EP0842257A1 - Dish washer product in tablet form - Google Patents

Dish washer product in tablet form

Info

Publication number
EP0842257A1
EP0842257A1 EP96923846A EP96923846A EP0842257A1 EP 0842257 A1 EP0842257 A1 EP 0842257A1 EP 96923846 A EP96923846 A EP 96923846A EP 96923846 A EP96923846 A EP 96923846A EP 0842257 A1 EP0842257 A1 EP 0842257A1
Authority
EP
European Patent Office
Prior art keywords
agent
tablet
layer
silver
bleach
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
EP96923846A
Other languages
German (de)
French (fr)
Other versions
EP0842257B1 (en
Inventor
Guido Wäschenbach
Paul Robinson
Brigitte Sandmann
Harald Magg
Wilfried HÖFLINGER
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 NV
Original Assignee
Joh A Benckiser GmbH
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 Joh A Benckiser GmbH filed Critical Joh A Benckiser GmbH
Publication of EP0842257A1 publication Critical patent/EP0842257A1/en
Application granted granted Critical
Publication of EP0842257B1 publication Critical patent/EP0842257B1/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/391—Oxygen-containing compounds
    • C11D3/3912—Oxygen-containing compounds derived from saccharides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • the present invention relates to a dishwashing machine dishwashing detergent in the form of a tablet containing a bleaching agent and a bleach activator as well as other conventional components.
  • detergent compositions in tablet form have a poorer cleaning action than those in Can have powder form. This can be attributed to the fact that in compressed tablets the individual components are connected much more closely than in powders, so that negative interactions that individual components can exert on one another can occur to an increased extent. This can result in partial inactivation of individual components.
  • the applicant has now found that such a problem also occurs when bleaching agents and bleach activators are combined with silver / copper corrosion inhibitors.
  • EP-A 634 478 discloses machine dishwashing detergents with nitrogen-containing corrosion inhibitors and an oxygen-releasing bleaching agent. According to the statements in this publication, the machine dishwashing detergents can be in any form, and tablets are also mentioned in passing, although the difficulties which may arise when formulating corrosion inhibitors with bleaching agents or bleach activators have not been recognized.
  • EP-A 481 547 discloses that enzymes are deactivated in the presence of a chlorine bleach during the storage of a machine dishwashing detergent and in the aqueous cleaning solution in a dishwasher. To solve this problem, EP-A 481 547 discloses a machine dishwashing detergent with enzymes and chlorine bleaching agents in the form of a complex, at least three-layer tablet, which contains an inner layer, a barrier layer and an outer layer. The enzymes and the chlorine bleach are separated in different layers of the tablet.
  • This complex structure of the detergent tablets is intended to ensure that, on the one hand, there is no interface between the layer containing the chlorine bleach and the layer containing the enzyme during storage and, on the other hand, the two layers are not dissolved simultaneously but successively and therefore the chlorine bleach and the enzymes are not dissolved simultaneously the dishwashing water from the dishwasher.
  • EP-A 481793 discloses detergent compositions in tablet form which contain sodium percarbonate as a bleaching agent and are to be used in textile washing machines.
  • a shelf-stable tablet which contains, besides sodium percarbonate, other constituents which can interact with the bleaching agent, it is proposed to separate the percarbonate in the tablet from the other constituents, for example in two layers.
  • the tablets produced in this way are also said to have an increased dissolution rate in the wash liquor.
  • EP-A 481792 discloses a product in tablet form for treating fabrics in washing machines, which contains a combination of a persalt and a bleach activator to improve the bleaching effect, the bleach activator having to have a certain rate constant for perhydrolysis.
  • DE-OS 2527534 discloses a multi-layer cleaning tablet for artificial dentures, the first layer containing an enzyme and dissolving before the second layer containing active oxygen. As a result, the enzyme can initially act without being deactivated by the released active oxygen.
  • the tablet according to the invention dissolves completely in the dishwashing machine preferably not faster than in three minutes.
  • the dishwashing detergents according to the invention preferably contain chlorine-free, active oxygen-releasing bleaches, such as inorganic perhydrates or organic peracids and their salts, as bleaching agents.
  • inorganic perhydrates are perborates, percarbonates and persulfates such as peroxymonopersulfates.
  • the inorganic perhydrates are normally alkali metal salts, such as lithium, sodium, potassium or rubidium salts, especially the sodium salts.
  • the inorganic perhydrates can be present in the detergent as crystalline solids without further protection. For certain perhydrates, however, it is advantageous to use them as granular compositions which are provided with a coating which gives the granular products better storage stability.
  • the preferred perborate is sodium perborate, which can be present as a monohydrate with the formula NaBO 2 H 2 O 2 or as a tetrahydrate with the formula NaBO 2 H 2 O 2 .3H 2 O.
  • the preferred percarbonate is sodium percarbonate with the formula 2Na 2 CO 3 3H 2 O 2 .
  • the percarbonate is preferably used for the tablet consists of at least two layers, the silver / copper corrosion protection agent not being present together in one layer together with the bleaching agent and the bleach activator.
  • the tablet according to the invention dissolves completely in the dishwashing machine preferably not faster than in three minutes.
  • the dishwashing detergents according to the invention preferably contain chlorine-free, active oxygen-releasing bleaches, such as inorganic perhydrates or organic peracids and their salts, as bleaching agents.
  • inorganic perhydrates are perborates, percarbonates and persulfates such as peroxymonopersulfates.
  • the inorganic perhydrates are normally alkali metal salts, such as lithium, sodium, potassium or rubidium salts, especially the sodium salts.
  • the inorganic perhydrates can be present in the detergent as crystalline solids without further protection. For certain perhydrates, however, it is advantageous to use them as granular compositions which are provided with a coating which gives the granular products better storage stability.
  • the preferred perborate is sodium perborate, which can be present as a monohydrate with the formula NaBO 2 H 2 O 2 or as a tetrahydrate with the formula NaBO 2 H 2 O 2 .3H 2 O.
  • the preferred percarbonate is sodium percarbonate with the formula 2Na 2 CO 3 3H 2 O 2 .
  • the percarbonate is preferably used for Used to increase its stability in a coated form.
  • Organic peracids include all organic peracids conventionally used as bleaching agents, including, for example, perbenzoic acid and peroxycarboxylic acids such as mono- or diperoxyphthalic acid, 2-octyldiperoxysuccinic acid, diperoxydodecanedicarboxylic acid, diper ⁇ xyazelaic acid and imidoperoxycarboxylic acid and optionally their salts.
  • perbenzoic acid and peroxycarboxylic acids such as mono- or diperoxyphthalic acid, 2-octyldiperoxysuccinic acid, diperoxydodecanedicarboxylic acid, diper ⁇ xyazelaic acid and imidoperoxycarboxylic acid and optionally their salts.
  • Chlorine-containing bleaching agents such as sodium dichloroisocyanurate or sodium trichloroisocyanurate can also be present in the detergent according to the invention.
  • the bleaching agent is normally present in the detergent at a level of 1 to 40% by weight, preferably 2 to 30% by weight and most preferably 5 to 20% by weight of the total weight of the tablet.
  • the dishwashing detergent according to the invention further contains one or more bleach activators. These are preferably used in dishwashing detergents for dishwashing operations at temperatures in the range below 60 ° C. in order to achieve a sufficient bleaching action.
  • N- and O-acyl compounds such as acylated arains, acylated glycolurils or acylated sugar compounds are particularly suitable.
  • TAED is most preferred.
  • bleach activators are disclosed in WO 95/01416, the content of which is hereby expressly incorporated by reference.
  • the bleach activator can be present in the detergent according to the invention in an amount in the range from 0.1 to 20% by weight and preferably from 1 to 10% by weight of the total weight of the tablet.
  • the dishwashing detergent according to the invention further contains a silver / copper corrosion protection agent.
  • a silver / copper corrosion protection agent includes agents that are intended to prevent or reduce the tarnishing of non-ferrous metals, especially silver and copper.
  • Preferred silver / copper corrosion inhibitors are benzotriazole or bis-benzotriazoles and their substituted derivatives.
  • Suitable agents are organic and / or inorganic redox-active substances and paraffin oil.
  • Benzotriazole derivatives are those compounds in which the available substitution sites of the aromatic ring are partially or completely substituted.
  • Linear or branched chain C 1-20 alkyl groups as well as hydroxy, thio, phenyl or halogen such as fluorine, chlorine, bromine and iodine are suitable as substituents.
  • Preferred substituted benzotriazole is tolyltriazole.
  • Suitable bis-benzotriazoles are those in which the benzotriazole groups are each connected in the 6-position by a group X, in which X is a bond, a straight-chain alkylene group which is optionally substituted by one or more C 1-4 alkyl groups and preferably has 1-6 carbon atoms , a cycloalkyl radical having at least 5 carbon atoms, a carbonyl group, a sulfuryl group, an oxygen or a sulfur atom.
  • the aromatic rings of the bis-benzotriazole can be substituted as defined above for the benzotriazole.
  • Suitable organic redox-active substances are, for example, ascorbic acid, indole, methionine, an N-mono- (C 1 -C 4 alkyl) glycine, an N, N-di (C 1 -C 4 alkyl) glycine, 2-phenylglycine or a coupler and / or developer compound selected from the group of the diaminopyridines, aminohydroxypyridines , Dihydroxypyridines, heterocyclic hydrazones, aminohydroxypyrimidines, dihydroxypyrimidines, tetraaminopyrimidines, triaminohydroxypyrimidines,
  • Suitable inorganic redox-active substances are, for example, metal salts and / or metal complexes selected from the group consisting of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, in which the metals are in one of the oxidation stages II, III, IV, V or VI are present.
  • Suitable paraffin oil are predominantly branched aliphatic hydrocarbons with a number of carbon atoms in the range from 20 to 50.
  • the paraffin oil is preferably selected from predominantly branched chain C 25-45 species with a ratio of cyclic to non-cyclic hydrocarbons from 1:10 to 2: 1, preferably from 1: 5 to 1: 1.
  • the silver / copper anticorrosive agent is preferably present in the dishwasher detergent of the present invention with 0.01 to 5% by weight, particularly preferably with 0.1 to 2% by weight of the total weight of the tablet.
  • the dishwashing detergent according to the invention may further contain other conventional ingredients. These include builders, masking agents, surface-active agents, enzymes, foam control agents, fragrances, dyes and other auxiliaries.
  • Suitable builders are, for example, homo- and copolymeric polycarboxylic acids and their partially or completely neutralized salts, monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts, carbonates, bicarbonates, borates, phosphates, silicates, aluminosilicates and mixtures of such substances.
  • Preferred salts of the above compounds are the ammonium and / or alkali salts, i.e. the lithium, sodium, potassium and rubidium salts and particularly preferably the sodium salt.
  • Suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic and aromatic carboxylic acids, these containing at least two carboxy groups which are each separated from one another by preferably no more than two carbon atoms.
  • Polycarboxylates containing two carboxy groups include, for example, water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid.
  • Polycarboxylates containing three carboxy groups include for example, water-soluble citrates. Accordingly, citric acid is suitable as the hydroxycarboxylic acid.
  • the homopolymer of acrylic acid is also suitable as the polycarboxylic acid.
  • borate builders which contain borate-forming materials and which release borates under the detergent storage conditions or rinsing conditions can also be used as borate builders.
  • Polyphosphates such as tripolyphosphate, pyrophosphate, orthophosphate and the polymeric metaphosphate are suitable as phosphates.
  • Alkaline tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate and sodium polymetaphosphate may be mentioned, for example, in which the degree of polymerization preferably ranges from 5 to 21.
  • Sodium silicates such as sodium disilicate, sodium metasilicate and crystalline layered silicates are suitable as silicates.
  • Sodium aluminosilicates (zeolites) are also suitable.
  • the dishwashing detergent according to the invention can contain from 40 to 90% by weight, preferably from 60 to 80% by weight, of the total weight of the tablet of builders. Both single builders and mixtures of different builders mentioned above can be used. For example, mixtures of carbonates and silicates are suitable.
  • Suitable masking agents for complexing heavy metal ions which can be used according to the invention are organic phosphonates such as, for example, aminoalkylene poly (alkylene phosphonate), alkali-ethane-1-hydroxydiphosphonates and nitrilotrimethylene phosphonates.
  • Preferred phosphonates are diethylene triamine penta (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate.
  • Aminopolycarboxylates such as, for example, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and polyaspartates are also suitable.
  • the masking agent can be present in a proportion of 0.01 to 10% by weight, preferably 0.1 to 2% by weight, of the total weight of the tablet.
  • nonionic surfactants are suitable as surfactants. These include, for example, water-soluble ethoxylated C 6-16 fatty alcohols and C 6-16 mixed ethoxylated / propoxylated fatty alcohols and mixtures thereof, and also alkyl polyglucosides.
  • Another class of nonionic surfactants includes polyhydroxy fatty acid amides.
  • the surface-active agent can be present in a proportion of 0.1 to 10% by weight, preferably 1 to 5% by weight, of the total weight of the tablet.
  • the dishwashing detergent according to the invention may further contain one or more enzymes conventionally used herein selected from, for example, proteases, amylases, lipases and esterases.
  • the enzymes can be present in the detergent with a content of 0.1 to 10% by weight, preferably 1 to 5% by weight, of the total weight of the detergent.
  • the dishwashing detergent according to the invention can also contain one or more foam control agents. All foam control agents used in this area, such as silicones and paraffin oils, are suitable for this.
  • the foam control agents are preferably contained in the dishwashing machine dishwasher detergent according to the invention with less than 5 percent by weight of the total weight of the detergent.
  • the dishwashing detergent according to the invention can contain other customary additives such as fragrances, dyes and / or other auxiliaries.
  • various auxiliaries such as polyvinylpyrrolidone, polyvinylpolypyrrolidone or polyethylene glycol (preferably with a molecular weight of 100-10,000) or glycerol can be used as auxiliaries which facilitate the preparation of the tablets.
  • a preferred dishwashing detergent according to the invention consists of two layers, the first layer a) as a bleaching agent, a perborate, b) as a builder, sodium tripolyphosphate, a disilicate and a carbonate, c) a nonionic surface-active agent, d) as a silver / copper corrosion inhibitor, benzotriazole and optionally others Contains auxiliaries and the second layer a) as bleach activator N, N, N ', N'-tetraacetylethylenediamine, b) as builders sodium tripolyphosphate, a homopolymeric acrylic acid polymer and a carbonate, c) as a masking agent, a phosphonate, d) a nonionic surface-active agent, e) one or more enzymes and optionally further auxiliaries.
  • Another preferred dishwashing detergent according to the invention consists of two layers, the first layer a) as a bleaching agent a perborate, b) as a builders a citrate, a bicarbonate and a carbonate, c) a nonionic surface-active agent, d) as a silver / copper corrosion protection agent benzotriazole and optionally contains further auxiliaries and the second layer a) as bleach activator N, N, N ', N'-tetraacetylethylene diamine, b) as builders citrate, a bicarbonate, a carbonate, a homopolymeric acrylic acid polymer and citric acid, c) as a masking agent, a phosphonate, d ) a nonionic surface-active agent, e) one or more enzymes and optionally further auxiliaries.
  • the tablets of the present invention can be made by any conventional method known in the art.
  • the constituents of the individual layers are premixed separately and then pressed together in layers to obtain a tablet.
  • the hardness of the tablet and the time it takes for this tablet to dissolve completely depend, among other things, on the pressure used during the pressing. The lower the pressure during the pressing process, the more crumbly the tablet obtained and the faster it dissolves in the wash liquor. A higher pressure leads to firmer tablets, which dissolve correspondingly more slowly.
  • pressures of 0.01 to 70 kN / cm 2 are suitable for the pressing process.
  • the pressing process can also be defined by the force required to close the tablet thus obtained break.
  • Such measurements of the hardness of the tablet can be carried out, for example, with an Erickson 464H hardness test machine.
  • the tablets according to the invention preferably have a hardness of 90-130 N.
  • the size of the tablet according to the invention depends on the desired amount of dishwasher detergent which the tablet is to contain.
  • the tablet can weigh, for example, 15-25 g.
  • the tablet preferably contains the amount of dishwashing detergent required for a dishwashing process.
  • the tablet can also consist of larger units which can be broken down into smaller parts in dosage form for dosing, for example at a predetermined breaking point.
  • the tablet can be of any suitable shape, especially of constant thickness, e.g. round or rectangular.
  • Two-layer tablets of the following composition were produced using a high-speed rotary press on a production scale.
  • the tablets weighed a total of 18 g, with 12.6 g in the first layer and 5.4 g in the second layer.
  • a powdered composition with the same amounts of ingredients as the total in the two-layer tablet was also prepared (Table 1). The only difference between the two preparations was the product form.
  • the tablet was pressed so that the force required to break the tablet was approximately 110 N was. This measurement was made using an Erickson 464H hardness test machine.
  • the dissolution rate of the tablets was also determined. The determination was made by measuring the time it took for the tablet to disintegrate to the point where it could exit through 4 large openings submerged in moving water at 40 ° C. This result is also shown in Table 1.
  • Two-layer tablets were produced on a production scale using a high speed rotary press.
  • the tablets weighed 20 g, the first layer contained 14 g and the second layer 6 g (Table 3).
  • the tablets were pressed sufficiently to obtain a hardness of 100 N (same hardness test machine as in Example 1). Again, it became a powdered composition prepared the same formulation (Table 3).
  • the dissolution time of the two-layer tablets is given in Table 3.
  • single-layer tablets were made according to a composition already on the market.
  • the tablets were pressed so that the strength of the tablet was approximately 125 N.
  • the dissolution time was also measured, the results are shown in Table 5.
  • a powdery composition of the same formulation was also made. The composition is given in Table 5.

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Medicines Containing Plant Substances (AREA)

Abstract

The invention relates to a dishwasher detergent in the form of a multi-layer tablet comprising a bleach, a bleach activator, a silver/copper corrosion inhibitor and also other customary constituents, where the silver/copper corrosion inhibitor is not present together with the bleach and the bleach activator in one layer.

Description

Geschirrwaschmaschinenspülmittel in Form einer Tablette  Dishwasher detergent in the form of a tablet
Die vorliegende Erfindung betrifft ein Geschirrwaschmaschinenspülmittel in Form einer Tablette enthaltend ein Bleichmittel und einen Bleichaktivator sowie andere übliche Bestandteile. The present invention relates to a dishwashing machine dishwashing detergent in the form of a tablet containing a bleaching agent and a bleach activator as well as other conventional components.
Herkömmliche Spülmittel zur maschinellen Reinigung von Geschirr sind im allgemeinen pulverförmige, granuläre oder flüssige Produkte. Tablettenförmige Reinigungsmittelzusammensetzungen sind ebenfalls seit einigen Jahren bekannt. Prinzipiell besitzen tablettenförmige Produkte einige Vorteile gegenüber pulverförmigen und flüssigen Produkten: Sie benötigen kein genaues Dosieren und sind daher leichter zu handhaben und in die Geschirrwaschmaschine einzubringen, sie sind kompakter und benötigen daher weniger Verpackungsmaterial und Lagerraum und sie sind im Haushalt sicherer anzuwenden, da ein Verschütten der vielfach aggressiven Substanzen nicht möglich ist. Conventional detergents for the automatic cleaning of dishes are generally powdery, granular or liquid products. Tablet detergent compositions have also been known for several years. In principle, tablet-shaped products have several advantages over powdered and liquid products: they do not require precise dosing and are therefore easier to handle and put in the dishwasher, they are more compact and therefore require less packaging material and storage space and they are safer to use in the household because they spill which is often not possible with aggressive substances.
Es hat sich allerdings herausgestellt, daß Reinigungsmittelzusammensetzungen in Tablettenform eine verschlechterte Reinigungswirkung gegebenüber solchen in Pulverform aufweisen können. Dieses kann darauf zurückgeführt werden, daß in zusammengepreßten Tabletten die einzelnen Bestandteile wesentlich enger miteinander verbunden sind als in Pulvern, so daß negative Wechselwirkungen, die einzelne Bestandteile aufeinander ausüben können, verstärkt auftreten können. Es kann somit zu einer teilweisen Inaktivierung einzelner Bestandteile kommen. Die Anmelderin hat nunmehr gefunden, daß ein solches Problem auch auftritt bei der kombinierten Anwendung von Bleichmitteln und Bleichaktivatoren mit Silber- /Kupferkorrosionsschutzmitteln. However, it has been found that detergent compositions in tablet form have a poorer cleaning action than those in Can have powder form. This can be attributed to the fact that in compressed tablets the individual components are connected much more closely than in powders, so that negative interactions that individual components can exert on one another can occur to an increased extent. This can result in partial inactivation of individual components. The applicant has now found that such a problem also occurs when bleaching agents and bleach activators are combined with silver / copper corrosion inhibitors.
Ein weiteres Problem, das bei Geschiirwaschmasclώienspülmitteln in Tabletternform auftritt und die Spülleistung verschlechten bestehr darin, daß solche Geschirrwaschmaschmenspülmittel weniger wirksam sind als vergleichbare Pulver, da sich die Tabletten langsamer auflösen und daher in der Waschflotte erst später als bei der Verwendung von Pulvern zur Verfügung stehen. Dieses Problem tritt insbesondere bei Geschirrwaschmaschinenspülmitteϊn auf, die ein Bleichmittel enthalten, da bei Verwendung solcher Mittel in Tabiettenform eine für die Bleiche notwendige Konzentration des Bleichmittels erst relativ spät während des Spülvorgangs erreicht wird. In der EP-A- 504091 wird zur Lösung dieses Problems vorgeschlagen, eine bestimmte Kombination aus Alkalicarbonat, Polycarboxylat, einer polyfunktionellen Carbonsäure, Natriumsilicat, einem nichtionischen Tensid und dem Bleichmittel einzusetzen, damit der Bleicheffekt bei zusammengepreßten Tabletten erhalten bleibt. Another problem that occurs with dishwashing detergents in tablet form and worsens the washing performance is that such dishwashing detergents are less effective than comparable powders, since the tablets dissolve more slowly and are therefore only available in the wash liquor later than when using powders. This problem occurs in particular in dishwashing detergents which contain a bleaching agent, since when using such agents in the form of a tablet, the bleaching agent concentration required for bleaching is achieved relatively late during the washing process. To solve this problem, EP-A-504091 proposes using a certain combination of alkali carbonate, polycarboxylate, a polyfunctional carboxylic acid, sodium silicate, a nonionic surfactant and the bleaching agent, so that the bleaching effect is retained in compressed tablets.
Die EP-A 634 478 offenbart Maschinengeschirrspülmittel mit stickstoffhaltigen Korrosionsinhibitoren und einem sauerstofffreisetzenden Bleichmittel. Nach den Ausführungen dieser Druckschrift können die Maschinengeschirrspülmittel in beliebiger Form vorliegen, und es werden am Rande auch Tabletten erwähnt, wobei offensichtlich die Schwierigkeiten, die bei der Formulierung von Korrosionsinhibitoren mit Bleichmitteln bzw. Bleichaktivatoren auftreten können, nicht erkannt wurden. EP-A 634 478 discloses machine dishwashing detergents with nitrogen-containing corrosion inhibitors and an oxygen-releasing bleaching agent. According to the statements in this publication, the machine dishwashing detergents can be in any form, and tablets are also mentioned in passing, although the difficulties which may arise when formulating corrosion inhibitors with bleaching agents or bleach activators have not been recognized.
Die EP-A 481 547 offenbart, daß während der Lagerung eines Maschinengeschirrspülmittels und in der wäßrigen Reinigungslösung in einer Geschirrspülmaschine Enzyme in Gegenwart eines Chlorbleichmittels deaktiviert werden. Zur Lösung dieses Problems offenbart die EP-A 481 547 ein Maschinengeschirrspülmittel mit Enzymen und Chlorbleichmitteln in Form einer komplex aufgebauten zumindest dreischichtigen Tablette, die eine innere Schicht, ein Sperrschicht und eine äußere Schicht enthält. Die Enzyme und die Chlorbleichmittel sind dabei in verschiedenen Schichten der Tablette getrennt. Dieser komplexe Aufbau der Reinigungsmitteltabletten soll sicherstellen, daß einerseits während der Lagerung keine Grenzfläche zwischen der das Chlorbleichmittel enthaltenden Schicht und der das Enzym enthaltenden Schicht besteht und zum anderen die beiden Schichten nicht gleichzeitig sondern nacheinander aufgelöst werden und daher das Chlorbleichmittel und die Enzyme nicht gleichzeitig in dem Spülwasser der Geschirrspülmaschine vorliegen. EP-A 481 547 discloses that enzymes are deactivated in the presence of a chlorine bleach during the storage of a machine dishwashing detergent and in the aqueous cleaning solution in a dishwasher. To solve this problem, EP-A 481 547 discloses a machine dishwashing detergent with enzymes and chlorine bleaching agents in the form of a complex, at least three-layer tablet, which contains an inner layer, a barrier layer and an outer layer. The enzymes and the chlorine bleach are separated in different layers of the tablet. This complex structure of the detergent tablets is intended to ensure that, on the one hand, there is no interface between the layer containing the chlorine bleach and the layer containing the enzyme during storage and, on the other hand, the two layers are not dissolved simultaneously but successively and therefore the chlorine bleach and the enzymes are not dissolved simultaneously the dishwashing water from the dishwasher.
Die EP-A 481793 offenbart Reinigungsmittelzusammensetzungen in Tablettenform, die Natriumpercarbonat als Bleichmittel enthalten und in Textilwaschmaschinen eingesetzt werden sollen. Um eine lagerstabile Tablette erhalten zu können, die neben Natriumpercarbonat andere Bestandteile, die mit dem Bleichmittel wechselwirken können, enthält, wird vorgeschlagen, das Percarbonat in der Tablette von den anderen Bestandteilen zu separieren, beispielsweise in zwei Schichten. Die so produzierten Tabletten sollen zudem eine erhöhte Auflösegeschwindigkeit in der Waschflotte besitzen. EP-A 481793 discloses detergent compositions in tablet form which contain sodium percarbonate as a bleaching agent and are to be used in textile washing machines. In order to be able to obtain a shelf-stable tablet which contains, besides sodium percarbonate, other constituents which can interact with the bleaching agent, it is proposed to separate the percarbonate in the tablet from the other constituents, for example in two layers. The tablets produced in this way are also said to have an increased dissolution rate in the wash liquor.
In der EP-A 481792 wird ein Produkt in Tablettenform zur Behandlung von Geweben in Waschmaschinen offenbart, das zur Verbesserung der Bleichwirkung eine Kombination aus einem Persalz und einem Bleichaktivator enthält, wobei der Bleichaktivator eine bestimmte Geschwindigkeitskonstante für die Perhydrolyse aufweisen muß. EP-A 481792 discloses a product in tablet form for treating fabrics in washing machines, which contains a combination of a persalt and a bleach activator to improve the bleaching effect, the bleach activator having to have a certain rate constant for perhydrolysis.
Die DE-OS 2527534 offenbart eine mehrschichtige Reinigungstablette für künstliche Gebisse, wobei die erste Schicht ein Enzym enthält und sich vor der zweiten, aktiven Sauerstoff enthaltenden Schicht auflöst. Hierdurch kann das Enzym zunächst wirken, ohne von dem frei werdenden aktiven Sauerstoffdeaktiviert zu werden. DE-OS 2527534 discloses a multi-layer cleaning tablet for artificial dentures, the first layer containing an enzyme and dissolving before the second layer containing active oxygen. As a result, the enzyme can initially act without being deactivated by the released active oxygen.
Es ist eine Aufgabe der vorliegenden Erfindung, ein Geschiirwaschmaschinenspülmittel in Form einer Tablette zur Verfügung zu stellen, das neben einem Bleichmittel und einem Bleichaktivator sowie anderen üblichen Bestandteilen ein Silber-/Kupferkorrosionsschutzmittel enthält, das das Anlaufen von die Tablette aus mindestens zwei Schichten besteht, wobei das Silber-/Kupferkorrosionsschutzmittel nicht gemeinsam in einer Schicht zusammen mit dem Bleichmittel und dem Bleichaktivator enthalten ist. It is an object of the present invention to provide a dishwashing machine dishwashing detergent in the form of a tablet which, in addition to a bleaching agent and a bleach activator and other conventional constituents, contains a silver / copper corrosion inhibitor which prevents tarnishing the tablet consists of at least two layers, the silver / copper corrosion protection agent not being present together in one layer together with the bleaching agent and the bleach activator.
Die erfindungsgemäße Tablette löst sich in der Flotte in der Geschirrwaschmaschine bevorzugt nicht schneller als in drei Minuten vollständig auf. The tablet according to the invention dissolves completely in the dishwashing machine preferably not faster than in three minutes.
Unter "vollständig auflösen" wird hier verstanden, daß die Tabletten soweit zerfallen sind, daß sie in bewegtem Wasser bei 40ºC durch einen Korb mit 4 mm großen Öffnungen austreten können. By "completely dissolve" is meant here that the tablets have disintegrated to the point that they can emerge in moving water at 40 ° C through a basket with 4 mm openings.
Die erfindungsgemäßen Geschirrwaschmaschinenspülmittel enthalten als Bleichmittel bevorzugt chlorfreie, aktiven Sauerstoff freisetzende Bleichmittel wie anorganische Perhydrate oder organische Persäuren und deren Salze. The dishwashing detergents according to the invention preferably contain chlorine-free, active oxygen-releasing bleaches, such as inorganic perhydrates or organic peracids and their salts, as bleaching agents.
Beispiele für anorganische Perhydrate sind Perborate, Percarbonate und Persulfate wie Peroxymonopersulfate. Die anorganischen Perhydrate sind normalerweise Alkalimetallsalze, wie Lithium-, Natrium-, Kalium- oder Rubidiumsalze, insbesondere die Natriumsalze. Die anorganischen Perhydrate können in dem Spülmittel als kristalline Feststoffe ohne einen weiteren Schutz vorliegen. Für bestimmte Perhydrate ist es allerdings vorteilhaft, sie als granuläre Zusammensetzungen zu verwenden, die mit einem Überzug versehen sind, der den granulären Produkten eine bessere Lagerstabilität verleiht. Examples of inorganic perhydrates are perborates, percarbonates and persulfates such as peroxymonopersulfates. The inorganic perhydrates are normally alkali metal salts, such as lithium, sodium, potassium or rubidium salts, especially the sodium salts. The inorganic perhydrates can be present in the detergent as crystalline solids without further protection. For certain perhydrates, however, it is advantageous to use them as granular compositions which are provided with a coating which gives the granular products better storage stability.
Das bevorzugte Perborat ist Natriuraperborat, das als Monohydrat mit der Formel NaBO2H2O2 oder als Tetrahydrat mit der Formel NaBO2H2O2.3H2O vorliegen kann. The preferred perborate is sodium perborate, which can be present as a monohydrate with the formula NaBO 2 H 2 O 2 or as a tetrahydrate with the formula NaBO 2 H 2 O 2 .3H 2 O.
Das bevorzugte Percarbonat ist Natriumpercarbonat mit der Formel 2Na2CO33H2O2. Bevorzugt wird das Percarbonat zur die Tablette aus mindestens zwei Schichten besteht, wobei das Silber-/Kupferkorrosionsschutzmittel nicht gemeinsam in einer Schicht zusammen mit dem Bleichmittel und dem Bleichaktivator enthalten ist. The preferred percarbonate is sodium percarbonate with the formula 2Na 2 CO 3 3H 2 O 2 . The percarbonate is preferably used for the tablet consists of at least two layers, the silver / copper corrosion protection agent not being present together in one layer together with the bleaching agent and the bleach activator.
Die erfindungsgemäße Tablette löst sich in der Flotte in der Geschirrwaschmaschine bevorzugt nicht schneller als in drei Minuten vollständig auf. The tablet according to the invention dissolves completely in the dishwashing machine preferably not faster than in three minutes.
Unter "vollständig auflösen" wird hier verstanden, daß die Tabletten soweit zerfallen sind, daß sie in bewegtem Wasser bei 40ºC durch einen Korb mit 4 mm großen Öffnungen austreten können. By "completely dissolve" is meant here that the tablets have disintegrated to the point that they can emerge in moving water at 40 ° C through a basket with 4 mm openings.
Die erfindungsgemäßen Geschirrwaschmaschinenspülmittel enthalten als Bleichmittel bevorzugt chlorfreie, aktiven Sauerstoff freisetzende Bleichmittel wie anorganische Perhydrate oder organische Persäuren und deren Salze. The dishwashing detergents according to the invention preferably contain chlorine-free, active oxygen-releasing bleaches, such as inorganic perhydrates or organic peracids and their salts, as bleaching agents.
Beispiele für anorganische Perhydrate sind Perborate, Percarbonate und Persulfate wie Peroxymonopersulfate. Die anorganischen Perhydrate sind normalerweise Alkalimetallsalze, wie Lithium-, Natrium-, Kalium- oder Rubidiumsalze, insbesondere die Natriumsalze. Die anorganischen Perhydrate können in dem Spülmittel als kristalline Feststoffe ohne einen weiteren Schutz vorliegen. Für bestimmte Perhydrate ist es allerdings vorteilhaft, sie als granuläre Zusammensetzungen zu verwenden, die mit einem Überzug versehen sind, der den granulären Produkten eine bessere LagerStabilität verleiht. Examples of inorganic perhydrates are perborates, percarbonates and persulfates such as peroxymonopersulfates. The inorganic perhydrates are normally alkali metal salts, such as lithium, sodium, potassium or rubidium salts, especially the sodium salts. The inorganic perhydrates can be present in the detergent as crystalline solids without further protection. For certain perhydrates, however, it is advantageous to use them as granular compositions which are provided with a coating which gives the granular products better storage stability.
Das bevorzugte Perborat ist Natriumperborat, das als Monohydrat mit der Formel NaBO2H2O2 oder als Tetrahydrat mit der Formel NaBO2H2O2.3H2O vorliegen kann. The preferred perborate is sodium perborate, which can be present as a monohydrate with the formula NaBO 2 H 2 O 2 or as a tetrahydrate with the formula NaBO 2 H 2 O 2 .3H 2 O.
Das bevorzugte Percarbonat ist Natriumpercarbonat mit der Formel 2Na2CO33H2O2. Bevorzugt wird das Percarbonat zur Erhöhung seiner Stabilität in einer überzogenen Form eingesetzt. The preferred percarbonate is sodium percarbonate with the formula 2Na 2 CO 3 3H 2 O 2 . The percarbonate is preferably used for Used to increase its stability in a coated form.
Organische Persäuren schließen alle herkömmlich als Bleichmittel verwendeten organischen Persäuren ein, einschließlich beispielsweise Perbenzoesäure und Peroxycarbonsäuren wie Mono- oder Diperoxyphthalsäure, 2- Octyldiperoxybernsteinsäure, Diperoxydodecandicarbonsäure, Diperαxyazelainsäure und Imidoperoxycarbonsäure sowie gegebenenfalls deren Salze. Organic peracids include all organic peracids conventionally used as bleaching agents, including, for example, perbenzoic acid and peroxycarboxylic acids such as mono- or diperoxyphthalic acid, 2-octyldiperoxysuccinic acid, diperoxydodecanedicarboxylic acid, diperαxyazelaic acid and imidoperoxycarboxylic acid and optionally their salts.
Weiterhin können chlorhaltige Bleichmittel wie Natriumdichlorisocyanurat oder Natriumtrichlorisocyanurat in dem erfindungsgemäßen Spülmittel enthalten sein. Chlorine-containing bleaching agents such as sodium dichloroisocyanurate or sodium trichloroisocyanurate can also be present in the detergent according to the invention.
Das Bleichmittel liegt normalerweise mit einem Gehalt von 1 bis 40 Gew.-%, bevorzugt von 2 bis 30 Gew.-% und am bevorzugtesten von 5 bis 20 Gew.-% des Gesamtgewichts der Tablette in dem Spülaittel vor. The bleaching agent is normally present in the detergent at a level of 1 to 40% by weight, preferably 2 to 30% by weight and most preferably 5 to 20% by weight of the total weight of the tablet.
Das erfindungsgemäße Geschirrvaschmaschinenspülmittel enthält weiterhin einen oder mehrere Bleichaktivatoren. Diese werden bevorzugt in Spülnitteln für Geschirrspülvorgänge bei Temperaturen im Bereich unterhalb 60"C eingesetzt, um eine ausreichende Bleichwirkung zu erzielen. Insbesondere eignen sich beispielsweise N- und O-Acylverbindungen wie acylierte Araine, acylierte Glycolurile oder acylierte Zuckerverbindungen. Bevorzugt werden N,N,N',N'- Tetraacetylethylendiamin (TAED), Pentaacetylglucose (PAG) und Tetraacetylglycαluril (TAGU). Weiterhin eignen sich aber auch katalytisch aktive Metallkomplexe und bevorzugt Übergangsmetailkomplexe als Bleichaktivatoren. Am meisten bevorzugt wird TAED. The dishwashing detergent according to the invention further contains one or more bleach activators. These are preferably used in dishwashing detergents for dishwashing operations at temperatures in the range below 60 ° C. in order to achieve a sufficient bleaching action. N- and O-acyl compounds such as acylated arains, acylated glycolurils or acylated sugar compounds are particularly suitable. N, N, N ', N'-tetraacetylethylenediamine (TAED), pentaacetylglucose (PAG) and tetraacetylglycαluril (TAGU). However, catalytically active metal complexes and preferably transition metal complexes are also suitable as bleach activators. TAED is most preferred.
Weitere geeignete Bleichaktivatoren werden in der WO 95/01416 offenbart, auf deren Inhalt hiermit ausdrücklich Bezug genommen wird. Der Bleichaktivator kann in dem erfindungsgemäßen Spülmittel in einer Menge im Bereich von 0,1 bis 20 Gew.-% und bevorzugt von 1 bis 10 Gew.-% des Gesamtgewichts der Tablette vorliegen. Further suitable bleach activators are disclosed in WO 95/01416, the content of which is hereby expressly incorporated by reference. The bleach activator can be present in the detergent according to the invention in an amount in the range from 0.1 to 20% by weight and preferably from 1 to 10% by weight of the total weight of the tablet.
Das erfindungsgemäße Geschirrwaschmaschinenspülmittel enthält weiterhin ein Silber-/Kupferkorrosionsschutzmittel. Unter diesen Begriff fallen Mittel, die das Anlaufen von Nichteisenmetallen, insbesondere von Silber und Kupfer verhindern oder mindern sollen. Bevorzugte Silber- /Kupferkorrosionsschutzmittel sind Benzotriazol oder Bis- Benzotriazole sowie deren substituierte Derivate. The dishwashing detergent according to the invention further contains a silver / copper corrosion protection agent. This term includes agents that are intended to prevent or reduce the tarnishing of non-ferrous metals, especially silver and copper. Preferred silver / copper corrosion inhibitors are benzotriazole or bis-benzotriazoles and their substituted derivatives.
Weitere geeignete Mittel sind organische und/oder anorganische redoxaktive Substanzen und Paraffinöl. Other suitable agents are organic and / or inorganic redox-active substances and paraffin oil.
Benzotriazol-Derivate sind solche Verbindungen, in denen die verfügbaren Substitutionsstellen des aromatischen Rings teilweise oder vollständig substituiert sind. Als Substituenten eignen sich lineare oder verzweigtkettige C1-20-Alkylgruppen sowie Hydroxy, Thio, Phenyl oder Halogen wie Fluor, Chlor, Brom und Jod. Bevorzugtes substituiertes Benzotriazol ist Tolyltriazol. Benzotriazole derivatives are those compounds in which the available substitution sites of the aromatic ring are partially or completely substituted. Linear or branched chain C 1-20 alkyl groups as well as hydroxy, thio, phenyl or halogen such as fluorine, chlorine, bromine and iodine are suitable as substituents. Preferred substituted benzotriazole is tolyltriazole.
Geeignete Bis-Benzotriazole sind solche, in denen die Benzotriazolgruppen jeweils in 6-Stellung durch eine Gruppe X verbunden sind, worin X eine Bindung, eine geradkettige, gegebenenfalls mit einer oder mehreren C1-4-Alkylgruppen substituierte Alkylengruppe mit bevorzugt 1-6 Kohlenstoffatomen, ein Cycloalkylrest mit mindestens 5 Kohlenstoffatomen, eine Carbonylgruppe, eine Sulfurylgruppe, ein Sauerstoff- oder ein Schwefelatom sein kann. Die aromatischen Ringe des Bis-Benzotriazols können wie oben für das Benzotriazol definiert substituiert sein. Suitable bis-benzotriazoles are those in which the benzotriazole groups are each connected in the 6-position by a group X, in which X is a bond, a straight-chain alkylene group which is optionally substituted by one or more C 1-4 alkyl groups and preferably has 1-6 carbon atoms , a cycloalkyl radical having at least 5 carbon atoms, a carbonyl group, a sulfuryl group, an oxygen or a sulfur atom. The aromatic rings of the bis-benzotriazole can be substituted as defined above for the benzotriazole.
Geeignete organische redoxaktive Substanzen sind beispielsweise Ascorbinsäure, Indol, Methionin, ein N-Mono- (C1-C4-alkyl)-glycin, ein N,N-Di-(C1-C4-alkyl)-glycin, 2- Phenylglycin oder eine Kuppler- und/oder Entwicklerverbindung ausgewählt aus der Gruppe der Diaminopyridine, Aminohydroxypyridine, Dihydroxypyridine, heterocyclischen Hydrazone, Aminohydroxypyrimidine, Dihydroxypyrimidine, Tetraaminopyrimidine, Triaminohydroxypyrimidine,Suitable organic redox-active substances are, for example, ascorbic acid, indole, methionine, an N-mono- (C 1 -C 4 alkyl) glycine, an N, N-di (C 1 -C 4 alkyl) glycine, 2-phenylglycine or a coupler and / or developer compound selected from the group of the diaminopyridines, aminohydroxypyridines , Dihydroxypyridines, heterocyclic hydrazones, aminohydroxypyrimidines, dihydroxypyrimidines, tetraaminopyrimidines, triaminohydroxypyrimidines,
Diaminodihydroxypyrimidine, Dihydroxynaphtaline, Naphtole, Pyrazolone, Hydroxychinoline, Aminochinoline, der primären aromatischen Amine, die in ortho-, meta- oder para-Position eine weitere freie oder mit C1-C4-Alkyl- oder C2-C4- Hydroxyalkylgruppen substituierte Hydroxy- oder Aminogruppen haben und der Di- oder Trihydroxybenzole. Diaminodihydroxypyrimidines, dihydroxynaphtalins, naphthols, pyrazolones, hydroxyquinolines, aminoquinolines, the primary aromatic amines, which in the ortho, meta or para position substituted another free or substituted by C 1 -C 4 alkyl or C 2 -C 4 - hydroxyalkyl groups Have hydroxy or amino groups and the di- or trihydroxybenzenes.
Geeignete anorganische redoxaktive Substanzen sind beispielsweise Metallsalze und/oder Metallkomplexe ausgewählt aus der Gruppe der Mangan-, Titan-, Zirkonium-, Hafnium-, Vanadium-, Cobalt- und Cer-Salze und/oder -Komplexe, worin die Metalle in einer der Oxidationsstufen II, III, IV, V oder VI vorliegen. Suitable inorganic redox-active substances are, for example, metal salts and / or metal complexes selected from the group consisting of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, in which the metals are in one of the oxidation stages II, III, IV, V or VI are present.
Insbesondere geeignet sind Metallsalze und/oder Metallkomplexe, ausgewählt aus der Gruppe MnSO4, Mn(II)- citrat, Mn(II)-stearat, Mn(II)-acetylacetonat, Mn(II)-[1- Hydroxyethan-1,1-diphosphonat], V2O5, V2O4, VO2, TiOSO4, K2TiF6, K2ZrF6, CoSO4, Co(NO3)2, Ce(NO3)3. Metal salts and / or metal complexes selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1 are particularly suitable -diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , CoSO 4 , Co (NO 3 ) 2 , Ce (NO 3 ) 3 .
Organische und anorganische redoxaktive Substanzen, die als Silber-/Kupferkorrosionsschutzmittel geeignet sind, werden auch in der WO 94/26860 und WO 94/26859 genannt, auf derenOrganic and inorganic redox-active substances which are suitable as silver / copper corrosion protection agents are also mentioned in WO 94/26860 and WO 94/26859, on the
Inhalt hiermit Bezug genommen wird. Content hereby referred.
Als Paraffinöl eignen sich überwiegend verzweigte aliphatische Kohlenwasserstoffe mit einer Anzahl von Kohlenstoffatcmen im Bereich von 20 bis 50. Bevorzugt wird das Paraffinöl ausgewählt aus überwiegend verzweigtkettigen C25-45-Spezies mit einem Verhältnis von cyclischen zu nichtcyclischen Kohlenwasserstoffen von 1:10 bis 2:1, bevorzugt von 1:5 bis 1:1. Suitable paraffin oil are predominantly branched aliphatic hydrocarbons with a number of carbon atoms in the range from 20 to 50. The paraffin oil is preferably selected from predominantly branched chain C 25-45 species with a ratio of cyclic to non-cyclic hydrocarbons from 1:10 to 2: 1, preferably from 1: 5 to 1: 1.
Das Silber-/Kupferkorrosionsschutzmittel liegt in dem Geschirrwaschmaschinenspülmittel der vorliegenden Erfindung bevorzugt mit 0,01 bis 5 Gew.-%, besonders bevorzugt mit 0,1 bis 2 Gew.-% des Gesamtgewichts der Tablette vor. The silver / copper anticorrosive agent is preferably present in the dishwasher detergent of the present invention with 0.01 to 5% by weight, particularly preferably with 0.1 to 2% by weight of the total weight of the tablet.
Das erfindungsgemäße Geschirrwaschmaschinenspülmittel kann weiterhin andere übliche Bestandteile enthalten. Hierzu gehören Gerüststoffe, Maskierungsmittel, oberflächenaktive Mittel, Enzyme, Schaumkontrollmittel, Duftstoffe, Farbstoffe und sonstige Hilfsstoffe. The dishwashing detergent according to the invention may further contain other conventional ingredients. These include builders, masking agents, surface-active agents, enzymes, foam control agents, fragrances, dyes and other auxiliaries.
Als Gerüststoffe eignen sich beispielsweise homo- und copolymere Polycarbonsäuren sowie deren teilweise oder vollständig neutralisierten Salze, monomere Polycarbonsäuren und Hydroxycarbonsäuren und deren Salze, Carbonate, Bicarbonate, Borate, Phosphate, Silicate, Aluminosilicate sowie Mischungen solcher Substanzen. Suitable builders are, for example, homo- and copolymeric polycarboxylic acids and their partially or completely neutralized salts, monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts, carbonates, bicarbonates, borates, phosphates, silicates, aluminosilicates and mixtures of such substances.
Als Salze der oben genannten Verbindungen werden bevorzugt die Ammonium- und/oder Alkalisalze, d.h. die Lithium-, Natrium-, Kalium- und Rubidiumsalze und besonders bevorzugt das Natriumsalz eingesetzt. Preferred salts of the above compounds are the ammonium and / or alkali salts, i.e. the lithium, sodium, potassium and rubidium salts and particularly preferably the sodium salt.
Als Polycarbonsäuren eignen sich acyclische, alicyclische, heterocyclische und aromatische Carbonsäuren, wobei diese mindestens zwei Carboxygruppen enthalten, die jeweils durch vorzugsweise nicht mehr als zwei Kohlenstoffatome voneinander getrennt sind. Suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic and aromatic carboxylic acids, these containing at least two carboxy groups which are each separated from one another by preferably no more than two carbon atoms.
Polycarboxylate, die zwei Carboxygruppen enthalten, schließen beispielsweise wasserlösliche Salze der Bernsteinsäure, Malonsäure, (Ethylendioxy)diessigsäure, Maleinsäure, Diglycolsäure, Weinsäure, Tartronsäure und Fumarsäure ein.Polycarboxylates containing two carboxy groups include, for example, water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid.
Polycarboxylate, die drei Carboxygruppen enthalten, schließen beispielsweise wasserlösliche Citrate ein. Entsprechend eignet sich als Hydroxycarbonsäure beispielsweise Citronensäure. Polycarboxylates containing three carboxy groups include for example, water-soluble citrates. Accordingly, citric acid is suitable as the hydroxycarboxylic acid.
Als Polycarbonsäure eignet sich weiterhin das Homopolymer der Acrylsäure. The homopolymer of acrylic acid is also suitable as the polycarboxylic acid.
Als Boratgerüststoffe können neben Boraten wie Natriumborat auch solche Gerüststoffe verwendet werden, die boratbildende Materialien enthalten, die Borate unter den Reinigungsmittellagerbedingungen oder Spülbedingungen freisetzen. In addition to borates such as sodium borate, those borate builders which contain borate-forming materials and which release borates under the detergent storage conditions or rinsing conditions can also be used as borate builders.
Als Phosphate eignen sich Polyphosphate wie Tripolyphosphat, Pyrophosphat, Orthophosphat und das polymere Metaphosphat. Beispielsweise seien Alkalitripolyphosphate, Natrium-, Kalium- und Ammoniumpyrophosphat, Natrium- und Kaliumorthophosphat sowie Natriumpolymetaphosphat genannt, worin der Polymerisationsgrad bevorzugt von 5 bis 21 reicht. Polyphosphates such as tripolyphosphate, pyrophosphate, orthophosphate and the polymeric metaphosphate are suitable as phosphates. Alkaline tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate and sodium polymetaphosphate may be mentioned, for example, in which the degree of polymerization preferably ranges from 5 to 21.
Als Silicate eignen sich Natriumsilicate wie Natriumdisilicat, Natriummetasilicat und kristalline Schichtsilicate. Weiterhin eignen sich Natriumaluminosilicate (Zeolite). Sodium silicates such as sodium disilicate, sodium metasilicate and crystalline layered silicates are suitable as silicates. Sodium aluminosilicates (zeolites) are also suitable.
Weitere geeignete Gerüststoffe werden in der WO 95/01416 offenbart, auf deren Inhalt hiermit ausdrücklich Bezug genommen wird. Further suitable builders are disclosed in WO 95/01416, the content of which is hereby expressly incorporated by reference.
Das erfindungsgemäße Geschirrwaschmaschinenspülmittel kann von 40 bis 90 Gew.-%, bevorzugt von 60 bis 80 Gew.-% des Gesamtgewichts der Tablette an Gerüststoffen enthalten. Hierbei können sowohl einzelne Gerüststoffe als auch Mischungen von verschiedenen oben genannten Gerüststoffen verwendet werden. Beispielsweise eignen sich Mischungen von Carbonaten und Silicaten. Geeignete Maskierungsmittel zum Komplexieren von Schwermetallionen, die erfindungsgemäß eingesetzt werden können, sind organische Phosphonate wie beispielsweise Aminoalkylenpoly(alkylenphosphonat), Alkali-Ethan-1- hydroxydiphosphonate und Nitrilotrimethylenphosphonate. Bevorzugte Phosphonate sind Diethylentriamin- penta(methylenphosphonat), Hexamethylendiamintetra(methylenphosphonat) und Hydroxyethylen-1,1-diphosphonat. Weiterhin eignen sich Aminopolycarboxylate wie beispielsweise Nitrilotriessigsäure (NTA), Methylglycindiessigsäure (MGDA) sowie Polyaspartate. The dishwashing detergent according to the invention can contain from 40 to 90% by weight, preferably from 60 to 80% by weight, of the total weight of the tablet of builders. Both single builders and mixtures of different builders mentioned above can be used. For example, mixtures of carbonates and silicates are suitable. Suitable masking agents for complexing heavy metal ions which can be used according to the invention are organic phosphonates such as, for example, aminoalkylene poly (alkylene phosphonate), alkali-ethane-1-hydroxydiphosphonates and nitrilotrimethylene phosphonates. Preferred phosphonates are diethylene triamine penta (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate. Aminopolycarboxylates such as, for example, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and polyaspartates are also suitable.
Das Maskierungsmittel kann erfindungsgemäß mit einem Anteil von 0,01 bis 10 Gew.-%, bevorzugt von 0,1 bis 2 Gew.-% am Gesamtgewicht der Tablette anwesend sein. According to the invention, the masking agent can be present in a proportion of 0.01 to 10% by weight, preferably 0.1 to 2% by weight, of the total weight of the tablet.
Als oberflächenaktive Mittel eignen sich beispielsweise nichtionische oberflächenaktive Mittel. Hierzu zählen beispielsweise wasserlösliche ethoxylierte C6-16 Fettsäurealkohole und C6-16 gemischte ethoxylierte/propoxylierte Fettsäurealkohole und Mischungen davon sowie Alkylpolyglucoside. For example, nonionic surfactants are suitable as surfactants. These include, for example, water-soluble ethoxylated C 6-16 fatty alcohols and C 6-16 mixed ethoxylated / propoxylated fatty alcohols and mixtures thereof, and also alkyl polyglucosides.
Eine weitere Klasse nichtionischer oberflächenaktiver Mittel umfaßt Polyhydroxyfettsäureamide. Another class of nonionic surfactants includes polyhydroxy fatty acid amides.
Weitere geeignete oberflächenaktive Mittel werden in der WO 95/01416 offenbart, auf deren Inhalt hiermit ausdrücklich Bezug genommen wird. Further suitable surface-active agents are disclosed in WO 95/01416, the content of which is hereby expressly incorporated by reference.
Das oberflächenaktive Mittel kann erfindungsgemäß mit einem Anteil von 0,1 bis 10 Gew.-%, bevorzugt von 1 bis 5 Gew.-% am Gesamtgewicht der Tablette anwesend sein. Das erfindungsgemäße Geschirrwaschmaschinenspülmittel kann weiterhin ein oder mehrere herkömmlich hierin verwendete Enzyme ausgewählt aus beispielsweise Proteasen, Amylasen, Lipasen und Esterasen enthalten. According to the invention, the surface-active agent can be present in a proportion of 0.1 to 10% by weight, preferably 1 to 5% by weight, of the total weight of the tablet. The dishwashing detergent according to the invention may further contain one or more enzymes conventionally used herein selected from, for example, proteases, amylases, lipases and esterases.
Die Enzyme können in dem Spülmittel mit einem Gehalt von 0,1 bis 10 Gew.-%, bevorzugt 1 bis 5 Gew.-% des Gesamtgewichts des Spülmittels anwesend sein. The enzymes can be present in the detergent with a content of 0.1 to 10% by weight, preferably 1 to 5% by weight, of the total weight of the detergent.
Das erfindungsgemäße Geschirrwaschmaschinenspülmittel kann weiterhin ein oder mehrere Schaumkontrollmittel enthalten. Hierzu eignen sich alle in diesem Bereich eingesetzten Schaumkontrollmittel wie beispielsweise Silicone und Paraffinöle. The dishwashing detergent according to the invention can also contain one or more foam control agents. All foam control agents used in this area, such as silicones and paraffin oils, are suitable for this.
Die Schaumkontrollmittel sind in dem erfindungsgemäßen Geschirrwaschmaschinenspülmittel bevorzugt mit weniger als 5 Gewichtsprozent des Gesamtgewichts des Spülmittels enthalten. The foam control agents are preferably contained in the dishwashing machine dishwasher detergent according to the invention with less than 5 percent by weight of the total weight of the detergent.
Weiterhin kann das erfindungsgemäße Geschirrwaschmaschinenspülmittel sonstige übliche Zusatzstoffe wie Duftstoffe, Farbstoffe und/oder weitere Hilfsstoffe enthalten. Beispielsweise können als Hilfsstoffe, die die Herstellung der Tabletten erleichtern, verschiedene Polymere wie Polyvinylpyrrolidon, Polyvinylpolypyrrolidon oder Polyethylenglycol (bevorzugt mit einem Molekulargewicht von 100-10.000) oder Glycerin eingesetzt werden. Furthermore, the dishwashing detergent according to the invention can contain other customary additives such as fragrances, dyes and / or other auxiliaries. For example, various auxiliaries such as polyvinylpyrrolidone, polyvinylpolypyrrolidone or polyethylene glycol (preferably with a molecular weight of 100-10,000) or glycerol can be used as auxiliaries which facilitate the preparation of the tablets.
Ein bevorzugtes erfindungsgemäßes Geschirrwaschmaschinenspülmittel besteht aus zwei Schichten, wobei die erste Schicht a) als Bleichmittel ein Perborat, b) als Gerüststoffe Natriumtripolyphosphat, ein Disilicat und ein Carbonat, c) ein nichtionisches oberflächenaktives Mittel, d) als silber-/Kupferkorrosionsschutzmittel Benzotriazol sowie gegebenenfalls weitere Hilfsstoffe enthält und die zweite Schicht a) als Bleichaktivator N,N,N',N'-Tetraacetylethylendiamin, b) als Gerüststoffe Natrium- tripolyphosphat, ein homopolymeres Acrylsäurepolymer und ein Carbonat, c) als Maskierungsmittel ein Phosphonat, d) ein nichtionisches oberflächenaktives Mittel, e) ein oder mehrere Enzyme sowie gegebenenfalls weitere Hilfsstoffe enthält. A preferred dishwashing detergent according to the invention consists of two layers, the first layer a) as a bleaching agent, a perborate, b) as a builder, sodium tripolyphosphate, a disilicate and a carbonate, c) a nonionic surface-active agent, d) as a silver / copper corrosion inhibitor, benzotriazole and optionally others Contains auxiliaries and the second layer a) as bleach activator N, N, N ', N'-tetraacetylethylenediamine, b) as builders sodium tripolyphosphate, a homopolymeric acrylic acid polymer and a carbonate, c) as a masking agent, a phosphonate, d) a nonionic surface-active agent, e) one or more enzymes and optionally further auxiliaries.
Ein weiteres bevorzugtes erfindungsgemäßes Geschirrwaschmaschinenspülmittel besteht aus zwei Schichten, wobei die erste Schicht a) als Bleichmittel ein Perborat, b) als Gerüststoffe ein Citrat, ein Bicarbonat und ein Carbonat, c) ein nichtionisches oberflächenaktives Mittel, d) als Silber- /Kupferkorrosionsschutzmittel Benzotriazol sowie gegebenenfalls weitere Hilfsstoffe enthält und die zweite Schicht a) als Bleichaktivator N,N,N',N'- Tetraacetylethylendiamin, b) als Gerüststoffe Citrat, ein Bicarbonat, ein Carbonat, ein homopolymeres Acrylsäurepolymer und Citronensäure, c) als Maskierungsmittel ein Phosphonat, d) ein nichtionisches oberflächenaktives Mittel, e) ein oder mehrere Enzyme sowie gegebenenfalls weitere Hilfsstoffe enthält. Another preferred dishwashing detergent according to the invention consists of two layers, the first layer a) as a bleaching agent a perborate, b) as a builders a citrate, a bicarbonate and a carbonate, c) a nonionic surface-active agent, d) as a silver / copper corrosion protection agent benzotriazole and optionally contains further auxiliaries and the second layer a) as bleach activator N, N, N ', N'-tetraacetylethylene diamine, b) as builders citrate, a bicarbonate, a carbonate, a homopolymeric acrylic acid polymer and citric acid, c) as a masking agent, a phosphonate, d ) a nonionic surface-active agent, e) one or more enzymes and optionally further auxiliaries.
Die Tabletten der vorliegenden Erfindung können nach jedem herkömmlichen, im Stand der Technik bekannten Verfahren hergestellt werden. Beispielsweise werden die Bestandteile der einzelnen Schichten getrennt vorgemischt und dann in Schichten zusammengepreßt, um eine Tablette zu erhalten. Die Härte der Tablette sowie die Zeit, die diese Tablette benötigt, um sich vollständig aufzulösen, ist unter anderm von dem Druck abhängig, der während des Pressens eingesetzt wird. Je niedriger der Druck während des Preßvorgangs ist, umso bröckeliger ist die erhaltene Tablette und umso schneller löst sie sich in der Waschflotte auf. Ein höherer Druck führt zu festeren Tabletten, die sich entsprechend langsamer auflösen. Beispielsweise eignen sich für den Preßvorgang Drücke von 0,01 bis 70 kN/cm2. The tablets of the present invention can be made by any conventional method known in the art. For example, the constituents of the individual layers are premixed separately and then pressed together in layers to obtain a tablet. The hardness of the tablet and the time it takes for this tablet to dissolve completely depend, among other things, on the pressure used during the pressing. The lower the pressure during the pressing process, the more crumbly the tablet obtained and the faster it dissolves in the wash liquor. A higher pressure leads to firmer tablets, which dissolve correspondingly more slowly. For example, pressures of 0.01 to 70 kN / cm 2 are suitable for the pressing process.
Der Preßvorgang kann weiterhin durch die Kraft definiert werden, die benötigt wird, die so erhaltene Tablette zu brechen. Solche Messungen der Härte der Tablette können beispielsweise mit einer Erickson 464H Härtetestmaschine durchgeführt werden. Bevorzugt besitzen die erfindungsgemäßen Tabletten eine Härte von 90-130 N. The pressing process can also be defined by the force required to close the tablet thus obtained break. Such measurements of the hardness of the tablet can be carried out, for example, with an Erickson 464H hardness test machine. The tablets according to the invention preferably have a hardness of 90-130 N.
Die Größe der erindungsgemäßen Tablette hängt von der gewünschten Geschirrwaschmaschinenspülmittelmenge ab, die die Tablette enthalten soll. Die Tablette kann beispielsweise 15- 25 g wiegen. Bevorzugt enthält die Tablette die Geschirrwaschmaschinenspülmittelmenge, die für einen Geschirrwaschvorgang benötigt wird. Die Tablette kann aber auch aus größeren Einheiten bestehen, die zur Dosierung beispielsweise an einer vorgegebenen Bruchstelle in kleinere Teile in Dosisform zerbrochen werden kann. The size of the tablet according to the invention depends on the desired amount of dishwasher detergent which the tablet is to contain. The tablet can weigh, for example, 15-25 g. The tablet preferably contains the amount of dishwashing detergent required for a dishwashing process. However, the tablet can also consist of larger units which can be broken down into smaller parts in dosage form for dosing, for example at a predetermined breaking point.
Die Tablette kann jede geeignete Form, insbesondere mit gleichbleibender Dicke, wie z.B. rund oder rechteckig, aufweisen. The tablet can be of any suitable shape, especially of constant thickness, e.g. round or rectangular.
Die folgenden Beispiele sollen die vorliegende Erfindung näher erläutern. Prozentangaben sind in Gewichtsprozent gemacht. The following examples are intended to explain the present invention in more detail. Percentages are given in percent by weight.
Beispiel 1 example 1
Zweischichttabletten der folgenden Zusammensetzung (Tabelle 1) wurden unter Verwendung einer Hochgeschwindigkeitsrotationspresse im Produktionsmaßstab hergestellt. Die Tabletten wogen insgesamt 18 g, wobei 12,6 g in der ersten Schicht und 5,4 g in der zweiten Schicht waren. Eine pulverförmige Zusammensetzung mit denselben Mengen an Bestandteilen wie die Gesamtmenge in der Zweischichttablette wurde ebenfalls hergestellt (Tabelle 1). Der einzige Unterschied zwischen den beiden Zubereitungen war die Produktform. Die Tablette wurde so gepreßt, daß die Kraft, die benötigt wurde, um die Tablette zu brechen, ungefähr 110 N betrug. Diese Messung wurde unter Verwendung einer Erickson 464H Härtetestnaschins durchgeführt. Two-layer tablets of the following composition (Table 1) were produced using a high-speed rotary press on a production scale. The tablets weighed a total of 18 g, with 12.6 g in the first layer and 5.4 g in the second layer. A powdered composition with the same amounts of ingredients as the total in the two-layer tablet was also prepared (Table 1). The only difference between the two preparations was the product form. The tablet was pressed so that the force required to break the tablet was approximately 110 N was. This measurement was made using an Erickson 464H hardness test machine.
Die Aufiösegeschwindigkeit der Tabletten wurde ebenfalls bestimmt. Die Bestimmung wurde durch Messung der Zeit durchgeführt, die die Tablette benötigte, bis zu einem Grad zu zerfallen, vo sie durch 4 am große Öffnungen in einem Korb untergetaucht in bewegtem Wasser bei 40ºC austreten konnte. Dieses Ergebnis wird ebenfalls in Tabelle 1 angegeben. The dissolution rate of the tablets was also determined. The determination was made by measuring the time it took for the tablet to disintegrate to the point where it could exit through 4 large openings submerged in moving water at 40 ° C. This result is also shown in Table 1.
Die Wirkung sowohl der Zweischichttablette als auch des Pulvers derselben Zusammensetzung wurde dann nach DIN 44990 bestimmt. Diese Methode beschreibt das Testen von Geschirrspülmitteln über eine visuelle Bestimmung der Wirkung auf einer Skala von 1 bis 5 (wobei 5 als perfekt sauber angenommen wird). Eine Geschirrwaschmaschine von Bosch wurde mit dem normalen 65ºC Waschprogramm verwendet. Die Wasserhärte betrug 18ºd. Fünf Waschgänge wurden für jedes Produkt durchgeführt, wobei in jedem Fall das Produkt automatisch durch die maschineneigene Spülmittelspendevorrichtung dosiert wurde.  The effect of both the two-layer tablet and the powder of the same composition was then determined in accordance with DIN 44990. This method describes the testing of dishwashing detergents by visually determining the effect on a scale from 1 to 5 (5 being assumed to be perfectly clean). A Bosch dishwasher was used with the normal 65ºC wash program. The water hardness was 18 ° d. Five washes were carried out for each product, in each case the product being dosed automatically by the machine's own detergent dispenser.
Die Ergebnisse für die wesentliche enzymrelevante Verschmutzung, Milch, werden in Tabelle 2 wiedergegeben. The results for the essential enzyme-relevant pollution, milk, are shown in Table 2.
Beispiel 2  Example 2
Zweischichttabletten wurden unter Verwendung einer Hochgeschwindigkeitsrotationspresse im Produktionmaßstab hergestellt. Die Tabletten wogen 20 g, die erste Schicht enthielt 14 g und die zweite Schicht 6 g (Tabelle 3). Die Tabletten wurden ausreichend gepreßt, um eine Härte von 100 N zu erhalten (gleiche Härtetestmaschine wir in Beispiel 1). Wiederum wurde auch eine pulverförmige Zusammensetzung derselben Formulierung hergestellt (Tabelle 3). Die Auflösezeit der Zweischichttabletten ist in Tabelle 3 angegeben. Two-layer tablets were produced on a production scale using a high speed rotary press. The tablets weighed 20 g, the first layer contained 14 g and the second layer 6 g (Table 3). The tablets were pressed sufficiently to obtain a hardness of 100 N (same hardness test machine as in Example 1). Again, it became a powdered composition prepared the same formulation (Table 3). The dissolution time of the two-layer tablets is given in Table 3.
Die Wirkung sowohl der Zweischichttablette als auch des Pulvers derselben Zusammensetzung wurde dann nach DIN 44990 bestimmt. Es wurde eine Geschirrwaschmaschine von Bosch mit dem normalen 65ºC Waschprogramm verwendet. Die Wasserhärte betrug 18ºd. Die Ergebnisse für die wesentliche enzymrelevante Verschmutzung, Milch, werden in Tabelle 4 wiedergegeben. The effect of both the two-layer tablet and the powder of the same composition was then determined in accordance with DIN 44990. A Bosch dishwashing machine with the normal 65ºC washing program was used. The water hardness was 18 ° d. The results for the essential enzyme-relevant contamination, milk, are shown in Table 4.
Vergleichsbeispiel 3 Comparative Example 3
In diesem Beispiel wurden Einschichttabletten gemäß einer bereits auf dem Markt vorhandenen Zusammensetzung hergestellt. Die Tabletten wurden so gepreßt, daß die Festigkeit der Tablette ungefähr 125 N betrug. Die Auflösezeit wurde ebenfalls gemessen, die Ergebnisse sind in Tabelle 5 wiedergegeben. Eine pulverige Zusammensetzung derselben Formulierung wurde ebenfalls hergestellt. Die Zusammensetzung wird in Tabelle 5 angegeben. In this example, single-layer tablets were made according to a composition already on the market. The tablets were pressed so that the strength of the tablet was approximately 125 N. The dissolution time was also measured, the results are shown in Table 5. A powdery composition of the same formulation was also made. The composition is given in Table 5.
Die Wirkung sowohl der Tablette als auch des Pulvers wurde wiederum nach DIN 44990 bestimmt. Wie zuvor wurde eine Geschirrwaschmaschine von Bosch verwendet. Wiederum wurde das normale 65°C Waschprogramm verwendet und das Wasser hatte eine Härte von 18°d. The effect of both the tablet and the powder was again determined in accordance with DIN 44990. As before, a Bosch dishwasher was used. Again the normal 65 ° C wash program was used and the water had a hardness of 18 ° d.
Die Ergebnisse für die wesentliche enzymrelevante Veschmutzung, Milch, werden in Tabelle 6 wiedergegeben. The results for the essential enzyme-relevant contamination, milk, are shown in Table 6.
An diesen Beispielen und Vergleichsbeispielen wird deutlich, daß ein erfindungsgemäßes Geschirrwaschmascmnenspülmittel, das als einfache zweischichtige Tablette aufgebaut ist, eine bessere Spülleistung erzielt als ein vergleichbares Pulver, obwohl die einzelnen Bestandteile des erfindungsgemäßen Mittels vollständig erst nach ca.8 bis 13 Minuten für die Spülleistung zur Verfügung stehen, während bei einem vergleichbaren Pulver alle Bestandteile sofort zur Verfügung stehen. These examples and comparative examples clearly show that a dishwashing detergent according to the invention, which is constructed as a simple two-layer tablet, achieves a better washing performance than a comparable powder, although the individual components of the composition according to the invention are only completely ready for the washing performance after about 8 to 13 minutes Are available, while with a comparable powder all components are immediately available.

Claims

Patentansprüche claims
1. Geschirrwaschmaschinenspülmittel in Form einer Tablette, enthaltend ein Bleichmittel und einen Bleichaktivator sowie andere übliche Bestandteile, dadurch gekennzeichnet, daß es außerdem ein Silber-/Kupferkorrosionsschutzmittel enthält und die Tablette aus mindestens zwei Schichten besteht, wobei das Silber-/Kupferkorrosionsschutzmittel nicht gemeinsam in einer Schicht zusammen mit dem Bleichmittel und dem Bleichaktivator enthalten ist. 1. Dishwasher detergent in the form of a tablet, containing a bleach and a bleach activator and other conventional ingredients, characterized in that it also contains a silver / copper corrosion protection agent and the tablet consists of at least two layers, the silver / copper corrosion protection agent not together in one Layer together with the bleach and the bleach activator is included.
2. Geschirrwaschmaschinenspülmittel nach Anspruch 1, dadurch gekennzeichnet, daß sich die gesamte Tablette in der Flotte in der Geschirrwaschmaschine nicht schneller als in drei Minuten vollständig auflöst. 2. Dishwashing detergent according to claim 1, characterized in that the entire tablet in the fleet in the dishwashing machine does not completely dissolve faster than in three minutes.
3. Geschirrwaschmaschinenspülmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Silber-/Kupferkorrosionsschutzmittel eine oder mehrere Verbindungen umfaßt, ausgewählt aus der Gruppe bestehend aus Benzotriazol und Bis-Benzotriazolen, wobei die verfügbaren Substitutionsstellen des/der aromatischen Ringe(s) teilweise oder vollständig substituiert sein können, organischen und/oder anorganischen redoxaktiven Substanzen und Paraffinöl. 3. Dishwashing detergent according to one of the preceding claims, characterized in that the silver / copper anti-corrosion agent comprises one or more compounds selected from the group consisting of benzotriazole and bis-benzotriazoles, the available substitution sites of the aromatic ring (s) partially or Can be completely substituted, organic and / or inorganic redox-active substances and paraffin oil.
4. Geschirrwaschmaschinenspülmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Bleichmittel eine oder mehrere Verbindungen umfaßt, ausgewählt aus der Gruppe bestehend aus Perboraten, Percarbonaten, Peroxymonopersulfaten und organischen Persäuren sowie deren Salzen. 4. Dishwashing detergent according to one of the preceding claims, characterized in that the bleach comprises one or more compounds selected from the group consisting of perborates, percarbonates, peroxymonopersulfates and organic peracids and their salts.
5. Geschirrwaschmaschinenspülmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Bleichaktivator eine oder mehrere Verbindungen umfaßt, ausgewählt aus der Gruppe bestehend aus N,N,N',N'- Tetraacetylethylendiamin (TAED), Pentaacetylglucose (PAG), Tetraacetalglycoluril (TAGU) und katalytisch aktiven Metallkomplexen. 5. Dishwashing detergent according to one of the preceding claims, characterized in that the bleach activator comprises one or more compounds selected from the group consisting of N, N, N ', N'-tetraacetylethylene diamine (TAED), pentaacetyl glucose (PAG), tetraacetal glycoluril (TAGU ) and catalytically active metal complexes.
6. Geschirrwaschmaschinenspülmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß es außerdem einen oder mehrere Bestandteile ausgewählt aus der Gruppe bestehend aus Gerüststoffen, Maskierungsmitteln, Chlorbleichmitteln, oberflächenaktiven Mitteln, Enzymen, Schaumkontrollmitteln, Duftstoffen, Farbstoffen und sonstigen Hilfsstoffen enthält. 6. Dishwashing detergent according to one of the preceding claims, characterized in that it also contains one or more components selected from the group consisting of builders, masking agents, chlorine bleaches, surface-active agents, enzymes, foam control agents, fragrances, dyes and other auxiliaries.
7. Geschirrwaschmaschinenspülmittel nach einem der vorhergehenden Ansprüche, bestehend aus zwei Schichten, wobei die erste Schicht a) als Bleichmittel ein Perborat, b) als Gerüststoffe Natriumtripolyphosphat, ein Disilicat und ein Carbonat, c) ein nichtionisches oberflächenaktives Mittel, d) als Silber-/Kupferkorrosionsschutzmittel Benzotriazol sowie gegebenenfalls weitere Hilfsstoffe enthält und die zweite Schicht a) als Bleichaktivator N,N,N',N'-Tetraacetylethylendiamin, b) als Gerüststoffe Natriumtripolyphosphat, ein homopolymeres Acrylsäurepolymer und ein Carbonat, c) als Maskierungsmittel ein Phosphonat, d) ein nichtionisches oberflächenaktives Mittel, e) ein oder mehrere Enzyme sowie gegebenenfalls weitere Hilfsstoffe enthält. 7. Dishwashing detergent according to one of the preceding claims, consisting of two layers, the first layer a) as a bleaching agent a perborate, b) as builders sodium tripolyphosphate, a disilicate and a carbonate, c) a nonionic surface-active agent, d) as a silver / Contains copper corrosion inhibitor benzotriazole and optionally other auxiliaries and the second layer a) as bleach activator N, N, N ', N'-tetraacetylethylene diamine, b) as builders sodium tripolyphosphate, a homopolymeric acrylic acid polymer and a carbonate, c) as a masking agent, a phosphonate, d) a nonionic surface-active agent, e) one or more enzymes and optionally further auxiliaries.
8. Geschirrwaschmaschinenspülmittel nach einem der Ansprüche 1 bis 7, bestehend aus zwei Schichten, wobei die erste Schicht a) als Bleichmittel ein Perborat, b) als Gerüststoffe ein Citrat, ein Bicarbonat und ein Carbonat, c) ein nichtionisches oberflächenaktives Mittel, d) als Silber¬/Kupferkorrosionsschutzmittel Benzotriazol sowie gegebenenfalls weitere Hilfsstoffe enthält und die zweite Schicht a) als Bleichaktivator N,N,N',N'-Tetraacetylethylendiamin, b) als Gerüststoffe Citrat, ein Bicarbonat, ein Carbonat, ein homopolymeres Acrylsäurepolymer und Citronensäure, c) als Maskierungsmittel ein Phosphonat, d) ein nichtionisches oberflächenaktives Mittel, e) ein oder mehrere Enzyme sowie gegebenenfalls weitere Hilfsstoffe enthält. 8. Dishwashing detergent according to one of claims 1 to 7, consisting of two layers, the first layer a) as a bleaching agent a perborate, b) as builders a citrate, a bicarbonate and a carbonate, c) a nonionic surface-active agent, d) as Contains silver / copper corrosion inhibitor benzotriazole and optionally other auxiliaries and the second Layer a) as a bleach activator N, N, N ', N'-tetraacetylethylene diamine, b) as builders citrate, a bicarbonate, a carbonate, a homopolymeric acrylic acid polymer and citric acid, c) as a masking agent, a phosphonate, d) a nonionic surface-active agent, e ) contains one or more enzymes and optionally other auxiliary substances.
EP96923846A 1995-07-13 1996-07-15 Dish washer product in tablet form Expired - Lifetime EP0842257B1 (en)

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DE19525569 1995-07-13
DE19525569 1995-07-13
PCT/DE1996/001283 WO1997003177A1 (en) 1995-07-13 1996-07-15 Dish washer product in tablet form

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EP (1) EP0842257B1 (en)
AT (1) ATE198349T1 (en)
AU (1) AU6413096A (en)
CA (1) CA2226143C (en)
DE (1) DE59606257D1 (en)
ES (1) ES2155613T3 (en)
WO (1) WO1997003177A1 (en)

Families Citing this family (83)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5900395A (en) * 1996-12-23 1999-05-04 Lever Brothers Company Machine dishwashing tablets containing an oxygen bleach system
US5783540A (en) * 1996-12-23 1998-07-21 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets delivering a rinse aid benefit
DE19716094A1 (en) * 1997-04-17 1998-10-22 Henkel Kgaa Anti-corrosion detergent
ZA984570B (en) 1997-06-06 1999-11-29 Unilever Plc Cleaning compositions.
GB9711829D0 (en) 1997-06-06 1997-08-06 Unilever Plc Detergent compositions
US6274538B1 (en) 1997-11-10 2001-08-14 The Procter & Gamble Company Detergent compositions
WO1999024547A1 (en) * 1997-11-10 1999-05-20 The Procter & Gamble Company Detergent compositions
DE69812403T2 (en) 1997-11-10 2004-01-29 Procter & Gamble METHOD FOR PRODUCING A DETERGENT TABLET
GB2331994A (en) * 1997-12-02 1999-06-09 Procter & Gamble Detergent tablet
WO1999024548A1 (en) 1997-11-10 1999-05-20 The Procter & Gamble Company Detergent tablet
BR9807007A (en) 1997-11-26 2000-03-14 Procter & Gamble Multilayer detergent tablet having both compressed and uncompressed portions
ES2244096T3 (en) 1997-11-26 2005-12-01 THE PROCTER & GAMBLE COMPANY DETERGENT PAD.
DE19758177A1 (en) * 1997-12-30 1999-07-01 Henkel Kgaa Process for producing a dishwasher detergent tablet
DE19758180A1 (en) * 1997-12-30 1999-07-01 Henkel Kgaa Detergent tablets with bleach activators
DE19758181A1 (en) * 1997-12-30 1999-07-01 Henkel Kgaa Dishwasher detergent tablets with soil release polymers
DE19758175A1 (en) * 1997-12-30 1999-07-01 Henkel Kgaa Dishwasher detergent tablets with specific solubility
US6410500B1 (en) 1997-12-30 2002-06-25 Henkel Kommanditgesellschaft Auf Aktien Moulded body dishwasher detergents with soil release polymers
EP1051476A1 (en) * 1998-01-26 2000-11-15 The Procter & Gamble Company Multi-layer detergent tablet
DE19803410A1 (en) * 1998-01-28 1999-07-29 Henkel Kgaa Multiphase laundry detergent tablets exhibiting high hardness and rapid disintegration
DE29824160U1 (en) * 1998-01-28 2000-08-10 Henkel Kgaa Multi-phase detergent tablets
FR2778666B1 (en) * 1998-05-14 2003-01-17 Chimiotechnic THREE-LAYERED DETERGENT TABLET
GB9815525D0 (en) * 1998-07-17 1998-09-16 Procter & Gamble Detergent tablet
US6544943B1 (en) * 1998-07-17 2003-04-08 Procter & Gamble Company Detergent tablet
DE29911484U1 (en) * 1998-07-17 2000-02-24 Procter & Gamble Detergent tablet
IES990570A2 (en) * 1998-07-17 2000-03-08 Procter & Gamble Detergent tablet
DE69933709T2 (en) * 1998-07-17 2007-08-23 The Procter & Gamble Company, Cincinnati Tablet detergent
ES2168835T3 (en) * 1998-07-17 2002-06-16 Procter & Gamble METHOD TO PREPARE DETERGENT TABLETS.
US6686329B1 (en) * 1998-08-13 2004-02-03 The Procter & Gamble Company Multilayer detergent tablet with different hardness
EP0979862A1 (en) * 1998-08-13 2000-02-16 The Procter & Gamble Company Multilayer detergent tablet with different hardness
EP0979863A1 (en) * 1998-08-13 2000-02-16 The Procter & Gamble Company Multilayer detergent tablet with different elasticities
EP0999262A1 (en) * 1998-11-05 2000-05-10 The Procter & Gamble Company Multilayered detergent tablets
EP0999261A1 (en) * 1998-11-05 2000-05-10 The Procter & Gamble Company Coloured tablet
DE19855381A1 (en) * 1998-12-01 2000-06-08 Henkel Kgaa Solid surfactant mixture for use as a detergent and cleaning agent
DE19856214C1 (en) * 1998-12-05 2000-03-09 Henkel Kgaa Point tablet shaped washing agent formed from granular material
GB9901688D0 (en) 1999-01-26 1999-03-17 Unilever Plc Detergent compositions
DE19914812A1 (en) * 1999-03-31 2000-10-05 Henkel Kgaa Detergent tablets include a cyanomethyl ammonium salt bleach activator in a controlled pH environment to improve stability
DE19914353A1 (en) * 1999-03-31 2000-10-05 Henkel Kgaa Detergent formed bodies, which exhibit good hardness and good disintegration properties, include cationic nitrile compounds as bleach activators
DE19919444B4 (en) * 1999-04-29 2016-06-30 Henkel Ag & Co. Kgaa Detergent tablets with binder compound, process for its preparation and use of binder compounds
GB9911949D0 (en) * 1999-05-21 1999-07-21 Unilever Plc Detergent compositions
DE19925518B4 (en) * 1999-06-04 2016-06-30 Henkel Ag & Co. Kgaa Multiphase detergent tablets with perfume and process for their preparation
DE19959589A1 (en) * 1999-12-10 2001-07-12 Henkel Kgaa Multi-phase detergent tablets
GB0015350D0 (en) * 2000-06-23 2000-08-16 Reckitt Benckiser Nv Improvements in or relating to compositions
GB0020379D0 (en) * 2000-08-21 2000-10-04 Clariant Int Ltd Enzyme composition in tablet form
US6750186B2 (en) 2002-02-04 2004-06-15 Robert Black Composition and method for cleaning dishwashers
DE10236227A1 (en) * 2002-08-07 2004-02-26 Buck-Chemie Gmbh Cleansing and/or deliming tablets for use on hard surfaces (especially in toilets or dishwashers) have visible color centers comprising dyed alkali (ne earth) or aluminum salts
US6852238B2 (en) * 2002-08-29 2005-02-08 Steller Technology Company Layered tablet water treatment compositions and method of use
US7309444B2 (en) * 2002-08-29 2007-12-18 Stellar Technology Company Layered tablet water treatment compositions and method of use
US7285171B2 (en) * 2002-12-19 2007-10-23 The Procter & Gamble Company Anti-filming materials, compositions and methods
DE10320196A1 (en) * 2002-12-20 2004-07-08 Henkel Kg Auf Aktien Detergents or cleaning agents containing bleach
WO2004056954A1 (en) * 2002-12-20 2004-07-08 Degussa Ag Coated peroxygen compounds with controlled release, a process for their preparation and their use
ES2274296T3 (en) * 2002-12-20 2007-05-16 Degussa Gmbh LIQUID COMPOSITION OF DETERGENT AND CLEANING AGENT.
SI1475350T1 (en) * 2003-05-07 2005-12-31 Degussa Coated sodium percarbonate granules with improved storage stability
JP2007504089A (en) * 2003-05-23 2007-03-01 デグサ　アクチエンゲゼルシャフト Use of a powdery mixture containing hydrogen peroxide and hydrophobized silicon dioxide for the controlled release of hydrogen peroxide or oxygen
DE10334725A1 (en) * 2003-07-30 2005-02-24 Degussa Ag Bleaching machine dishwashing detergents with increased yellowing resistance and process for their preparation
US6863830B1 (en) * 2003-08-21 2005-03-08 Biolab Services, Inc. Dual layer tablet, method of making and use thereof
AU2005234777B2 (en) * 2004-04-20 2009-02-19 Wm. Wrigley Jr. Company Breath freshening confectionery products and methods of making and using same
FR2873113B1 (en) * 2004-07-19 2007-06-15 Eurotab Sa COMPACT SOLID BILOUCHE PRODUCT FOR WATER PURIFICATION
US20060019854A1 (en) * 2004-07-21 2006-01-26 Johnsondiversey. Inc. Paper mill cleaner with taed
DE102004054495A1 (en) 2004-11-11 2006-05-24 Degussa Ag Sodium percarbonate particles with a thiosulfate containing shell layer
DE102004060011A1 (en) * 2004-12-14 2006-07-06 Degussa Ag Pressed shaped bodies containing coated sodium percarbonate particles
US10767268B2 (en) * 2005-05-06 2020-09-08 Swimc Llc Articles having improved corrosion resistance
GB0616444D0 (en) * 2006-08-18 2006-09-27 Reckitt Benckiser Nv Detergent composition
JP2009099945A (en) * 2007-09-28 2009-05-07 Fujifilm Corp Cleaning agent for semiconductor device and cleaning method using the same
GB0718944D0 (en) 2007-09-28 2007-11-07 Reckitt Benckiser Nv Detergent composition
DE102009029636A1 (en) * 2009-09-21 2011-03-24 Henkel Ag & Co. Kgaa Machine dishwashing detergent
DE102011077098A1 (en) * 2011-06-07 2012-12-13 Henkel Kgaa Silver-protecting dishwashing detergent
FR2982854B1 (en) * 2011-11-21 2014-08-08 Aquitab PASTILLE BICOUCHES FOR PROCESSING POOLS, COMPOSITION THEREOF AND PROCESS FOR PRODUCING THE PASTILLE
EP3022280B1 (en) * 2013-07-19 2019-01-02 Ecolab USA Inc. Mild alkaline solid instrument cleaner
WO2015055234A1 (en) * 2013-10-15 2015-04-23 Ecolab Inc. Use of an active solid for cleaning and inactivating unconventional infectious agents on surfaces
US9920288B2 (en) 2014-07-11 2018-03-20 Diversey, Inc. Tablet dishwashing detergent and methods for making and using the same
US20160010034A1 (en) * 2014-07-11 2016-01-14 Diversey, Inc. Dishwashing detergent and methods of making and using the same
ES2574332B1 (en) * 2014-12-16 2017-03-27 Ercros, S.A. Tablets for water treatment and disinfection
US10280386B2 (en) 2015-04-03 2019-05-07 Ecolab Usa Inc. Enhanced peroxygen stability in multi-dispense TAED-containing peroxygen solid
US9783766B2 (en) 2015-04-03 2017-10-10 Ecolab Usa Inc. Enhanced peroxygen stability using anionic surfactant in TAED-containing peroxygen solid
US9839212B2 (en) 2015-04-16 2017-12-12 Bio-Lab, Inc. Multicomponent and multilayer compacted tablets
WO2016175895A1 (en) 2015-04-29 2016-11-03 Shutterfly, Inc. Image product creation based on face images grouped using image product statistics
EP3118296A1 (en) * 2015-07-16 2017-01-18 Clearwhite GmbH Cleaning tablet for carafes
DE102015213943A1 (en) * 2015-07-23 2017-01-26 Henkel Ag & Co. Kgaa Washing or cleaning agent comprising at least two phases
CN106590985A (en) * 2016-12-08 2017-04-26 青岛友诚高新技术有限公司 Disinfecting and sterilizing dishwashing liquid
DE102017201097A1 (en) * 2017-01-24 2018-07-26 Henkel Ag & Co. Kgaa Washing or cleaning agent comprising at least two phases
WO2019241629A1 (en) 2018-06-15 2019-12-19 Ecolab Usa Inc. Enhanced peroxygen stability using fatty acid in bleach activating agent containing peroxygen solid
GB201814188D0 (en) * 2018-08-31 2018-10-17 Reckitt Benckiser Finish Bv Automatic dishwashing product
EP3623456A1 (en) 2018-09-12 2020-03-18 CLARO Products GmbH Silver protection agent

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3962107A (en) 1974-06-24 1976-06-08 Johnson & Johnson Enzyme-containing denture cleanser tablet
US4219436A (en) * 1977-06-01 1980-08-26 The Procter & Gamble Company High density, high alkalinity dishwashing detergent tablet
GB2041966A (en) * 1977-11-29 1980-09-17 Procter & Gamble Detergent tablet having a hydrated salt coating and process for preparing the tablet
DE3225292A1 (en) 1982-07-07 1984-01-12 Henkel KGaA, 4000 Düsseldorf CLEANING AND DISINFECTANT TABLET FOR THE WATER CASE OF RINSING TOILETS
DE3541146A1 (en) * 1985-11-21 1987-05-27 Henkel Kgaa MULTILAYERED DETERGENT TABLETS FOR MACHINE DISHWASHER
US5089270A (en) 1990-05-15 1992-02-18 L. Perrigo Company Capsule-shaped tablet
US5133892A (en) * 1990-10-17 1992-07-28 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing detergent tablets
GB9022724D0 (en) 1990-10-19 1990-12-05 Unilever Plc Detergent compositions
DK166548B1 (en) * 1991-03-15 1993-06-07 Cleantabs As PHOSPHATE-FREE MACHINE DISHWASH
DK167364B1 (en) 1991-11-08 1993-10-18 Cleantabs As MACHINE DETERGENT
CZ286401B6 (en) 1993-05-08 2000-04-12 Henkel Kgaa Use of inorganic redox-active substances
DK0697036T3 (en) * 1993-05-08 2000-01-31 Henkel Kgaa Silver corrosion protection agent II
WO1995000714A1 (en) 1993-06-21 1995-01-05 Barone, Inc. Quick coupler for heavy equipment implements
AU7216594A (en) * 1993-07-01 1995-01-24 Procter & Gamble Company, The Machine dishwashing composition containing oxygen bleach and paraffin oil and benzotriazole compound silver tarnishing inhibitors
DE69328679T2 (en) 1993-07-16 2001-01-11 Procter & Gamble Detergent compositions for dishwashers
DE4344215A1 (en) * 1993-12-23 1995-06-29 Cognis Bio Umwelt Silver corrosion inhibitor-containing enzyme preparation
US5453216A (en) * 1994-04-28 1995-09-26 Creative Products Resource, Inc. Delayed-release encapsulated warewashing composition and process of use
US5783540A (en) * 1996-12-23 1998-07-21 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets delivering a rinse aid benefit

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9703177A1 *

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EP0842257B1 (en) 2000-12-27
US6194368B1 (en) 2001-02-27
CA2226143A1 (en) 1997-01-30
CA2226143C (en) 2007-11-20
ATE198349T1 (en) 2001-01-15
DE59606257D1 (en) 2001-02-01
WO1997003177A1 (en) 1997-01-30
AU6413096A (en) 1997-02-10

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