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
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/0013—Liquid compositions with insoluble particles in suspension
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/14—Fillers; 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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• Inorganic Chemistry (AREA)
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• 1999
  • 1999-04-22 DE DE1999118265 patent/DE19918265A1/de not_active Withdrawn
• 2000
  • 2000-04-13 WO PCT/EP2000/003304 patent/WO2000065019A1/de active Application Filing
  • 2000-04-13 AU AU52101/00A patent/AU5210100A/en not_active Abandoned
  • 2000-04-18 CO CO00028624A patent/CO5231231A1/es not_active Application Discontinuation
  • 2000-04-19 AR ARP000101848 patent/AR023551A1/es unknown
  • 2000-04-20 CA CA 2306397 patent/CA2306397A1/en not_active Abandoned

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