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WO2000065019A1 - Detergent containing abrasive material and microcapsules - Google Patents

Detergent containing abrasive material and microcapsules Download PDF

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Publication number
WO2000065019A1
WO2000065019A1 PCT/EP2000/003304 EP0003304W WO0065019A1 WO 2000065019 A1 WO2000065019 A1 WO 2000065019A1 EP 0003304 W EP0003304 W EP 0003304W WO 0065019 A1 WO0065019 A1 WO 0065019A1
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WO
WIPO (PCT)
Prior art keywords
microcapsules
amounts
composition according
weight
water
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.)
Ceased
Application number
PCT/EP2000/003304
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German (de)
French (fr)
Inventor
Hermann Jonke
Daniela Poethkow
Alexander Ditze
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AU52101/00A priority Critical patent/AU5210100A/en
Publication of WO2000065019A1 publication Critical patent/WO2000065019A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013Liquid compositions with insoluble particles in suspension
    • 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
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/14Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures

Definitions

  • the invention relates to thickened surfactant and abrasive liquid abrasives with microcapsules for cleaning hard surfaces.
  • Abrasives are powdery, liquid or pasty cleaning agents with a high content of mostly water-insoluble abrasive components such as finely ground quartz powder, marble powder, sometimes also chalk, feldspar and pumice stone. To protect the surfaces to be treated, the abrasive material must have a very fine and uniform grain. To improve the cleaning ability, most abrasives contain tensides, phosphates, soda and possibly also bleaching, disinfecting or deodorising agents. Abrasives are suitable for cleaning hard surfaces such as wood, metal, earthenware, enamel and stone in the home and business. Commercial liquid abrasives usually contain marble powder as an abrasive, which due to its low hardness can also be used on mechanically sensitive surfaces, e.g. Tiles, glass and enamel, no scratch marks.
  • the cleaning agent After storage and transport, the cleaning agent should have its optimum effect at the time of use on the object to be cleaned. This means that ingredients have not previously settled, decomposed or volatilized. Elaborate and correspondingly expensive packaging can counteract the loss of volatile components and protect the agent from the ingress of moisture. Chemically incompatible components can be preserved, for example, by cumbersome assembly in separate means, which then have to be combined with additional effort for use. Light-sensitive ingredients prohibit the presentation in transparent packaging, which allows the consumer to see the appearance and amount of the cleaner as well as possible.
  • microcapsules An elegant method for incorporating sensitive, chemically or physically incompatible and volatile ingredients is the use of microcapsules, in which these ingredients are enclosed during storage and transport and from which they are released mechanically, chemically, thermally or enzymatically for use.
  • Microcapsules 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.
  • the microscopic capsules also called nanocapsules, can be dried like powder. In this way, for example, gasoline, water, alcohol, pharmaceuticals, solvents, vitamins, enzymes, liquid crystals, food flavors and perfumes can be converted into a dry mass that cannot dry out.
  • the microencapsulation is used, for example, for perfume powders which, as microcapsules, are easier to handle and more effective for longer.
  • EP 0 763 595 relates to surfactant-containing structured liquid detergents with a sufficient amount of salting-out electrolyte for structuring the surfactants, in which "needle-shaped" solid particles measuring at least 3 to 25 ⁇ m in at least one spatial direction provide a stable suspension of larger, 200 to 1000 ⁇ m diameter particles, for example encapsulated bleach activators or enzymes.
  • the total content of surfactants is preferably above 20% by weight and electrolyte is preferably present in amounts of 7 to 45% by weight.
  • the solid particles for example calcium citrate, the dihydrate of calcium sulfate and calcium or magnesium chloride, are not abrasives.
  • EP 0 328 176 relates to surfactant and electrolyte-containing structured aqueous cleaning agents with a suspended phase composed of solid particles containing surfactant and / or non-encapsulated drops, which may contain mineral abrasive particles as a further suspended phase.
  • the suspended phase has a higher weight concentration of surfactant than the aqueous phase.
  • the total content of surfactants is preferably at least 15% by weight, the viscosity at a shear rate of 21 s "1 is preferably below 2,500 mPa-s, in particular below 1,000 mPa-s.
  • EP 0 397 246 discloses a powdery abrasive with 85% by weight of abrasives, which contains perfume capsules with a diameter of up to 100 ⁇ m with a water-insoluble, fragile shell.
  • the object of the invention was to provide high-cleaning liquid abrasives in which the physically or chemically incompatible or sensitive ingredients in temperature, storage and transport stable, easy to handle and visually appealing form are incorporated.
  • the invention relates to a thickened liquid abrasive cleaning agent for hard surfaces, which contains surfactant, abrasive, thickener and microcapsules, in which one or more ingredients are wholly or partly enclosed.
  • the microcapsules are chemically and physically, in particular spatially, stable, i.e. on average neither decomposition nor settling of the microcapsules occurs.
  • microcapsules contain at least one solid or liquid core which is enclosed by at least one continuous shell. Accordingly, two or more cores are distributed in the continuous shell material in multi-core microcapsules, also called microspheres, and single or multi-core microcapsules can be enclosed by an additional second, third, etc. shell. Mononuclear microcapsules with a continuous shell are preferred.
  • the shell can consist of natural, semi-synthetic or synthetic materials.
  • hematica are, for example, gum arabic, agar, agarose, maltodexthne, alginic acid or its salts, e.g. Sodium or calcium alginate, fats and fatty acids, cetyl alcohol, gelatin, albumin, shellac, polysaccharides such as starch or dextran, sucrose and waxes.
  • Semi-synthetic wrapping materials include chemical modified celluloses, especially cellulose esters and ethers, e.g.
  • Synthetic covering materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.
  • the cores of the microcapsules can be solids or liquids in the form of solutions or emulsions or suspensions and preferably contain one or more active ingredients.
  • active substances in the sense of the invention are essential oils, for example perfumes, limonene, geraniol or nerol, bleaching system components, for example bleach activator, Enzymes as well as care and protection components for the hard surface such as, for example, cationic polymers, silicone oils (for the care of ceramic surfaces) or stearyl mercaptan as silver protection Mixtures or their salts
  • Active ingredients according to the invention for improving the appearance are dyes, colored pigments or pearlescent components.
  • Active ingredients in the sense of the invention are also other ingredients customary in detergents and cleaning agents and cosmetics, including dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, Vitamin C, vitamin E, D-panthenol, rice rice, collagen partial hydrolyzate, various vegetable protein partial hydrolyzates, protein hydrolyzate fatty acid condensates, liposomes, cholestones, vegetable and animal oils such as lecithin, soybean oil, etc., Plant extracts such as aloe vera, Azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA complexes
  • dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, Vitamin C, vitamin E, D-panthenol, rice rice, collagen partial hydrolyzate, various vegetable protein partial hydrolyzates, protein hydrolyzate fatty acid condensates, liposomes, cholestones, vegetable and animal oils such as lecithin, soybean oil, etc.
  • Plant extracts such as aloe
  • microcapsules can have any shape in the production-related frame, but they are preferably egg-shaped or ellipsoidal or approximately spherical, their diameter along their greatest spatial extent is usually between 10 nm (visually not recognizable as a capsule) and 10 mm, depending on the active ingredient and application Visible microcapsules with a diameter in the range from 0.01 to 6 mm, in particular from 0.05 to 4 mm, extremely preferably from 0.1 to 2 mm are preferred. Microcapsules which can no longer be seen with the naked eye preferably have a diameter in the range from 20 to 500 nm, preferably 50 to 200 nm
  • microcapsules are accessible by methods known in the art, with coacervation and interfacial polymer satton being of the greatest importance
  • microcapsules All surfactant-stable microcapsules available on the market can be used as microcapsules, for example the commercial products Hallcrest Microcapsules (Hullmate ⁇ al gelatin, gum arabic) from Hallcrest, Ine (US), Coletica Thalaspheres (Hullmatenal maritime collagen) from Coletica (FR), Upotec Millicapsules (Hullmatenal alginic acid, agar-agar) from Lipotec SA (ES), Induchem Unispheres (Hullmatenal lactose, microcrystalline cellulose, hydroxypropylmethylcellulose) and Unicenn C30 (Hullmatenal lactose, microcrystalline cellulose, hydroxypropyl- methylcellulose) from Induchem AG (CH), Kobo Glycospheres (shell material: modified starch, fatty acid esters, phospholipids) and Softspheres (shell material: modified agar agar) from Kobo (US) and Kuhs Probiol Nanospheres (shell material: phospho
  • the active ingredients are released from the microcapsules during or during use by destroying the shell by mechanical, thermal, chemical or enzymatic action.
  • the release is preferably carried out by mechanical action, in particular by mechanical forces, to which the microcapsules exit when they leave the packaging, e.g. in a dispenser or spray valve, are exposed for this purpose, for example in the form of the microcapsules crushing shear forces or with a capsule diameter of about 1 mm blades cutting them, as well as by frictional forces to which the microcapsules are exposed when the abrasive agent is used.
  • compositions contain identical or different microcapsules in amounts of 0.1 to 10% by weight, in particular 0.2 to 8% by weight, extremely preferably 0.5 to 6% by weight.
  • Surfactants in the sense of the teaching according to the invention are one or more anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants, in particular one or more anionic and / or nonionic surfactants.
  • the total content of surfactants in the agents according to the invention is usually not more than 35% by weight, preferably 0.1 to 25% by weight, in particular 0.2 to 20% by weight and particularly preferably 0.4 to 15% by weight. -%.
  • Suitable anionic surfactants are, for example, C 1 -C 8 -carboxylic acids and their salts, C 1 -C 20 -alkyl-benzenesulfonates or alkylbenzenesulfonic acids, C 1 -C -alkyl sulfates and C 1 -C 20 -alkyl ether sulfates with 1 to 20 (average degree of alkoxylation) ethyleneoxy and / or propylene oxy units.
  • Preferred anionic surfactants are unbranched or branched, saturated or mono- or polyunsaturated (Fatty acids) and their salts, for example their alkali metal and alkaline earth metal salts, in particular sodium and potassium salts, and their ammonium and mono-, di- or trialkylammonium salts, such as monoethanolammonium salts.
  • Preferred fatty acids are oleic acid (9-octadecenoic acid), Palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid) and mixtures thereof, in particular palmitic / stearic acid mixtures, preferably in a molar ratio of about 1 to 1.
  • the compositions contain one or more anionic surfactants, in particular fatty acids and / or their salts, in amounts of 0.1 to 10% by weight, in particular 0.2 to 8% by weight, extremely preferably 1 up to 6% by weight.
  • Suitable nonionic surfactants are, for example, C 1- fatty alcohols and oxo alcohols as well as the adducts of ethylene oxide and / or propylene oxide with fatty alcohols or oxo alcohols or C 1- alkyl polyglycosides, in particular alkyl polyglucosides, with a degree of oligomerization of 1 to 10, preferably of 1, 1 to 2 , 5th
  • Nonionic surfactants preferred according to the invention are C 6-22 alkyl polyglycol ethers, in particular alkoxylated C 8 . 18 -fatty alcohols with 1 to 20, preferably 2 to 14, in particular 3 to 10 (average degree of alkoxylation) ethyleneoxy (EO) and / or propyleneoxy units (PO), for example C 10 . 14 - fatty alcohol + 1, 2PO + 6.4EO, C 12 . 14 -Coconut fatty alcohol + 6EO or C 12 . 14 -Coconut fatty alcohol + 4EO.
  • compositions contain one or more nonionic surfactants, in particular alkyl polyglycol ethers, in amounts of 0.1 to 10% by weight, in particular 0.2 to 7% by weight, extremely preferably 0.5 to 5% by weight .-%.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R 1 ) (R 2 ) (R 3 ) N + CH 2 COO ⁇ in which R 1 is an alkyl radical with 8 to 25, preferably 10 to 21, carbon atoms and optionally interrupted by hetero atoms or hetero atom groups R 2 and R 3 are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 -alkyl-dimethylcarboxymethylbetaine and Cn-C ⁇ -alkylamidopropyl-dimethylcarboxymethylbetaine.
  • Suitable cationic surfactants are, for example, quaternary ammonium compounds of the general formula (R 4 N + ) X ⁇ , in particular those in which the nitrogen group is substituted by two long and two short alkyl radicals, for example dimethyldistearylammonium chloride.
  • the agents according to the invention contain one or more abrasives.
  • the abrasive is preferably finely divided, with an average grain size in the range of approximately 5 ⁇ m up to 100 ⁇ m, with at most 10% of the particles having a grain size of more than 150 ⁇ m.
  • the average grain size of the particles forming the solid phase is preferably 10 ⁇ m to 80 ⁇ m and in particular 10 ⁇ m to 60 ⁇ m, the maximum grain size being below 200 ⁇ m, in particular below 150 ⁇ m.
  • the average grain size relates to the volume distribution of the particles, which can be determined by known methods (for example using a Coulter Counter).
  • a water-insoluble, a sparingly water-soluble or a water-soluble substance can be used as the abrasive substance.
  • the water-insoluble abrasives that can be used in the context of the present invention include, for example, quartz powder, aluminum oxide, marble powder, chalk, pumice, layered silicates and / or fetidate.
  • Poorly soluble abrasives in water are, for example, poorly soluble salts such as anhydrite and anhydrous CaSO 4 .
  • Anhydrite is characterized in particular by the fact that it is particularly easy to rinse or wash after using the abrasive.
  • Preferred anhydrite is colorless, that is to say invisibly colored by addition, and has an average grain size of about 26 ⁇ m determined by sieve analysis, with about 10% having a grain size of up to 3.5 ⁇ m and 90% having a grain size of up to 61 ⁇ m.
  • Such an anhydrite is available as calcium anhydrite ⁇ ® from Südharzer Gipswerke.
  • Water-soluble abrasives are generally water-soluble salts selected from the group of chlorides, carbonates, bicarbonates, sulfates, phosphates, borates or silicates. These are preferably alkali metal salts, particularly preferably the salts of sodium and / or potassium.
  • Water-soluble abrasives are preferably used when the agent has a low water content, since the use of water-soluble abrasives in water-containing agents requires that the amount of added abrasive exceeds the abrasive-related solvency of the water. Accordingly, the use of water-soluble abrasives with increasing water content of the agent or increasing abrasive-related dissolving power is less and less preferred.
  • the agent according to the invention preferably contains one or more water-soluble and / or water-insoluble abrasives, in particular from the group calcium carbonate (for example DurcaP l ⁇ from Omya GmbH), aluminum oxide (for example polishing clay 11 'P 730 or Alcoa Chemie) and silica with a quartz: kaolinite weight ratio of 74:26 (e.g. Sillitin ® Z 86 from Hoffmann & Sons).
  • group calcium carbonate for example DurcaP l ⁇ from Omya GmbH
  • aluminum oxide for example polishing clay 11 'P 730 or Alcoa Chemie
  • silica with a quartz: kaolinite weight ratio of 74:26 e.g. Sillitin ® Z 86 from Hoffmann & Sons.
  • the abrasives are contained in the agents according to the invention preferably in amounts of 5 to 80% by weight, in particular 10 to 70% by weight, particularly preferably 15 to 60% by weight, extremely preferably 20 to 50% by weight.
  • the agents according to the invention contain one or more thickeners.
  • thickeners are organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein), organic modified natural substances (carboxymethyl cellulose and cellulose ether , Hydroxyethyl and propyl cellulose and the like, core meal ether), organic fully synthetic thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides) and inorganic thickeners (polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas) .
  • organic natural thickeners agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein
  • Thickeners preferred according to the invention are xanthan gum (for example Ke / fro / ® RD from Kelco, Rhodopof ® 50 MD from Rhone Poulenc), anionic methacrylic acid / ethyl acrylate copolymer (for example Rohagif SD 15 from Röhm GmbH) and swelling-delayed hydroxyethyl cellulose (for example Tylose ® H 60000 YP 2 from Clariant).
  • xanthan gum for example Ke / fro / ® RD from Kelco, Rhodopof ® 50 MD from Rhone Poulenc
  • anionic methacrylic acid / ethyl acrylate copolymer for example Rohagif SD 15 from Röhm GmbH
  • swelling-delayed hydroxyethyl cellulose for example Tylose ® H 60000 YP 2 from Clariant.
  • the thickener content of the agents according to the invention is preferably 0.01 to 10% by weight, in particular 0.05 to 6% by weight, most preferably 0.1 to 3% by weight.
  • the agents according to the invention can contain one or more builder components, preferably citric acid (for example citric acid-1 H 2 O) or alkali, in particular monoethanolamine, diethanolamine, triethanolamine and / or ammonia, in quantities of 0.01 to 10% by weight, contain in particular 0.1 to 5% by weight.
  • citric acid for example citric acid-1 H 2 O
  • alkali in particular monoethanolamine, diethanolamine, triethanolamine and / or ammonia
  • the agents according to the invention can advantageously contain one or more foam inhibitors, for example natural fats and oils or fatty alcohols, long-chain soaps (e.g. sodium behenate), silicone-based defoamers and symmetrical or asymmetrical dialkyl ethers (e.g. etherified with (fatty) alcohols) Fatty alcohol polyglycol ethers).
  • foam inhibitors are preferred Dimethylpolysiloxanmischungen (for example, Dow Corning ® DB 31 EU of Dow Corning) and Carbonklareester (eg Degressat ® SD 30 from BASF AG).
  • the foam inhibitor content in the agents according to the invention is preferably not more than 5% by weight and in particular between 0.0001 and 3% by weight.
  • the liquid phase of the agents according to the invention are usually based on water, their water content then being about 15 to 90% by weight, preferably 20 to 80% by weight, in particular 30 to 70% by weight.
  • the water content can also be less than 15% by weight, preferably 0.1 to 10% by weight, in particular 0.2 to 5% by weight, in particular if the surfactant content is high and / or water-soluble abrasives are used .
  • the aqueous compositions according to the invention can also contain one or more non-aqueous solvents, for example alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol), ethers and glycol ethers (diethyl ether, dibutyl ether, mono-, di -, tri, polyethylene glycol ether, propylene glycol monobutyl ether).
  • a preferred solvent is ethanol.
  • These solvents are preferably present in the compositions according to the invention in amounts of 0.01 to 20% by weight, in particular 0.1 to 12% by weight, extremely preferably 0.5 to 8% by weight.
  • the viscosity of the agents according to the invention at a temperature of 22 ° C. and a shear rate of 20 min '1 is preferably in the range from 500 to 20,000 mPa-s, in particular from 1,000 to 15,000 mPa-s, particularly preferably from 1,500 to 10,000 mPa-s.
  • agents according to the invention can contain other customary additives, for example colorants and fragrances, preservatives, corrosion inhibitors, antistatic agents or microbicides.
  • the pH of the agents according to the invention is to be selected in accordance with the particular application.
  • the agents can accordingly be acidic, preferably with a pH of 1 to 6, in particular 1.5 to 4, neutral, preferably with a pH between 6 and 8, in particular 6.5 to 7.5, or alkaline, preferably with a pH of 8 to 12, in particular 9 to 11.
  • acid or alkali for example citric acid or sodium hydroxide solution.
  • the thickener is preferably first thickened in water and then surfactants and, if appropriate, further ingredients mentioned above are mixed in except for the abrasive component. If perfume and / or dye are used, they are added last. Then the abrasive component is added, if necessary the pH is adjusted as described above and finally the microcapsules are mixed in.
  • Agents E1 to E3 according to the invention were produced and their pH and viscosity were determined.
  • compositions of the compositions E1 to E3 according to the invention in% by weight and the specific properties are given below.
  • the pH of the agents E1 to E4 according to the invention was adjusted to the specified values of 2.5 and 10 using citric acid or sodium hydroxide solution.
  • the viscosity was determined using a Brookfield RVT Series 3227 rotary viscometer using spindle 4 at a shear rate of 20 min -1 and a temperature of 22 ° C.
  • the capsules were stable in the means E1 to E4 at 40 ° C. for 3 months. There was no change in the shape of the capsules or their spatial distribution on average.
  • Example 1 E1 abrasive for hard surfaces in the household
  • composition of E2 in% by weight is Composition of E2 in% by weight:
  • microcapsules of the D / HC 188 type from Hallcrest had a diameter of 50 to 100 ⁇ m and contained about 38% by weight of water in a casing made of about 4% by weight gelatin and gum arabic, and as a care component for ceramic surfaces approx. 58% by weight silicone oil in the form of a dimethylcyclosiloxane pentamer / polydimethylsiloxanol mixture, as is sold, for example, by Dow Corning as Dow Corning® 1401 fluid.
  • microcapsules (h) had an average diameter of 1 mm and contained about 35% by weight of water and about 60% by weight of stearyl mercaptan as a silver protection component in a casing made of about 5% by weight of gelatin and gum arabic.
  • microcapsules (i) obtained from Lipotec ® had an average diameter of 0.8 mm and contained a fragrance in an aqueous glycerol-containing medium in a casing made of alginic acid and agar.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention relates to a thickened, liquid, aqueous and abrasive detergent for hard surfaces. Said detergent contains a surfactant, abrasive material, thickening agents and microcapsules in which one or more constituents are entirely or partially enclosed.

Description

"Abrasivstoffhaltiges Reinigungsmittel mit Mikrokapseln" "Abrasive cleaning agent with microcapsules"

Die Erfindung betrifft verdickte tensid- und abrasivstoffhaltige flüssige Scheuermittel mit Mikrokapseln zur Reinigung harter Oberflächen.The invention relates to thickened surfactant and abrasive liquid abrasives with microcapsules for cleaning hard surfaces.

Scheuermittel sind pulverförmige, flüssige oder pastöse Reinigungsmittel mit einem hohen Gehalt an zumeist wasserunlöslichen Abrasivkomponenten wie feingemahlenem Quarzmehl, Marmormehl, zuweilen auch Kreide, Feldspat und Bimsstein. Zur Schonung der zu behandelnden Flächen muss der Abrasivstoff eine sehr feine und einheitliche Körnung besitzen. Zur Verbesserung des Reinigungsvermögens enthalten die meisten Scheuermittel Tenside, Phosphate, Soda und gegebenenfalls auch bleichende, desinfizierende oder desodorierende Wirkstoffe. Scheuermittel sind geeignet zum Reinigen harter Oberflächen wie Holz, Metall, Steingut, Emaille und Stein in Haushalt und Gewerbe. Flüssige Scheuermittel des Handels enthalten als Abrasivstoff meist Marmormehl, das wegen seiner geringen Härte auch auf mechanisch empfindlichen Oberflächen, z.B. Fliesen, Glas und Emaille, keine Kratzspuren hinterlässt.Abrasives are powdery, liquid or pasty cleaning agents with a high content of mostly water-insoluble abrasive components such as finely ground quartz powder, marble powder, sometimes also chalk, feldspar and pumice stone. To protect the surfaces to be treated, the abrasive material must have a very fine and uniform grain. To improve the cleaning ability, most abrasives contain tensides, phosphates, soda and possibly also bleaching, disinfecting or deodorising agents. Abrasives are suitable for cleaning hard surfaces such as wood, metal, earthenware, enamel and stone in the home and business. Commercial liquid abrasives usually contain marble powder as an abrasive, which due to its low hardness can also be used on mechanically sensitive surfaces, e.g. Tiles, glass and enamel, no scratch marks.

Nach Lagerung und Transport soll das Reinigungsmittel zum jeweiligen Zeitpunkt der Anwendung am zu reinigenden Objekt optimal seine Wirkung entfalten. Das bedingt, dass sich Inhaltsstoffe zuvor weder abgesetzt, noch zersetzt oder verflüchtigt haben. Aufwendige und dementsprechend teure Verpackungen können dem Verlust flüchtiger Komponenten entgegenwirken sowie das Mittel vor eindringender Feuchtigkeit schützen. Chemisch inkompatible Komponenten können beispielsweise durch umständliche Konfektionierung in getrennten Mitteln konserviert werden, die dann zur Anwendung unter zusätzlichem Aufwand vereinigt werden müssen. Lichtempfindliche Inhaltsstoffe verbieten die Darbietung in durchsichtiger Verpackung, die dem Konsumenten Aussehen und Menge des Reinigers möglichst gut zu sehen erlaubt.After storage and transport, the cleaning agent should have its optimum effect at the time of use on the object to be cleaned. This means that ingredients have not previously settled, decomposed or volatilized. Elaborate and correspondingly expensive packaging can counteract the loss of volatile components and protect the agent from the ingress of moisture. Chemically incompatible components can be preserved, for example, by cumbersome assembly in separate means, which then have to be combined with additional effort for use. Light-sensitive ingredients prohibit the presentation in transparent packaging, which allows the consumer to see the appearance and amount of the cleaner as well as possible.

Eine elegante Methode zur Einarbeitung empfindlicher, chemisch oder physikalisch inkompatibler sowie flüchtiger Inhaltsstoffe besteht im Einsatz von Mikrokapseln, in denen diese Inhaltsstoffe lager- und transportstabil eingeschlossen sind und aus denen sie zur bzw. bei der Anwendung mechanisch, chemisch, thermisch oder enzymatisch freigesetzt werden. Mikrokapseln sind 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. Die mikroskopisch kleinen Kapseln, auch Nanokapseln genannt, lassen sich wie Pulver trocknen. Auf diese Weise können z.B. Benzin, Wasser, Alkohol, Pharmazeutika, Lösungsmittel, Vitamine, Enzyme, flüssige Kristalle, Lebensmittelaromen und Parfüms in eine Trockenmasse umgewandelt werden, die nicht eintrocknen kann. Die Mikroverkap- selung findet Verwendung z.B. für Parfümpulver, die als Mikrokapseln in der Handhabung bequemer und länger wirksam sind.An elegant method for incorporating sensitive, chemically or physically incompatible and volatile ingredients is the use of microcapsules, in which these ingredients are enclosed during storage and transport and from which they are released mechanically, chemically, thermally or enzymatically for use. Microcapsules 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. The microscopic capsules, also called nanocapsules, can be dried like powder. In this way, for example, gasoline, water, alcohol, pharmaceuticals, solvents, vitamins, enzymes, liquid crystals, food flavors and perfumes can be converted into a dry mass that cannot dry out. The microencapsulation is used, for example, for perfume powders which, as microcapsules, are easier to handle and more effective for longer.

Die EP 0 763 595 betrifft tensidhaltige strukturierte flüssige Waschmittel mit einer zur Strukturierung der Tenside ausreichenden Menge aussalzenden Elektrolyts, in denen "nadeiförmige" in wenigstens einer Raumrichtung 3 bis 25 μm messende feste Partikel eine stabile Suspendierung größerer, 200 bis 1000 μm durchmessender Teilchen, beispielsweise verkapselter Bleichaktivatoren oder Enzyme, ermöglichen sollen. Hierbei liegt der Gesamtgehalt an Tensiden vorzugsweise über 20 Gew.-% und ist Elektrolyt bevorzugt in Mengen von 7 bis 45 Gew.-% enthalten. Die festen Partikel, beispielsweise Calciumcitrat, das Dihydrat des Calciumsulfats sowie Calcium- oder Magnesiumchlorid, stellen keine Abrasivstoffe dar.EP 0 763 595 relates to surfactant-containing structured liquid detergents with a sufficient amount of salting-out electrolyte for structuring the surfactants, in which "needle-shaped" solid particles measuring at least 3 to 25 μm in at least one spatial direction provide a stable suspension of larger, 200 to 1000 μm diameter particles, for example encapsulated bleach activators or enzymes. The total content of surfactants is preferably above 20% by weight and electrolyte is preferably present in amounts of 7 to 45% by weight. The solid particles, for example calcium citrate, the dihydrate of calcium sulfate and calcium or magnesium chloride, are not abrasives.

Die EP 0 328 176 betrifft tensid- und elektrolythaltige strukturierte wässrige Reinigungsmittel mit einer suspendierten Phase aus tensidhaltigen festen Partikeln und/oder nicht- verkapselten Tropfen, die als weitere suspendierte Phase mineralische abrasive Partikel enthalten können. Hierbei weist die suspendierte Phase eine höhere Gewichtskonzentration an Tensid als die wässrige Phase auf. Der Gesamtgehalt an Tensiden beträgt vorzugsweise mindestens 15 Gew.-%, die Viskosität liegt bei einer Scherrate von 21 s"1 bevorzugt unter 2.500 mPa-s, insbesondere unter 1.000 mPa-s.EP 0 328 176 relates to surfactant and electrolyte-containing structured aqueous cleaning agents with a suspended phase composed of solid particles containing surfactant and / or non-encapsulated drops, which may contain mineral abrasive particles as a further suspended phase. The suspended phase has a higher weight concentration of surfactant than the aqueous phase. The total content of surfactants is preferably at least 15% by weight, the viscosity at a shear rate of 21 s "1 is preferably below 2,500 mPa-s, in particular below 1,000 mPa-s.

Aus der EP 0 397 246 ist ein pulverförmiges Scheuermittel mit 85 Gew.-% Abrasivstoffen bekannt, das Parfümkapseln mit einem Durchmesser von bis zu 100 μm mit einer wasserunlöslichen brüchigen Hülle enthält.EP 0 397 246 discloses a powdery abrasive with 85% by weight of abrasives, which contains perfume capsules with a diameter of up to 100 μm with a water-insoluble, fragile shell.

Aufgabe der Erfindung war es, reinigungsstarke flüssige Scheuermittel bereitzustellen, in denen die physikalisch oder chemisch inkompatiblen bzw. empfindlichen Inhaltsstoffe in temperatur-, lager- und transportstabiler, leicht handhabbarer und optisch ansprechender Form eingearbeitet sind.The object of the invention was to provide high-cleaning liquid abrasives in which the physically or chemically incompatible or sensitive ingredients in temperature, storage and transport stable, easy to handle and visually appealing form are incorporated.

Gegenstand der Erfindung ist ein verdicktes flüssiges abrasives Reinigungsmittel für harte Oberflächen, das Tensid, Abrasivstoff, Verdickungsmittel sowie Mikrokapseln enthält, in denen ein oder mehrere Inhaltsstoffe ganz oder teilweise eingeschlossen sind.The invention relates to a thickened liquid abrasive cleaning agent for hard surfaces, which contains surfactant, abrasive, thickener and microcapsules, in which one or more ingredients are wholly or partly enclosed.

Mengenangaben in Gewichtsprozent (Gew.-%) beziehen sich, soweit nicht anders angegeben, immer auf das gesamte Mittel.Unless otherwise stated, quantities in percent by weight (% by weight) always relate to the entire composition.

Die Mikrokapseln sind in den erfindungsgemäßen Mitteln chemisch und physikalisch, insbesondere räumlich, stabil, d.h. im Mittel tritt weder eine Zersetzung noch ein Absetzen der Mikrokapseln auf.In the agents according to the invention, the microcapsules are chemically and physically, in particular spatially, stable, i.e. on average neither decomposition nor settling of the microcapsules occurs.

Die Mikrokapseln enthalten mindestens einen festen oder flüssigen Kern, der von mindestens einer kontinuierlichen Hülle umschlossen ist. Dementsprechend sind in mehrkernigen Mikrokapseln, auch Mikrosphären genannt, zwei oder mehr Kerne im kontinuierlichen Hüllmaterial verteilt und können ein- oder mehrkernige Mikrokapseln von einer zusätzlichen zweiten, dritten etc. Hülle umschlossen sein. Bevorzugt sind einkernige Mikrokapseln mit einer kontinuierlichen Hülle.The microcapsules contain at least one solid or liquid core which is enclosed by at least one continuous shell. Accordingly, two or more cores are distributed in the continuous shell material in multi-core microcapsules, also called microspheres, and single or multi-core microcapsules can be enclosed by an additional second, third, etc. shell. Mononuclear microcapsules with a continuous shell are preferred.

Die Hülle kann aus natürlichen, halbsynthetischen oder synthetischen Materialien bestehen. Natürlich Hülimatehalien sind beispielsweise Gummi arabicum, Agar, Agarose, Maltodexthne, Alginsäure bzw. ihre Salze, z.B. Natrium- oder Caiciumalginat, Fette und Fettsäuren, Cetylalkohol, Gelatine, Albumin, Schellack, Polysaccharide wie Stärke oder Dextran, Sukrose und Wachse. Halbsynthetische Hüllmaterialien sind unter anderem chemische modifizierte Cellulosen, insbesondere Celluloseester und -ether, z.B. Cellulo- seacetat, Ethylcellulose, Hydroxypropylcellulose, Hydroxypropylmethylcellulose und Car- boxymethylcellulose, sowie Stärke-Derivate, insbesondere Stärkeether und -ester. Synthetische Hüllmaterialien sind beispielsweise Polymere wie Polyacrylate, Polyamide, Po- lyvinylalkohol oder Polyvinylpyrrolidon.The shell can consist of natural, semi-synthetic or synthetic materials. Of course, hematica are, for example, gum arabic, agar, agarose, maltodexthne, alginic acid or its salts, e.g. Sodium or calcium alginate, fats and fatty acids, cetyl alcohol, gelatin, albumin, shellac, polysaccharides such as starch or dextran, sucrose and waxes. Semi-synthetic wrapping materials include chemical modified celluloses, especially cellulose esters and ethers, e.g. Cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose, as well as starch derivatives, in particular starch ethers and esters. Synthetic covering materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.

Die Kerne der Mikrokapseln können Feststoffe oder Flüssigkeiten in Form von Lösungen oder Emulsionen bzw. Suspensionen sein und enthalten vorzugsweise einen oder mehrere Wirkstoffe. Bevorzugte Wirkstoffe im Sinne der Erfindung sind ätherische öle, z.B. Parfüms, Limonen, Geraniol oder Nerol, Bleichsystemkomponenten, z.B. Bleichaktivator, Enzyme sowie Pflege- und Schutzkompoπenten für die harte Oberflache wie beispielsweise kationische Polymere, Siliconole (zur Pflege von Ceranflachen) oder Stearylmer- captan als Silberschutz Wirkstoffe im Sinne der Erfindung sind zudem antibakterielle Wirkstoffe, wie z B Benzoesaure, Milchsaure, Salicylsaure, Sorbinsaure oder deren Mischungen bzw deren Salze Erfindungsgemaße Wirkstoffe zur Verbesserung des Erscheinungsbildes sind Farbstoffe, Farbpigmente oder Perlglanzkomponente Weiterhin sind Wirkstoffe im Sinne der Erfindung auch andere in Wasch- und Reinigungsmitteln sowie Kosmetika übliche Inhaltsstoffe, unter anderem dermatologisch wirksame Substanzen wie Vitamin A, Vitamin B2, Vitamin B12, Vitamin C, Vitamin E, D-Panthenol, Se- riceπn, Collagen-Partial-Hydroiysat, verschiedene pflanzliche Protein-Partial-Hydrolysate, Proteinhydrolysat-Fettsaure-Kondensate, Liposome, Cholestenn, pflanzliche und tierische Öle wie z B Lecithin, Sojaol usw , Pflanzenextrakte wie z B Aloe Vera, Azulen, Hamamelisextrakte, Algenextrakte usw , Allantoin, A H A -KomplexeThe cores of the microcapsules can be solids or liquids in the form of solutions or emulsions or suspensions and preferably contain one or more active ingredients. Preferred active substances in the sense of the invention are essential oils, for example perfumes, limonene, geraniol or nerol, bleaching system components, for example bleach activator, Enzymes as well as care and protection components for the hard surface such as, for example, cationic polymers, silicone oils (for the care of ceramic surfaces) or stearyl mercaptan as silver protection Mixtures or their salts Active ingredients according to the invention for improving the appearance are dyes, colored pigments or pearlescent components. Active ingredients in the sense of the invention are also other ingredients customary in detergents and cleaning agents and cosmetics, including dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, Vitamin C, vitamin E, D-panthenol, rice rice, collagen partial hydrolyzate, various vegetable protein partial hydrolyzates, protein hydrolyzate fatty acid condensates, liposomes, cholestones, vegetable and animal oils such as lecithin, soybean oil, etc., Plant extracts such as aloe vera, Azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA complexes

Die Mikrokapseln können im herstellungsbedingten Rahmen eine beliebige Form aufweisen, sie sind jedoch bevorzugt eiförmig bzw ellipsoid geformt oder naherungsweise kugelförmig Ihr Durchmesser entlang ihrer größten raumlichen AusdehnungJiegt je nach Wirkstoff und Anwendung üblicherweise zwischen 10 nm (visuell nicht als Kapsel erkennbar) und 10 mm, ggf auch darüber Bevorzugt sind sichtbare Mikrokapseln mit einem Durchmesser im Bereich von 0,01 bis 6 mm, insbesondere von 0,05 bis 4 mm, äußerst bevorzugt von 0,1 bis 2 mm Nicht mehr mit bloßem Auge wahrnehmbare Mikrokapseln haben vorzugsweise einen Durchmesser im Bereich von 20 bis 500 nm, vorzugsweise 50 bis 200 nmThe microcapsules can have any shape in the production-related frame, but they are preferably egg-shaped or ellipsoidal or approximately spherical, their diameter along their greatest spatial extent is usually between 10 nm (visually not recognizable as a capsule) and 10 mm, depending on the active ingredient and application Visible microcapsules with a diameter in the range from 0.01 to 6 mm, in particular from 0.05 to 4 mm, extremely preferably from 0.1 to 2 mm are preferred. Microcapsules which can no longer be seen with the naked eye preferably have a diameter in the range from 20 to 500 nm, preferably 50 to 200 nm

Die Mikrokapseln sind nach im Stand der Technik bekannten Verfahren zugänglich, wobei der Koazervation und der Grenzflachenpolymeπsatton die größte Bedeutung zukommtThe microcapsules are accessible by methods known in the art, with coacervation and interfacial polymer satton being of the greatest importance

Als Mikrokapseln lassen sich sämtliche auf dem Markt angebotene tensidstabile Mikrokapseln einsetzen, beispielsweise die Handelsprodukte Hallcrest Microcapsules (Hullmateπal Gelatine, Gummi Arabicum) der Firma Hallcrest, Ine (US), Coletica Tha- laspheres (Hullmatenal maritimes Collagen) der Firma Coletica (FR), Upotec Millicap- seln (Hullmatenal Alginsäure, Agar-Agar) der Firma Lipotec S A (ES), Induchem Unispheres (Hullmatenal Lactose, mikrokristalline Cellulose, Hydroxypropylmethylcellu- lose) und Unicenn C30 (Hullmatenal Lactose, mikrokristalline Cellulose, Hydroxypropyl- methylcellulose) der Firma Induchem AG (CH), Kobo Glycospheres (Hüllmaterial: modifizierte Stärke, Fettsäureester, Phospholipide) und Softspheres (Hüllmaterial: modifiziertes Agar-Agar) der Firma Kobo (US) sowie Kuhs Probiol Nanospheres (Hüllmaterial: Phospholipide) der Firma Kuhs (DE).All surfactant-stable microcapsules available on the market can be used as microcapsules, for example the commercial products Hallcrest Microcapsules (Hullmateπal gelatin, gum arabic) from Hallcrest, Ine (US), Coletica Thalaspheres (Hullmatenal maritime collagen) from Coletica (FR), Upotec Millicapsules (Hullmatenal alginic acid, agar-agar) from Lipotec SA (ES), Induchem Unispheres (Hullmatenal lactose, microcrystalline cellulose, hydroxypropylmethylcellulose) and Unicenn C30 (Hullmatenal lactose, microcrystalline cellulose, hydroxypropyl- methylcellulose) from Induchem AG (CH), Kobo Glycospheres (shell material: modified starch, fatty acid esters, phospholipids) and Softspheres (shell material: modified agar agar) from Kobo (US) and Kuhs Probiol Nanospheres (shell material: phospholipids) from Kuhs (DE).

Die Freisetzung der Wirkstoffe aus den Mikrokapseln erfolgt zur bzw. während der Anwendung durch Zerstörung der Hülle durch mechanische, thermische, chemische oder enzymatische Einwirkung. Vorzugsweise erfolgt die Freisetzung bei den üblicherweise unverdünnt eingesetzten Scheuermitteln durch mechanische Einwirkung, insbesondere durch mechanische Kräfte, denen die Mikrokapseln beim Austritt aus der Verpackung, z.B. in einem Spender- oder Sprühventil, zu diesem Zweck ausgesetzt werden, beispielsweise in Form die Mikrokapseln zerquetschender Scherkräfte oder bei einem Kapseldurchmesser ab etwa 1 mm sie zerschneidender Klingen, sowie durch Reibungskräfte, denen die Mikrokapseln bei der Anwendung des abrasiven Mittel ausgesetzt sind.The active ingredients are released from the microcapsules during or during use by destroying the shell by mechanical, thermal, chemical or enzymatic action. In the case of the abrasives which are usually used undiluted, the release is preferably carried out by mechanical action, in particular by mechanical forces, to which the microcapsules exit when they leave the packaging, e.g. in a dispenser or spray valve, are exposed for this purpose, for example in the form of the microcapsules crushing shear forces or with a capsule diameter of about 1 mm blades cutting them, as well as by frictional forces to which the microcapsules are exposed when the abrasive agent is used.

In einer bevorzugten Ausführungsform der Erfindung enthalten die Mittel gleiche oder verschiedene Mikrokapseln in Mengen von 0,1 bis 10 Gew.-%, insbesondere 0,2 bis 8 Gew.-%, äußerst bevorzugt 0,5 bis 6 Gew.-%.In a preferred embodiment of the invention, the compositions contain identical or different microcapsules in amounts of 0.1 to 10% by weight, in particular 0.2 to 8% by weight, extremely preferably 0.5 to 6% by weight.

Tensid im Sinne der erfindungsgemäßen Lehre sind ein oder mehrere Aniontenside, Ka- tiontenside, nichtionische Tenside und Amphotenside, insbesondere ein oder mehrere anionische und/oder nichtionische Tenside. Der Gesamtgehalt an Tensiden beträgt in den erfindungsgemäßen Mitteln üblicherweise nicht mehr als 35 Gew.-%, vorzugsweise 0,1 bis 25 Gew.-%, insbesondere 0,2 bis 20 Gew.-% und besonders bevorzugt 0,4 bis 15 Gew.-%.Surfactants in the sense of the teaching according to the invention are one or more anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants, in particular one or more anionic and / or nonionic surfactants. The total content of surfactants in the agents according to the invention is usually not more than 35% by weight, preferably 0.1 to 25% by weight, in particular 0.2 to 20% by weight and particularly preferably 0.4 to 15% by weight. -%.

Geeignete anionische Tenside sind beispielsweise C^-Carbonsäuren sowie deren Salze, Cj β-Albylbenzolsulfonate bzw. -Alkylbenzolsulfonsäuren, C^-Alkylsulfate und C^- Alkylethersulfate mit 1 bis 20 (mittlerer Alkoxylierungsgrad) Ethylenoxy- und/oder Propy- ienoxyeinheiten.Suitable anionic surfactants are, for example, C 1 -C 8 -carboxylic acids and their salts, C 1 -C 20 -alkyl-benzenesulfonates or alkylbenzenesulfonic acids, C 1 -C -alkyl sulfates and C 1 -C 20 -alkyl ether sulfates with 1 to 20 (average degree of alkoxylation) ethyleneoxy and / or propylene oxy units.

Bevorzugte anionische Tenside sind unverzweigte oder verzweigte, gesättigte oder ein oder mehrfach ungesättigte

Figure imgf000007_0001
(Fettsäuren) sowie deren Salze, beispielsweise deren Alkalimetall- und Erdalkalimetallsalze, insbesondere Natrium- und Kaliumsalze, sowie deren Ammonium und Mono-, Di- bzw. Trialkylammoniumsalze, wie Monoethanolammoniumsalze. Bevorzugte Fettsäuren sind ölsäure (9-Octadecensäure), Palmitinsäure (Hexadecansäure), Stearinsäure (Octadecansäure) sowie deren Mischungen, insbesondere Palmitin-/Stearinsäuregemische, vorzugsweise im Molverhältnis von etwa 1 zu 1.Preferred anionic surfactants are unbranched or branched, saturated or mono- or polyunsaturated
Figure imgf000007_0001
(Fatty acids) and their salts, for example their alkali metal and alkaline earth metal salts, in particular sodium and potassium salts, and their ammonium and mono-, di- or trialkylammonium salts, such as monoethanolammonium salts. Preferred fatty acids are oleic acid (9-octadecenoic acid), Palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid) and mixtures thereof, in particular palmitic / stearic acid mixtures, preferably in a molar ratio of about 1 to 1.

In einer bevorzugten Ausführungsform der Erfindung enthalten die Mittel ein oder mehrere anionische Tenside, insbesondere Fettsäuren und/oder deren Salze, in Mengen von 0,1 bis 10 Gew.-%, insbesondere 0,2 bis 8 Gew.-%, äußerst bevorzugt 1 bis 6 Gew.-%.In a preferred embodiment of the invention, the compositions contain one or more anionic surfactants, in particular fatty acids and / or their salts, in amounts of 0.1 to 10% by weight, in particular 0.2 to 8% by weight, extremely preferably 1 up to 6% by weight.

Geeignete nichtionische Tenside sind beispielsweise C^-Fettalkohoie und -Oxoalkohole sowie die Anlagerungsprodukte von Ethylenoxid und/oder Propylenoxid an Fettalkohole bzw. Oxoalkohole oder C^-Alkylpolyglykoside, insbesondere Alkylpolyglucoside, mit einem Oligomerisierungsgrad von 1 bis 10, vorzugsweise von 1 ,1 bis 2,5.Suitable nonionic surfactants are, for example, C 1- fatty alcohols and oxo alcohols as well as the adducts of ethylene oxide and / or propylene oxide with fatty alcohols or oxo alcohols or C 1- alkyl polyglycosides, in particular alkyl polyglucosides, with a degree of oligomerization of 1 to 10, preferably of 1, 1 to 2 , 5th

Erfindungsgemäß bevorzugte Niotenside sind C6-22-Alkylpolyglykolether, insbesondere alkoxylierte C8.18-Fettalkohole, mit 1 bis 20, vorzugsweise 2 bis 14, insbesondere 3 bis 10 (mittlerer Alkoxylierungsgrad) Ethylenoxy- (EO) und/oder Propylenoxyeinheiten (PO), beispielsweise C10.14-Fettalkohol+1 ,2PO+6,4EO, C12.14-Kokosfettalkohol+6EO oder C12.14-Kokosfettalkohol+4EO.Nonionic surfactants preferred according to the invention are C 6-22 alkyl polyglycol ethers, in particular alkoxylated C 8 . 18 -fatty alcohols with 1 to 20, preferably 2 to 14, in particular 3 to 10 (average degree of alkoxylation) ethyleneoxy (EO) and / or propyleneoxy units (PO), for example C 10 . 14 - fatty alcohol + 1, 2PO + 6.4EO, C 12 . 14 -Coconut fatty alcohol + 6EO or C 12 . 14 -Coconut fatty alcohol + 4EO.

In einer bevorzugten Ausführungsform der Erfindung enthalten die Mittel ein oder mehrere nichtionische Tenside, insbesondere Alkylpolyglykolether, in Mengen von 0,1 bis 10 Gew.-%, insbesondere 0,2 bis 7 Gew.-%, äußerst bevorzugt 0,5 bis 5 Gew.-%.In a preferred embodiment of the invention, the compositions contain one or more nonionic surfactants, in particular alkyl polyglycol ethers, in amounts of 0.1 to 10% by weight, in particular 0.2 to 7% by weight, extremely preferably 0.5 to 5% by weight .-%.

Geeignete Amphotenside sind beispielsweise Betaine der Formel (R1)(R2)(R3)N+CH2COO\ in der R1 einen gegebenenfalls durch Heteroatome oder Hetero- atomgruppen unterbrochenen Alkylrest mit 8 bis 25, vorzugsweise 10 bis 21 Kohlenstoffatomen und R2 sowie R3 gleichartige oder verschiedene Alkylreste mit 1 bis 3 Kohlenstoffatomen bedeuten, insbesondere C10-C18-Alkyl-dimethylcarboxymethylbetain und Cn-C^-Alkylamidopropyl-dimethylcarboxymethylbetain.Suitable amphoteric surfactants are, for example, betaines of the formula (R 1 ) (R 2 ) (R 3 ) N + CH 2 COO \ in which R 1 is an alkyl radical with 8 to 25, preferably 10 to 21, carbon atoms and optionally interrupted by hetero atoms or hetero atom groups R 2 and R 3 are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 -alkyl-dimethylcarboxymethylbetaine and Cn-C ^ -alkylamidopropyl-dimethylcarboxymethylbetaine.

Geeignete kationische Tenside sind beispielsweise quartären Ammonium-Verbindungen der allgemeinen Formel (R4N+)X~, insbesondere solche, bei denen die Stickstoff-Gruppe mit zwei langen und zwei kurzen Alkyl-Resten substituiert ist, z.B. Dimethyldistearyl- ammoniumchlorid.Suitable cationic surfactants are, for example, quaternary ammonium compounds of the general formula (R 4 N + ) X ~ , in particular those in which the nitrogen group is substituted by two long and two short alkyl radicals, for example dimethyldistearylammonium chloride.

Die erfindungsgemäßen Mittel enthalten einen oder mehrere Abrasivstoffe. Der Abrasivstoff ist vorzugsweise feinteilig, mit einer mittleren Korngröße im Bereich von etwa 5 μm bis 100 μm, wobei höchstens 10 % der Teilchen eine Korngröße von mehr als 150 μm aufweisen. Vorzugsweise beträgt die mittlere Korngröße der die feste Phase bildenden Teilchen 10 μm bis 80 μm und insbesondere 10 μm bis 60 μm, wobei die maximale Korngröße unterhalb 200 μm, insbesondere unter 150 μm, liegt. Die mittlere Korngröße bezieht sich auf die Volumen-Verteilung der Teilchen, die nach bekannten Methoden (beispielsweise mittels Coulter Counter) bestimmt werden kann.The agents according to the invention contain one or more abrasives. The abrasive is preferably finely divided, with an average grain size in the range of approximately 5 μm up to 100 μm, with at most 10% of the particles having a grain size of more than 150 μm. The average grain size of the particles forming the solid phase is preferably 10 μm to 80 μm and in particular 10 μm to 60 μm, the maximum grain size being below 200 μm, in particular below 150 μm. The average grain size relates to the volume distribution of the particles, which can be determined by known methods (for example using a Coulter Counter).

Als Abrasivstoff kann ein wasserunlöslicher, ein in Wasser schwerlöslicher oder ein wasserlöslicher Stoff eingesetzt werden. Zu den wasserunlöslichen Abrasivstoffen, die im Rahmen der vorliegenden Erfindung eingesetzt werden können, zählen beispielsweise Quarzmehl, Aluminiumoxid, Marmormehl, Kreide, Bimsstein, Schichtsilikate und/oder Feti- spat.A water-insoluble, a sparingly water-soluble or a water-soluble substance can be used as the abrasive substance. The water-insoluble abrasives that can be used in the context of the present invention include, for example, quartz powder, aluminum oxide, marble powder, chalk, pumice, layered silicates and / or fetidate.

In Wasser schwerlöslicher Abrasivstoff sind beispielsweise schwerlösliche Salze wie Anhydrit, wasserfreies CaSO4. Anhydrit zeichnet sich insbesondere dadurch aus, dass es nach der Anwendung des Scheuermittels besonders leicht abspül- bzw. -waschbar ist. Bevorzugtes Anhydrit ist farblos, d.h. nicht sichtbar durch Beimengen gefärbt, und weist siebanalytisch bestimmt eine mittlere Korngröße von etwa 26μm auf, wobei etwa 10 % eine Korngröße von bis zu 3,5 μm und 90 % eine Korngröße von bis zu 61 μm haben. Ein solches Anhydrit ist als Calciumanhydrit ß® von der Fa. Südharzer Gipswerke erhältlich.Poorly soluble abrasives in water are, for example, poorly soluble salts such as anhydrite and anhydrous CaSO 4 . Anhydrite is characterized in particular by the fact that it is particularly easy to rinse or wash after using the abrasive. Preferred anhydrite is colorless, that is to say invisibly colored by addition, and has an average grain size of about 26 μm determined by sieve analysis, with about 10% having a grain size of up to 3.5 μm and 90% having a grain size of up to 61 μm. Such an anhydrite is available as calcium anhydrite β ® from Südharzer Gipswerke.

Wasserlösliche Abrasivstoffe sind in der Regel wasserlösliche Salze, ausgewählt aus der Gruppe der Chloride, Carbonate, Hydrogencarbonate, Sulfate, Phosphate, Borate oder Silicate. Vorzugsweise handelt es sich dabei um Alkalimetallsalze, besonders bevorzugt um die Salze von Natrium und/oder Kalium.Water-soluble abrasives are generally water-soluble salts selected from the group of chlorides, carbonates, bicarbonates, sulfates, phosphates, borates or silicates. These are preferably alkali metal salts, particularly preferably the salts of sodium and / or potassium.

Wasserlösliche Abrasivstoffe werden vorzugsweise bei geringem Wassergehalt des Mittels eingesetzt, da der Einsatz von wasserlöslichen Abrasivstoffen in wasserhaltigen Mitteln erfordert, dass die Menge an zugesetztem Abrasivstoff das abrasivstofbezogene Lösungsvermögen des Wassers überschreitet. Dementsprechend ist der Einsatz wasserlöslicher Abrasivstoffe mit zunehmendem Wassergehalt des Mittels bzw. zunehmendem abrasv- stoffbezogenem Lösungsvermögen immer weniger bevorzugt.Water-soluble abrasives are preferably used when the agent has a low water content, since the use of water-soluble abrasives in water-containing agents requires that the amount of added abrasive exceeds the abrasive-related solvency of the water. Accordingly, the use of water-soluble abrasives with increasing water content of the agent or increasing abrasive-related dissolving power is less and less preferred.

Bevorzugt enthält das erfindungsgemäße Mittel einen oder mehrere wasserlösliche und/oder wasserunlösliche Abrasivstoffe, insbesondere aus der Gruppe Calciumcarbonat (z.B. DurcaP lδ der Omya GmbH), Aluminiumoxid (z.B. Poliertonerde11' P 730 der Alcoa Chemie) und Kieselerde mit einem Gewichtsverhältnis Quarz : Kaolinit von 74 : 26 (z.B. Sillitin® Z 86 von Hoffmann & Söhne).The agent according to the invention preferably contains one or more water-soluble and / or water-insoluble abrasives, in particular from the group calcium carbonate (for example DurcaP lδ from Omya GmbH), aluminum oxide (for example polishing clay 11 'P 730 or Alcoa Chemie) and silica with a quartz: kaolinite weight ratio of 74:26 (e.g. Sillitin ® Z 86 from Hoffmann & Sons).

Die Abrasivstoffe sind in den erfindungsgemäßen Mitteln vorzugsweise in Mengen von 5 bis 80 Gew.-%, insbesondere 10 bis 70 Gew.-%, besonders bevorzugt 15 bis 60 Gew.-%, äußerst bevorzugt 20 bis 50 Gew.-%, enthalten.The abrasives are contained in the agents according to the invention preferably in amounts of 5 to 80% by weight, in particular 10 to 70% by weight, particularly preferably 15 to 60% by weight, extremely preferably 20 to 50% by weight.

Zur Einstellung der Viskosität enthalten die erfindungsgemäßen Mittel ein oder mehrere Verdickungsmittel.To adjust the viscosity, the agents according to the invention contain one or more thickeners.

Verdickungsmittel im Sinne der Erfindung sind organische natürliche Verdickungsmittel (Agar-Agar, Carrageen, Tragant, Gummi arabicum, Alginate, Pektine, Polyosen, Guar- Mehl, Johannisbrotbaumkernmehl, Stärke, Dextrine, Gelatine, Casein), organische abgewandelte Naturstoffe (Carboxymethylcellulose und. Celluioseether, Hydroxyethyl- und -propylcellulose und dgl., Kernmehlether), organische vollsynthetische Verdickungsmittel (Polyacryl- und Polymethacryl-Verbindungen, Vinylpolymere, Polycarbonsäuren, Polye- ther, Polyimine, Polyamide) und anorganische Verdickungsmittel (Polykieselsäuren, Tonmineralien wie Montmorillonite, Zeolithe, Kieselsäuren).For the purposes of the invention, thickeners are organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein), organic modified natural substances (carboxymethyl cellulose and cellulose ether , Hydroxyethyl and propyl cellulose and the like, core meal ether), organic fully synthetic thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides) and inorganic thickeners (polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas) .

Erfindungsgemäß bevorzugte Verdickungsmittel sind Xanthan Gum (z.B. Ke/fro/® RD von Kelco, Rhodopof® 50 MD von Rhone Poulenc), anionisches Methacrylsäure-Ethylacrylat- Copolymer (z.B. Rohagif SD 15 der Röhm GmbH) und anquellverzögerte Hydroxyethyl- cellulose (z.B. Tylose® H 60000 YP 2 von Clariant).Thickeners preferred according to the invention are xanthan gum (for example Ke / fro / ® RD from Kelco, Rhodopof ® 50 MD from Rhone Poulenc), anionic methacrylic acid / ethyl acrylate copolymer (for example Rohagif SD 15 from Röhm GmbH) and swelling-delayed hydroxyethyl cellulose (for example Tylose ® H 60000 YP 2 from Clariant).

Der Gehalt der erfindungsgemäßen Mittel an Verdickungsmittel beträgt vorzugsweise 0,01 bis 10 Gew.-%, insbesondere 0,05 bis 6 Gew.-%, äußerst bevorzugt 0,1 bis 3 Gew.-%.The thickener content of the agents according to the invention is preferably 0.01 to 10% by weight, in particular 0.05 to 6% by weight, most preferably 0.1 to 3% by weight.

Weiterhin können die erfindungsgemäßen Mittel eine oder mehrere Builderkomponenten, vorzugsweise Citronensäure (z.B. Citronensäure-1 H2Ö) oder Alkali, insbesondere Mo- noethanolamin, Diethanolamin, Triethanolamin und/oder Ammoniak, in Mengen von 0,01 bis 10 Gew.-%, insbesondere 0,1 bis 5 Gew-% enthalten.Furthermore, the agents according to the invention can contain one or more builder components, preferably citric acid (for example citric acid-1 H 2 O) or alkali, in particular monoethanolamine, diethanolamine, triethanolamine and / or ammonia, in quantities of 0.01 to 10% by weight, contain in particular 0.1 to 5% by weight.

Je nach Anwendungszweck können die erfindungsgemäßen Mittel vorteilhaft einen oder mehrere Schauminhibitoren enthalten, beispielsweise natürliche Fette und öle oder Fettalkohole, langkettige Seifen (z.B. Natriumbehenat), Entschäumer auf Silicon-Basis sowie symmetrische oder asymmetrische Dialkylether (z.B. mit (Fett-)Alkoholen veretherte Fettalkoholpolyglykolethern). Im Rahmen der Erfindung bevorzugte Schauminhibitoren sind Dimethylpolysiloxanmischungen (z.B. Dow Corning® DB 31 EU von Dow Corning) und Carbonsäureester (z.B. Degressat® SD 30 der BASF AG). Der Gehalt an Schauminhibitor liegt in den erfindungsgemäßen Mitteln vorzugsweise nicht über 5 Gew.-% und insbesondere zwischen 0,0001 und 3 Gew.-%.Depending on the intended use, the agents according to the invention can advantageously contain one or more foam inhibitors, for example natural fats and oils or fatty alcohols, long-chain soaps (e.g. sodium behenate), silicone-based defoamers and symmetrical or asymmetrical dialkyl ethers (e.g. etherified with (fatty) alcohols) Fatty alcohol polyglycol ethers). In the invention, foam inhibitors are preferred Dimethylpolysiloxanmischungen (for example, Dow Corning ® DB 31 EU of Dow Corning) and Carbonsäureester (eg Degressat ® SD 30 from BASF AG). The foam inhibitor content in the agents according to the invention is preferably not more than 5% by weight and in particular between 0.0001 and 3% by weight.

Die flüssige Phase der erfindungsgemäßen Mittel basieren üblicherweise auf Wasser, wobei ihr Wassergehalt dann bei etwa 15 bis 90 Gew.-%, vorzugsweise 20 bis 80 Gew.-%, insbesondere 30 bis 70 Gew.-%, liegt. Der Wassergehalt kann aber auch, insbesondere bei einem höheren Tensidgehalt und/oder dem Einsatz wasserlöslicher Abrasivstoffe, weniger als 15 Gew.-%, vorzugsweise 0,1 bis 10 Gew.-%, insbesondere 0,2 bis 5 Gew.-%, betragen.The liquid phase of the agents according to the invention are usually based on water, their water content then being about 15 to 90% by weight, preferably 20 to 80% by weight, in particular 30 to 70% by weight. However, the water content can also be less than 15% by weight, preferably 0.1 to 10% by weight, in particular 0.2 to 5% by weight, in particular if the surfactant content is high and / or water-soluble abrasives are used .

Die erfindungsgemäß wässrigen Mittel können außerdem ein oder mehrere nichtwässri- ge Lösungsmittel enthalten, beispielsweise Alkohole (Methanol, Ethanol, Propanole, Butanole, Octanole, Cyclohexanol), Glykole (Ethylenglykol, Diethylenglykol), Ether und Glykolether (Diethylether, Dibutylether, Mono-, Di-, Tri-, Polyethylenglykolether, Propy- lenglykolmonobutylether). Ein bevorzugtes Lösungsmittel ist Ethanol. Diese Lösungsmittel sind vorzugsweise in Mengen von 0,01 bis 20 Gew.-%, insbesondere 0,1 bis 12 Gew.-%, äußerst bevorzugt 0,5 bis 8 Gew.-%, in den erfindungsgemäßen Mitteln enthalten.The aqueous compositions according to the invention can also contain one or more non-aqueous solvents, for example alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol), ethers and glycol ethers (diethyl ether, dibutyl ether, mono-, di -, tri, polyethylene glycol ether, propylene glycol monobutyl ether). A preferred solvent is ethanol. These solvents are preferably present in the compositions according to the invention in amounts of 0.01 to 20% by weight, in particular 0.1 to 12% by weight, extremely preferably 0.5 to 8% by weight.

Die Viskosität der erfindungsgemäßen Mittel liegt bei einer Temperatur von 22 °C und einer Scherrate von 20 min'1 vorzugsweise im Bereich von 500 bis 20.000 mPa-s, insbesondere von 1.000 bis 15.000 mPa s, besonders bevorzugt von 1.500 bis 10.000 mPa-s.The viscosity of the agents according to the invention at a temperature of 22 ° C. and a shear rate of 20 min '1 is preferably in the range from 500 to 20,000 mPa-s, in particular from 1,000 to 15,000 mPa-s, particularly preferably from 1,500 to 10,000 mPa-s.

Darüber hinaus können die erfindungsgemäßen Mittel sonstige übliche Additive enthalten, beispielsweise Färb- und Duftstoffe, Konservierungsstoffe, Korrosionsinhibitoren, Antistatika oder Mikrobizide.In addition, the agents according to the invention can contain other customary additives, for example colorants and fragrances, preservatives, corrosion inhibitors, antistatic agents or microbicides.

Der pH-Wert der erfindungsgemäßen Mittel ist in Anpassung an die jeweilige Anwendung zu wählen. Die Mittel können dementsprechend sauer, bevorzugt mit einem pH-Wert von 1 bis 6, insbesondere 1 ,5 bis 4, neutral, bevorzugt mit einem pH-Wert zwischen 6 und 8, insbesondere von 6,5 bis 7,5, oder alkalisch, bevorzugt mit einem pH-Wert von 8 bis 12, insbesondere von 9 bis 11 , eingestellt sein. Soweit sich der gewünschte pH-Wert nicht allein durch Zusammenführen der Inhaltsstoffe ergibt, erfolgt die Einstellung durch Zugabe von Säure oder Lauge, beispielsweise Zitronensäure oder Natronlauge.The pH of the agents according to the invention is to be selected in accordance with the particular application. The agents can accordingly be acidic, preferably with a pH of 1 to 6, in particular 1.5 to 4, neutral, preferably with a pH between 6 and 8, in particular 6.5 to 7.5, or alkaline, preferably with a pH of 8 to 12, in particular 9 to 11. As far as the desired pH is not results only by combining the ingredients, the adjustment is made by adding acid or alkali, for example citric acid or sodium hydroxide solution.

Zur Herstellung der erfindungsgemäßen Mittel wird vorzugsweise zunächst das Verdik- kungsmittel in Wasser angedickt und anschließend Tenside sowie gegebenenfalls weitere der zuvor genannten Inhaltsstoffe bis auf die Abrasivkomponente untergerührt. Insofern Parfüm und/oder Farbstoff eingesetzt werden, erfolgt deren Zugabe hierbei zuletzt. Danach wird die Abrasivkomponente beigemengt, gegebenenfalls wird der pH-Wert wie zuvor beschrieben eingestellt und zuletzt werden die Mikrokapseln untergemischt. To produce the agents according to the invention, the thickener is preferably first thickened in water and then surfactants and, if appropriate, further ingredients mentioned above are mixed in except for the abrasive component. If perfume and / or dye are used, they are added last. Then the abrasive component is added, if necessary the pH is adjusted as described above and finally the microcapsules are mixed in.

BeispieleExamples

Die erfindungsgemäßen Mittel E1 bis E3 wurden hergestellt und ihr pH-Wert sowie ihre Viskosität bestimmt.Agents E1 to E3 according to the invention were produced and their pH and viscosity were determined.

Die Zusammensetzungen der erfindungsgemäßen Mittel E1 bis E3 in Gew.-% sowie die bestimmten Eigenschaften sind nachstehend angegeben. Der pH-Wert der erfindungsgemäßen Mittel E1 bis E4 wurde mit Citronensäure bzw. Natronlauge auf die angegebenen Werte von 2,5 bzw. 10 eingestellt. Die Viskosität wurde mit einem Rotationsviskosi- meter des Typs Brookfield RVT Serie 3227 unter Verwendung der Spindel 4 bei einer Scherrate von 20 min"1 und einer Temperatur von 22 °C bestimmt.The compositions of the compositions E1 to E3 according to the invention in% by weight and the specific properties are given below. The pH of the agents E1 to E4 according to the invention was adjusted to the specified values of 2.5 and 10 using citric acid or sodium hydroxide solution. The viscosity was determined using a Brookfield RVT Series 3227 rotary viscometer using spindle 4 at a shear rate of 20 min -1 and a temperature of 22 ° C.

Die Kapseln waren in den Mitteln E1 bis E4 bei 40 °C über 3 Monate stabil. Es war weder eine Änderung der Form der Kapseln noch ihrer räumlichen Verteilung im Mittel zu beobachten.The capsules were stable in the means E1 to E4 at 40 ° C. for 3 months. There was no change in the shape of the capsules or their spatial distribution on average.

Bei der manuellen Anwendung der Mittel E1 bis E4 wurden die Mikrokapseln problemlos durch die abrasiven Reibungskräfte unter Freisetzung der Wirkstoffe zerstört.When the agents E1 to E4 were applied manually, the microcapsules were easily destroyed by the abrasive friction forces with the release of the active ingredients.

Beispiel 1 Scheuermittel E1 für harte Oberflächen im HaushaltsbereichExample 1 E1 abrasive for hard surfaces in the household

Zusammensetzung von E1 in Gew.-%:Composition of E1 in% by weight:

(a) Cl2.14-Kokosfettalkohol+6EO 2(a) C l2 . 14 -Coconut fatty alcohol + 6EO 2

(b) Cιr 14-Fettalkohol+1 ,2PO+6,4EO 1(b) C ιr 14 fatty alcohol + 1, 2PO + 6.4EO 1

(c) Calciumcarbonat 41(c) Calcium carbonate 41

(d) Methacrylsäure-Ethylacrylat- 0,3 Copolymer anionisch(d) Methacrylic acid-ethyl acrylate-0.3 copolymer anionic

(e) Monoethanolamin 0,2(e) Monoethanolamine 0.2

(f) Dimethylpolysiloxan-Emulgator- 0,0003 Gemisch(f) Dimethylpolysiloxane emulsifier - 0.0003 mixture

(g) Duftstoff + (h) grüne Mikrokapseln mit Parfüm Lipotec® 5 (i) Wasser ad 100 pH-Wert 10 Viskosität [mPa-s] 4.000 Die von der Firma Lipotec® bezogenen Mikrokapseln wiesen einen mittleren Durchmesser von 2 mm auf und enthielten in einer Hülle aus Alginsäure und Agar einen Duftstoff in wässrigem Polyethylenglykol- und Giycerin-haltigem Medium.(g) fragrance + (h) green microcapsules with perfume Lipotec ® 5 (i) water ad 100 pH value 10 viscosity [mPa-s] 4,000 The microcapsules obtained from Lipotec ® had an average diameter of 2 mm and contained a fragrance in an aqueous medium containing polyethylene glycol and glycerin in a casing made of alginic acid and agar.

Nach dreimonatiger Lagerzeit war der Duftstoff bei der Anwendung des Mittels für den Anwender deutlich wahrnehmbar, während ein Vergleichsmittel, das statt Parfümkapseln den Duftstoff in der flüssigen Phase enthielt, nach der gleichen Zeit merklich weniger duftete.After three months of storage, the fragrance was clearly perceptible to the user when using the agent, while a comparison agent which contained the fragrance in the liquid phase instead of perfume capsules smelled significantly less after the same time.

Beispiel 2 Reinigungsmittel E2 für Ceraπ®-KochfelderExample 2 cleaning agent E2 for Ceraπ ® cooktops

Zusammensetzung von E2 in Gew.-%:Composition of E2 in% by weight:

(a) C12-14-Kokosfettalkohol+4EO 3(a) C 12-14 coconut fatty alcohol + 4EO 3

(b) Aluminiumoxid >A/coa® P 730 32,5(b) alumina> A / coa ® P 730 32.5

(c) Xanthan Gum 0,25(c) Xanthan Gum 0.25

(d) Magnesium-Aluminium-Silikat 1 hydratisiert(d) Hydrated magnesium aluminum silicate 1

(e) Ethanol - 5(e) Ethanol - 5

(f) Carbonsäureester 1(f) Carboxylic acid ester 1

(g) Citronensäure-1 H2O 4,25 (h) Duftstoff +(g) Citric Acid-1 H 2 O 4.25 (h) Perfume +

(i) blaue Mikrokapseln mit Siliconöl Hallcresf D/HC 188 4(i) blue microcapsules with silicone oil Hallcresf D / HC 188 4

(j) Wasser ad 100 pH-Wert 2,5(j) water ad 100 pH 2.5

Viskosität [mPa-s] 2.500Viscosity [mPa-s] 2,500

Die Mikrokapseln des Typs D/HC 188 der Firma Hallcrest wiesen einen Durchmesser von 50 bis 100 μm auf und enthielten in einer Hülle aus etwa 4 Gew.-% Gelatine und Gummi arabicum etwa 38 Gew.-% Wasser sowie als Pflegekomponente für Ceranflä- chen ca. 58 Gew.-% Siliconöl in Form eines Dimethylcyclosiloxan-Pentamer/Polydi- methylsiloxanol-Gemisches, wie es beispielsweise von Dow Corning als Dow Corning® 1401 Fluid vertrieben wird.The microcapsules of the D / HC 188 type from Hallcrest had a diameter of 50 to 100 μm and contained about 38% by weight of water in a casing made of about 4% by weight gelatin and gum arabic, and as a care component for ceramic surfaces approx. 58% by weight silicone oil in the form of a dimethylcyclosiloxane pentamer / polydimethylsiloxanol mixture, as is sold, for example, by Dow Corning as Dow Corning® 1401 fluid.

Während das Einarbeiten des Siliconöls in die flüssige Phase des Mittels den zusätzlichen Einsatz eines Emulgators erfordert hätte, um ein Absetzen des Siliconöls zu ver- hindern, war das Einbringen der Siiiconölkomponente in Form von Mikrokapseln problemlos möglich.While incorporating the silicone oil into the liquid phase of the agent would have required the additional use of an emulsifier in order to prevent the silicone oil from settling. prevent it, the introduction of the Siiiconöl component in the form of microcapsules was easily possible.

Beispiel 3 Reinigungsmittel E3 für Metalloberflächen im HaushaltExample 3 Cleaning agent E3 for metal surfaces in the household

Zusammensetzung von E3 in Gew.-%:Composition of E3 in% by weight:

(a) Ölsäure 4,8(a) Oleic acid 4.8

(b) Palmitinsäure-Stearinsäure-Gemisch 0,2 (Molverhältnis von 1 : 1)(b) Palmitic acid-stearic acid mixture 0.2 (molar ratio of 1: 1)

(c) Kieselerde (Quarz : Kaolinit = 74 : 26) Sillitin® Z 86 22,5(c) silica (quartz: kaolinite = 74: 26) Sillitin ® Z 86 22.5

(d) Hydroxyethylcellulose Tylose® H 60000 YP 2 1 anquellverzögert(d) hydroxyethyl cellulose tylose H ® 60000 YP 2 1 delayed solubility

(e) Ethanol 1(e) Ethanol 1

(f) Citronensäure-1H2O 2(f) Citric acid-1H 2 O 2

(g) Ammoniak 1,5 (h) rote Mikrokapseln mit Stearylmercaptan 3,5 (i) blaue Mikrokapseln mit Duftstoff Lipotec® 2,5 (j) Wasser ad 100 pH-Wert 10 Viskosität [mPa-s] 2.500(g) ammonia 1.5 (h) red microcapsules with stearyl mercaptan 3.5 (i) blue microcapsules with fragrance Lipotec ® 2.5 (j) water ad 100 pH value 10 viscosity [mPa-s] 2,500

Die Mikrokapseln (h) wiesen einen mittleren Durchmesser von 1 mm auf und enthielten in einer Hülle aus etwa 5 Gew.-% Gelatine und Gummi arabicum etwa 35 Gew.-% Wasser sowie ca. 60 Gew.-% Stearylmercaptan als Silberschutzkomponente.The microcapsules (h) had an average diameter of 1 mm and contained about 35% by weight of water and about 60% by weight of stearyl mercaptan as a silver protection component in a casing made of about 5% by weight of gelatin and gum arabic.

Die von der Firma Lipotec® bezogenen Mikrokapseln (i) wiesen einen mittleren Durchmesser von 0,8 mm auf und enthielten in einer Hülle aus Alginsäure und Agar einen Duftstoff in wässrigem Glycerin-haltigem Medium.The microcapsules (i) obtained from Lipotec ® had an average diameter of 0.8 mm and contained a fragrance in an aqueous glycerol-containing medium in a casing made of alginic acid and agar.

Nach dreimonatiger Lagerzeit war der Duftstoff bei der Anwendung des Mittels für den Anwender deutlich wahrnehmbar, während ein Vergleichsmittel, das statt Parfümkapseln den Duftstoff in der flüssigen Phase enthielt, nach der gleichen Zeit merklich weniger duftete. After three months of storage, the fragrance was clearly perceptible to the user when using the agent, while a comparison agent which contained the fragrance in the liquid phase instead of perfume capsules smelled significantly less after the same time.

Claims

Patentansprüche claims 1. Verdicktes flüssiges wässriges abrasives Reinigungsmittel für harte Oberflächen, enthaltend Tensid, Abrasivstoff, Verdickungsmittel sowie Mikrokapseln, in denen ein oder mehrere Inhaltsstoffe ganz oder teilweise eingeschlossen sind.1. Thickened liquid aqueous abrasive cleaning agent for hard surfaces, containing surfactant, abrasive, thickener and microcapsules, in which one or more ingredients are wholly or partly enclosed. 2. Mittel nach Anspruch 1 , dadurch gekennzeichnet, dass es Mikrokapseln in Mengen von 0,1 bis 10 Gew.-% enthält.2. Composition according to claim 1, characterized in that it contains microcapsules in amounts of 0.1 to 10 wt .-%. 3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass es Mikrokapseln eines Durchmessers entlang ihrer größten räumlichen Ausdehnung von 10 nm bis 10 mm, vorzugsweise 0,05 bis 4 mm, enthält.3. Composition according to claim 1 or 2, characterized in that it contains microcapsules of a diameter along their greatest spatial extent of 10 nm to 10 mm, preferably 0.05 to 4 mm. 4. Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es ein oder mehrere anionische und/oder nichtionische Tenside enthält.4. Composition according to one of claims 1 to 3, characterized in that it contains one or more anionic and / or nonionic surfactants. 5. Mittel nach Anspruch 4, dadurch gekennzeichnet, dass es nichtionische Tenside, insbesondere ein oder mehrere C6.22-Alkylpolyglykolether mit 1 bis 20^thylenoxy- und/oder Propylenoxyeneinheiten, in Mengen von 0,1 bis 10 Gew.-% enthält.5. Composition according to claim 4, characterized in that it is nonionic surfactants, in particular one or more C 6 . 22 -Alkylpolyglykolether containing 1 to 20 ^ thyleneoxy and / or propyleneoxyen units, in amounts of 0.1 to 10 wt .-%. 6. Mittel nach Anspruch 4, dadurch gekennzeichnet, dass es anionische Tenside, insbesondere ein oder mehrere C^-Carbonsäuren und/oder deren Salze, in Mengen von 0,1 bis 10 Gew.-% enthält.6. Composition according to claim 4, characterized in that it contains anionic surfactants, in particular one or more C ^ -carboxylic acids and / or their salts, in amounts of 0.1 to 10 wt .-%. 7. Mittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass es einen oder mehrere wasserlösliche und/oder wasserunlösliche Abrasivstoffe, insbesondere aus der Gruppe Calciumcarbonat, Aluminiumoxid und Kieselerde, in Mengen von 5 bis 80 Gew.-% enthält.7. Agent according to one of the preceding claims, characterized in that it contains one or more water-soluble and / or water-insoluble abrasives, in particular from the group calcium carbonate, aluminum oxide and silica, in amounts of 5 to 80 wt .-%. 8. Mittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass es ein oder mehrere Verdickungsmittel aus der Gruppe der organischen natürlichen Verdickungsmittel, organischen abgewandelten Naturstoffe, organischen vollsynthetischen Verdickungsmittel und anorganischen Verdickungsmittel, vorzugsweise in Mengen von 0,01 bis 10 Gew.-% enthält.8. Composition according to one of the preceding claims, characterized in that there are one or more thickeners from the group of organic natural thickeners, organic modified natural products, organic fully synthetic thickeners and inorganic thickeners, preferably in amounts of 0.01 to 10 wt .-% contains. 9. Mittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass es zusätzlich ein oder mehrere Lösungsmittel, bevorzugt Alkohole, Glykole, Ether, Gly- kolether, insbesondere Ethanol, vorzugsweise in Mengen von 0,01 bis 20 Gew.-% enthält.9. Agent according to one of the preceding claims, characterized in that it additionally contains one or more solvents, preferably alcohols, glycols, ethers, Gly- Kolether, especially ethanol, preferably in amounts of 0.01 to 20 wt .-%. 10. Mittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass es weiterhin eine oder mehrere Builderkomponenten in Mengen von 0,01 bis 10 Gew.-% enthalten.10. Agent according to one of the preceding claims, characterized in that it further contains one or more builder components in amounts of 0.01 to 10 wt .-%. 11. Mittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass es eine Viskosität, gemessen bei einer Temperatur von 22 °C und einer Scherrate von 20 min 1, im Bereich von 500 bis 20.000 mPa-s aufweist.11. Agent according to one of the preceding claims, characterized in that it has a viscosity, measured at a temperature of 22 ° C and a shear rate of 20 min 1 , in the range from 500 to 20,000 mPa-s. 12. Mittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass es einen pH-Wert von 1 bis 6 oder einen pH-Wert von 8 bis 12 aufweist. 12. Composition according to one of the preceding claims, characterized in that it has a pH of 1 to 6 or a pH of 8 to 12.
PCT/EP2000/003304 1999-04-22 2000-04-13 Detergent containing abrasive material and microcapsules Ceased WO2000065019A1 (en)

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AU52101/00A AU5210100A (en) 1999-04-22 2000-04-13 Detergent containing abrasive material and microcapsules

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DE19918265.5 1999-04-22
DE1999118265 DE19918265A1 (en) 1999-04-22 1999-04-22 Abrasive-containing aqueous liquid cleaning or scouring agent for hard surfaces contains microcapsules containing an ingredient to be protected e.g. a perfume

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DE10346081A1 (en) * 2003-10-04 2005-05-12 Steinmax Gmbh Surface treatment of cut stone or concrete block to produce a stain- and abrasion-resistant surface involves treating with a special stone cleaner followed by silicic acid and then silica sol, and then abrading the surface
US12227720B2 (en) 2020-10-16 2025-02-18 The Procter & Gamble Company Consumer product compositions with at least two encapsulate populations
US12398348B2 (en) 2020-10-16 2025-08-26 The Procter & Gamble Company Consumer product compositions comprising a population of encapsulates
US12486478B2 (en) 2021-10-14 2025-12-02 The Procter & Gamble Company Consumer products comprising delivery particles with high core:wall ratios

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DE10131722A1 (en) * 2001-06-30 2003-01-16 Henkel Kgaa Multiphase detergent
HUP0401706A2 (en) * 2001-11-06 2004-12-28 Unilever N.V., Liquid, abrasive cleaning compositions, and a process for cleaning hard surfaces
US20100197557A1 (en) * 2007-07-31 2010-08-05 The Dial Corporation Shear-thinning, dispensable liquid abrasive cleanser with improved soil removal, rinseability and phase stability
WO2009137051A2 (en) * 2008-05-06 2009-11-12 Andrew Armstrong Method for extending and improving the functionality of a hard surface
US9186642B2 (en) 2010-04-28 2015-11-17 The Procter & Gamble Company Delivery particle
US9993793B2 (en) 2010-04-28 2018-06-12 The Procter & Gamble Company Delivery particles
JP6283607B2 (en) 2011-04-07 2018-02-21 ザ プロクター アンド ギャンブル カンパニー Personal cleansing composition with increased deposition of polyacrylate microcapsules
WO2012138690A2 (en) 2011-04-07 2012-10-11 The Procter & Gamble Company Conditioner compositions with increased deposition of polyacrylate microcapsules
EP2694016B2 (en) 2011-04-07 2025-03-19 The Procter & Gamble Company Shampoo compositions with increased deposition of polyacrylate microcapsules

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GB1501942A (en) * 1974-10-12 1978-02-22 Thomae Gmbh Dr K Cleansing composition
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Cited By (5)

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Publication number Priority date Publication date Assignee Title
DE10346081A1 (en) * 2003-10-04 2005-05-12 Steinmax Gmbh Surface treatment of cut stone or concrete block to produce a stain- and abrasion-resistant surface involves treating with a special stone cleaner followed by silicic acid and then silica sol, and then abrading the surface
DE10346081B4 (en) * 2003-10-04 2009-01-15 Steinmax Gmbh Process for the surface treatment of stone
US12227720B2 (en) 2020-10-16 2025-02-18 The Procter & Gamble Company Consumer product compositions with at least two encapsulate populations
US12398348B2 (en) 2020-10-16 2025-08-26 The Procter & Gamble Company Consumer product compositions comprising a population of encapsulates
US12486478B2 (en) 2021-10-14 2025-12-02 The Procter & Gamble Company Consumer products comprising delivery particles with high core:wall ratios

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AU5210100A (en) 2000-11-10
AR023551A1 (en) 2002-09-04
CA2306397A1 (en) 2000-10-22
CO5231231A1 (en) 2002-12-27
DE19918265A1 (en) 2000-10-26

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