee payment: 20

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IT

    Payment date: 20220221

    Year of fee payment: 20

    Ref country code: FR

    Payment date: 20220224

    Year of fee payment: 20

    Ref country code: ES

    Payment date: 20220311

    Year of fee payment: 20

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R071

    Ref document number: 50307461

    Country of ref document: DE

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: PE20

    Expiry date: 20230217

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FD2A

    Effective date: 20230427

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

    Effective date: 20230217

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: ES

    Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

    Effective date: 20230219