EP1200549B1 - Detergent for glass-ceramic surfaces - Google Patents

Detergent for glass-ceramic surfaces Download PDF

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Publication number
EP1200549B1
EP1200549B1 EP00953091A EP00953091A EP1200549B1 EP 1200549 B1 EP1200549 B1 EP 1200549B1 EP 00953091 A EP00953091 A EP 00953091A EP 00953091 A EP00953091 A EP 00953091A EP 1200549 B1 EP1200549 B1 EP 1200549B1
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EP
European Patent Office
Prior art keywords
detergent
abrasive
abrasive agent
glass
abrasives
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EP00953091A
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German (de)
French (fr)
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EP1200549A1 (en
Inventor
Edgar Endlein
Mike Kosub
Marion Hackenthal
Alexandra Hary
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Reckitt Benckiser NV
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Reckitt Benckiser NV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • the invention relates to a cleaning agent for glass-ceramic surfaces with a content of abrasive and a pH between 2 and 3.
  • Glass-ceramic materials are polycrystalline solids produced by ceramization, i. controlled devitrification, made of glasses. Glass-ceramic products are molded by glass technology and have after a heat treatment, the properties and processability of special ceramics, in particular a very high thermal shock resistance. This latter feature makes them particularly suitable for use in cooking hobs and dishes, for which they have been increasingly used in recent years.
  • a particular type of soiling involving proteins, starch and fat also includes limescale, especially in areas of high water hardness.
  • acidic detergents containing abrasive substances are usually used, for example toner mixtures of different particle sizes, as described, for example, in US Pat EP 0 388 629 A1 .
  • All commercially available cleaners for glass-ceramic surfaces contain as abrasives water-insoluble minerals with a typical Mohs hardness between 7 and 9. These abrasives are indeed very effective, but attack because of their hardness in many cases, the surfaces to be cleaned. This leads, especially in the case of glass ceramics, to unsightly, ie scratched, surfaces relatively quickly.
  • US-A-3,645,904 suggests the use of synthetic resin particles for skin cleansers.
  • the relatively soft polyolefins in particular polyethylene, polypropylene and polystyrene, are described.
  • the particles have a diameter between 74 and 420 microns and their content in the product is 3 to 15 wt .-%.
  • DE 16 69 094 D2 discloses detergent with 100 parts of liquid soap and 10 to 900 parts of polyethylene abrasive having a particle size of 10 to 1000 microns.
  • the compositions are described as being suitable for the cleaning of hands and mild cleaning of hard surfaces, especially painted metal.
  • JP (06) 033414 B2 discloses the use of from 5 to 30% by weight of organic abrasive having a particle size of from 10 to 500 microns in personal cleansers and to remove rust or carbon deposits on machines.
  • organic abrasive having a particle size of from 10 to 500 microns in personal cleansers and to remove rust or carbon deposits on machines.
  • abrasives described are, inter alia, polyurethanes and polyolefins. The minimum content of 5% abrasive is required by this reference for sufficient performance.
  • plastic abrasives mostly to allow a mild cleaning of sensitive surfaces.
  • EP 0 011 984 A1 discloses liquid alkaline detergents containing water insoluble polyvalent metal soaps to impart thixotropy and stability to the formulations.
  • milled polymeric materials such as ground polyurethane foam, are referred to as abrasives.
  • mineral abrasives are preferred.
  • EP 0 030 986 A1 discloses a liquid hand dishwashing detergent having a pH of 6 to 11 and comprising surfactants, builders and 3 to 20% abrasives having a Mohs hardness of 2 to 7 and a particle size of 1 to 150 ⁇ m. Both inorganic and plastic materials, eg, polystyrene and polyacrylates, are disclosed for the abrasive. However, there is no concrete example of the use of plastic abrasives.
  • EP 0 206 534 A1 discloses liquid alkaline detergents comprising a thickening system consisting of an inorganic colloid and an anionic fatty acid surfactant.
  • inorganic materials are disclosed as abrasives, but organic materials are also mentioned in passing.
  • EP 0 216 416 A2 discloses a liquid detergent containing from 1 to 50% by weight of water-soluble mild abrasive, both inorganic and organic materials being mentioned. When using organic materials, the preferred range is 5 to 15% by weight.
  • the preferred abrasive used alone in the examples is calcium carbonate.
  • EP 0 335 471 A1 discloses a creamy detergent with 10 to 60% by weight of an abrasive. Inorganic and organic abrasives are mentioned, with the use of the organic abrasive in particular being noted that this reduces the scratching of sensitive surfaces, for example made of plastic. However, the only abrasive that is evident in the examples is calcite.
  • WO97 / 47724 A1 discloses a liquid detergent in liquid crystal form comprising up to 20% by weight of an abrasive selected from the group consisting of hydrated silica, calcite and polyethylene particles having a particle size between 200 and 500 ⁇ m. No reasons are given for a selection of these abrasives.
  • plastic abrasives can be used when a milder scrubbing action is desired than with mineral abrasives, e.g. In order to protect sensitive surfaces, there is no evidence for the cleaning effect of such abrasives, especially in comparison with mineral abrasives. In addition, no acidic cleaning agent with a content of plastic abrasives is known.
  • the invention is therefore based on the object to provide a generic cleaning agent with improved cleaning effect.
  • this object is achieved by a generic cleaning agent in which the abrasive comprises particles of polyurethane having a particle size in a range of 100 to 1000 microns.
  • the abrasive agent is preferably 20 wt .-% or, more preferably, substantially entirely of organic material.
  • the invention provides that the abrasive agent in the cleaning agent according to the invention preferably with a content of 10 wt .-% or less, more preferably 5 wt .-% or less, is included.
  • the organic material is present in a particle size in a range of 100 to 200 microns.
  • the particle size of the organic material is preferably between 100 and 200 microns, but may also be smaller (down to 10 microns) or larger (up to 1000 microns).
  • organic polyurethane When used together with inorganic abrasives (the ratio in a corresponding mixture is not particularly critical, although it is preferably at least 20% by weight of organic material), these can be selected from the whole variety of mineral compounds used hitherto Abrasivstoff are selected, such as, for example, alumina, silica, sillitin, boehmite, hydrargillite, aluminum silicate, kaolinite, etc.
  • surfactants are surfactants.
  • nonionic surfactants such as the entire range of fatty alcohol ethoxylates or alkyl ethoxylates
  • amphoteric surfactants such as amidobetaines, betaines, alkylaminocarboxylates, iminodipropionates, etc .
  • anionic surfactants such as alkyl sulfates, alkyl ether sulfates, sulfosuccinates, etc .
  • cationic surfactants such as protonated alkylamines, ethoxylated alkylamines, etc.
  • acid or an acid mixture preferably selected from organic acids, such as, for example, citric acid, amidosulfuric acid, glycolic acid, lactic acid, etc.
  • the preferred pH for a generic cleaning agent is between 2 and 5, more preferably between 2 and third
  • solvents such as isopropyl alcohol, polyethylene glycol, N-methyl-2-pyrrolidone, etc .
  • Thickeners such as xanthan gum or modified organic silicates (eg Optigel WX ®);
  • Care additives such as polydimethylsiloxane (having a viscosity between 100 mPas and 12500 mPas), organo-modified silicones, amino-functionalized silicones, silicone quats, polyvinylpyrrolidones, etc .; Fragrances; dyes; Preservatives, etc.
  • the test method used for the cleaning effect of cleaning agents for glass-ceramic surfaces uses household-typical soiling and simulates splashes of food during their preparation.
  • the temperature of the glass-ceramic surface near the heated area is typically about 200 ° C.
  • the heated area itself, which reaches temperatures of up to 500 ° C, is usually not hit by splashes.
  • contamination that hits areas heated to these high temperatures immediately carbonises and is therefore not suitable for providing reproducible substrates for distinctive testing.
  • the glass ceramic surface (glass ceramic tiles 25x25 cm) is cleaned using an alkaline detergent (pH 10) and a hand dishwashing detergent.
  • the glass ceramic tiles used are soaked in a hot solution of hand dishwashing detergent solution and limestone remover for about 2 hours. This is followed by two cycles of cleaning in a laboratory dishwasher using a chlorine-containing dishwashing detergent and deionized water (duration of one cycle about 45 minutes).
  • the dirty area has the dimensions 25 x 10 cm.
  • the dirt is applied using a standard squeegee.
  • the soiled glass ceramic tile is subjected to a temperature of 200 ° C, the residence time in the oven varies depending on the soiling (gravy: 15 minutes, tomato puree: 12 minutes, canned milk: 7 minutes, lime spots / starch: 30 minutes) ,
  • an automatic wiper device for example from Erichsen, Hemer.
  • This automatic wiper works with a damp sponge, which is pressed with 300 g / 3600 mm 2 (sponge surface).
  • the automatic wiper wipes at a speed of 37 strokes per minute.
  • the experiment is carried out using a commercially available cleaning agent for glass-ceramic surfaces (A) and two different formulations of a cleaning agent (B and C) according to the invention.
  • the tiles are evaluated independently by at least 3 trained persons.
  • the tiles are rated on a scale from 0 (no cleaning effect) to 10 (completely clean).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Detergent Compositions (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

A detergent for glass-ceramic surfaces has a certain abrasive agent content and a pH value lower than about 6. The abrasive agent contains particles of an organic material, preferably in an amount of at least about 20% of the abrasive agent, and more preferably substantially the entire abrasive agent. The organic material may be a polyolefin or polyurethane, for example, and may be predominantly present as particles with a particle size in the range of about 10 to 1000 mum. The abrasive agent may also include mineral particles.

Description

Die Erfindung betrifft ein Reinigungsmittel für glaskeramische Oberflächen mit einem Gehalt an Abrasivmittel und einem pH-Wert zwischen 2 und 3.The invention relates to a cleaning agent for glass-ceramic surfaces with a content of abrasive and a pH between 2 and 3.

Glaskeramische Werkstoffe sind polykristalline Festkörper, die durch Keramisierung, d.h. gesteuerte Entglasung, von Gläsern hergestellt werden. Glaskeramische Produkte werden nach glastechnischen Verfahren geformt und besitzen nach einer Wärmebehandlung die Eigenschaften und Verarbeitbarkeit spezieller Keramiken, insbesondere eine sehr hohe Temperaturwechselbeständigkeit. Diese letztere Eigenschaft macht sie besonders geeignet zur Verwendung für Kochfelder und Geschirr, wofür sie in den letzten Jahren in verstärktem Maße eingesetzt werden.Glass-ceramic materials are polycrystalline solids produced by ceramization, i. controlled devitrification, made of glasses. Glass-ceramic products are molded by glass technology and have after a heat treatment, the properties and processability of special ceramics, in particular a very high thermal shock resistance. This latter feature makes them particularly suitable for use in cooking hobs and dishes, for which they have been increasingly used in recent years.

Insbesondere bei Kochfeldern aus Glaskeramik tritt eine besondere Art von Verschmutzung auf, die neben Proteinen, Stärke und Fett (z.B. Bratensauce, Tomatenpüree, Milch, Nudeln, Reis oder Kartoffeln) auch Kalkflecken umfaßt, insbesondere in Gegenden mit einem hohen Härtegrad des Wassers.Particularly in vitroceramic hobs, a particular type of soiling involving proteins, starch and fat (e.g., gravy, tomato puree, milk, pasta, rice or potatoes) also includes limescale, especially in areas of high water hardness.

Um derartige Verschmutzungen zu beseitigen, werden üblicherweise saure Reinigungsmittel mit einem Gehalt an Abrasivmitteln eingesetzt, beispielsweise Tonerdegemischen verschiedenen Teilchengrößen, wie z.B. beschrieben in EP 0 388 629 A1 . Sämtliche kommerziell erhältlichen Reinigungsmittel für glaskeramische Oberflächen enthalten als Abrasivmittel wasserunlösliche Mineralien mit einer typischen Mohs-Härte zwischen 7 und 9. Diese Abrasivmittel sind zwar sehr wirkungsvoll, greifen aber aufgrund ihrer Härte in vielen Fällen die zu reinigenden Oberflächen an. Dies führt insbesondere bei Glaskeramik relativ schnell zu unansehnlichen, d.h. zerkratzten, Oberflächen.In order to eliminate such contamination, acidic detergents containing abrasive substances are usually used, for example toner mixtures of different particle sizes, as described, for example, in US Pat EP 0 388 629 A1 , All commercially available cleaners for glass-ceramic surfaces contain as abrasives water-insoluble minerals with a typical Mohs hardness between 7 and 9. These abrasives are indeed very effective, but attack because of their hardness in many cases, the surfaces to be cleaned. This leads, especially in the case of glass ceramics, to unsightly, ie scratched, surfaces relatively quickly.

Für Körperreinigungsmittel, insbesondere Handreinigungsmittel, ist die Verwendung von Kunststoffen als Abrasivmitteln bereits seit längerem bekannt, um eine mildere, hautfreundlichere Variante zu den stark scheuernden mineralischen Abrasivmitteln zur Verfügung zu stellen.For personal cleansers, especially hand cleansers, the use of plastics as abrasives has long been known to provide a milder, skin-friendly alternative to the highly abrasive mineral abrasives.

US-A-3,645,904 schlägt die Verwendung von Kunstharzteilchen für Hautreinigungsmittel vor. Unter anderem werden die relativ weichen Polyolefine, insbesondere Polyethylen, Polypropylen und Polystyrol, beschrieben. Die Teilchen haben einen Durchmesser zwischen 74 und 420 µm und ihr Gehalt im Produkt liegt bei 3 bis 15 Gew.-%. US-A-3,645,904 suggests the use of synthetic resin particles for skin cleansers. Among others, the relatively soft polyolefins, in particular polyethylene, polypropylene and polystyrene, are described. The particles have a diameter between 74 and 420 microns and their content in the product is 3 to 15 wt .-%.

DE 16 69 094 D2 offenbart Reinigungsmittel mit 100 Teilen Flüssigseife und 10 bis 900 Teilen Polyethylen-Abrasivmittel mit einer Teilchengröße von 10 bis 1000 µm. Die Zusammensetzungen werden als geeignet für die Reinigung von Händen und milde Reinigung von harten Oberflächen, insbesondere lackiertem Metall, beschrieben. DE 16 69 094 D2 discloses detergent with 100 parts of liquid soap and 10 to 900 parts of polyethylene abrasive having a particle size of 10 to 1000 microns. The compositions are described as being suitable for the cleaning of hands and mild cleaning of hard surfaces, especially painted metal.

JP(06)033414 B2 offenbart die Verwendung von 5 bis 30 Gew.-% organischem Abrasivmittel mit einer Teilchengröße von 10 bis 500 µm in Körperwaschmitteln sowie zur Entfernung von Rost oder Kohlenstoffablagerungen auf Maschinen. Unter den beschriebenen Abrasivmitteln finden sich u.a. Polyurethane und Polyolefine. Der minimale Gehalt von 5 % Abrasivmittel ist gemäß dieser Entgegenhaltung für eine ausreichende Leistung erforderlich. JP (06) 033414 B2 discloses the use of from 5 to 30% by weight of organic abrasive having a particle size of from 10 to 500 microns in personal cleansers and to remove rust or carbon deposits on machines. Among the abrasives described are, inter alia, polyurethanes and polyolefins. The minimum content of 5% abrasive is required by this reference for sufficient performance.

Auch im Zusammenhang mit anderen Haushaltsreinigungsmitteln sind Abrasivmittel aus Kunststoff erwähnt, meist um eine milde Reinigung empfindlicher Oberflächen zu ermöglichen.Also in the context of other household cleaning agents are mentioned plastic abrasives, mostly to allow a mild cleaning of sensitive surfaces.

EP 0 011 984 A1 offenbart flüssige alkalische Reinigungsmittel, die wasserunlösliche mehrwertige Metallseifen enthalten, um den Formulierungen Thixotropie und Stabilität zu verleihen. Unter anderem werden gemahlene polymere Materialien, wie etwa vermahlener Polyurethanschaum, als Abrasivmittel genannt. Mineralische Abrasivstoffe sind jedoch bevorzugt. EP 0 011 984 A1 discloses liquid alkaline detergents containing water insoluble polyvalent metal soaps to impart thixotropy and stability to the formulations. Among others, milled polymeric materials, such as ground polyurethane foam, are referred to as abrasives. However, mineral abrasives are preferred.

EP 0 030 986 A1 offenbart ein flüssiges Handgeschirrspülmittel mit einem pH-Wert von 6 bis 11, das Tenside, Builder und 3 bis 20 % Abrasivmittel mit einer Mohs-Härte von 2 bis 7 und einer Teilchengröße von 1 bis 150 µm umfaßt. Es werden sowohl anorganische als auch Kunststoffmaterialien, z.B. Polystyrol und Polyacrylate, für das Abrasivmittel offenbart. Ein konkretes Beispiel für den Einsatz von Kunststoff-Abrasivmitteln findet sich jedoch nicht. EP 0 030 986 A1 discloses a liquid hand dishwashing detergent having a pH of 6 to 11 and comprising surfactants, builders and 3 to 20% abrasives having a Mohs hardness of 2 to 7 and a particle size of 1 to 150 μm. Both inorganic and plastic materials, eg, polystyrene and polyacrylates, are disclosed for the abrasive. However, there is no concrete example of the use of plastic abrasives.

EP 0 206 534 A1 offenbart flüssige alkalische Reinigungsmittel, die ein Verdickungssystem umfassen, das aus einem anorganischen Kolloid und einem anionischen Fettsäuretensid besteht. Als Abrasivmittel werden insbesondere anorganische Materialien offenbart, organische Materialien aber auch am Rande erwähnt. EP 0 206 534 A1 discloses liquid alkaline detergents comprising a thickening system consisting of an inorganic colloid and an anionic fatty acid surfactant. In particular, inorganic materials are disclosed as abrasives, but organic materials are also mentioned in passing.

EP 0 216 416 A2 offenbart ein flüssiges Reinigungsmittel, das 1 bis 50 Gew.-% wasserlösliches mildes Abrasivmittel enthält, wobei sowohl anorganische als auch organische Materialien genannt sind. Bei Verwendung von organischen Materialien beträgt der bevorzugte Bereich 5 bis 15 Gew.-%. Das bevorzugte Abrasivmittel, das als einziges in den Beispielen belegt ist, ist Calciumcarbonat. EP 0 216 416 A2 discloses a liquid detergent containing from 1 to 50% by weight of water-soluble mild abrasive, both inorganic and organic materials being mentioned. When using organic materials, the preferred range is 5 to 15% by weight. The preferred abrasive used alone in the examples is calcium carbonate.

EP 0 335 471 A1 offenbart ein cremiges Reinigungsmittel mit 10 bis 60 Gew.-% eines Abrasivmittels. Es werden anorganische und organische Abrasivmittel genannt, wobei bei der Verwendung des organischen Abrasivmittels insbesondere darauf hingewiesen wird, daß dieses das Zerkratzen empfindlicher Oberflächen, z.B. aus Kunststoff, verringert. Das einzige Abrasivmittel, das in den Beispielen beleg ist, ist jedoch Calcit. EP 0 335 471 A1 discloses a creamy detergent with 10 to 60% by weight of an abrasive. Inorganic and organic abrasives are mentioned, with the use of the organic abrasive in particular being noted that this reduces the scratching of sensitive surfaces, for example made of plastic. However, the only abrasive that is evident in the examples is calcite.

WO97/47724 A1 offenbart ein flüssiges Reinigungsmittel in Flüssigkristallform, das bis zu 20 Gew.-% eines Abrasivmittels umfaßt, das aus der Gruppe ausgewählt ist, die aus hydratisiertem Silica, Calcit und Polyethylenteilchen mit einer Teilchengröße zwischen 200 und 500 µm besteht. Es werden keine Gründe für eine Auswahl dieser Abrasivmittel angegeben. WO97 / 47724 A1 discloses a liquid detergent in liquid crystal form comprising up to 20% by weight of an abrasive selected from the group consisting of hydrated silica, calcite and polyethylene particles having a particle size between 200 and 500 μm. No reasons are given for a selection of these abrasives.

Obgleich es somit Hinweise im Stand der Technik gibt, daß Abrasivmittel aus Kunststoff eingesetzt werden können, wenn eine mildere Scheuerwirkung erwünscht ist als mit mineralischen Abrasivmitteln, z.B. um empfindliche Oberflächen zu schonen, gibt es keine Anhaltspunkte zur Reinigungswirkung derartiger Abrasivmittel, insbesondere im Vergleich mit mineralischen Abrasivmitteln. Darüberhinaus ist kein saures Reinigungsmittel mit einem Gehalt an Abrasivmittel aus Kunststoff bekannt.Thus, although there is evidence in the art that plastic abrasives can be used when a milder scrubbing action is desired than with mineral abrasives, e.g. In order to protect sensitive surfaces, there is no evidence for the cleaning effect of such abrasives, especially in comparison with mineral abrasives. In addition, no acidic cleaning agent with a content of plastic abrasives is known.

Der Erfindung liegt daher die Aufgabe zugrunde, ein gattungsgemäßes Reinigungsmittel mit verbesserter Reinigungswirkung zur Verfügung zu stellen.The invention is therefore based on the object to provide a generic cleaning agent with improved cleaning effect.

Erfindungsgemäß wird diese Aufgabe durch ein gattungsgemäßes Reinigungsmittel gelöst, bei dem das Abrasivmittel Teilchen aus Polyurethan mit einer Teilchengröße in einem Bereich von 100 bis 1000 µm umfaßt. Dabei besteht das Abrasivmittel bevorzugt zu 20 Gew.-% oder, besonders bevorzugt, im wesentlichen vollständig aus organischem Material.According to the invention, this object is achieved by a generic cleaning agent in which the abrasive comprises particles of polyurethane having a particle size in a range of 100 to 1000 microns. In this case, the abrasive agent is preferably 20 wt .-% or, more preferably, substantially entirely of organic material.

Die Erfindung sieht vor, daß das Abrasivmittel im erfindungsgemäßen Reinigungsmittel bevorzugt mit einem Gehalt von 10 Gew.-% oder weniger, besonders bevorzugt 5 Gew.-% oder weniger, enthalten ist.The invention provides that the abrasive agent in the cleaning agent according to the invention preferably with a content of 10 wt .-% or less, more preferably 5 wt .-% or less, is included.

Bevorzugt liegt das organische Material in einer Teilchengröße in einem Bereich von 100 bis 200 µm vor.Preferably, the organic material is present in a particle size in a range of 100 to 200 microns.

Völlig überraschenderweise hat sich erwiesen, daß saure Reinigungsmittel für glaskeramische Oberflächen, wie z.B. Glaskeramikkochfeldem, dann eine überlegene Reinigungswirkung zeigen, wenn das übliche mineralische Abrasivmittel teilweise oder vollständig durch Abrasivmittel aus Polyurethan ersetzt wird. Noch überraschender war, daß die Reinigungsleistung selbst bei einem niedrigen Gehalt an Abrasivmitteln von unter 10 Gew.-% im Vergleich mit handelsüblichen Reinigungsmitteln mit einem Gehalt an mineralischem Abrasivmittel von z.B. 26 Gew.-% eine überlegene Reinigungswirkung zeigte. Als zusätzlicher Vorteil ergab sich erwartungsgemäß ein stärkere Schonung der Oberflächen durch die geringere Härte und größere Teilchengröße des organischen Abrasivmittels.Quite surprisingly, it has been found that acidic cleaners for glass-ceramic surfaces, such as e.g. Glaskeramikkochfeldem, then show a superior cleaning effect, when the usual mineral abrasive is partially or completely replaced by abrasive polyurethane. Even more surprisingly, the cleaning performance was low even with a low abrasive content of less than 10% by weight compared with commercial cleaners containing mineral abrasive of e.g. 26 wt .-% showed a superior cleaning effect. As an additional advantage, it was expected that a greater protection of the surfaces resulted from the lower hardness and larger particle size of the organic abrasive.

Die Teilchengröße des organischen Materials liegt bevorzugt zwischen 100 und 200 µm, kann aber auch kleiner sein (bis hinunter zu 10 µm) oder größer (bis zu 1000 µm).The particle size of the organic material is preferably between 100 and 200 microns, but may also be smaller (down to 10 microns) or larger (up to 1000 microns).

Wenn das organische Polyurethan zusammen mit anorganischen Abrasivmitteln verwendet wird (wobei das Verhältnis in einer entsprechenden Mischung nicht besonders kritisch ist, obgleich es bevorzugt bei einem Anteil von mindestens 20 Gew.-% organischem Material liegt), können diese aus der ganzen Vielfalt bisher verwendeter mineralischer Abrasivmittel ausgewählt werden, wie bspw. Aluminiumoxid, Siliciumdioxid, Sillitin, Boehmit, Hydrargillit, Aluminiumsilikat, Kaolinit etc.When the organic polyurethane is used together with inorganic abrasives (the ratio in a corresponding mixture is not particularly critical, although it is preferably at least 20% by weight of organic material), these can be selected from the whole variety of mineral compounds used hitherto Abrasivmittel are selected, such as, for example, alumina, silica, sillitin, boehmite, hydrargillite, aluminum silicate, kaolinite, etc.

Weitere wichtige funktionale Inhaltsstoffe des erfindungsgemäßen Reinigungsmittels sind Tenside. Hierbei kommen im wesentlichen alle bekannten Tenside, die in einem sauren Medium eingesetzt werden können, in Betracht, d.h. nicht-ionische Tenside, wie bspw. der gesamte Bereich der Fettalkoholethoxylate oder Alkylethoxylate; amphotere Tenside, wie Amidobetaine, Betaine, Alkylaminocarboxylate, Iminodipropionate, etc.; und anionische Tenside, wie Alkylsulfate, Alkylethersulfate, Sulfosuccinate, etc; und kationische Tenside, wie protonierte Alkylamine, ethoxylierte Alkylamine etc..Further important functional ingredients of the cleaning agent according to the invention are surfactants. Essentially, all known surfactants that can be used in an acidic medium come into consideration, i. E. nonionic surfactants, such as the entire range of fatty alcohol ethoxylates or alkyl ethoxylates; amphoteric surfactants such as amidobetaines, betaines, alkylaminocarboxylates, iminodipropionates, etc .; and anionic surfactants such as alkyl sulfates, alkyl ether sulfates, sulfosuccinates, etc .; and cationic surfactants such as protonated alkylamines, ethoxylated alkylamines, etc.

Ein weiterer wichtiger Inhaltsstoff ist Säure oder ein Säuregemisch, bevorzugt ausgewählt aus organischen Säuren, wie bspw. Zitronensäure, Amidoschwefelsäure, Glykolsäure, Milchsäure, etc.. Der bevorzugte pH-Wert für ein gattungsgemäßes Reinigungsmittel liegt zwischen 2 und 5, besonders bevorzugt zwischen 2 und 3.Another important ingredient is acid or an acid mixture, preferably selected from organic acids, such as, for example, citric acid, amidosulfuric acid, glycolic acid, lactic acid, etc. The preferred pH for a generic cleaning agent is between 2 and 5, more preferably between 2 and third

Weitere Inhaltsstoffe, die im erfindungsgemäßen Reinigungsmittel vorgesehen sein können, sind Lösungsmittel wie Isopropylalkohol, Polyethylenglykol, N-Methyl-2-pyrrolidon, etc.; Verdickungsmittel, wie Xanthan-Gummi oder organische modifizierte Silikate (z.B. Optigel®WX); Pflegezusätze, wie Polydimethylsiloxan (mit einer Viskosität zwischen 100 mPas bis 12500 mPas), organomodifizierte Silikone, aminofunktionalisierte Silikone, Silikon-Quats, Polyvinylpyrrolidone, etc; Duftstoffe; Farbstoffe; Konservierungsmittel, etc.Other ingredients which may be provided in the cleaning agent according to the invention are solvents such as isopropyl alcohol, polyethylene glycol, N-methyl-2-pyrrolidone, etc .; Thickeners, such as xanthan gum or modified organic silicates (eg Optigel WX ®); Care additives, such as polydimethylsiloxane (having a viscosity between 100 mPas and 12500 mPas), organo-modified silicones, amino-functionalized silicones, silicone quats, polyvinylpyrrolidones, etc .; Fragrances; dyes; Preservatives, etc.

Weitere Details der durchgeführten Untersuchungen ergeben sich aus dem nachfolgenden Beispiel.Further details of the investigations carried out are shown in the following example.

Beispielexample Testverfahrentest method

Das eingesetzte Testverfahren für die Reinigungswirkung von Reinigungsmitteln für glaskeramische Oberflächen verwendet haushaltstypische Verschmutzungen und simuliert Spritzer von Nahrungsmitteln während deren Zubereitung. Die Temperatur der glaskeramischen Oberfläche in der Nähe des erhitzten Bereiches liegt typischerweise bei etwa 200°C. Der erhitzte Bereich selbst, der Temperaturen von bis zu 500°C erreicht, wird üblicherweise nicht von Spritzern getroffen. Verschmutzung, die die auf diese hohe Temperaturen erhitzten Bereiche trifft, carbonisiert jedoch sofort und ist daher nicht geeignet, um reproduzierbare Substrate für unterscheidungskräftige Tests zu liefern.The test method used for the cleaning effect of cleaning agents for glass-ceramic surfaces uses household-typical soiling and simulates splashes of food during their preparation. The temperature of the glass-ceramic surface near the heated area is typically about 200 ° C. The heated area itself, which reaches temperatures of up to 500 ° C, is usually not hit by splashes. However, contamination that hits areas heated to these high temperatures immediately carbonises and is therefore not suitable for providing reproducible substrates for distinctive testing.

a. Vorbereitung der Bewertunga. Preparation of the rating a.1 Vorreinigung der Oberflächea.1 Pre-cleaning of the surface

Zunächst wird die glaskeramische Oberfläche (Glaskeramikfliesen 25x25 cm) unter Verwendung eines alkalischen Reinigungsmittels (pH 10) und eines Handgeschirrspülmittels gesäubert. Die verwendeten Glaskeramikfliesen werden in einer heißen Lösung von Handgeschirrspülmittellösung und Kalksteinentferner für etwa 2 Stunden eingeweicht. Darauf folgen zwei Reinigungszyklen in einem Laborgeschirrspüler unter Verwendung von chlorhaltigem Geschirrspülmittel und entionisiertem Wasser (Dauer eines Zyklus etwa 45 Minuten).First, the glass ceramic surface (glass ceramic tiles 25x25 cm) is cleaned using an alkaline detergent (pH 10) and a hand dishwashing detergent. The glass ceramic tiles used are soaked in a hot solution of hand dishwashing detergent solution and limestone remover for about 2 hours. This is followed by two cycles of cleaning in a laboratory dishwasher using a chlorine-containing dishwashing detergent and deionized water (duration of one cycle about 45 minutes).

a.2 Herstellung der Substratea.2 Preparation of the substrates

Der verschmutzte Bereich hat die Abmessungen 25 x 10 cm. Die Verschmutzung wird mit einem üblichen Rakel aufgebracht. Im vorgeheizten Ofen wird die verschmutzte glaskeramische Fliese einer Temperatur von 200°C unterworfen, wobei die Verweilzeit im Ofen in Abhängigkeit von der Verschmutzung variiert (Bratensauce: 15 min; Tomatenpüree: 12 min; Dosenmilch: 7 min; Kalkflecken/Stärke: 30 min).The dirty area has the dimensions 25 x 10 cm. The dirt is applied using a standard squeegee. In the preheated oven, the soiled glass ceramic tile is subjected to a temperature of 200 ° C, the residence time in the oven varies depending on the soiling (gravy: 15 minutes, tomato puree: 12 minutes, canned milk: 7 minutes, lime spots / starch: 30 minutes) ,

b. Bewertung der Reinigungswirkungb. Evaluation of the cleaning effect

Für die Reinigung wird eine automatische Wischvorrichtung verwendet, z.B. von der Firma Erichsen, Hemer. Diese automatische Wischvorrichtung arbeitet mit einem feuchten Schwamm, der mit 300 g/3600 mm2 (Schwammfläche) angedrückt wird. Der automatische Wischer wischt mit einer Geschwindigkeit von 37 Wischbewegungen pro Minute.For cleaning, an automatic wiper device is used, for example from Erichsen, Hemer. This automatic wiper works with a damp sponge, which is pressed with 300 g / 3600 mm 2 (sponge surface). The automatic wiper wipes at a speed of 37 strokes per minute.

Das Experiment wird unter Verwendung eines handelsüblichen Reinigungsmittels für Glaskeramikoberflächen (A) sowie zwei unterschiedlichen Formulierungen eines erfindungsgemäßen Reinigungsmittels (B und C) durchgeführt.The experiment is carried out using a commercially available cleaning agent for glass-ceramic surfaces (A) and two different formulations of a cleaning agent (B and C) according to the invention.

In einem Vortest wird zunächst bestimmt, welche der drei Formulierungen die wirkungsvollste ist. Mit dieser Formulierung wird der Versuch solange durchgeführt, bis etwa 75 % der Verschmutzung entfernt sind. Die hierfür benötigte Zeit bestimmt die Versuchsdauer auch für die anderen Formulierungen. Jeder Testvorgang wird wenigstens 5-mal wiederholt.In a preliminary test, it is first determined which of the three formulations is the most effective. With this formulation, the experiment is carried out until about 75% of the pollution is removed. The time required for this determines the duration of the test also for the other formulations. Each test is repeated at least 5 times.

Wenn die Experimente an einer Fliese abgeschlossen sind, werden diese mit Leitungswasser und anschließend mit entionisiertem Wasser abgespült, um Wasserflecken zu vermeiden. Die Fliesen werden zur Trocknung vertikal bei Raumtemperatur aufbewahrt.When the experiments on a tile are completed, they are rinsed with tap water and then with deionized water to avoid water stains. The tiles are stored vertically at room temperature for drying.

Die Fliesen werden durch wenigstens 3 geschulte Personen unabhängig voneinander bewertet. Die Fliesen werden auf einer Skala von 0 (keine Reinigungswirkung) bis 10 (vollständig sauber) bewertet.The tiles are evaluated independently by at least 3 trained persons. The tiles are rated on a scale from 0 (no cleaning effect) to 10 (completely clean).

Formulierungenformulations

AA BB CC Alkylsulfonatalkylsulfonate 1,81.8 1,81.8 1,81.8 Ethoxylierter AlkoholEthoxylated alcohol 33 33 33 Amidoschwefelsäuresulfamic 22 22 22 Zitronensäurecitric acid 0,250.25 0,250.25 0,250.25 Silikonölsilicone oil 2,52.5 2,52.5 2,52.5 Verdickungsmittel (Xanthan)Thickener (xanthan gum) 0,50.5 0,50.5 0,50.5 NaOHNaOH zur Einstellung auf pH 3for adjustment to pH 3 QuartzQuartz -- -- 44 Aluminiumoxid, 3 µmAlumina, 3 μm 2626 -- -- Polyurethan, 200 µmPolyurethane, 200 μm -- 55 55 Andere (Duftstoff, Pigment, Konservierungsmittel)Others (perfume, pigment, preservatives) 0,460.46 0,460.46 0,460.46 Wasserwater Restrest

Testergebnissetest results

AA BB CC BratensauceBratensauce 55 99 99 Tomatenpüreetomato puree 66 99 88th Dosenmilchcanned milk 33 88th 88th Kalk/StärkeLime / starch 66 88th 88th

Die besten Ergebnisse ergeben sich - trotz des deutlich niedrigeren Gehalts an Abrasivmittel, als herkömmlicherweise bei mineralischem Abrasivmittel üblich ist - für das erfindungsgemäße Reinigungsmittel B, das völlig ohne mineralisches Abrasivmittel auskommt. Etwa gleichwertig sind die Ergebnisse mit einer Mischung aus Quartz und Polyurethan, während die Reinigungsergebnisse für das handelsübliche Reinigungsmittel mit Aluminiumoxid (3 µm) als Abrasivmittel - trotz des hohen Gehaltes von 26 Gew.-% - signifikant schlechter ausfallen.The best results are - despite the significantly lower content of abrasive, as is customary in mineral abrasives usual - for the inventive cleaning agent B, which manages completely without mineral abrasive. The results are approximately equivalent with a mixture of quartz and polyurethane, while the cleaning results for the commercial cleaning agent with aluminum oxide (3 μm) as abrasive - despite the high content of 26 wt .-% - significantly worse.

Die in der vorstehenden Beschreibung sowie den Ansprüchen offenbarten Merkmale der Erfindung können sowohl einzeln als auch in beliebiger Kombination für die Verwirklichung der Erfindung in ihren verschiedenen Ausführungsformen wesentlich sein.The features of the invention disclosed in the foregoing description and the claims may be essential both individually and in any combination for the realization of the invention in its various embodiments.

Claims (6)

  1. A detergent for glass ceramic surfaces, having an abrasive agent content and a pH between 2 and 3, characterized in that said abrasive agent comprises polyurethane particles having a particle size within a range from 100 to 1000 µm.
  2. A detergent as claimed in claim 1, characterized in that at least 20 wt-% of said abrasive agent consists of organic material.
  3. A detergent as claimed in claim 2, characterized that said abrasive agent consists of organic material essentially in its entirety.
  4. A detergent as claimed in any preceding claim, characterized in that the abrasive agent content is 10 wt-% or less.
  5. A detergent as claimed in claim 4, characterized in that the abrasive agent content is 5 wt-% or less.
  6. A detergent as claimed in any preceding claim, characterized in that said organic material is present predominantly in a particle size within a range from 100 to 200 µm.
EP00953091A 1999-07-29 2000-07-26 Detergent for glass-ceramic surfaces Expired - Lifetime EP1200549B1 (en)

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DE19935083 1999-07-29
DE19935083A DE19935083A1 (en) 1999-07-29 1999-07-29 Detergent for glass ceramic surfaces
PCT/EP2000/007157 WO2001009279A1 (en) 1999-07-29 2000-07-26 Detergent for glass-ceramic surfaces

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ATE447606T1 (en) 2009-11-15
ES2336072T3 (en) 2010-04-08
US20020137647A1 (en) 2002-09-26
WO2001009279A1 (en) 2001-02-08
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US6759377B2 (en) 2004-07-06
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DE50015780D1 (en) 2009-12-17

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