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WO2004005448A1 - Preparations dosees d'agent detergent ou nettoyant liquide - Google Patents

Preparations dosees d'agent detergent ou nettoyant liquide Download PDF

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Publication number
WO2004005448A1
WO2004005448A1 PCT/EP2003/006733 EP0306733W WO2004005448A1 WO 2004005448 A1 WO2004005448 A1 WO 2004005448A1 EP 0306733 W EP0306733 W EP 0306733W WO 2004005448 A1 WO2004005448 A1 WO 2004005448A1
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WIPO (PCT)
Prior art keywords
preparations according
alkyl
preparations
carbon atoms
fatty acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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PCT/EP2003/006733
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German (de)
English (en)
Inventor
Gilabert Nuria BONASTRE
Augustin Sanchez
Maria De Moragas
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Cognis Iberia SL
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Cognis Iberia SL
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Publication of WO2004005448A1 publication Critical patent/WO2004005448A1/fr
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Classifications

    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) compositions
    • 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
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes

Definitions

  • the invention is in the field of detergents and relates to liquid preparations in water-soluble sachets which contain microencapsulated active ingredients.
  • Liquid preparations especially liquid detergents
  • the actual liquid surfactant phase is enclosed in a polymer shell, which dissolves in the wash liquor and thereby releases the surface-active compounds.
  • Most surfactants are solids that are sold in the form of more or less dilute aqueous pastes.
  • the incorporation, for example, of anionic or amphoteric surfactants into the formulation is unsuccessful, since this would require the presence of water. However, this is out of the question, since otherwise the portion bag would dissolve long before its actual predetermined end.
  • customary portioned liquid detergents contain all or practically exclusively nonionic surfactants, especially those of the fatty alcohol polyglycol ether type, since these are liquid even in the anhydrous state.
  • nonionic surfactants especially those of the fatty alcohol polyglycol ether type
  • they have a high content of non-ionic surfactants, since they are easy to assemble and in particular have the advantage of inverse solubility, ie they have better water solubility at lower temperatures than in Warmth.
  • Liquid detergents are therefore preferred for washing at 30 to 60 ° C. Conversely, of course, this also reveals their weakness: they are of little use in the field of cooked laundry, and they are hardly effective when it comes to removing greasy dirt.
  • the object of the present invention was therefore to improve the known portioned preparations on the market to such an extent that the use, in particular, of anionic, amphoteric or zwitterionic or cationic surfactants and of active ingredients which are otherwise difficult or impossible dissolve or disperse in the usual nonionic surfactant phase.
  • the new agents accessible in this way should not only distinguish themselves from other portioned preparations, but also from conventional liquid products on the market, by virtue of their advantageous technical properties, and if possible they should also have an interesting, appealing appearance. Description of the invention
  • the invention relates to portioned liquid detergent and cleaning agent preparations, such as, for example, liquid detergent, dishwashing detergent, universal detergent or softener, consisting of
  • the active ingredients lead to a significant improvement in the application properties of the preparations - in some cases even compared to conventional liquid products - because the active ingredients are delayed but then released in a concentrated manner so that, for example, a locally very high concentration is generated in the wash liquor.
  • Another advantage of the preparations is that sensitive active ingredients or ingredients that are incompatible with other components can be incorporated in a microencapsulated manner without decomposition or chemical reactions.
  • the capsules can be dispersed homogeneously and stably in the liquid phase, for example with the use of polymeric thickeners. If they additionally (or also exclusively) contain dyes, preparations with a particularly appealing appearance are obtained, for example if yellow-colored microcapsules are present in a green-colored liquid matrix.
  • the preparations are portioned in such a way that the liquid phase is enclosed by a solid shell, which preferably consists of at least one water-soluble polymer.
  • a solid shell which preferably consists of at least one water-soluble polymer.
  • water-soluble is to be understood in such a way that the shell completely dissolves in an aqueous environment within a period of 1 to 20 minutes, depending on the water temperature.
  • the shell preferably consists entirely or predominantly of polyvinyl alcohol.
  • liquid phase enclosed by the casing is anhydrous or has such a low water content that the casing does not prematurely dissolve or become permeable.
  • water contents can have a maximum of 5, preferably a maximum of 3 and in particular a maximum of 1% by weight.
  • the liquid phase is usually a non-ionic surfactant phase.
  • nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, (hydroxy) mixed ethers or mixed formals, alk (en) yloligoglycosides, fatty acids, especially vegetable hydrolysates, especially fatty acid-N-alkyl glucose amines Wheat-based products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides.
  • nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • Fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters, hydroxy mixed ethers or alkyl oligoglucosides are preferably used.
  • R 1 is a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms
  • R 2 is hydrogen or methyl and nl is
  • Numbers from 1 to 20 stands. 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, isostanol , 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. Especially Addition products of 3, 5 or 7 moles of ethylene oxide with technical coconut oil alcohols are preferred.
  • Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (II)
  • R 3 CO stands for a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms
  • R 4 for hydrogen or methyl
  • R 5 for linear or branched alkyl radicals with 1 to 4 carbon atoms
  • n2 for numbers of 1 to 20 stands.
  • Typical examples are the formal insert 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,
  • the products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, e.g. 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.
  • Hydroxy mixed ethers are known nonionic surfactants with an asymmetrical ether structure and polyalkylene glycol components, which can be obtained, for example, by subjecting olefin epoxides to a ring-opening reaction with fatty alcohol polyglycol ethers.
  • hydroxy mixed ethers typically following hydroxy mixed ethers of the general formula
  • R 6 CH-CHR 7 O (CH 2 CH2 ⁇ ) n3 (CH 2 CHO) m (CH 2 CH 2 O) n4 R 8 (TO) in which R 6 represents a linear or branched alkyl radical having 2 to 18, preferably 10 to 16 carbon atoms, R 7 represents hydrogen or a linear or branched alkyl radical having 2 to 18 carbon atoms, R 8 represents a linear or branched alkyl and / or alkenyl radical with 1 to 22, preferably 8 to 18 carbon atoms, n3 and n4 independently of one another for 0 or numbers from 1 to 60, preferably 2 to 25 and in particular 5 to 15 and m for 0 or numbers from 0.5 to 5, preferably 1 to 2, with the provisos that the sum of the carbon atoms in the radicals R and R is at least 6 and preferably 12 to 18 and the sum (n3 + m + n4) is different from 0.
  • the HME ring opening products can be either from internal olefins (R 7 not hydrogen) or terminal olefins (R 7 is hydrogen), the latter being preferred in view of the easier preparation and the more advantageous application properties.
  • the polar part of the molecule can be a polyethylene or a polypropylene chain; Mixed chains of PE and PP units are also suitable, be it in statistical or block distribution.
  • Typical examples are ring opening products of 1,2-hexenepoxide, 2,3-hexenepoxide, 1,2-octene epoxide, 2,3-octene epoxide, 3,4-octene epoxide, 1,2-decene epoxide, 2,3-decene epoxide, 3,4 -Decenepoxid, 4,5-Decenepoxid, 1,2-Dodecenepoxid, 2,3-Dodecenepoxid, 3,4-Dodecenepoxid, 4,5-Dodecenepoxid, 5,6-Dodecenepoxid, 1,2-Tetradecenepoxid, 2,3-Tetradecenepoxid , 3,4-Tetradecenepoxid, 4,5-Tetradecenepoxid, 5,6-Tetradecenepoxid, 6,7-Tetradecenepoxid, 1,2-Hexadecen epoxide,
  • R 6 for a linear alkyl radical with 8 to 10 carbon atoms
  • R 7 for hydrogen
  • R 8 for a linear alkyl radical with 8 to 10 carbon atoms
  • n3 stands for numbers from 0.5 to 2
  • n4 for numbers from 20 to 40, such as the commercial products Dehypon® KE 3447 and Dehypon® KE 3557 (Cognis).
  • R 6 is a linear alkyl radical having 8 to 10 carbon atoms
  • R 7 is hydrogen
  • R 8 is a branched alkyl radical having 8 to 10 carbon atoms
  • n3 and m are 0 and n4 are numbers from 20 to 40;
  • R 6 is a linear alkyl radical with 8 to 10 carbon atoms
  • R 7 is hydrogen
  • R 8 is a linear alkyl radical with 8 to 10 carbon atoms
  • n3 and m are 0 and n4 are numbers from 40 to 60.
  • Alkyl and alkenyl oligoglycosides which are also preferred nonionic surfactants, usually follow the formula (IV),
  • R 9 represents an alkyl and or alkenyl radical having 4 to 22 carbon atoms
  • G represents a sugar radical having 5 or 6 carbon atoms
  • p represents numbers 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 oligoglucosides.
  • 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, as well as their technical mixtures, such as are obtained, for example, from 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 the technical mixtures described above, which can be obtained as described above, and their technical mixtures.
  • Alkyl oligoglucosides are preferred
  • the preparations such a high viscosity that the microcapsules remain stable, ie do not sediment over time.
  • increased viscosity is understood to mean a rheology which ensures the stabilization of the microcapsules in the liquid (non-surfactant) phase.
  • Such viscosities are 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 those substances which give the surfactant preparations a correspondingly high viscosity.
  • 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, furthermore higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, ( eg Carbopole® and Pemulen types from Goodrich; Synthalene® from Sigma; Keltrol types from Kelco; Sepigel types from Seppic; Salcare types from Allied Colloids), polyacrylamides, polymers, polyvinyl alcohol and polyvinylpyrrolidone.
  • Aerosil types hydrophilic silicas
  • polysaccharides especially xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl and hydroxypropyl cellulose, furthermore higher molecular weight poly
  • 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 liquid phase can be 0.1 to 5, preferably 0.5 to 3 and in particular 1 to 2% by weight.
  • 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, they are finely dispersed liquid or solid phases coated with film-forming polymers, in the production of which the polymers are deposited 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.
  • microsponge a matrix
  • the microscopic capsules, also called nanocapsules can be dried like powders.
  • multinuclear aggregates are also , also known as microspheres, which contain two or more cores distributed in the continuous shell material, mono-core or multi-core microcapsules can also be enclosed by an additional second, third, etc.
  • the shell can consist of natural, semisynthetic or synthetic materials
  • Enveloping 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 ydrolysate, sucrose and waxes.
  • Semi-synthetic wrapping materials include chemically modified celluloses, especially cellulose esters and ethers, e.g.
  • 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, hydroxypropylmethylcellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar-agar) and Kuhs Probipheres Nanospheres Primasponges (chitosan, alginates) and Primasys (phospholipids) Chitosan microcapsules and processes for their production are the subject of earlier patent applications by the applicant [WO 01/01926, WO 01/01927, WO 01/01928, WO 01/019
  • a matrix is prepared from gel formers, chitosans and active ingredients, (a2) if appropriate, the matrix is dispersed in an oil phase,
  • the dispersed matrix is treated with aqueous solutions of anionic polymers and, if appropriate, the oil phase is removed in the process.
  • a matrix is prepared from gel formers, anionic polymers and active ingredients,
  • thermogelling heteropolysaccharides are agaroses
  • the main constituent of the agaroses are linear polysaccharides from D-galactose and 3,6-anhydro-L galactose, which are alternately linked by ⁇ -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 colored and tasteless.
  • Alternatives are pectins, xanthans (also xanthan gu) and their mixtures. Preference is furthermore given to those types which still form gels in 1% by weight aqueous solution, which do not melt below 80 ° C. and solidify again above 40 ° C.
  • the various types of gelatin from the group of thermogelating proteins are examples.
  • Chitosans are biopolymers and belong to the group of hydrocoids. From a chemical point of view, these are partially deacetylated chitins of different molecular weights that contain 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.
  • the production of chitosans is based on chitin, preferably the shell remnants of Krastentiere, which are available in large quantities as cheap raw materials.
  • the chitin is used in a process that was first developed byhackmann 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.
  • cationic polymers can also be used to form the membrane.
  • Suitable cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose, which is available from Amerchol under the name Polymer JR 400®, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such as, for example, Lu - viquat® (BASF), genpolypeptide condensation products of polyglycols and amines, quaternized collagen, such as Lauryldimom 'to hydroxypropyl Hydrolyzed collagen (Lamequat®L / Grunau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, for example amodimethicones, copolymers of adipic acid and minohydroxypropyldiethylen
  • the active substances which are suitable for microencapsulation can be divided into two groups, namely those
  • the first group includes ionic, i.e. anionic, cationic, amphoteric or zwitterionic surfactants, which are insoluble in the nonionic surfactant phase and could otherwise only be introduced as aqueous solutions.
  • suitable anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, alkyl ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxymether ether sulfates, (hydroxymether ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates,
  • anionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution.
  • Typical examples of cationic surfactants are quaternary ammonium compounds, such as, for example, dimethyldistearylammonium chloride, and esterquats, in particular quaternized fatty acid trialkanolamine ester salts.
  • Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, niazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds.
  • fatty alcohol (polyglycol ether) sulfates for reasons of application technology, fatty alcohol (polyglycol ether) sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid glutamates, esterquats, alkylamidobetaines, amphoacetals and / or protein fatty acid condensates, the latter preferably based on wheat proteins, are particularly preferred.
  • the microcapsules can also contain nonionic surfactants if they should not be a direct component of the liquid phase for other reasons.
  • the second group includes substances which are intended to protect and care for the skin when the preparations are used, for example during the manual rinsing process, or which are used, for example, to attach to the fibers during washing and to finish them.
  • biogenic agents and antioxidants such as vitamin E and its derivatives (e.g. tocopherol, tocopherol acetate, tocopherol palmitate), vitamin A and its derivatives (e.g.
  • carotenes caffeine, ascorbic acid, (deoxy) ribonucleic acid and their fragmentation products, ß -Glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, chitosan, menthol, squalane, vegetable oils (e.g. jojoba oil), vegetable proteins and their hydrolysis products as well as plant extracts and vitamin complexes.
  • ß -Glucans ß -Glucans
  • retinol bisabolol
  • allantoin phytantriol
  • panthenol panthenol
  • AHA acids amino acids
  • ceramides pseudoceramides
  • chitosan chitosan
  • menthol e.g. jojoba oil
  • squalane e.g. jojoba oil
  • squalane chitosan
  • menthol retinol
  • retinol vitamin A
  • caffeine vegetable proteins and their hydrolysis products
  • carolina and jojoba oil are particularly preferred, since these do not contribute to the balance of the cutane hydrolipids, prevent water loss and, for example, the skin give a soft and elastic feel after rinsing.
  • substances that protect the fibers in particular color stabilizers, such as Polyvinyl pyrrolidone, poly (4-vinyl pyridinium betaine) or poly (4-vibyl pyridine oxide).
  • Natural fragrances are extracts of flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, mountain pine), resins and balms (galbanum, elemi, benzoin, myrrh, olibanum, opoponax).
  • Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylethylphenylglycinate, allylcyclohexylproylateylateylateylateylateylateylateylateylatepylpropionate.
  • the ethers include, for example, benzyl ethyl ether
  • Aldehydes e.g. the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, ⁇ -isomethylionon and methylcedryl ketone, to the alcohols
  • the hydrocarbons mainly include terpenes and balms.
  • Essential oils of lower volatility which are mostly used as aroma components, are also suitable as perfume oils, e.g. Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil.
  • Suitable flavors are, for example, peppermint oil, spearmint oil, anise oil, star anise oil, caraway oil, eucalyptus oil, fennel oil, lemon oil, winter green oil, clove oil, menthol and the like.
  • the proportion of active substances in the microcapsules can be 1 to 30, preferably 5 to 25 and in particular 15 to 20% by weight.
  • oil phase
  • the matrix can optionally be dispersed in an oil phase before the membrane is formed.
  • Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C 6 -C 22 fatty acids with linear C 6 -C 22 fatty alcohols, esters of branched C 6 come as oils for this purpose, for example -C 13 carboxylic acids with linear C 6 -C fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palateate, cetyl styrate, cetyl styrate, cetyl styrate, cetyl styrene stearyl stearate, Stearyhsostearat, steary
  • esters of linear C 6 -C 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 acids are suitable Alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on Ce-Cio fatty acids, liquid mono- / di- / triglyceride mixtures based on C 6 -C 18 fatty acids, esters of C6-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
  • 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 as meaning both their complete and their partial neutralization products, in particular the alkali metal salts and among them preferably the sodium alginate (“algin”) and the ammonium and alkaline earth metal salts, mixed alginates such as Na around magnesium or natri are particularly preferred
  • anionic chitosan derivatives such as carboxylation and especially succinylation products, are also suitable for this purpose, or alternatively poly (meth) acrylates with average molecular weights in the range from 5,000 to 50,000 Dalton as well as the various carboxymethyl celluloses in question.
  • anionic surfactants or low molecular weight inorganic salts such as pyrophosphates can also be used for the formation of the envelope membrane.
  • Suitable emulsifiers are, for example, nonionic surfactants from at least one of the following groups:
  • Partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides with (e.g. / or unsaturated, linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;
  • Block copolymers e.g. Polyethylene glycol 30 dipolyhydroxystearate;
  • Polymer emulsifiers e.g. Pemulen types (TR-1, TR-2) from Goodrich;
  • the adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are mixtures of homologs whose average degree of alkoxylation is the ratio of the amounts of ethylene oxide and / or propylene oxide and Substrate with which the addition reaction is carried out corresponds. Of C 12/18 - Fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known as refatting agents for cosmetic preparations.
  • Alkyl and / or alkenyl ogoglycosides their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms.
  • glycoside residue both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to preferably about 8 are suitable.
  • the degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.
  • Suitable partial glycerides are rid Hydroxystearin Textremonoglyce-, hydroxystearic acid diglyceride, isostearic acid, Isostearinklaredigly- cerid, oleic acid monoglyceride, oleic acid diglyceride, Ricinolklaremoglycerid, diglyceride Ricinolklare-, Linolklaremonoglycerid, Linolklarediglycerid, LinolenTalkremonoglycerid, Linolenchurediglycerid, Erucaklaklamonoglycerid, Erucaklakladiglycerid, Weinklaremo- noglycerid, Weinklarediglycerid, Citronenklamonoglycerid, Citronendiglycerid, Malic acid monoglyceride, malic acid diglyceride and their technical mixtures, which may still contain minor amounts of triglyceride from the manufacturing process. Addition products of 1 to 30, preferably
  • polyglycerol esters are polyglyceryl-2 dipolyhydroxystearate (Dehymuls® PGPH), polyglycerol-3-diisostearate (Lameform® TGI), polyglyceryl-4 isostearate (Isolan® GI 34), polyglyceryl-3 oleate, diisostearoyl polygly- ceryl-3 diisostearate (Isolan® PDI), polyglyceryl-3 methylglucose distearate (Tego Care® 450), polyglyceryl-3 beeswax (Cera Bellina®), polyglyceryl-4 caprate (polyglycerol caprate T2010 / 90), polyglyceryl-3 cetyl Ether (Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate I
  • polystyrene resin examples include the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like which are optionally reacted with 1 to 30 mol of ethylene oxide.
  • Typical anionic emulsifiers are aliphatic fatty acids with 12 to 22 carbon atoms, such as palmitic acid, stearic acid or behenic acid, and dicarboxylic acids with 12 to 22 carbon atoms, such as azelaic acid or sebacic acid.
  • Zwitterionic surfactants can also be used as emulsifiers.
  • Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyl dimethylammomumglycinate, N-acylaminopropyl-N, N- dimethylammom ' umglycinate, for example the cocoacylaminopropyldimethylamomumglycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
  • betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyl dimethylammomumglycinate, N-acylaminopropyl-N, N- dimethylammom ' umglyc
  • fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred.
  • Suitable emulsifiers are ampholytic surfactants.
  • Ampholytic surfactants are surface-active compounds which, in addition to a C 8/18 alkyl or acyl group, contain at least one free amino group and at least one COOH or SO H group in the molecule and are capable of forming internal salts.
  • ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid in each case about 8 to 18 carbon atoms in the alkyl group .
  • particularly preferred ampholytic surfactants are N-coconut alkylaminopropionate, cocoacylaminoethyl aminopropionate and C 1/18 -
  • cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.
  • the loading of the microcapsules with active ingredients can therefore also be 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 point in time to adjust the viscosity, these being generally added in the form of aqueous or aqueous / alcoholic dispersions.
  • emulsifiers and / or solubilizers to the matrix.
  • the matrix After the matrix has been produced from gelling agent, chitosan and active ingredients, the matrix can optionally be very finely dispersed in an oil phase under high shear in order to produce the smallest possible particles in the subsequent encapsulation. It has proven to be particularly advantageous to heat the matrix to temperatures in the range from 40 to 60 ° C.
  • the actual encapsulation then takes place, ie the formation of the envelope membrane by bringing the chitosan in the matrix into contact with the anionic polymers.
  • the matrix 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% by weight aqueous solution of the anion polymer to treat and - if necessary - to remove the oil phase at the same time or subsequently.
  • the resulting aqueous preparations generally have a microcapsule content in the range from 1 to 10% by weight.
  • the solution of the polymers contains further ingredients, for example emulsifiers or preservatives.
  • microcapsules After filtration, microcapsules are obtained which have an average diameter in the range of preferably about 1 mm. It is advisable to sieve the capsules to ensure that the size is distributed as evenly as possible.
  • the microcapsules thus obtained can have any shape in the production-related framework, but they are preferably approximately spherical.
  • the anionic polymers can also be used to produce the matrix and encapsulated with the chitosans.
  • an O / W emulsion is first prepared which, in addition to the oil body, water and the active ingredients, contains an effective amount of emulsifier.
  • a corresponding amount of an aqueous anion polymer solution is added to this preparation with vigorous stirring.
  • the membrane is formed by adding the chitosan solution.
  • the microcapsules are separated from the aqueous phase, for example by decanting, filtering or centrifuging.
  • the liquid phase is first loaded with the microcapsules.
  • the mixture is then enclosed in the polymer shell by means of machines specially designed for this purpose.
  • the sachets usually have a weight of 1 to 10 and in particular 2 to 5 g.
  • the dimensions can be between 1 x 1 to 5 x 5 cm, the portion bags can be square, round or oval in shape.
  • microencapsulated active ingredients for the production of portioned liquid detergents and cleaning agents, which can be, for example, liquid detergents, dishwashing detergents, Universaheimger or finishing agents.
  • the microcapsules can be used in amounts of 0.1 to 10, preferably 1 to 8 and in particular 3 to 5% by weight, based on the portioned preparations.
  • a nonionic surfactant phase was loaded with various microcapsules and then enclosed in a polyvinyl alcohol shell.
  • the sachets had dimensions of 4 x 4 cm, weighed about 5 g and were square in shape.
  • Table 1 below contains a number of formulation examples. The recipes mean the following:
  • Primaspheres® A Chitosan microcapsules loaded with alkyl sulfate Primaspheres® B: CMtosan microcapsules loaded with alkyl ether sulfate Primaspheres® C: CMtosan microcapsules loaded with retinol Primaspheres® D: CWtosarimicro capsules loaded with esterquats

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Abstract

La présente invention concerne des préparations dosées d'agent détergent ou nettoyant liquide, constituées (a) d'une enveloppe hydrosoluble, (b) d'une phase liquide entourée par ladite enveloppe et (c) de substances actives encapsulées en dispersion dans ladite phase liquide.
PCT/EP2003/006733 2002-07-05 2003-06-26 Preparations dosees d'agent detergent ou nettoyant liquide Ceased WO2004005448A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP02015053A EP1378564A1 (fr) 2002-07-05 2002-07-05 Détergents liquides en portions
EP02015053.8 2002-07-05

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WO2004005448A1 true WO2004005448A1 (fr) 2004-01-15

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016096323A1 (fr) * 2014-12-19 2016-06-23 Henkel Ag & Co. Kgaa Composition de détergent liquide nacré
US10954372B2 (en) 2016-09-05 2021-03-23 Polye Materials Co., Ltd. Water soluble shopping bag and preparation method thereof
CN117384711A (zh) * 2023-09-21 2024-01-12 广东聚石科技研究院有限公司 一种流变剂及其制备方法、日化用品

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2005240189A1 (en) * 2004-05-06 2005-11-17 Ivrea Pharmaceuticals, Inc. Particles for the delivery of active agents
EP2079825A2 (fr) * 2006-11-13 2009-07-22 The Procter and Gamble Company Sachet de détergent hydrosoluble
JP2011511123A (ja) * 2008-01-31 2011-04-07 ザ プロクター アンド ギャンブル カンパニー キトサンのアセチル化

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115292A (en) * 1977-04-20 1978-09-19 The Procter & Gamble Company Enzyme-containing detergent articles
US4929380A (en) * 1986-06-27 1990-05-29 Henkel Kommanditgesellschaft Aug Aktien Process for the preparation of a storage-stable liquid detergent composition
EP1064911A1 (fr) * 1999-07-02 2001-01-03 Primacare S.A. Microcapsules
EP1064913A1 (fr) * 1999-07-02 2001-01-03 Primacare S.A. Microcapsules
EP1064910A1 (fr) * 1999-07-02 2001-01-03 Primacare S.A. Microcapsules
EP1064912A1 (fr) * 1999-07-02 2001-01-03 Primacare S.A. Microcapsules
EP1129771A1 (fr) * 2000-03-04 2001-09-05 Primacare S.A. Microcapsules
WO2002057402A1 (fr) * 2001-01-19 2002-07-25 The Procter & Gamble Company Composition liquide contenue dans un sachet

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115292A (en) * 1977-04-20 1978-09-19 The Procter & Gamble Company Enzyme-containing detergent articles
US4929380A (en) * 1986-06-27 1990-05-29 Henkel Kommanditgesellschaft Aug Aktien Process for the preparation of a storage-stable liquid detergent composition
EP1064911A1 (fr) * 1999-07-02 2001-01-03 Primacare S.A. Microcapsules
EP1064913A1 (fr) * 1999-07-02 2001-01-03 Primacare S.A. Microcapsules
EP1064910A1 (fr) * 1999-07-02 2001-01-03 Primacare S.A. Microcapsules
EP1064912A1 (fr) * 1999-07-02 2001-01-03 Primacare S.A. Microcapsules
EP1129771A1 (fr) * 2000-03-04 2001-09-05 Primacare S.A. Microcapsules
WO2002057402A1 (fr) * 2001-01-19 2002-07-25 The Procter & Gamble Company Composition liquide contenue dans un sachet

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016096323A1 (fr) * 2014-12-19 2016-06-23 Henkel Ag & Co. Kgaa Composition de détergent liquide nacré
US10954372B2 (en) 2016-09-05 2021-03-23 Polye Materials Co., Ltd. Water soluble shopping bag and preparation method thereof
CN117384711A (zh) * 2023-09-21 2024-01-12 广东聚石科技研究院有限公司 一种流变剂及其制备方法、日化用品

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