EP1242573A2 - Composition for use in a dishwasher - Google Patents

Composition for use in a dishwasher

Info

Publication number
EP1242573A2
EP1242573A2 EP00991269A EP00991269A EP1242573A2 EP 1242573 A2 EP1242573 A2 EP 1242573A2 EP 00991269 A EP00991269 A EP 00991269A EP 00991269 A EP00991269 A EP 00991269A EP 1242573 A2 EP1242573 A2 EP 1242573A2
Authority
EP
European Patent Office
Prior art keywords
substance
dishwasher
composition according
rinse cycle
cycle
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.)
Granted
Application number
EP00991269A
Other languages
German (de)
French (fr)
Other versions
EP1242573B1 (en
Inventor
Guido Wäschenbach
Harald Magg
Richard Neergaard
Enric Carbonell
Ralf Wiedemann
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.)
Reckitt Benckiser Finish BV
Original Assignee
Reckitt Benckiser NV
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 Reckitt Benckiser NV filed Critical Reckitt Benckiser NV
Priority to EP10182407A priority Critical patent/EP2330179A1/en
Publication of EP1242573A2 publication Critical patent/EP1242573A2/en
Application granted granted Critical
Publication of EP1242573B1 publication Critical patent/EP1242573B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets

Definitions

  • the present invention relates to a composition for use in a dishwasher.
  • Rinse aids are intended to prevent water droplets from remaining on the dishes when rinsing with water, which, after drying, leave stains from substances dissolved / dispersed in the drops, in particular salts.
  • antibacterial activity e.g. cationic compounds or triclosan
  • silver protection e.g. benzotriazole
  • fragrance fragments, perfume
  • bleaching / disinfection e.g. chlorine bleach
  • odor masking e.g. polyvinylpyrrolidone
  • anti-scale agents e.g. lipase for Removal of fat deposits in the dishwasher.
  • alkaline cleaning agent mixtures must be used in the dishwasher in combination with softened tap water, so that limescale deposits on machine parts and washware are avoided.
  • the tap water is softened in the dishwasher by an ion exchanger.
  • regular salt for example sodium chloride, are poured into a device provided for this purpose in the dishwasher.
  • Citric acid and used as a complexing agent nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA).
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • the detergent function, the functions of the substances to be added in the rinse aid and the function that prevents limescale deposits when using hard water and alkaline detergents have not been achieved with the same possible performance compared to the results that can be achieved with separate doses to combine or combine in one product, in particular that an ion exchanger and the associated regeneration thereof can be dispensed with.
  • the aim of the present invention was to combine the three functions mentioned above in a single product, so that the user only has to dose the product once into the dishwasher.
  • a machine dishwashing cleaning tablet is known from EP 0 851 024 A2, which is intended to enable the functional ingredients to be released in a controlled manner into the washing cycle.
  • the tablet comprises two layers, the first layer when dissolved dissolves a pH of 8.5 to 1 1 in the wash water and the second layer a pH of 6.5 to 9.
  • the components of the second layer are embedded in a continuous medium, which should only melt in the final rinse and release the components.
  • This temperature-dependent system has not proven itself in practice, in particular because, given the likewise high temperatures in the main rinse cycle, a controlled release of the components of the second layer does not function reliably in the rinse cycle and therefore satisfactory cleaning results cannot be achieved.
  • the temperature program most frequently selected in European households has the same temperature in the main wash cycle as in the rinse cycle. This leads to premature release of the active substances from the second layer.
  • the waxes used for the medium of the second layer often form residues in the machine and on the wash ware.
  • the present invention is based on the described prior art, the task of creating a composition that combines the cleaning function, the functions of the substances to be added in the rinse aid and the function that prevent limescale deposits when using hard water, and these functions during of a dishwashing cycle activated at specified times, ie Appropriate functional substances are released in a controlled manner during the dishwashing cycle.
  • this object is achieved in an alternative by a generic composition, which is characterized by a basic composition, which unfolds its function essentially in the main cleaning cycle of the dishwasher, in the form of a tablet; at least one area which is arranged separately in or on the tablet and which comprises at least one substance which is to function essentially in the rinse cycle of the dishwasher and at least one substance which prevents limescale deposits in the dishwasher and / or on the dishes; and means to ensure that at least the substance that is to function essentially in the rinse aid of the dishwasher, is at least predominantly released at the earliest at the beginning of the rinse aid.
  • the substances are mixed together in the separately arranged area.
  • the substances in the separately arranged area are present separately in two sub-areas, in particular that the substance (s), which is to function essentially in the rinse aid of the dishwasher, in which a sub-area and the substance ( en) that prevents (prevent) limescale deposits in the dishwasher and / or on the wash ware in which the other sub-area is present.
  • the region (s) has a core which essentially comprises the substance which is to function essentially in the rinse cycle of the dishwasher; and a sheath around this core which comprises the substance which prevents limescale deposits in the dishwasher and / or on the wash ware.
  • a separating layer which is essentially impermeable to the substances is preferably provided between the two partial areas.
  • the agents for preventing premature release of the rinse aid substance
  • the agents comprise a suitably arranged covering which comprises at least one compound whose solubility increases with a decreasing concentration of a specific ion in the surrounding medium.
  • the object according to the invention is achieved by a generic composition, which is characterized by a basic composition, its Function unfolds essentially in the main cleaning cycle of the dishwasher, in the form of a tablet; two areas arranged separately in or on the tablet, of which a first area comprises at least one substance which is supposed to function essentially in the rinse cycle of the dishwasher, and a second area which comprises at least one substance the limescale deposits in the dishwasher and / or prevented on the wash ware; and in each case an envelope substantially completely surrounding the areas, which comprises at least one compound whose solubility increases with decreasing concentration of a specific ion in the surrounding medium.
  • means are provided to ensure that the substance (s) that prevent limescale in the dishwasher and / or on the wash ware is (at least partially) released before the rinse cycle.
  • the invention further proposes that an additional water-soluble protective covering is provided as the outermost layer.
  • the substance for preventing limescale deposits is a substance which is capable of complex formation, in particular a substance which is selected from the group consisting of phosphonates and polymers, polymers preferably polyacrylates or copolymers thereof are.
  • the substance for preventing limescale deposits is preferably a substance which shifts the carbonate / bicarbonate equilibrium in the rinsing medium towards bicarbonate in the rinse cycle, preferably an acid or an acid mixture.
  • This is preferably an acid from the group of carboxylic acids, preferably fruit acids, particularly preferably citric acid.
  • the invention provides that the covering comprises at least one compound, the solubility of which increases with decreasing OH " ion concentration and thus decreasing pH in the surrounding medium.
  • the composition according to the invention is distinguished by the fact that it delivers excellent results both in the main cleaning cycle and in the rinse cycle of a dishwasher and, moreover, makes the use of an ion exchanger or the use of salt for its regeneration superfluous in most cases (at least in households with water hardness) up to 35 ° dH).
  • the tablet is released during the main cleaning cycle and can have its intended effect.
  • the area (s) arranged on the tablet contains the substances with the desired further functionalities, namely on the one hand the substance (s) for the rinse cycle, e.g. Rinse aid, on the other hand the substances), which make the use of ion exchangers superfluous.
  • the substances in the separately arranged area (s) can be protected by a coating which is stable at the concentration of a specific ion, for example the OH " ion and thus at the pH, and the temperature of the main cleaning cycle does not dissolve or dissolves only insignificantly.Only when this concentration drops significantly by dilution, for example the pH value is shifted towards neutral or acidic, ie at the earliest at the beginning of the rinse aid, is the solubility of the wrapping material reduced so much that it quickly dissolves or dissolves and releases the actually effective core material into the surrounding medium.
  • a coating which is stable at the concentration of a specific ion, for example the OH " ion and thus at the pH, and the temperature of the main cleaning cycle does not dissolve or dissolves only insignificantly.Only when this concentration drops significantly by dilution, for example the pH value is shifted towards neutral or acidic, ie at the earliest at the beginning of the rinse aid, is the solubility of the wrapping material reduced so much that it quickly dissolves or dissolve
  • the substances can be protected by a component in the casing which has a so-called cloud point.
  • These components are less soluble at high temperatures and protect against premature release of active substances in applications with high temperatures in the cleaning cycle.
  • Examples of substances with such a cloud point are celluloses, some polyacrylate derivatives, etc.
  • this protection makes sense for the substance (s) that are to function essentially in the rinse aid of the dishwasher, such as a rinse aid. This substance (s) should therefore at least predominantly (ie more than 50%) only be released at the earliest at the beginning of the rinse aid cycle.
  • the substance (s) which prevents limescale deposits in the dishwasher and / or on the wash ware can also be protected from premature release by, for example, an appropriate covering, so that these substance (s) are only released in the rinse cycle.
  • the substance (s) which protect (protect) against limescale deposits are released at an earlier point in time, ie before the start of the rinse cycle, in order to be effective not only in the rinse cycle but over a longer period of time to exercise in the wash cycle.
  • Figure 1 shows a first embodiment of the composition according to the invention in cross section.
  • Fig. 4 shows a fourth embodiment of the composition according to the invention in cross section.
  • a tablet 1 which is designed as a two-layer tablet with a lower layer 2 and an upper layer 3.
  • a two-layer tablet with a lower layer 2 and an upper layer 3.
  • one of the customary, commercially available two-layer tablets can be used as the basis, in which the two layers usually have a different composition and are colored differently.
  • a recess 4 is formed in the upper layer 3, in which a particle 10 is received.
  • the particle 10 (usually produced separately) can be fixed in the recess 4, for example, by an adhesive.
  • the particle 10 is shown as a core 12 with a multi-layer coating (13, 14, 15, 16), it being pointed out that both this illustration and the illustrations of FIGS. 2 and Fig. 3 is not to scale for illustrative purposes.
  • the core 12 of the particle 10 comprises the substance (s) which have their main effect (unfold) essentially in the rinse aid of the dishwasher, e.g. one or more surfactants that can be used as rinse aid.
  • This rinse aid core 12 is surrounded by a first separating layer 13, which consists of a water-soluble material which is essentially impermeable to the substances in the core 12, but which can quickly dissolve in the rinse aid of the dishwasher in order to release the substances in the core 12.
  • a further covering 14 is formed around this jacket 13, which is constructed in such a way that it only dissolves at the beginning of the rinse cycle.
  • this jacket 13 comprises at least one compound, the solubility of which increases with decreasing concentration of a specific ion in the surrounding medium.
  • solubility can be coupled with a falling concentration of the OH " ion and thus a falling pH.
  • examples of such compounds are described in (not prepublished) patent application 198 34 180.6, which is hereby expressly incorporated in its entire disclosure should be included.
  • polymers which are suitable for the purposes of the present invention are polymers of isomers or derivatives of pyridine, preferably copolymers with styrene or acrylonitrile of the following formulas III and IV, in which G represents a substituent at any point on the pyridine ring.
  • An example of an ion concentration-sensitive polymer is the polysaccharide K-carrageenan with the following formula VI
  • the substances that can be used in the casing 14 are not limited to those just described, but rather include all known or suitable compounds with the corresponding functionality.
  • a jacket 15 is formed around this covering 14, which comprises the second functional substance for the rinse aid, namely the substance which is intended to prevent limescale deposits in the dishwasher and on the dishes, such as one of those substances mentioned above, ie either a complexing agent, such as phosphonate or polymer, or a substance which, by providing sufficient acidity, the carbonate / bicarbonate Balance is shifted towards the bicarbonate in order to prevent carbonate deposits in the dishwasher and on the dishes, such as a fruit acid such as citric acid.
  • the second functional substance for the rinse aid namely the substance which is intended to prevent limescale deposits in the dishwasher and on the dishes, such as one of those substances mentioned above, ie either a complexing agent, such as phosphonate or polymer, or a substance which, by providing sufficient acidity, the carbonate / bicarbonate Balance is shifted towards the bicarbonate in order to prevent carbonate deposits in the dishwasher and on the dishes, such as a fruit acid such as citric acid.
  • a water-soluble protective covering 16 can preferably also be provided as the outermost layer in order to protect the particles 10 during storage and transport.
  • the protective covering 16 will essentially dissolve during the dissolution of the tablet 1 already in the main wash cycle of the dishwasher.
  • both the clear active component and the limescale-preventing component can be present (at least partially) in the core 12.
  • the jacket 15 is no longer absolutely necessary, but can additionally be provided as a carrier for additional amounts of the limescale-preventing component and / or a (possibly further) active component for preventing deposits.
  • FIG. 2 shows a further embodiment of the composition according to the invention in the form of a tablet 1, which in this case consists of only a single layer 2, in which - as in FIG. 1 - a trough 4 is formed for receiving a corresponding bifunctional particle.
  • the core consists of two half-cores 12, 12 ', a first core 12 comprising the substance with one functionality, the second half-core 12' comprising the substance with the other functionality.
  • the two half-cores are preferably separated by a separating layer 13, the composition of which can correspond to that of the corresponding separating layer 13 from FIG. 1. This is particularly useful if the substances in the half-cores are not compatible with one another.
  • FIG. 3 describes a further alternative of the composition according to the invention, in which the tablet 1 - as in FIG. 1 - again consists of two layers, a lower layer 2 and an upper layer 3. In this case, however, a trough 4 or 4 'is formed in both layers, which serve to receive corresponding particles 10 or 10'.
  • the cores 12 and 12 'of the particles 10 and 10' are designed so that the one core (for example 12) comprises the substance which is supposed to function essentially in the rinse aid, for example a surfactant suitable as rinse aid, during the another core (12 ') contains the substance which prevents limescale deposits in the dishwasher and on the wash ware, for example a complexing agent such as phosphonates or corresponding polymers or an acidifying agent such as citric acid.
  • core 12 is, as before, surrounded by a covering 14, which preferably, but not necessarily, consists of the same material and which - as described above - ensures that the substance contained in the core is only released in the rinse cycle, core 12 'can only be used by be surrounded by a protective sheath 16, as previously described.
  • the particles described can be produced either by a pressing process or by another manufacturing process. If two or more particles are used, as in the embodiment according to FIG. 3 or the subsequent embodiment according to FIG. 4, the particles can of course also be produced by different methods.
  • Tablet 1 shows another alternative of the composition according to the invention.
  • Tablet 1 consisting of a single layer 2, has two troughs 4, 4 'in one surface.
  • the surface with the depressions 4 and 4 ' is then covered with a film 20, which consists, for example, of one of the materials described for the protective covering 14 in the previous embodiments.
  • depression 4 is filled with a rinse-active material 12 and depression 4 'with a limescale-preventing material 12'.
  • the materials 12 and 12 ' can - as in the previous embodiments - be shaped into a particle, but can also be filled in as powder compositions or viscous, gel-like compositions.
  • another film 20 ' is applied, the same or a similar recipe to film 20. In this way, the rinse-active material 12 and the limescale-preventing material 12 'are also completely covered by a protective coating (and / or both are only released in the rinse cycle).
  • the formulation of the tablet can correspond to that of a commercially available two-layer tablet.
  • Core 12 contains 57% by weight polyethylene glycol (molecular weight approx. 35,000) and 28% by weight fatty alcohol ethoxylate propoxylate as rinse-active substances.
  • the core contains 12 15% by weight of citric acid as a substance to prevent limescale deposits.
  • all or part of the citric acid in core 12 can be omitted and all or part of it can be provided in the casing 14.
  • Protective sheathing 15 contains (in% by weight of the entire particle) 1.3% of the polymer described in more detail above according to Japanese Patent Application Kokai 61-28440, 3.0% hydroxypropylmethyl cellulose and 3.0% polyvinyl alcohol.
  • a separating layer 13 and a protective covering 16 are not provided in the present case.
  • cores with a diameter of approx. 12 mm (1 g) were produced and coated with the described coating materials in suitable devices.

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

Abstract

The invention relates to a composition for use in a dishwasher. The inventive composition is characterized by a base composition in the form of a tablet which becomes active substantially during the main wash cycle of the dishwasher. At least one separate zone in or on said tablet is provided with a substance that becomes active substantially during the rinse cycle of the dishwasher and with at least one substance that prevents limescale build-up in the dishwasher and/or on the washed articles. The inventive composition further comprises agents that guarantee that at least the substance that becomes active substantially during the rinse cycle of the dishwasher is at least mainly released at the beginning of the rinse cycle at the earliest.

Description

Zusammensetzung zur Verwendung in einer Geschirrspülmaschine Composition for use in a dishwasher
Die vorliegende Erfindung betrifft eine Zusammensetzung zur Verwendung in einer Geschirrspülmaschine.The present invention relates to a composition for use in a dishwasher.
Obgleich moderne Geschirrspülmaschinen in den meisten Fällen eine Vielzahl von unterschiedlichen Spülprogrammen besitzen, die sich in Dauer und Temperatur der einzelnen Spülgänge unterscheiden, bestehen alle im wesentlichen aus den folgenden Grundschritten: Vorspülgang; Hauptreinigungsgang; ein oder mehrere Zwischenspülgänge; ein Klarspülgang; und Trocknung. Im Verlauf eines Geschirrspülzyklus werden dabei eine Reihe von Produkten in die Geschirrspülmaschine zudosiert, um die jeweilige Zyklusstufe zu unterstützen. So wird, z.B., das eigentliche Maschinengeschirrspülmittel, das die Reinigungswirkung entfalten soll, zu Beginn des Hauptreinigungsgangs zugesetzt.Although modern dishwashers in most cases have a large number of different washing programs, which differ in the duration and temperature of the individual wash cycles, all essentially consist of the following basic steps: pre-wash cycle; Main wash cycle; one or more intermediate rinse cycles; a rinse aid; and drying. In the course of a dishwashing cycle, a number of products are metered into the dishwasher in order to support the respective cycle stage. For example, the actual machine dishwashing detergent that is supposed to have the cleaning effect is added at the beginning of the main cleaning cycle.
Im Klarspülgang kommen spezielle Mittel zum Einsatz, z.B. Klarspüler. Klarspüler sollen verhindern, daß beim Spülen mit Wasser Wassertröpfchen auf dem Spülgut zurückbleiben, die nach Antrocknen Flecken aus in den Tropfen gelösten/dispergierten Substanzen, insbesondere Salzen, zurücklassen.Special agents are used in the rinse cycle, e.g. Rinse aid. Rinse aids are intended to prevent water droplets from remaining on the dishes when rinsing with water, which, after drying, leave stains from substances dissolved / dispersed in the drops, in particular salts.
Neben dem Einsatz von Klarspülem können weitere Mittel, die ihre Aktivität im Klarspülgang entfalten, verwendet werden, z.B. antibakterielle Aktivität (z.B. kationische Verbindungen oder Triclosan), Silberschutz (z.B. Benzotriazol), Duftwirkung (Duftstoffe, Parfüm), Bleichwirkung/Desinfektion (z.B. Chlorbleiche), Geruchsmaskierung (z.B. Polyvinylpyrrolidon), Antibe- lagmittel und Enzyme (z..B. Lipase zur Entfernung von Fettablagerungen im Geschirrspüler).In addition to the use of rinse aid, other agents that develop their activity in the rinse aid cycle can be used, e.g. antibacterial activity (e.g. cationic compounds or triclosan), silver protection (e.g. benzotriazole), fragrance (fragrances, perfume), bleaching / disinfection (e.g. chlorine bleach), odor masking (e.g. polyvinylpyrrolidone), anti-scale agents and enzymes (e.g. lipase for Removal of fat deposits in the dishwasher).
Es ist bekannt, daß alkalische Reinigungsmittelgemische in der Geschirspülmaschine in Kombination mit enthärtetem Leitungswasser eingesetzt werden müssen, damit Kalkbeläge auf Maschinenteilen und Spülgut vermieden werden. Die Enthärtung des Leitungswassers erfolgt in der Geschirrspülmaschine durch einen lonentauscher. Zur Regenerierung des lonentauschers muß regelmäßig Salz, z.B. Natriumchlorid, in eine dafür vorgesehene Vorrichtung der Geschirrspülmaschine eingefüllt werden.It is known that alkaline cleaning agent mixtures must be used in the dishwasher in combination with softened tap water, so that limescale deposits on machine parts and washware are avoided. The tap water is softened in the dishwasher by an ion exchanger. To regenerate the ion exchanger regular salt, for example sodium chloride, are poured into a device provided for this purpose in the dishwasher.
Möchte man eine Geschirrspülmaschine ohne Ionenaustauscher oder ohne lästiges Nachfüllen von Salz betreiben, so gilt es einen leistungsfähigen Weg zur Verhinderung von Kalkbelägen oder ähnlichen Ablagerungen zu finden.If you want to operate a dishwasher without an ion exchanger or without the hassle of refilling salt, you have to find a powerful way to prevent limescale deposits or similar deposits.
Ein Lösungsansatz ist die Verwendung saurer Reinigungsmittelgemische. In diesem Falle kann man mit hartem Leitungswasser arbeiten und auf den Einsatz eines lonentauschers in der Geschirrspülmaschine ganz verzichten, womit auch der Einsatz und damit das Nachfüllen des Regeneriersalzes überflüssig wird. Der pH- Wert dieser Reiniger sorgt dabei für eine Verschiebung des Carbonat-Bicarbonat-Gleichgewichtes in der Weise, daß vorwiegend Bicarbonat vorliegt, das nicht zur Bildung der genannten Beläge führt. So ist z.B. in der deutschen Patentschrift DE 38 33 047 C2 ein pulverförmiges, saures Maschinengeschirrspülmittel auf Basis nicht-ionischer Tenside beschrieben, dessen 0,5 bis 0,7 %ige wäßrige Lösung einen pH-Wert von 2 bis 6 aufweist und den Einsatz eines lonentauschers überflüssig macht. Als Buildersubstanzen werden hier Hydroxycarbonsäuren, z.B. Zitronensäure, und als Komplexbildner Nitrilotriessigsäure (NTA) und Ethylendiamintetraessigsäure (EDTA) verwendet. Ein wesentlicher Nachteil dieser Reinigerrezepturen ist die unbefriedigende Reinigungskraft, die insbesondere auf der Abwesenheit von Alkalität beruht, vor allem auf Anschmutzungen, die auf Stärke basieren.One solution is the use of acidic detergent mixtures. In this case you can work with hard tap water and do without the use of an ion exchanger in the dishwasher, making the use and thus refilling of the regeneration salt unnecessary. The pH of these cleaners ensures a shift in the carbonate-bicarbonate balance in such a way that predominantly bicarbonate is present which does not lead to the formation of the deposits mentioned. For example, German patent DE 38 33 047 C2 describes a powdery, acidic machine dishwashing detergent based on nonionic surfactants, the 0.5 to 0.7% aqueous solution of which has a pH of 2 to 6 and makes the use of an ion exchanger unnecessary , Hydroxycarboxylic acids, e.g. Citric acid, and used as a complexing agent nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA). A major disadvantage of these cleaning formulations is the unsatisfactory cleaning power, which is based in particular on the absence of alkalinity, especially on soiling based on starch.
Bislang ist es nicht gelungen, die Reinigerfunktion, die Funktionen der im Klarspülgang zuzusetzenden Substanzen und die Funktion, die Kalkablagerungen bei Verwendung von hartem Wasser und alkalischen Reinigungsmittel verhindert, bei möglichst gleichbleibender Leistung gegenüber den Ergebnissen, die mit jeweils separaten Dosierungen erzielt werden können, so in einem Produkt zu kombinieren bzw. zu vereinigen, daß insbesondere auf einen lonentauscher und die damit verbundene Regenerierung desselben verzichtet werden kann. Ziel der vorliegenden Erfindung war es, die drei obengenannten Funktionen in einem einzigen Produkt zu vereinen, so daß nur eine einmalige Dosierung des Produkts in die Geschirrspülmaschine durch den Benutzer vorgenommen werden muß. Aus der EP 0 851 024 A2 ist eine Maschinengeschirrspülreinigungstablette bekannt, die eine kontrollierte Freigabe der funktionalen Inhaltsstoffe in den Spülzyklus ermöglichen soll. Die Tablette umfaßt zwei Schichten, wobei die erste Schicht beim Auflösen einen pH- Wert von 8,5 bis 1 1 im Waschwasser erzeugt, und die zweite Schicht einen pH-Wert von 6,5 bis 9. Mit dieser Zweischichttablette soll es möglich sein, spezielle Inhaltsstoffe, insbesondere eine Säurequelle, Anti-Ablagerungsmittel und oberflächenaktive Stoffe, erst verzögert in den Klarspülgang der Geschirrspülmaschine abzugeben. Dabei sind die Komponenten der zweiten Schicht in ein kontinuierliches Medium eingebettet sind, das erst im abschließenden Spülgang aufschmelzen und die Komponenten freisetzen soll. Dieses temperaturabhängige System hat sich in der Praxis nicht bewährt, insbesondere weil angesichts der ebenfalls hohen Temperaturen im Hauptspülgang eine kontrollierte Freisetzung der Komponenten der zweiten Schicht erst im Klarspülgang nicht zuverlässig funktioniert und daher keine befriedigenden Reinigungsergebnisse erzielt werden können. So weist das in europäischen Haushalten am häufigsten gewählte Temperaturprogramm im Hauptspülgang die gleiche Temperatur auf wie im Klarspülgang. Dies führt zu einer verfrühten Freisetzung der Aktivstoffe aus der zweiten Schicht. Darüber hinaus bilden die für das Medium der zweiten Schicht verwendeten Wachse oft Rückstände in der Maschine und auf dem Spülgut.So far, the detergent function, the functions of the substances to be added in the rinse aid and the function that prevents limescale deposits when using hard water and alkaline detergents have not been achieved with the same possible performance compared to the results that can be achieved with separate doses to combine or combine in one product, in particular that an ion exchanger and the associated regeneration thereof can be dispensed with. The aim of the present invention was to combine the three functions mentioned above in a single product, so that the user only has to dose the product once into the dishwasher. A machine dishwashing cleaning tablet is known from EP 0 851 024 A2, which is intended to enable the functional ingredients to be released in a controlled manner into the washing cycle. The tablet comprises two layers, the first layer when dissolved dissolves a pH of 8.5 to 1 1 in the wash water and the second layer a pH of 6.5 to 9. With this two-layer tablet it should be possible to dispensing special ingredients, especially an acid source, anti-deposition agents and surface-active substances, into the rinse aid of the dishwasher with a delay. The components of the second layer are embedded in a continuous medium, which should only melt in the final rinse and release the components. This temperature-dependent system has not proven itself in practice, in particular because, given the likewise high temperatures in the main rinse cycle, a controlled release of the components of the second layer does not function reliably in the rinse cycle and therefore satisfactory cleaning results cannot be achieved. The temperature program most frequently selected in European households has the same temperature in the main wash cycle as in the rinse cycle. This leads to premature release of the active substances from the second layer. In addition, the waxes used for the medium of the second layer often form residues in the machine and on the wash ware.
Der vorliegenden Erfindung liegt angesichts des geschilderten Standes der Technik die Aufgabe zugrunde, eine Zusammensetzung zu schaffen, die die Reinigerfunktion, die Funktionen der im Klarspülgang zuzusetzenden Substanzen und die Funktion, die Kalkablagerung bei Verwendung von hartem Wasser verhindern, in sich kombiniert und diese Funktionen während eines Geschirrspülzyklus zu festgelegten Zeitpunkten aktiviert, d.h. entsprechende funktioneile Substanzen während des Geschirrspülzyklus kontrolliert freisetzt.The present invention is based on the described prior art, the task of creating a composition that combines the cleaning function, the functions of the substances to be added in the rinse aid and the function that prevent limescale deposits when using hard water, and these functions during of a dishwashing cycle activated at specified times, ie Appropriate functional substances are released in a controlled manner during the dishwashing cycle.
Erfindungsgemäß wird diese Aufgabe in einer Alternative durch eine gattungsgemäße Zusammensetzung gelöst, die gekennzeichnet ist durch eine Basiszusammensetzung, die ihre Funktion im wesentlichen im Hauptreinigungsgang der Geschirrspülmaschine entfaltet, in Form einer Tablette; mindestens einen in oder an der Tablette separat angeordneten Bereich, der sowohl wenigstens eine Substanz, die ihre Funktion im wesentlichen im Klarspülgang der Geschirrspülmaschine entfalten soll, als auch wenigstens eine Substanz, die Kalkablagerungen in der Geschirrspülmaschine und/oder auf dem Spülgut verhindert, umfaßt; und Mittel, um sicherzustellen, daß wenigstens diejenige Substanz, die ihre Funktion im wesentlichen im Klarspülgang der Geschirrspülmaschine entfalten soll, zumindest überwiegend erst frühestens zu Beginn des Klarspülganges freigesetzt wird.According to the invention, this object is achieved in an alternative by a generic composition, which is characterized by a basic composition, which unfolds its function essentially in the main cleaning cycle of the dishwasher, in the form of a tablet; at least one area which is arranged separately in or on the tablet and which comprises at least one substance which is to function essentially in the rinse cycle of the dishwasher and at least one substance which prevents limescale deposits in the dishwasher and / or on the dishes; and means to ensure that at least the substance that is to function essentially in the rinse aid of the dishwasher, is at least predominantly released at the earliest at the beginning of the rinse aid.
Es kann vorgesehen sein, daß die Substanzen in dem separat angeordneten Bereich miteinander vermischt vorliegen.It can be provided that the substances are mixed together in the separately arranged area.
Besonders bevorzugt ist vorgesehen, daß die Substanzen in dem separat angeordneten Bereich getrennt in zwei Teilbereichen vorliegen, insbesondere daß die Substanz(en), die ihre Funktion im wesentlichen im Klarspülgang der Geschirrspülmaschine entfalten soll(en), in dem einen Teilbereich und die Substanz(en), die Kalkablagerungen in der Geschirrspülmaschine und/oder auf dem Spülgut verhindert (verhindern), in dem anderen Teilbereich vorliegt (vorliegen).It is particularly preferably provided that the substances in the separately arranged area are present separately in two sub-areas, in particular that the substance (s), which is to function essentially in the rinse aid of the dishwasher, in which a sub-area and the substance ( en) that prevents (prevent) limescale deposits in the dishwasher and / or on the wash ware in which the other sub-area is present.
Besonders bevorzugt ist vorgesehen, daß der (die) Bereich(e) einen Kern, der im wesentlichen die Substanz umfaßt, die ihre Funktion im wesentlichen im Klarspülgang der Geschirrspülmaschine entfalten soll; und einen Mantel um diesen Kern, der die Substanz umfaßt, die Kalkablagerungen in der Geschirrspülmaschine und/oder auf dem Spülgut verhindert, umfaßt (umfassen).It is particularly preferably provided that the region (s) has a core which essentially comprises the substance which is to function essentially in the rinse cycle of the dishwasher; and a sheath around this core which comprises the substance which prevents limescale deposits in the dishwasher and / or on the wash ware.
Bevorzugt ist zwischen den beiden Teilbereichen eine für die Substanzen im wesentlichen undurchlässige Trennschicht vorgesehen ist.A separating layer which is essentially impermeable to the substances is preferably provided between the two partial areas.
Besonders bevorzugt ist vorgesehen, daß die Mittel (zur Verhinderung einer vorzeitigen Freisetzung der Klarspülsubstanz) eine geeignet angeordnete Umhüllung umfassen, die mindestens eine Verbindung umfaßt, deren Löslichkeit mit sinkender Konzentration eines spezifischen Ions im umgebenden Medium zunimmt.It is particularly preferably provided that the agents (for preventing premature release of the rinse aid substance) comprise a suitably arranged covering which comprises at least one compound whose solubility increases with a decreasing concentration of a specific ion in the surrounding medium.
In einer zweiten Alternative wird die erfindungsgemäße Aufgabe durch eine gattungsgemäße Zusammensetzung gelöst, die gekennzeichnet ist durch eine Basiszusammensetzung, die ihre Funktion im wesentlichen im Hauptreinigungsgang der Geschirrspülmaschine entfaltet, in Form einer Tablette; zwei in oder an der Tablette separat angeordnete Bereiche, von denen ein erster Bereich mindestens eine Substanz umfaßt, die ihre Funktion im wesentlichen im Klarspülgang der Geschirrspülmaschine entfalten soll, und ein zweiter Bereich, der mindestens eine Substanz umfaßt, die Kalkablagerungen in der Geschirrspülmaschine und/oder auf dem Spülgut verhindert; und jeweils eine die Bereiche im wesentlichen vollständig umgebende Umhüllung, die mindestens eine Verbindung umfaßt, deren Löslichkeit mit sinkender Konzentration eines spezifischen Ions im umgebenden Medium zunimmt.In a second alternative, the object according to the invention is achieved by a generic composition, which is characterized by a basic composition, its Function unfolds essentially in the main cleaning cycle of the dishwasher, in the form of a tablet; two areas arranged separately in or on the tablet, of which a first area comprises at least one substance which is supposed to function essentially in the rinse cycle of the dishwasher, and a second area which comprises at least one substance the limescale deposits in the dishwasher and / or prevented on the wash ware; and in each case an envelope substantially completely surrounding the areas, which comprises at least one compound whose solubility increases with decreasing concentration of a specific ion in the surrounding medium.
Für beide Alternativen ist bevorzugt vorgesehen, daß Mittel vorgesehen sind, um sicherzustellen, daß die Substanz(en), die Kalkablagerung in der Geschirrspülmaschine und/oder auf dem Spülgut verhindert (verhindern), zumindest teilweise vor dem Klarspülgang freigesetzt wird (werden).For both alternatives, it is preferably provided that means are provided to ensure that the substance (s) that prevent limescale in the dishwasher and / or on the wash ware is (at least partially) released before the rinse cycle.
Die Erfindung schlägt weiterhin vor, daß als äußerste Schicht eine zusätzliche wasserlösliche Schutzumhüllung vorgesehen ist.The invention further proposes that an additional water-soluble protective covering is provided as the outermost layer.
Weiterhin ist vorgesehen, daß die Substanz zur Verhinderung von Kalkablagerungen eine Substanz ist, die zur Komplexbildung in der Lage ist, insbesondere eine Substanz, die ausgewählt ist aus der Gruppe, die aus Phosphonaten und Polymeren besteht, wobei Polymere bevorzugt Po- lyacrylate oder Copolymere derselben sind.It is further provided that the substance for preventing limescale deposits is a substance which is capable of complex formation, in particular a substance which is selected from the group consisting of phosphonates and polymers, polymers preferably polyacrylates or copolymers thereof are.
Alternativ ist die Substanz zur Verhinderung von Kalkablagerungen bevorzugt eine Substanz, die im Klarspülgang das Gleichgewicht Carbonat/Bicarbonat im Spülmedium in Richtung Bicar- bonat verschiebt, vorzugsweise eine Säure oder ein Säuregemisch. Bevorzugt handelt es sich hierbei um eine Säure aus der Gruppe der Carbonsäuren, vorzugsweise der Fruchtsäuren, besonders bevorzugt um Zitronensäure. Die Erfindung sieht in einer bevorzugten Ausführungsform vor, daß die Umhüllung wenigstens eine Verbindung umfaßt, deren Löslichkeit mit sinkender OH"-Ionenkonzentration und damit abnehmendem pH-Wert im umgebenden Medium zunimmt.Alternatively, the substance for preventing limescale deposits is preferably a substance which shifts the carbonate / bicarbonate equilibrium in the rinsing medium towards bicarbonate in the rinse cycle, preferably an acid or an acid mixture. This is preferably an acid from the group of carboxylic acids, preferably fruit acids, particularly preferably citric acid. In a preferred embodiment, the invention provides that the covering comprises at least one compound, the solubility of which increases with decreasing OH " ion concentration and thus decreasing pH in the surrounding medium.
Die erfindungsgemäße Zusammensetzung zeichnet sich dadurch aus, daß sie hervorragende Ergebnisse sowohl im Hauptreinigungsgang als auch im Klarspülgang einer Geschirrspülmaschine liefert und zudem den Einsatz eines lonentauschers bzw. den Einsatz von Salz zu dessen Regenerierung in den meisten Fällen überflüssig macht (zumindest in Haushalten mit einer Wasserhärte bis zu 35° dH). Die Tablette wird während des Hauptreinigungsganges gelöst und kann ihre entsprechende beabsichtigte Wirkung entfalten. Der bzw. die an der Tablette angeordneten Bereiche^) enthält (enthalten) die Substanzen mit den gewünschten weiteren Funktionalitäten, nämlich zum einen die Substanz(en) für den Klarspülgang, z.B. Klarspüler, zum anderen die Substanzen), die den Einsatz von Ionentauschern überflüssig macht (machen).The composition according to the invention is distinguished by the fact that it delivers excellent results both in the main cleaning cycle and in the rinse cycle of a dishwasher and, moreover, makes the use of an ion exchanger or the use of salt for its regeneration superfluous in most cases (at least in households with water hardness) up to 35 ° dH). The tablet is released during the main cleaning cycle and can have its intended effect. The area (s) arranged on the tablet contains the substances with the desired further functionalities, namely on the one hand the substance (s) for the rinse cycle, e.g. Rinse aid, on the other hand the substances), which make the use of ion exchangers superfluous.
Die Substanzen in dem (den) separat angeordneten Bereich(en) können durch eine Umhüllung geschützt sein, die bei der Konzentration eines spezifischen Ions, z.B. des OH"-Ions und damit bei dem pH- Wert, und der Temperatur des Hauptreinigungsganges stabil ist und sich nicht oder nur unwesentlich auf- oder ablöst. Erst wenn diese Konzentration durch Verdünnung signifikant absinkt, z.B. der pH- Wert zum Neutralen bzw. Sauren hin verschoben wird, d.h. frühestens zu Beginn des Klarspülgangs, wird die Löslichkeit des Umhüllungsmaterials so stark herabgesetzt, daß diese sich schnell auf- oder ablöst und das eigentlich wirksame Kernmaterial in das umgebende Medium freisetzt.The substances in the separately arranged area (s) can be protected by a coating which is stable at the concentration of a specific ion, for example the OH " ion and thus at the pH, and the temperature of the main cleaning cycle does not dissolve or dissolves only insignificantly.Only when this concentration drops significantly by dilution, for example the pH value is shifted towards neutral or acidic, ie at the earliest at the beginning of the rinse aid, is the solubility of the wrapping material reduced so much that it quickly dissolves or dissolves and releases the actually effective core material into the surrounding medium.
Zusätzlich können die Substanzen durch eine Komponente in der Umhüllung geschützt werden, die einen sogenannten Trübungspunkt aufweist. Diese Komponenten sind bei hohen Temperaturen vermindert löslich und schützen bei Anwendungen mit hohen Temperaturen im Reinigungsgang vor verfrühter Freisetzung von Aktivsubstanzen. Beispiele für Substanzen mit einem derartigen Trübungspunkt sind Cellulosen, einige Polyacrylatderivate, etc. Insbesondere ist dieser Schutz für diejenige(n) Substanz(en) sinnvoll, die ihre Funktion im wesentlichen im Klarspülgang der Geschirrspülmaschine entfalten soll, wie bspw. ein Klarspüler. Diese Substanz(en) soll(en) daher auch zumindest überwiegend (d.h. zu mehr als 50 %) erst frühestens zu Beginn des Klarspülganges freigesetzt werden. Zwar kann auch diejenige(n) Substanzen), die Kalkablagerungen in der Geschirrspülmaschine und/oder auf dem Spülgut verhindert, durch z.B. eine entsprechende Umhüllung vor einer vorzeitigen Freisetzung geschützt werden, so daß auch diese Substanz(en) erst im Klarspülgang freigesetzt werden. In einer bevorzugten Ausführungsform wird (werden) aber die Substanz(en), die vor Kalkablagerungen schützt (schützen), bereits zu einem früheren Zeitpunkt, d.h. vor dem Beginn des Klarspülganges freigesetzt, um ihre Wirkung nicht nur im Klarspülgang, sondern über eine längere Zeit im Waschzyklus auszuüben.In addition, the substances can be protected by a component in the casing which has a so-called cloud point. These components are less soluble at high temperatures and protect against premature release of active substances in applications with high temperatures in the cleaning cycle. Examples of substances with such a cloud point are celluloses, some polyacrylate derivatives, etc. In particular, this protection makes sense for the substance (s) that are to function essentially in the rinse aid of the dishwasher, such as a rinse aid. This substance (s) should therefore at least predominantly (ie more than 50%) only be released at the earliest at the beginning of the rinse aid cycle. The substance (s) which prevents limescale deposits in the dishwasher and / or on the wash ware can also be protected from premature release by, for example, an appropriate covering, so that these substance (s) are only released in the rinse cycle. In a preferred embodiment, however, the substance (s) which protect (protect) against limescale deposits are released at an earlier point in time, ie before the start of the rinse cycle, in order to be effective not only in the rinse cycle but over a longer period of time to exercise in the wash cycle.
Die Erfindung wird nunmehr detaillierter anhand der folgenden Beispiele, die durch die beigefügte Zeichnung veranschaulicht sind, beschrieben. In den Zeichnungen zeigen:The invention will now be described in more detail with reference to the following examples, which are illustrated by the accompanying drawing. The drawings show:
Fig. 1 eine erste Ausführungsform der erfindungsgemäßen Zusammensetzung im Querschnitt;Figure 1 shows a first embodiment of the composition according to the invention in cross section.
Fig. 2 eine zweite Ausführungsform der erfindungsgemäßen Zusammensetzung im Querschnitt;2 shows a second embodiment of the composition according to the invention in cross section;
Fig. 3 eine dritte Ausführungsform der erfindungsgemäßen Zusammensetzung im Querschnitt; und3 shows a third embodiment of the composition according to the invention in cross section; and
Fig. 4 eine vierte Ausführungsform der erfindungsgemäßen Zusammensetzung im Querschnitt.Fig. 4 shows a fourth embodiment of the composition according to the invention in cross section.
Fig. 1 zeigt eine Tablette 1, die als Zweischichttablette mit einer unteren Schicht 2 und einer oberen Schicht 3 ausgebildet ist. Beispielsweise kann als Grundlage eine der üblichen, kommerziell vertriebenen Zweischichttabletten verwendet werden, bei der die beiden Schichten üblicherweise eine unterschiedliche Zusammensetzung aufweisen und unterschiedlich eingefärbt sind. In der oberen Schicht 3 ist eine Mulde 4 ausgebildet, in der ein Teilchen 10 aufgenommen ist. Das (üblicherweise separat hergestellte) Teilchen 10 kann beispielsweise durch einen Kleber in der Mulde 4 fixiert sein.1 shows a tablet 1 which is designed as a two-layer tablet with a lower layer 2 and an upper layer 3. For example, one of the customary, commercially available two-layer tablets can be used as the basis, in which the two layers usually have a different composition and are colored differently. A recess 4 is formed in the upper layer 3, in which a particle 10 is received. The particle 10 (usually produced separately) can be fixed in the recess 4, for example, by an adhesive.
In der dargestellten Ausführungsform ist das Teilchen 10 als Kern 12 mit einer mehrschichtige Umhüllung (13, 14, 15, 16) dargestellt, wobei darauf hinzuweisen ist, daß es sich sowohl bei dieser Darstellung als auch bei den Darstellungen von Fig. 2 und Fig. 3 aus Veranschaulichungs- gründen nicht um maßstabsgerechte Darstellungen handelt.In the embodiment shown, the particle 10 is shown as a core 12 with a multi-layer coating (13, 14, 15, 16), it being pointed out that both this illustration and the illustrations of FIGS. 2 and Fig. 3 is not to scale for illustrative purposes.
In der in Fig. 1 dargestellten Ausführungsform umfaßt der Kern 12 des Teilchens 10 diejenige Substanz(en), die ihre hauptsächliche Wirkung im wesentlichen im Klarspülgang der Geschirrspülmaschine entfaltet (entfalten), z.B. ein oder mehrere als Klarspüler einsetzbare Tenside. Dieser Klarspüler-Kern 12 ist von einer ersten Trennschicht 13 umgeben, die aus einem wasserlöslichen Material besteht, das für die Substanzen des Kerns 12 im wesentlichen undurchlässig ist, sich aber im Klarspülgang der Geschirrspülmaschine schnell auflösen kann, um die Substanzen im Kern 12 freizusetzen.In the embodiment shown in Fig. 1, the core 12 of the particle 10 comprises the substance (s) which have their main effect (unfold) essentially in the rinse aid of the dishwasher, e.g. one or more surfactants that can be used as rinse aid. This rinse aid core 12 is surrounded by a first separating layer 13, which consists of a water-soluble material which is essentially impermeable to the substances in the core 12, but which can quickly dissolve in the rinse aid of the dishwasher in order to release the substances in the core 12.
Um diesen Mantel 13 herum ist eine weitere Umhüllung 14 ausgebildet, die so aufgebaut ist, daß sie sich im wesentlichen erst zu Beginn des Klarspülganges auflöst. Zu diesem Zweck umfaßt sie mindestens eine Verbindung, deren Löslichkeit mit sinkender Konzentration eines spezifischen Ions im umgebenden Medium zunimmt.A further covering 14 is formed around this jacket 13, which is constructed in such a way that it only dissolves at the beginning of the rinse cycle. For this purpose, it comprises at least one compound, the solubility of which increases with decreasing concentration of a specific ion in the surrounding medium.
Im einfachsten Fall kann die Löslichkeit mit einer sinkenden Konzentration des OH"-Ions und damit einem sinkenden pH- Wert gekoppelt sein. Beispiele für derartige Verbindungen sind in der (nicht vorveröffentlichten) Patentanmeldung 198 34 180.6 beschrieben, die hierdurch ausdrücklich in ihrer gesamten Offenbarung mit einbezogen werden soll.In the simplest case, the solubility can be coupled with a falling concentration of the OH " ion and thus a falling pH. Examples of such compounds are described in (not prepublished) patent application 198 34 180.6, which is hereby expressly incorporated in its entire disclosure should be included.
Ein beispielhaftes Umhüllungsmaterial, das in der genannten Patentanmeldung aufgeführt ist, ist das aus der Japanischen Patentanmeldung KOKAI 61-28440 beschriebene Polymer mit der folgenden Formel, wobei l/(l+m+n) = 0,35; m/(B-m+n) = 0,45; 1+m+n = 1.500 bis 1.800. An exemplary wrapping material which is listed in the cited patent application is the polymer described in Japanese patent application KOKAI 61-28440 with the following formula, where l / (l + m + n) = 0.35; m / (B-m + n) = 0.45; 1 + m + n = 1,500 to 1,800.
Weitere Beispiele, die in der DE 198 34 180.6 genannt sind, sind die weiteren in den japanischen Patentanmeldungen KOKAI 60-141705, 61-28440, 61-28441, 61-28596, 61-28597 und 61- 28598 genannten Polymere.Further examples which are mentioned in DE 198 34 180.6 are the other polymers mentioned in Japanese patent applications KOKAI 60-141705, 61-28440, 61-28441, 61-28596, 61-28597 and 61-28597.
Ein weiteres pH-empfindliches Polymer, mit der Wiederholungseinheit IIAnother pH-sensitive polymer, with repeat unit II
ist kommerziell von der Firma SANKYO unter dem Markennamen AEA" erhältlich.is commercially available from SANKYO under the AEA brand name.
Weitere Polymere, die für die Zwecke der vorliegenden Erfindung geeignet sind, sind Polymere von Isomeren oder Derivaten von Pyridin, vorzugsweise Copolymere mit Styrol oder Acrylnitril der folgenden Formel III und IV, in denen G einen Substituenten an einer beliebigen Stelle des Pyridinringes darstellt.Further polymers which are suitable for the purposes of the present invention are polymers of isomers or derivatives of pyridine, preferably copolymers with styrene or acrylonitrile of the following formulas III and IV, in which G represents a substituent at any point on the pyridine ring.
sowie (z.B. statistische) Polymere, die von Chitosan abgeleitet sind, auf der Grundlage der folgenden Monomer-Einheiten V und VI and (e.g. statistical) polymers derived from chitosan based on the following monomer units V and VI
Ein Beispiel für ein Ionenkonzentrations-empfindliches Polymer ist das Polysaccharid K- Carrageenan mit der folgenden Formel VIAn example of an ion concentration-sensitive polymer is the polysaccharide K-carrageenan with the following formula VI
das ein von der Kalium-Ionen-Konzentration im umgebenden Medium abhängiges Polymer ist.which is a polymer dependent on the potassium ion concentration in the surrounding medium.
Selbstverständlich sind die in der Umhüllung 14 einsetzbaren Substanzen nicht auf die soeben beschriebenen beschränkt, sondern umfassen sämtliche bekannten bzw. geeigneten Verbindungen mit der entsprechenden Funktionalität.Of course, the substances that can be used in the casing 14 are not limited to those just described, but rather include all known or suitable compounds with the corresponding functionality.
Um diese Umhüllung 14 herum ist ein Mantel 15 ausgebildet, der die zweite funktionelle Substanz für den Klarspül gang umfaßt, nämlich diejenige Substanz, die Kalkablagerungen in der Geschirrspülmaschine und auf dem Spülgut verhindern soll, wie bspw. eine derjenigen Substanzen, die oben erwähnt sind, d.h. entweder ein Komplexbildner, wie Phosphonat oder Polymer, oder eine Substanz, die durch Bereitstellung ausreichender Acidität das Carbonat/Bicarbonat- Gleichgewicht zum Bicarbonat hin verschiebt, um Ablagerungen von Carbonat in der Geschirrspülmaschine und auf dem Spülgut zu verhindern, wie z.B. eine Fruchtsäure wie Zitronensäure.A jacket 15 is formed around this covering 14, which comprises the second functional substance for the rinse aid, namely the substance which is intended to prevent limescale deposits in the dishwasher and on the dishes, such as one of those substances mentioned above, ie either a complexing agent, such as phosphonate or polymer, or a substance which, by providing sufficient acidity, the carbonate / bicarbonate Balance is shifted towards the bicarbonate in order to prevent carbonate deposits in the dishwasher and on the dishes, such as a fruit acid such as citric acid.
Als äußerste Schicht kann vorzugsweise noch eine wasserlösliche Schutzumhüllung 16 vorgesehen sein, um die Teilchen 10 während Lagerung und Transport zu schützen.A water-soluble protective covering 16 can preferably also be provided as the outermost layer in order to protect the particles 10 during storage and transport.
Die Schutzumhüllung 16 wird sich während der Auflösung der Tablette 1 im wesentlichen bereits im Hauptspülgang der Geschirrspülmaschine auflösen.The protective covering 16 will essentially dissolve during the dissolution of the tablet 1 already in the main wash cycle of the dishwasher.
Alternativ zu dieser Ausführungsform können sowohl die klarsnülaktive Komponente als auch die kalkbelagsverhindernde Komponente (zumindest teilweise) im Kern 12 vereint vorliegen. In dieser Ausführungsform ist der Mantel 15 nicht mehr zwingend erforderlich, kann aber zusätzlich als Träger von zusätzlichen Mengen der kalkbelagsverhindernden Komponente und/oder einer (ggf. weiteren) Aktivkomponente zur Verhinderung von Belägen vorgesehen werden.As an alternative to this embodiment, both the clear active component and the limescale-preventing component can be present (at least partially) in the core 12. In this embodiment, the jacket 15 is no longer absolutely necessary, but can additionally be provided as a carrier for additional amounts of the limescale-preventing component and / or a (possibly further) active component for preventing deposits.
Fig. 2 zeigt eine weitere Ausführungsform der erfindungsgemäßen Zusammensetzung in Form einer Tablette 1 , die in diesem Falle nur aus einer einzigen Schicht 2 besteht, in der - wie in Fig. 1 - eine Mulde 4 zur Aufnahme eines entsprechenden bifunktionellen Teilchens ausgebildet ist. In diesem Falle besteht der Kern aus zwei Halbkernen 12, 12', wobei ein erster Kern 12 die Substanz mit der einen Funktionalität, der zweite Halbkern 12' die Substanz mit der anderen Funktionalität umfaßt. Vorzugsweise sind beide Halbkerne durch eine Trennschicht 13 getrennt, die in ihrer Zusammensetzung der entsprechenden Trεnnschicht 13 aus Fig. 1 entsprechen kann. Dies ist insbesondere dann sinnvoll, wenn die Substanzen in den Halbkernen nicht miteinander verträglich sind. Der Kern 12, 12' ist von der Umhüllung 14 umschlossen, die sicherstellt, daß die Inhaltsstoffe des Kernes erst im Klarspülgang freigesetzt werden. In dieser Ausführungsform werden daher beide Substanzen, d.h. Klarspüler-Substanz und Kalkbelagverhinderungs- Substanz, erst im Klarspülgang freigesetzt. Aus Vereinfachungsgründen ist im vorliegenden Fall die weitere Schutzumhüllung 16 weggelassen worden. Fig. 3 beschreibt schließlich eine weitere Alternative der erfindungsgemäßen Zusammensetzung, bei der die Tablette 1 - wie in Fig. 1 - wieder aus zwei Schichten, einer unteren Schicht 2 und einer oberen Schicht 3, besteht. In diesem Falle ist allerdings in beiden Schichten eine Mulde 4 bzw. 4' ausgebildet, die zur Aufnahme entsprechender Teilchen 10 bzw. 10' dienen. Die Kerne 12 bzw. 12' der Teilchen 10 bzw. 10' sind dabei so ausgebildet, daß der eine Kern (bspw. 12) diejenige Substanz umfaßt, die ihre Funktion im wesentlichen im Klarspülgang entfalten soll, z.B. als Klarspüler geeignetes Tensid, während der andere Kern (12') diejenige Substanz enthält, die Kalkablagerungen in der Geschirrspülmaschine und auf dem Spülgut verhindert, bspw. ein Komplexbildner wie Phosphonate oder entsprechende Polymere oder ein Acidierungsmittel wie Zitronensäure. Während Kern 12 wie zuvor mit einer Umhüllung 14 umgeben ist, die vorzugsweise, aber nicht notwendigerweise aus demselben Material besteht und die - wie zuvor beschrieben - sicherstellt, daß die Freisetzung der im Kern enthaltenden Substanz erst im Klarspülgang erfolgt, kann Kern 12' lediglich von einer Schutzumhüllung 16 umgeben sein, wie zuvor beschrieben. Natürlich ist es auch möglich, auch Kern 12' mit derselben Umhüllung 14 zu umgeben wie Kern 12.FIG. 2 shows a further embodiment of the composition according to the invention in the form of a tablet 1, which in this case consists of only a single layer 2, in which - as in FIG. 1 - a trough 4 is formed for receiving a corresponding bifunctional particle. In this case, the core consists of two half-cores 12, 12 ', a first core 12 comprising the substance with one functionality, the second half-core 12' comprising the substance with the other functionality. The two half-cores are preferably separated by a separating layer 13, the composition of which can correspond to that of the corresponding separating layer 13 from FIG. 1. This is particularly useful if the substances in the half-cores are not compatible with one another. The core 12, 12 'is enclosed by the sheath 14, which ensures that the contents of the core are only released in the rinse cycle. In this embodiment, therefore, both substances, ie rinse aid substance and limescale-preventing substance, are only released in the rinse aid cycle. For reasons of simplification, the further protective sheath 16 has been omitted in the present case. Finally, FIG. 3 describes a further alternative of the composition according to the invention, in which the tablet 1 - as in FIG. 1 - again consists of two layers, a lower layer 2 and an upper layer 3. In this case, however, a trough 4 or 4 'is formed in both layers, which serve to receive corresponding particles 10 or 10'. The cores 12 and 12 'of the particles 10 and 10' are designed so that the one core (for example 12) comprises the substance which is supposed to function essentially in the rinse aid, for example a surfactant suitable as rinse aid, during the another core (12 ') contains the substance which prevents limescale deposits in the dishwasher and on the wash ware, for example a complexing agent such as phosphonates or corresponding polymers or an acidifying agent such as citric acid. While core 12 is, as before, surrounded by a covering 14, which preferably, but not necessarily, consists of the same material and which - as described above - ensures that the substance contained in the core is only released in the rinse cycle, core 12 'can only be used by be surrounded by a protective sheath 16, as previously described. Of course, it is also possible to also surround core 12 ′ with the same covering 14 as core 12.
Die beschriebenen Teilchen können dabei entweder durch einen Preßvorgang oder durch ein anderes Herstellungsverfahren hergestellt werden. Wenn zwei oder mehr Teilchen verwendet werden, wie in der Ausführungsform nach Fig. 3 oder der nachfolgenden Ausführungsform nach Fig. 4, können die Teilchen selbstverständlich auch mit unterschiedlichen Verfahren hergestellt werden.The particles described can be produced either by a pressing process or by another manufacturing process. If two or more particles are used, as in the embodiment according to FIG. 3 or the subsequent embodiment according to FIG. 4, the particles can of course also be produced by different methods.
Fig. 4 zeigt schließlich eine weitere Alternative der erfindungsgemäßen Zusammensetzung. Tablette 1, bestehend aus einer einzigen Schicht 2, weist in einer Oberfläche zwei Mulden 4, 4' auf. Die Oberfläche mit den Mulden 4 und 4' wird dann mit einem Film 20 überzogen, der bspw. aus einem der Materialien besteht, die in den vorherigen Ausführungsformen für die Schutzumhüllung 14 beschrieben sind. Daraufhin wird Mulde 4 mit einem klarspülaktiven Material 12 und Mulde 4' mit einem kalkbelagsverhindernden Material 12' gefüllt. Die Materialien 12 und 12' können - wie in den vorherigen Ausführungsformen - zu einem Teilchen ausgeformt sein, können aber auch als Pulverzusammensetzungen oder viskose, gelartige Zusammensetzungen eingefüllt werden. Abschließend wird ein weiterer Film 20' aufgebracht, der die gleiche oder eine ähnliche Rezeptur wie Film 20 aufweist. Auf diese Weise werden das klarspülaktive Material 12 und das kalkbelagverhindernde Material 12' ebenfalls vollständig von einem Schutzüberzug umhüllt (und/oder auch beide erst im Klarspülgang freigesetzt).4 shows another alternative of the composition according to the invention. Tablet 1, consisting of a single layer 2, has two troughs 4, 4 'in one surface. The surface with the depressions 4 and 4 'is then covered with a film 20, which consists, for example, of one of the materials described for the protective covering 14 in the previous embodiments. Thereupon, depression 4 is filled with a rinse-active material 12 and depression 4 'with a limescale-preventing material 12'. The materials 12 and 12 'can - as in the previous embodiments - be shaped into a particle, but can also be filled in as powder compositions or viscous, gel-like compositions. Finally, another film 20 'is applied, the same or a similar recipe to film 20. In this way, the rinse-active material 12 and the limescale-preventing material 12 'are also completely covered by a protective coating (and / or both are only released in the rinse cycle).
Zu weiteren möglichen Ausgestaltungen von Tabletten mit darin oder daran angeordneten Teilchen bzw. weiteren Details zur Zusammensetzung und Herstellung von Klarspülerteilchen bzw. pH- bzw. Ionenkonzentrations-empfindlichen Umhüllungen, wird erneut Bezug genommen auf die bereits zuvor genannte Patentanmeldung DE 198 34 180.6.For further possible configurations of tablets with particles arranged therein or thereon or further details on the composition and manufacture of rinse aid particles or coatings sensitive to pH or ion concentration, reference is again made to the previously mentioned patent application DE 198 34 180.6.
Beispielexample
Zur weiteren Veranschaulichung wird im folgenden ein Beispiel für eine mögliche Ausführungs- form vorgelegt. Dabei kann die Rezeptur der Tablette derjenigen einer handelsüblichen Zweischichttablette entsprechen. Kern 12 enthält als klarspülaktive Substanzen 57 Gew.-% Polyethy- lenglykol (Molekulargewicht ca. 35.000) sowie 28 Gew.-% Fettalkohol-ethoxylat-propoxylat. Als Substanz zur Verhinderung von Kalkablagerungen sind im Kern 12 15 Gew.-% Zitronensäure enthalten.For further illustration, an example of a possible embodiment is presented below. The formulation of the tablet can correspond to that of a commercially available two-layer tablet. Core 12 contains 57% by weight polyethylene glycol (molecular weight approx. 35,000) and 28% by weight fatty alcohol ethoxylate propoxylate as rinse-active substances. The core contains 12 15% by weight of citric acid as a substance to prevent limescale deposits.
Alternativ kann die Zitronensäure in Kern 12 ganz oder teilweise weggelassen und ganz oder teilweise in der Umhüllung 14 vorgesehen werden.Alternatively, all or part of the citric acid in core 12 can be omitted and all or part of it can be provided in the casing 14.
Schutzumhüllung 15 enthält (in Gew.-% des gesamten Teilchens) 1,3 % des oben näher beschriebenen Polymers gemäß der Japanischen Patentanmeldung Kokai 61-28440, 3,0% Hy- droxypropylmethylcellulose und 3,0 % Polyvinylalkohol.Protective sheathing 15 contains (in% by weight of the entire particle) 1.3% of the polymer described in more detail above according to Japanese Patent Application Kokai 61-28440, 3.0% hydroxypropylmethyl cellulose and 3.0% polyvinyl alcohol.
Eine Trennschicht 13 und eine Schutzumhüllung 16 sind im vorliegenden Fall nicht vorgesehen. Für eine handelsübliche Zweischichttablette wurden Kerne mit einem Durchmesser von ca. 12 mm (1 g) hergestellt und in geeigneten Vorrichtungen mit den beschriebenen Umhüllungsmaterialien ummantelt.A separating layer 13 and a protective covering 16 are not provided in the present case. For a commercially available two-layer tablet, cores with a diameter of approx. 12 mm (1 g) were produced and coated with the described coating materials in suitable devices.
Die in der vorstehenden Beschreibung, den Ansprüchen sowie in den Zeichnungen 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 above description, the claims and in the drawings can be essential both individually and in any combination for realizing the invention in its various embodiments.

Claims

Ansprüche Expectations
1. Zusammensetzung zur Verwendung in einer Geschirrspülmaschine, gekennzeichnet durch1. Composition for use in a dishwasher, characterized by
eine Basiszusammensetzung, die ihre Funktion im wesentlichen im Hauptreinigungsgang der Geschirrspülmaschine entfaltet, in Form einer Tablette (1);a basic composition, which develops its function essentially in the main cleaning cycle of the dishwasher, in the form of a tablet (1);
- mindestens einen in oder an der Tablette (1) separat angeordneten Bereich (10). der sowohl wenigstens eine Substanz, die ihre Funktion im wesentlichen im Klarspülgang der Geschirrspülmaschine entfalten soll, als auch wenigstens eine Substanz, die Kalkablagerungen in der Geschirrspülmaschine und/oder auf dem Spülgut verhindert, umfaßt; und- At least one area (10) arranged separately in or on the tablet (1). which comprises at least one substance which is to function essentially in the rinse cycle of the dishwasher and at least one substance which prevents limescale deposits in the dishwasher and / or on the dishes; and
Mittel (14), um sicherzustellen, daß wenigstens diejenige Substanz, die ihre Funktion im wesentlichen im Klarspülgang der Geschirrspülmaschine entfalten soll, zumindest überwiegend erst frühestens zu Beginn des Klarspülganges freigesetzt wird.Means (14) to ensure that at least the substance that is supposed to function essentially in the rinse cycle of the dishwasher is at least predominantly released at the earliest at the beginning of the rinse cycle.
2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die Substanzen in dem separat angeordneten Bereich (10) miteinander vermischt vorliegen.2. Composition according to claim 1, characterized in that the substances are mixed together in the separately arranged area (10).
3. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die Substanzen in dem separat angeordneten Bereich (10) getrennt in zwei Teilbereichen (12, 15; 12, 12') vorliegen.3. Composition according to claim 1, characterized in that the substances in the separately arranged area (10) are present separately in two partial areas (12, 15; 12, 12 ').
4. Zusammensetzung nach Anspruch 3, dadurch gekennzeichnet, daß die Substanz(en), die ihre Funktion im wesentlichen im Klarspülgang der Geschirrspülmaschine entfalten soll(en), in dem einen Teilbereich (12 oder 15; 12 oder 12') und die Substanz(en), die Kalkablagerungen in der Geschirrspülmaschine und/oder auf dem Spülgut verhindert (verhindern), in dem anderen Teilbereich (15 oder 12; 12' oder 12) vorliegt (vorliegen). 4. Composition according to claim 3, characterized in that the substance (s), which should function in the final rinse cycle of the dishwasher (s), in which a partial area (12 or 15; 12 or 12 ') and the substance ( en) that prevents (prevents) limescale deposits in the dishwasher and / or on the wash ware in the other partial area (15 or 12; 12 'or 12).
5. Zusammensetzung nach Anspruch 4, dadurch gekennzeichnet, daß der (die) Bereich(e) (10) einen Kern (12), der im wesentlichen die Substanz umfaßt, die ihre Funktion im wesentlichen im Klarspülgang der Geschirrspülmaschine entfalten soll; und einen Mantel (15) um diesen Kern (12), der die Substanz umfaßt, die Kalkablagerungen in der Geschirrspülmaschine und/oder auf dem Spülgut verhindert, umfaßt (umfassen).5. Composition according to claim 4, characterized in that the region (s) (10) has a core (12) which essentially comprises the substance which is intended to develop its function essentially in the rinse cycle of the dishwasher; and a jacket (15) around this core (12), which comprises the substance that prevents limescale deposits in the dishwasher and / or on the wash ware.
6. Zusammensetzung nach einem der Ansprüche 3 bis 5, dadurch gekennzeichnet, daß zwischen den beiden Teilbereichen (12, 15; 12, 12') eine für die Substanzen im wesentlichen undurchlässige Trennschicht (13) vorgesehen ist.6. Composition according to one of claims 3 to 5, characterized in that between the two partial areas (12, 15; 12, 12 ') is provided for the substances substantially impermeable separating layer (13).
7. Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die Mittel (14) eine geeignet angeordnete Umhüllung umfassen, die mindestens eine Verbindung umfaßt, deren Löslichkeit mit sinkender Konzentration eines spezifischen Ions im umgebenden Medium zunimmt.7. Composition according to one of the preceding claims, characterized in that the means (14) comprise a suitably arranged envelope which comprises at least one compound whose solubility increases with decreasing concentration of a specific ion in the surrounding medium.
8. Zusammensetzung zur Verwendung in einer Geschirrspülmaschine, gekennzeichnet durch8. Composition for use in a dishwasher, characterized by
eine Basiszusammensetzung, die ihre Funktion im wesentlichen im Hauptreinigungsgang der Geschirrspülmaschine entfaltet, in Form einer Tablette (1);a basic composition, which develops its function essentially in the main cleaning cycle of the dishwasher, in the form of a tablet (1);
zwei in oder an der Tablette (1) angeordnete Bereiche (10, 10'), von denen ein erster Bereich (10) mindestens eine Substanz umfaßt, die ihre Funktion im wesentlichen im Klarspülgang der Geschirrspülmaschine entfalten soll, und ein zweiter Bereich (10'), der mindestens eine Substanz umfaßt, die Kalkablagerungen in der Geschirrspülmaschine und/oder auf dem Spülgut verhindert; undtwo areas (10, 10 ') arranged in or on the tablet (1), of which a first area (10) comprises at least one substance which is to function essentially in the rinse cycle of the dishwasher, and a second area (10' ), which comprises at least one substance that prevents limescale deposits in the dishwasher and / or on the dishes; and
- jeweils eine die Bereiche (10, 10') im wesentlichen vollständig umgebende Umhüllung (14), die mindestens eine Verbindung umfaßt, deren Löslichkeit mit sinkender Konzentration eines spezifischen Ions im umgebenden Medium zunimmt. - In each case one of the areas (10, 10 ') essentially completely surrounding the envelope (14), which comprises at least one compound, the solubility of which increases with a decreasing concentration of a specific ion in the surrounding medium.
9. Zusammensetzung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß Mittel vorgesehen sind, um sicherzustellen, daß die Substanz(en), die Kalkablagerungen in der Geschirrspülmaschine und/oder auf dem Spülgut verhindert (verhindern), zumindest teilweise vor dem Klarspülgang freigesetzt wird (werden).9. Composition according to one of claims 1 to 8, characterized in that means are provided to ensure that the substance (s), which prevents limescale deposits in the dishwasher and / or on the dishes, at least partially before the rinse cycle will be released.
10. Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß als äußerste Schicht eine zusätzliche wasserlösliche Schutzumhüllung (16) vorgesehen ist.10. Composition according to one of the preceding claims, characterized in that an additional water-soluble protective covering (16) is provided as the outermost layer.
1 1. Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die Substanz zur Verhinderung von Kalkablagerungen eine Substanz ist, die zur Komplexbildung in der Lage ist.1 1. Composition according to one of the preceding claims, characterized in that the substance for preventing limescale is a substance which is capable of complex formation.
12. Zusammensetzung nach Anspruch 11, dadurch gekennzeichnet, daß die Substanz ausgewählt ist aus der Gruppe, die aus Phosphonaten und Polymeren besteht.12. The composition according to claim 11, characterized in that the substance is selected from the group consisting of phosphonates and polymers.
13. Zusammensetzung nach Anspruch 12, dadurch gekennzeichnet, daß die Polymere Polyacry- late oder Copolymere derselben sind.13. The composition according to claim 12, characterized in that the polymers are polyacrylates or copolymers thereof.
H. Zusammensetzung nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die Substanz zur Verhinderung von Kalkablagerungen eine Substanz ist, die im Klarspülgang das Gleichgewicht Carbonat/Bicarbonat im Spülmedium in Richtung Bicarbonat verschiebt.H. Composition according to one of claims 1 to 10, characterized in that the substance for preventing limescale deposits is a substance which shifts the carbonate / bicarbonate balance in the rinsing medium in the direction of bicarbonate in the rinse cycle.
15. Zusammensetzung nach Anspruch 14, dadurch gekennzeichnet, daß die Substanz eine Säure oder ein Säuregemisch ist.15. The composition according to claim 14, characterized in that the substance is an acid or an acid mixture.
16. Zusammensetzung nach Anspruch 15, dadurch gekennzeichnet, daß die Säure(n) ausgewählt ist (sind) aus der Gruppe der Carbonsäuren. 16. The composition according to claim 15, characterized in that the acid (s) is (are) selected from the group of carboxylic acids.
17. Zusammensetzung nach Anspruch 16, dadurch gekennzeichnet, daß die Säure(n) ausgewählt ist (sind) aus der Gruppe der Fruchtsäuren.17. The composition according to claim 16, characterized in that the acid (s) is (are) selected from the group of fruit acids.
18. Zusammensetzung nach Anspruch 17, dadurch gekennzeichnet, daß die Fruchtsäure Zitronensäure ist.18. The composition according to claim 17, characterized in that the fruit acid is citric acid.
19. Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die Umhüllung (14) wenigstens eine Verbindung umfaßt, deren Löslichkeit mit sinkender OH"-Ionenkonzentration und damit abnehmendem pH-Wert im umgebenden Medium zunimmt. 19. Composition according to one of the preceding claims, characterized in that the sheath (14) comprises at least one compound whose solubility increases with falling OH " ion concentration and thus decreasing pH in the surrounding medium.
EP00991269.2A 1999-12-29 2000-12-27 Composition for use in a dishwasher Expired - Lifetime EP1242573B1 (en)

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ES2555149T3 (en) 2015-12-29
AU3164401A (en) 2001-07-16
CA2395870C (en) 2009-12-08
WO2001049815A2 (en) 2001-07-12
ZA200205662B (en) 2003-10-03
BR0016836A (en) 2002-09-10
DE19963569A1 (en) 2001-07-26
EP2330179A1 (en) 2011-06-08
PL356058A1 (en) 2004-06-14
PL195010B1 (en) 2007-07-31
US6727213B2 (en) 2004-04-27
CN1415010A (en) 2003-04-30
MXPA02006405A (en) 2003-02-12
CA2395870A1 (en) 2001-07-12
US20030060393A1 (en) 2003-03-27
DE19963569B4 (en) 2006-11-16
WO2001049815A3 (en) 2001-12-20
AU779119B2 (en) 2005-01-06
EP1242573B1 (en) 2015-10-21

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