EP1449912B1 - Compositions aqueuses contenant des matières actives microencapsulées - Google Patents

Compositions aqueuses contenant des matières actives microencapsulées Download PDF

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Publication number
EP1449912B1
EP1449912B1 EP03003177A EP03003177A EP1449912B1 EP 1449912 B1 EP1449912 B1 EP 1449912B1 EP 03003177 A EP03003177 A EP 03003177A EP 03003177 A EP03003177 A EP 03003177A EP 1449912 B1 EP1449912 B1 EP 1449912B1
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Prior art keywords
preparations
matrix
alcohol
polymers
active components
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EP03003177A
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German (de)
English (en)
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EP1449912A1 (fr
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Nuria Dr. Bonastre Gilabert
Agustin Sanchez
Maria Dr. De Moragas
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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Priority to EP03003177A priority Critical patent/EP1449912B1/fr
Priority to AT03003177T priority patent/ATE364682T1/de
Priority to ES03003177T priority patent/ES2287367T3/es
Priority to DE50307462T priority patent/DE50307462D1/de
Priority to US10/781,576 priority patent/US20040213997A1/en
Publication of EP1449912A1 publication Critical patent/EP1449912A1/fr
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/12—Processes in which the treating agent is incorporated in microcapsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the invention is in the field of laundry treatment compositions and relates to new formulations with microencapsulated agents that make re-soiling difficult, a process for treating textiles and the use of special microencapsulated active ingredients for laundry equipment.
  • WO 01/062376 A1 referenced from the micro- or nanocapsules are known, which can be loaded with a variety of active ingredients and are available by a variety of methods.
  • the hallmark of these capsules is that they are chemically modified in such a way that they carry on the surface positive charges that are to accelerate the mounting on fibers or hair.
  • Subject of the WO 01/01927 A1 are microcapsules that are formed by coacervation of chitosan and anionic polymers and have a matrix of gelling agents and active ingredients inside.
  • the object of the present invention was therefore to provide new aqueous preparations available with which textiles can be equipped so that a re-soiling prevented or at least made difficult ("soil repellant effect"), without causing the disadvantages of the prior Technology are connected.
  • the active ingredients should be easy to incorporate and the resulting aqueous preparations should be stable on storage.
  • Another desire was to use those active substances that have additional positive effects associated with the textile finish.
  • the invention relates to aqueous preparations, such as fabric softeners, liquid detergents or laundry aftertreatment agents, with microencapsulated active ingredients, which are characterized in that the active substances represent substances that prevent or at least complicate the Wiederanschmutzen of textiles, the shell of the capsules wholly or predominantly of chitosan consists.
  • microencapsulated preparations which contain the known active ingredients in microencapsulated form.
  • transparent preparations which contain the active ingredients in the form of clearly visible, for example blue or red colored spherical structures, which may be desirable for aesthetic reasons, because it provides the consumer with the presence of active adjuvants immediately before Eyes leads.
  • the microencapsulated agents pull on the fibers; The capsules are gradually broken up mechanically and then release the active ingredient in portions.
  • microencapsulated active ingredients are used in which the shell consists entirely or at least predominantly of chitosan. Chitosan also has a tendency to grow on fibers. Because it has nourishing and antibacterial properties, the added benefit of using Chitosan microcapsules is also achieved.
  • Suitable soil repellents are those which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, it being possible for the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate to be in the range from 50:50 to 90:10. More specifically, the molecular weight of the linking polyethylene glycol units is in the range of 750 to 5,000, that is, the degree of ethoxylation of the polymers containing polyethylene glycol groups may be about 15 to 100.
  • the polymers are characterized by an average molecular weight of about 5000 to 200,000 and may have a block, but preferably a random structure.
  • Preferred polymers are those having molar ratios of ethylene terephthalate / polyethylene glycol terephthalate of from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Further preferred are those polymers comprising linking polyethylene glycol units having a molecular weight of from 750 to 5,000, preferably from 1000 to about 3000 and a molecular weight of the polymer of about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhöne-Poulenc).
  • microcapsule is understood by those skilled spherical aggregates having a diameter in the range of about 0.0001 to about 5 mm, containing at least one solid or liquid core, which is enclosed by at least one continuous shell. More specifically, it is finely dispersed liquid or solid phases coated with film-forming polymers, in the preparation of which the polymers precipitate on the material to be enveloped after emulsification and coacervation or interfacial polymerization. According to another method, molten waxes are taken up in a matrix (“microsponge”), which may additionally be enveloped as microparticles with film-forming polymers. The microscopic capsules, also called nanocapsules, let to dry like powder.
  • multinuclear aggregates also called microspheres
  • Mono- or polynuclear microcapsules can also be enclosed by an additional second, third, etc., sheath.
  • the shell may be made of natural, semi-synthetic or synthetic materials.
  • Natural shell 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 hydrolysates, sucrose and waxes.
  • Semi-synthetic shell materials include chemically modified celluloses, in particular cellulose esters and ethers, for example cellulose acetate, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, and also starch derivatives, in particular starch ethers and esters.
  • Synthetic envelope materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.
  • microcapsules of the prior art are the following commercial products (in each case the cladding material is indicated): Hallcrest Microcapsules (gelatin, gum arabic), Coletica Thalaspheres (marine collagen), Lipotec Millicapseln (alginic acid, agar-agar), Induchem Unispheres (lactose , microcrystalline cellulose, hydroxypropylmethylcellulose); 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, alginates) and Primasys (phospholipids) ,
  • those substances which have the property of forming gels in aqueous solution at temperatures above 40 ° C. are preferably considered as gelling agents.
  • Typical examples are heteropolysaccharides and proteins.
  • Preferred thermogelling heteropolysaccharides are agaroses which, in the form of the agar agar to be obtained from red algae, may also be present together with up to 30% by weight of non-gel-forming agaropectins.
  • the main constituent of the agaroses are linear polysaccharides of D-galactose and 3,6-anhydro-L-galactose, which are linked alternately to ⁇ -1,3- and ⁇ -1,4-glycosidic compounds.
  • the heteropolysaccharides preferably have a molecular weight in the range of 110,000 to 160,000 and are both colorless and tasteless.
  • Pectins, xanthans (including xanthan gum) as well as their mixtures come into consideration as alternatives.
  • Chitosans are biopolymers and are counted among the group of hydrocolloids. Chemically, they are partially deacetylated chitins of different molecular weight containing the following - idealized - monomer unit:
  • 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.
  • chitosans is based on chitin, preferably the shell remains of crustaceans, which are available as cheap raw materials in large quantities.
  • the chitin is thereby used in a process first described by Hackmann et al. has been described, usually initially deproteinized by the addition of bases, demineralized by the addition of mineral acids and finally deacetylated by the addition of strong bases, wherein the molecular weights may be distributed over a broad spectrum.
  • the chitosans are generally used in the form of their salts, preferably as glycolates.
  • the matrix may optionally be dispersed in an oil phase prior to the formation of the membrane.
  • oils for this purpose 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, for example, 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,
  • 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 with polyhydric alcohols such as propylene glycol, dimerdiol or trimer triol
  • polyhydric alcohols such as propylene glycol, dimerdiol or trimer triol
  • Guerbet alcohols triglycerides based on C 6 -C 10 fatty acids, liquid mono- / di- / Triglyceridmisonne based on C 6 -C 18 fatty acids
  • esters of C 6 C 22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids in particular benzoic acid
  • 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 of 150,000 to 250,000.
  • Salts of alginic acid are to be understood as meaning both their complete and their partial neutralization products, in particular the alkali metal salts and, preferably, the sodium alginate ("algin") as well as the ammonium and alkaline earth salts.
  • algin the sodium alginate
  • ammonium and alkaline earth salts especially preferred are mixed alginates, e.g. Sodium / magnesium or sodium / calcium alginates.
  • anionic chitosan derivatives e.g. Carboxylation and especially Succinylmaschines.
  • poly (meth) acrylates having average molecular weights in the range of 5,000 to 50,000 daltons and the various carboxymethylcelluloses come into question.
  • anionic polymers it is also possible to use anionic surfactants or low molecular weight inorganic salts, for example pyrophosphates, for the formation of the enveloping membrane.
  • aqueous solution of the gelling agent preferably the agar agar ago and heated them under reflux.
  • a second aqueous solution is added, which contains the chitosan in amounts of 0.1 to 2, preferably 0.25 to 0.5 wt .-% and the active ingredients in amounts of 0 , 1 to 25 and in particular 0.25 to 10 wt .-%; this mixture is called a matrix.
  • the loading of the microcapsules with active ingredients can therefore also amount to 0.1 to 25% by weight, based on the capsule weight.
  • water-insoluble constituents for example inorganic pigments
  • inorganic pigments can also be added at this time to adjust the viscosity, these being added as a rule in the form of aqueous or aqueous / alcoholic dispersions.
  • emulsifiers and / or solubilizers to the matrix.
  • the matrix may optionally be in an oil phase be dispersed very finely under high shear to produce the smallest possible particles in the subsequent encapsulation.
  • the matrix has proved to be particularly advantageous to heat the matrix to temperatures in the range of 40 to 60 ° C, while the oil phase is cooled to 10 to 20 ° C.
  • the actual encapsulation takes place, ie the formation of the envelope membrane by contacting the chitosan in the matrix with the anionic polymers.
  • the optionally dispersed in the oil phase matrix at a temperature in the range of 40 to 100, preferably 50 to 60 ° C with an aqueous, about 1 to 50 and preferably 10 to 15 wt .-% aqueous solution of the anion polymer and, if necessary, at the same time or subsequently to remove the oil phase.
  • the resulting aqueous preparations generally have a microcapsule content in the range of 1 to 10 wt .-%. In some cases, it may be advantageous if the solution of the polymers contains other ingredients, such as emulsifiers or preservatives.
  • microcapsules After filtration, microcapsules are obtained which on average have a diameter in the range of preferably about 1 mm. It is recommended to sift the capsules to ensure the most even size distribution possible.
  • the microcapsules thus obtained may have any shape in the production-related framework, but they are preferably approximately spherical. Alternatively, one can also use the anionic polymers for the preparation of the matrix and perform the encapsulation with the chitosans.
  • an O / W emulsion is prepared which, in addition to the oil body, water and the active ingredients, contains an effective amount of emulsifier.
  • this preparation is mixed with vigorous stirring with an appropriate amount of an aqueous anionic polymer solution.
  • the membrane formation takes place by adding the chitosan solution.
  • microcapsules are separated from the aqueous phase, for example by decantation, filtration or centrifugation.
  • the preparations microencapsulated active ingredients in amounts of 0.1 to 10, preferably 1 to 8 and in particular 2 to 5 wt .-% - based on the means - included.
  • the agents are aqueous solutions containing only the microcapsules and optionally suitable thickening agents. This is the case, for example, with laundry aftertreatment agents.
  • the preparations may contain, above all, anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants.
  • anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, 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-acyl amino
  • anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using alkylbenzenesulfonates, alkyl sulfates, soaps, alkanesulfonates, olefinsulfonates, methyl ester sulfonates and mixtures thereof.
  • Preferred alkylbenzenesulfonates follow the formula (I) , R 1 -Ph-SO 3 X (I) 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. Particularly suitable of these are dodecylbenzenesulfonates, tetradecylbenzenesulfonates, Hexadecylbenzolsulfonate and their technical mixtures in the form of sodium salts.
  • Alkyl and / or alkenyl sulfates which are also frequently referred to as fatty alcohol sulfates, are the sulfation products of primary and / or secondary alcohols, which preferably follow the formula (II) , R 2 O-SO 3 X (II) in which R 2 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • alkyl sulfates which can be used according to the invention are the sulfation products of caproic alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures obtained by high-pressure hydrogenation of technical methyl ester fractions or aldehydes from the Roelen oxo synthesis.
  • the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Particular preference is given to 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.
  • 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.
  • branched primary alcohols are oxo alcohols, as they are accessible, for example, by reacting carbon monoxide and hydrogen to alpha-olefins by 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 as obtained by the classical oxo process of Enichema or the Condea by addition of carbon monoxide and hydrogen to olefins.
  • These alcohol mixtures are a mixture of highly 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 (III) in which R 3 CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and in turn X is alkali metal and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium.
  • Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, Linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
  • coconut or palm kernel fatty acids are used in the form of their sodium or potassium salts.
  • nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, alk (en) yloligoglycosides, fatty acid N-alkylglucamides, protein hydrolysates (especially wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters , Polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides.
  • the preferred fatty alcohol polyglycol ethers follow the formula (IV), R 4 O (CH 2 CHR 5 O) n 1 H (IV) in which R 4 is a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 5 is hydrogen or methyl and n 1 is a number 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 to caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol , Elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Particularly preferred are addition products of 3, 5 or 7 moles of ethylene oxide to technical Kokosfettalkohole.
  • Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V) , R 6 CO- (OCH 2 CHR 7) n2 OR 8 (V) in the 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 linear or branched alkyl radicals having 1 to 4 carbon atoms and n 2 is a number from 1 to 20 stands.
  • Typical examples are the formal charge products of an average of 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, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid, and technical mixtures thereof.
  • the products are prepared by insertion of the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite.
  • catalysts such as, for example, calcined hydrotalcite.
  • Particularly preferred are reaction products of on average 5 to 10 moles of ethylene oxide in the ester bond of technical Kokosfettklamethylestern.
  • Alkyl and alkenyl oligoglycosides which are also preferred nonionic surfactants, usually follow the formula (VI) , R 9 O- [G] p (VI) where 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 by the relevant methods of preparative organic chemistry.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred.
  • the alkyl or alkenyl radical R 9 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms.
  • Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis.
  • 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 technical mixtures thereof which can be obtained as described above.
  • Prefers are alkyl oligoglucosides based on hydrogenated C 12/14 cocoalcohol having a DP of 1 to 3.
  • cationic surfactants are in particular tetraalkylammonium compounds, such as dimethyldistearylammonium chloride or hydroxyethyl hydroxycetyl dimmonium chloride (Dehyquart E) or else esterquats, which are typically constituents of softening agents.
  • R 10 CO for an acyl radical having 6 to 22 carbon atoms
  • R 11 and R 12 are each independently hydrogen or R 10 CO
  • R 11 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) m4 H Group
  • m1, m2 and m3 are in total 0 or numbers from 1 to 12
  • m4 is numbers from 1 to 12
  • Y is halide, alkylsulfate or alkyl phosphate.
  • esterquats which 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, arachidic 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. It is preferred to use technical C 12/18 coconut fatty acids and, in particular, partially hydrogenated C 16/18 tallow or palm oil fatty acids and also high-acid C 16/18 fatty acid cuts having high elaidic acid content.
  • the fatty acids and the triethanolamine in a molar ratio of 1.1: 1 to 3: 1 can be used.
  • an employment 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 oil fatty acid (iodine value 0 to 40).
  • quaternized fatty acid triethanolamine ester salts of the formula (VII) have proven particularly advantageous in which R 10 CO is an acyl radical having 16 to 18 carbon atoms, R 11 is R 10 CO, R 12 is hydrogen, R 13 is a methyl group, m1 , m2 and m3 are 0 and Y is methylsulfate.
  • quaternized ester salts of fatty acids with diethanolalkylamines of the formula (VIII) are also suitable as esterquats.
  • R 14 CO for an acyl radical having 6 to 22 carbon atoms
  • R 15 is hydrogen or R 14 CO
  • R 16 and R 17 are independently alkyl radicals having 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.
  • R 18 CO for an acyl radical having 6 to 22 carbon atoms
  • R 19 is hydrogen or R 18 CO
  • R 20 , R 21 and R 22 are independently alkyl radicals having 1 to 4 carbon atoms, m7 and m8 in total for 0 or numbers from 1 to 12
  • X again represents halide, alkyl sulfate or alkyl phosphate.
  • suitable esterquats are substances in which the ester is replaced by an amide bond and which preferably follow the formula (X) based on diethylenetriamine, in which R 23 is CO for an acyl radical having 6 to 22 carbon atoms, R 24 is hydrogen or R 23 CO, R 25 and R 26 are independently alkyl radicals having 1 to 4 carbon atoms and Y is again halide, alkyl sulfate or alkyl phosphate.
  • Such Amidesterquats are available for example under the brand Incroquat® (Croda) in the market.
  • alkylbetaines examples include alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
  • alkylbetaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XI)
  • R 27 is alkyl and / or alkenyl radicals having from 6 to 22 carbon atoms
  • R 28 is hydrogen or alkyl radicals having from 1 to 4 carbon atoms
  • R 29 is alkyl radicals having from 1 to 4 carbon atoms
  • q 1 is from 1 to 6
  • Z is from 1 to 6 Alkali and / or alkaline earth metal or ammonium.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C 12/14 cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethylmethylamine, oleyldimethylamine, C 16/18 tallowalkyldimethylamine, and technical mixtures thereof.
  • carboxyalkylation products of amidoamines which follow the formula (XII) , in the R 30 CO for an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R 31 is hydrogen or alkyl radicals having 1 to 4 carbon atoms, R 32 is alkyl radicals having 1 to 4 carbon atoms, q 2 is from 1 to 4 6, q3 represents 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 having 6 to 22 carbon atoms, namely caproic, caprylic, capric, lauric, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic, elaeostearic, arachidic, gadoleic, behenic and erucic acids 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, aminoethylethanolamine (AEEA) or diethylenetriamine.
  • AEEA aminoethylethanolamine
  • the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
  • Typical examples are condensation products of the abovementioned 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 such a high viscosity that the microcapsules remain stably dispersed, ie do not sediment over time.
  • the term increased viscosity is thus to be understood as meaning a rheology which ensures the stabilization of the microcapsules in the aqueous (surfactant) phase.
  • Such viscosities are usually above 100 and preferably above 500 mPas, preferably in the range from 200 to 2000 and in particular 500 to 1000 mPas.
  • Suitable thickeners are all the substances which give the formulations a correspondingly high viscosity.
  • Typical examples are Aerosil types (hydrophilic silicic acids), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl and hydroxypropyl cellulose, furthermore higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, ( eg Carbopole® and Pemulen® grades from Goodrich; Sigma's Synthalene®; Keltrol grades from Kelco; Seppic Sepepic grades; Salcare grades from Allied Colloids), polyacrylamides, polymers, polyvinyl alcohol, and polyvinylpyrrolidone.
  • Aerosil types hydrophilic silicic acids
  • polysaccharides in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl and hydroxypropyl cellulose, furthermore
  • Bentonites such as Bentone® Gel VS-5PC (Rheox), which is a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate, have also proven to be particularly effective.
  • the proportion of these thickeners in the aqueous preparations may be 0.1 to 5, preferably 0.5 to 3 and in particular 1 to 2 wt .-% amount.
  • Two further objects of the present invention relate to preventing repulping of textiles by providing the fibers, yarns or fabrics with microencapsulated active ingredients selected from the group consisting of soil repellants, the ethylene terephthalate and / or Polyethylenglycolterephthalat phenomenon and in which the shell consists wholly or predominantly of chitosan, and the use of microencapsulated polymers ("soil repellants"), the ethylene terephthalate and / or Polyethylenglycolterephthalat phenomenon and in which the shell wholly or predominantly consists of chitosan , for the production of laundry treatment products.
  • microencapsulated active ingredients selected from the group consisting of soil repellants, the ethylene terephthalate and / or Polyethylenglycolterephthalat phenomenon and in which the shell consists wholly or predominantly of chitosan
  • microencapsulated polymers "soil repellants")
  • agar-agar were dissolved in 200 ml of water in the boiling heat. Thereafter, the mixture was stirred for about 30 minutes with vigorous stirring, first with a solution of 10 g of glycerol, 90 ml of water and then with a preparation of 2.5 g of sodium alginate in the form of a 10% strength by weight aqueous solution, 3 g of Milease® T, 0.5 g of preservative (Phenonip®) and 0.5 g of polysorbate-20 (Tween® 20, ICI) in 64 g of water. The resulting matrix was filtered, heated to 60 ° C and added dropwise to a 1% by weight solution of chitosan glycolate in water. To obtain microcapsules of the same diameter, the preparations were then sieved.
  • agar-agar were dissolved in 200 ml of water in the boiling heat.
  • the mixture was then stirred for about 30 minutes with vigorous stirring, first with a solution of 10 g of glycerol, 90 ml of water and then with a preparation of 2.5 g of sodium alginate in the form of a 10% strength by weight aqueous solution, 3 g of Repelotex® SRP 3, 0.5 g of preservative (Phenonip®) and 0.5 g of polysorbate-20 (Tween® 20, ICI) in 64 g of water.
  • the resulting matrix was filtered, heated to 60 ° C and added dropwise to a 1% by weight solution of chitosan glycolate in water. To obtain microcapsules of the same diameter, the preparations were then sieved.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Cosmetics (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Medicinal Preparation (AREA)

Claims (12)

  1. Préparations aqueuses comportant des agents actifs microencapsulés,
    caractérisées en ce que
    les agents actifs sont des substances qui empêchent que les textiles se ressalissent, l'enveloppe des capsules étant constituée entièrement ou pour l'essentiel de chitosane.
  2. Préparations selon la revendication 1,
    caractérisées en ce qu'
    il s'agit de produits adoucissants.
  3. Préparations selon la revendication 1,
    caractérisées en ce qu'
    il s'agit de produits de lavage liquides.
  4. Préparations selon la revendication 1,
    caractérisées en ce qu'
    il s'agit de produits de post-traitement du linge.
  5. Préparations selon au moins l'une des revendications 1 à 4,
    caractérisées en ce qu'
    elles contiennent comme agents actifs, des polymères ("soil repellants") qui présentent des groupes téréphtalate d'éthylène et/ou téréphtalate de polyéthylène-glycol.
  6. Préparations selon la revendication 5,
    caractérisées en ce que
    les polymères renferment des unités téréphtalate d'éthylène/téréphtalate de polyéthylène glycol dans un rapport molaire de 65:35 à 90:10.
  7. Préparations selon au moins l'une des revendications 1 à 6,
    caractérisées en ce qu'
    elles contiennent des microcapsules d'un diamètre moyen dans la plage de 0,0001 à 5 mm, constituées d'une membrane d'enveloppe et d'une matrice contenant les agents actifs, pouvant être obtenues
    (a1) en préparant une matrice à partir de gélifiants, de chitosanes et d'agents actifs,
    (a2) en dispersant le cas échéant la matrice dans une phase huileuse,
    (a3) en traitant la matrice dispersée avec des solutions aqueuses de polymères anioniques et en éliminant, le cas échéant, la phase huileuse,
    ou
    (b1) en préparant une matrice à partir de gélifiants, de polymères anioniques et d'agents actifs,
    (b2) en dispersant le cas échéant la matrice dans une phase huileuse,
    (b3) en traitant la matrice dispersée avec des solutions aqueuses de chitosane et en éliminant, le cas échéant, la phase huileuse,
    ou
    (c1) en transformant des préparations aqueuses d'agents actifs en émulsions H/E avec des corps huileux en présence d'émulsifiants,
    (c2) en traitant les émulsions ainsi obtenues avec des solutions aqueuses de polymères anioniques,
    (c3) en mettant la matrice ainsi obtenue en contact avec des solutions aqueuses de chitosane, et
    (c4) en séparant les produits d'encapsulation ainsi obtenus de la phase aqueuse.
  8. Préparations selon au moins l'une des revendications 1 à 7,
    caractérisées en ce qu'
    elles contiennent les agents actifs microencapsulés en quantités de 0,1 à 10 % en poids par rapport aux produits.
  9. Préparations selon au moins l'une des revendications 1 à 8,
    caractérisées en ce qu'
    elles contiennent en outre, des tensioactifs anioniques, non ioniques, cationiques et/ou amphotères ou zwitterioniques.
  10. Préparations selon au moins l'une des revendications 1 à 9,
    caractérisées en ce qu'
    elles contiennent en outre des agents épaississants.
  11. Procédé pour empêcher que les textiles se ressalissent selon lequel on apprête les fibres, fils ou articles textiles plats avec des agents actifs microencapsulés choisis dans le groupe constitué de polymères ("soil repellants"), présentant des groupes téréphtalate d'éthylène et/ou térephtalate de polyéthylène glycol, l'enveloppe des capsules étant constituée entièrement ou essentiellement de chitosane.
  12. Utilisation de polymères microencapsulés ("soil repellants"), présentant des groupes téréphtalate d'éthylène et/ou téréphtalate de polyéthylène glycol, et dont l'enveloppe des capsules est constituée entièrement ou essentiellement de chitosane, pour fabriquer des produits pour le traitement du linge.
EP03003177A 2003-02-18 2003-02-18 Compositions aqueuses contenant des matières actives microencapsulées Expired - Lifetime EP1449912B1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP03003177A EP1449912B1 (fr) 2003-02-18 2003-02-18 Compositions aqueuses contenant des matières actives microencapsulées
AT03003177T ATE364682T1 (de) 2003-02-18 2003-02-18 Wässrige zubereitungen mit mikroverkapselten wirkstoffen
ES03003177T ES2287367T3 (es) 2003-02-18 2003-02-18 Composiciones acuosas con compuestos activos microencapsulados.
DE50307462T DE50307462D1 (de) 2003-02-18 2003-02-18 Wässrige Zubereitungen mit mikroverkapselten Wirkstoffen
US10/781,576 US20040213997A1 (en) 2003-02-18 2004-02-18 Aqueous preparations containing microencapsulated active components

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP03003177A EP1449912B1 (fr) 2003-02-18 2003-02-18 Compositions aqueuses contenant des matières actives microencapsulées

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EP1449912A1 EP1449912A1 (fr) 2004-08-25
EP1449912B1 true EP1449912B1 (fr) 2007-06-13

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EP (1) EP1449912B1 (fr)
AT (1) ATE364682T1 (fr)
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Publication number Priority date Publication date Assignee Title
ES2249856T3 (es) * 1999-07-02 2006-04-01 Cognis Ip Management Gmbh Microcapsulas - iv.
DE102005003122A1 (de) * 2005-01-21 2006-07-27 Henkel Kgaa Antiadhäsive Polymere zur Verhinderung der Adhäsion von Mikroorganismen an Textilien und zur Verhinderung von Wäschegeruch
DE102005044521A1 (de) 2005-09-16 2007-03-22 Basf Ag Verfahren zur Beschichtung von Oberflächen und dafür geeignete Partikel
DE102005045138A1 (de) * 2005-09-22 2007-03-29 Cognis Ip Management Gmbh Wässrige Mikrokapseldispersionen
MY146540A (en) * 2005-11-17 2012-08-15 Colgate Palmolive Co Malodor reducing methods
DE102005056967A1 (de) * 2005-11-30 2007-05-31 Cognis Ip Management Gmbh Verfahren zur Ausrüstung von Textilien
EP2135931B1 (fr) * 2008-06-16 2012-12-05 The Procter & Gamble Company Utilisation d'un polymère de libération de salissures dans des compositions de traitement des tissus
GB0904700D0 (en) * 2009-03-19 2009-04-29 Unilever Plc Improvements relating to benefit agent delivery
GB201117231D0 (en) * 2011-10-06 2011-11-16 Givaudan Sa Composition
DE102014010875A1 (de) * 2014-07-25 2016-01-28 Basf Se Transparente Textilpflegemittel

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ES2213949T3 (es) * 1999-07-02 2004-09-01 Cognis Iberia, S.L. Microcapsulas i.
CN1237163C (zh) * 1999-12-03 2006-01-18 宝洁公司 载有添加剂特别如香料类的洗涤剂添加剂的已包胶多孔载体的输送系统
AU2001246459A1 (en) * 2000-02-23 2001-09-03 Henkel Kommanditgesellschaft Auf Aktien Microcapsules and/or nanocapsules

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DE50307462D1 (de) 2007-07-26
ATE364682T1 (de) 2007-07-15
ES2287367T3 (es) 2007-12-16
EP1449912A1 (fr) 2004-08-25
US20040213997A1 (en) 2004-10-28

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