EP0416366A2 - Dishwashing composition comprising layered silicates - Google Patents

Dishwashing composition comprising layered silicates Download PDF

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Publication number
EP0416366A2
EP0416366A2 EP90115975A EP90115975A EP0416366A2 EP 0416366 A2 EP0416366 A2 EP 0416366A2 EP 90115975 A EP90115975 A EP 90115975A EP 90115975 A EP90115975 A EP 90115975A EP 0416366 A2 EP0416366 A2 EP 0416366A2
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EP
European Patent Office
Prior art keywords
weight
gewichts
dishwashing detergent
alkali
sodium
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EP90115975A
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German (de)
French (fr)
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EP0416366A3 (en
EP0416366B1 (en
Inventor
Franz-Josef Dr. Dany
Hannsjörg Dr. Ulrich
Lothar Westermann
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Clariant Produkte Deutschland GmbH
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Hoechst AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites

Definitions

  • the present invention relates to a dishwashing detergent based on a crystalline alkali layer silicate.
  • Detergent mixtures are known as agents for machine washing dishes, which contain sodium tripolyphosphate as a builder, sodium metasilicate as an alkali carrier, chloroisocyanurate as an active chlorine carrier or alkali perborates, persulfates and percarbonates as an active oxygen carrier, and low-foaming block polymers with ethylene and propylene oxide groups or modified fatty alcohol oxide groups as modified as surfactants.
  • the cleaning agent mixtures can furthermore contain alkali metal citrates or aminopolycarboxylic acids.
  • the pH value of the detergent mixtures in a concentration of 1 percent by weight is at least 10 and occasionally up to 12 (see DE-OS 21 42 055, DE-AS 20 62 465).
  • the phosphate-free dishwashing detergent according to DE-OS 36 27 773 contains a crystalline alkali layer silicate in conjunction with a co-builder, for example acrylic acid polymers, polycarboxylates, maleic acid copolymers or vinyl ether carboxylates, in addition to an alkali carrier, a surfactant and an active chlorine carrier, with sodium metasilicate, sodium carbonate or sodium hydroxide as the alkali carrier is used.
  • a co-builder for example acrylic acid polymers, polycarboxylates, maleic acid copolymers or vinyl ether carboxylates
  • an alkali carrier for example acrylic acid polymers, polycarboxylates, maleic acid copolymers or vinyl ether carboxylates
  • a surfactant and an active chlorine carrier with sodium metasilicate, sodium carbonate or sodium hydroxide as the alkali carrier is used.
  • a disadvantage of the known agents is that they only develop their full cleaning action if their alkali carrier content is so large that the pH in the cleaning liquor is at least 11, which is with regard to the corrosive effect on skin and eyes is dangerous.
  • dishwashing detergent which, with good cleaning power, has the lowest possible pH in its cleaning liquor.
  • the dishwashing detergent contains a crystalline, largely water-insoluble sodium sheet silicate with a SiO2 / Na2O molar ratio of (1.9 to 3.5): 1 in combination with a proton donor whose 0.5% by weight aqueous solution has a pH Has a value of less than 10.
  • the dishwashing detergent according to the invention can 20 to 60% by weight of the crystalline layered silicate 10 to 40% by weight of the proton donor 1 to 2% by weight of a surfactant 1 to 30% by weight of an active chlorine or active oxygen carrier 0 to 7% by weight of a dispersant 0 to 50% by weight of an alkali phosphate and / or an alkali polyphosphate and Contain 0 to 40% by weight of a filler.
  • Proton donors in the dishwashing detergent according to the invention are polycarboxylic acids such as fumaric, adipic and glutaric acid, hydroxypolycarboxylic acids such as citric acid and tartaric acid and phosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, Amino-tri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid), 3-tert.alkyl-3-oxo-1-aminopropane-1,1-diphosphonic acid, 3-tert.alkyl-3-oxo-1-hydroxypropane-1, 1-diphosphonic acid and ⁇ -dimethylaminoalkane-1-hydroxy-1,1-diphosphonic acids are suitable.
  • polycarboxylic acids such as fumaric, adipic and glutaric acid
  • hydroxypolycarboxylic acids such as citric acid and tartaric
  • mineral acids their acidic salts and esters such as monosodium dihydrogen monophosphate, monopotassium dihydrogen monophosphate, disodium dihydrogen diphosphate, acidic esters of phosphoric acid, sodium hydrogen sulfate and sodium hydrogen carbonate can also be used as proton donors.
  • sodium sulfate as a filler sodium triphosphate as a builder, polymeric or copolymeric polycarboxylic acids or their water-soluble salts as a dispersant, block polymers of long-chain aliphatic alcohols with ethylene oxide or propylene oxide groups or modified fatty alcohol polyglycol ethers as surfactants, and sodium dichloro-isocyanurate, as an active chlorine carrier, Percarbonate and peroxycarboxylic acids and their salts such as dodecane peroxidicarboxylic acid or magnesium peroxiphthalate can be included.
  • the dishwashing detergent according to the invention is notable for good cleaning properties even in the case of critical soiling, such as burnt-on protein-containing food residues. Furthermore, it shows a high chlorine or active oxygen stability and causes a relatively low corrosion of sensitive washware.
  • the dishwashing detergent according to the invention is preferably used in household dishwashers, but can also be used in commercial dishwashers.
  • the concentration of the powdered dishwashing detergent according to the invention in the cleaning liquor is 3 to 10 g / l, preferably 4 to 5 g / l.
  • the pH value which can be achieved in the cleaning liquor of the dishwashing detergent according to the invention is primarily dependent on the concentration ratio of layered sodium silicate to proton donor. It would now be obvious to combine free layered silica with alkalis in order to maintain the same pH value in the cleaning liquor. It has been found, however, that despite the same pH value in the cleaning liquor in the case of the combination of layered silica / alkalis, the cleaning success achieved with the dishwashing detergent according to the invention cannot be achieved.
  • aqueous dishwashing detergent solutions The pH of aqueous dishwashing detergent solutions was determined as follows: 10 g of the dishwashing detergent were weighed into a 100 ml volumetric flask, 80 ml of demineralized water were added and the mixture was stirred vigorously for 1 hour using a magnetic stirrer at room temperature but avoiding foaming. After removing the magnetic stirrer, the volumetric flask was filled to the mark with demineralized water, the solution was mixed and immediately centrifuged. The pH measurements were carried out immediately afterwards with a glass electrode.
  • the mixtures A to M were tested in household dishwashers from MIELE for their cleaning action using a rinse aid.
  • Table 1 shows the results of the test, the first line being the pH of a 10% aqueous solution of the mixture, the second line being the pH of the cleaning liquor (5 g of mixture / l of water) and the cleaning index according to DIN 44 990, Part 2 (draft, December 1980).
  • Table 1 State of the art According to the invention mixture A B C. D E F G H I.
  • a comparison of the cleaning indices shows that the dishwashing detergents according to the invention have comparable cleaning successes in comparison to recipes according to the prior art, despite a considerable reduction in the pH in the washing liquors.
  • Porcelain plates and cups served as ballast for filling the prescribed amount of 12 items to be washed according to DIN 44 990, part 100 (draft, December 1981).
  • a scale divided into 5 levels was used to assess the damage, according to which the tests were evaluated visually after 125, 250, 500 and 1000 rinse cycles.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Lubricants (AREA)

Abstract

A dishwashing agent consists of a crystalline, largely water-insoluble sodium layer silicate having a molar ratio of SiO2/Na2O of (1.9 to 3.5):1 in combination with a proton donor, a 0.5% strength by weight aqueous solution of the dishwashing agent having a pH of less than 10. The dishwashing agent can furthermore contain a surfactant, an active chlorine or active oxygen carrier, a dispersing agent, an alkali metal phosphate or an alkali metal polyphosphate and a filler.

Description

Die vorliegende Erfindung betrifft ein Geschirrspülmittel auf der Basis eines kristallinen Alkalischichtsilikates.The present invention relates to a dishwashing detergent based on a crystalline alkali layer silicate.

Als Mittel zum maschinellen Spülen von Geschirr sind Reini­gungsmittelgemische bekannt, welche als Builder Natriumtri­polyphosphat, als Alkaliträger Natriummetasilikat, als Ak­tivchlorträger Chlorisocyanurate oder als Aktivsauerstoff­träger Alkaliperborate, -persulfate und -percarbonate sowie als Tenside schwachschäumende Blockpolymerisate mit Ethy­len- und Propylenoxidgruppen oder modifizierte Fettalkohol­polyglykolether enthalten. Weiterhin können die Reinigungs­mittelgemische Alkalicitrate oder Aminopolycarbonsäuren aufweisen. Der pH-Wert der Reinigungsmittelgemische in einer Konzentration von 1 Gewichtsprozent beträgt min­destens 10 und gelegentlich bis 12 (vergl. DE-OS 21 42 055, DE-AS 20 62 465).Detergent mixtures are known as agents for machine washing dishes, which contain sodium tripolyphosphate as a builder, sodium metasilicate as an alkali carrier, chloroisocyanurate as an active chlorine carrier or alkali perborates, persulfates and percarbonates as an active oxygen carrier, and low-foaming block polymers with ethylene and propylene oxide groups or modified fatty alcohol oxide groups as modified as surfactants. The cleaning agent mixtures can furthermore contain alkali metal citrates or aminopolycarboxylic acids. The pH value of the detergent mixtures in a concentration of 1 percent by weight is at least 10 and occasionally up to 12 (see DE-OS 21 42 055, DE-AS 20 62 465).

Das phosphatfreie Geschirrspülmittel nach der DE-OS 36 27 773 enthält ein kristallines Alkalischichtsilikat in Verbindung mit einem Co-Builder, beispielsweise Acrylsäure­polymerisate, Polycarboxylate, Maleinsäurecopolymerisate oder Vinylethercarboxylate, neben einem Alkaliträger, einem Tensid und einem Aktivchlorträger, wobei als Alkaliträger Natriummetasilikat, Natriumcarbonat oder Natriumhydroxid verwendet ist.The phosphate-free dishwashing detergent according to DE-OS 36 27 773 contains a crystalline alkali layer silicate in conjunction with a co-builder, for example acrylic acid polymers, polycarboxylates, maleic acid copolymers or vinyl ether carboxylates, in addition to an alkali carrier, a surfactant and an active chlorine carrier, with sodium metasilicate, sodium carbonate or sodium hydroxide as the alkali carrier is used.

Nachteilig ist bei den bekannten Mitteln, daß sie ihre volle Reinigungswirkung nur dann entfalten, wenn ihr Gehalt an Alkaliträger so groß ist, daß der pH-Wert in der Reini­gungsflotte wenigstens 11 beträgt, was im Hinblick auf die ätzende Wirkung auf Haut und Augen gefährlich ist.A disadvantage of the known agents is that they only develop their full cleaning action if their alkali carrier content is so large that the pH in the cleaning liquor is at least 11, which is with regard to the corrosive effect on skin and eyes is dangerous.

Es ist daher Aufgabe der vorliegenden Erfindung, ein Ge­schirrspülmittel anzugeben, welches bei guter Reinigungs­kraft einen möglichst niedrigeren pH-Wert in seiner Reini­gungsflotte aufweist. Das wird erfindungsgemäß dadurch er­reicht, daß das Geschirrspülmittel ein kristallines, weit­gehend wasserunlösliches Natriumschichtsilikat mit einem Molverhältnis SiO₂/Na₂O von (1,9 bis 3,5) : 1 in Kombi­nation mit einem Protonendonator enthält, dessen 0,5 ge­wichtsprozentige wäßrige Lösung einen pH-Wert von weniger als 10 aufweist.It is therefore an object of the present invention to provide a dishwashing detergent which, with good cleaning power, has the lowest possible pH in its cleaning liquor. This is achieved according to the invention in that the dishwashing detergent contains a crystalline, largely water-insoluble sodium sheet silicate with a SiO₂ / Na₂O molar ratio of (1.9 to 3.5): 1 in combination with a proton donor whose 0.5% by weight aqueous solution has a pH Has a value of less than 10.

Das Geschirrspülmittel gemäß der Erfindung kann
20 bis 60 Gewichts% des kristallinen Schichtsilikates
10 bis 40 Gewichts% des Protonendonators
1 bis 2 Gewichts% eines Tensids
1 bis 30 Gewichts% eines Aktivchlor- oder Aktivsauer­stoffträgers
0 bis 7 Gewichts% eines Dispergiermittels
0 bis 50 Gewichts% eines Alkaliphosphates und/oder eines Alkalipolyphosphates und
0 bis 40 Gewichts% eines Füllstoffes enthalten.The dishwashing detergent according to the invention can
20 to 60% by weight of the crystalline layered silicate
10 to 40% by weight of the proton donor
1 to 2% by weight of a surfactant
1 to 30% by weight of an active chlorine or active oxygen carrier
0 to 7% by weight of a dispersant
0 to 50% by weight of an alkali phosphate and / or an alkali polyphosphate and
Contain 0 to 40% by weight of a filler.

Das erfindungsgemäße Geschirrspülmittel kann weiterhin wahlweise auch noch dadurch ausgestaltet sein, daß

  • a) als Protonendonator Mineralsäuren und/oder Polycarbon­säuren und/oder Hydroxypolycarbonsäuren und/oder Phos­phonsäuren und/oder deren saure Salze bzw. Ester enthal­ten sind;
  • b) es 25 bis 35 Gewichts% kristallines Alkalischichtsilikat enthält;
  • c) es 10 bis 30 Gewichts% Alkaliphosphat und/oder Alkalipo­lyphosphat enthält.
The dishwashing detergent according to the invention can optionally also be designed such that
  • a) mineral acids and / or polycarboxylic acids and / or hydroxypolycarboxylic acids and / or phosphonic acids and / or their acid salts or esters are contained as proton donors;
  • b) it contains 25 to 35% by weight of crystalline alkali layer silicate;
  • c) it contains 10 to 30% by weight of alkali metal phosphate and / or alkali metal polyphosphate.

Beim Geschirrspülmittel gemäß der Erfindung sind als Proto­nendonatoren Polycarbonsäuren wie Fumar-, Adipin- und Glu­tarsäure, Hydroxypolycarbonsäuren wie Citronensäure und Weinsäure und Phosphonsäuren wie 1-Hydroxyethan-1,1-diphos­phonsäure, 2-Phosphono-butan-1,2,4-tricarbonsäure, Amino-­tri-(methylenphosphonsäure), Ethylendiamintetra-(methylen­phosphonsäure), 3-tert.Alkyl-3-oxo-1-aminopropan-1,1-di­phosphonsäure, 3-tert.Alkyl-3-oxo-1-hydroxypropan-1,1-di­phosphonsäure und ω -Dimethyl-aminoalkan-1-hydroxi-1,1-di­phosphonsäuren geeignet. Anstelle der Säuren können auch deren wasserlösliche saure Salze eingesetzt werden. Weiter­hin können als Protonendonatoren Mineralsäuren, deren saure Salze und Ester wie Mononatrium-dihydrogen-monophosphat, Monokalium-dihydrogenmonophosphat, Dinatrium-dihydrogen-di­phosphat, saure Ester der Phosphorsäure, Natriumhydrogen­sulfat und Natriumhydrogencarbonat zur Anwendung gelangen.Proton donors in the dishwashing detergent according to the invention are polycarboxylic acids such as fumaric, adipic and glutaric acid, hydroxypolycarboxylic acids such as citric acid and tartaric acid and phosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, Amino-tri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid), 3-tert.alkyl-3-oxo-1-aminopropane-1,1-diphosphonic acid, 3-tert.alkyl-3-oxo-1-hydroxypropane-1, 1-diphosphonic acid and ω -dimethylaminoalkane-1-hydroxy-1,1-diphosphonic acids are suitable. Instead of the acids, their water-soluble acid salts can also be used. Mineral acids, their acidic salts and esters such as monosodium dihydrogen monophosphate, monopotassium dihydrogen monophosphate, disodium dihydrogen diphosphate, acidic esters of phosphoric acid, sodium hydrogen sulfate and sodium hydrogen carbonate can also be used as proton donors.

Im erfindungsgemäßen Geschirrspülmittel können als Füll­stoff Natriumsulfat, als Builder Natriumtriphosphat, als Dispergiermittel polymere oder copolymere Polycarbonsäuren oder deren wasserlösliche Salze, als Tenside Blockpolymeri­sate langkettiger aliphatischer Alkohole mit Ethylenoxid- oder Propylenoxidgruppen oder modifizierte Fettalkoholpoly­glykolether und als Aktivchlorträger Natriumdichloriso­cyanurat oder als Aktivsauerstoffträger Alkaliperborat, -persulfat, -percarbonat sowie Peroxicarbonsäuren und deren Salze wie Dodecanperoxidicarbonsäure oder Magnesiumperoxi­phtalat enthalten sein.In the dishwashing detergent according to the invention, sodium sulfate as a filler, sodium triphosphate as a builder, polymeric or copolymeric polycarboxylic acids or their water-soluble salts as a dispersant, block polymers of long-chain aliphatic alcohols with ethylene oxide or propylene oxide groups or modified fatty alcohol polyglycol ethers as surfactants, and sodium dichloro-isocyanurate, as an active chlorine carrier, Percarbonate and peroxycarboxylic acids and their salts such as dodecane peroxidicarboxylic acid or magnesium peroxiphthalate can be included.

Das Geschirrspülmittel gemäß der Erfindung zeichnet sich durch ein gutes Reinigungsvermögen auch bei kritischen An­schmutzungen wie angebrannten eiweißhaltigen Speiserück­ständen aus. Des Weiteren zeigt es eine hohe Chlor- oder Aktivsauerstoffstabilität und verursacht eine verhältnis­mäßig geringe Korrosion an empfindlichem Spülgut.The dishwashing detergent according to the invention is notable for good cleaning properties even in the case of critical soiling, such as burnt-on protein-containing food residues. Furthermore, it shows a high chlorine or active oxygen stability and causes a relatively low corrosion of sensitive washware.

Das erfindungsgemäße Geschirrspülmittel wird vorzugsweise in Haushaltsgeschirrspülmaschinen eingesetzt, kann aber auch in gewerblichen Spülmaschinen verwendet werden.The dishwashing detergent according to the invention is preferably used in household dishwashers, but can also be used in commercial dishwashers.

Die Konzentration des pulverförmigen Geschirrspülmittels gemäß der Erfindung in der Reinigungsflotte beträgt 3 bis 10 g/l, vorzugsweise 4 bis 5 g/l.The concentration of the powdered dishwashing detergent according to the invention in the cleaning liquor is 3 to 10 g / l, preferably 4 to 5 g / l.

Der mit dem erfindungsgemäßen Geschirrspülmittel in seiner Reinigungsflotte erzielbare pH-Wert ist in erster Linie vom Konzentrationsverhältnis von Natriumschichtsilikat zu Pro­tonendonator abhängig. Es wäre nun naheliegend, freie Schichtkieselsäure mit Alkalien zu kombinieren, um den gleichen pH-Wert in der Reinigungsflotte zu erhalten. Es hat sich jedoch herausgestellt, daß trotz gleichen pH-Wer­tes in der Reinigungsflotte bei der Kombination Schichtkie­selsäure/Alkalien nicht der Reinigungserfolg wie mit dem erfindungsgemäßen Geschirrspülmittel erreicht werden kann.The pH value which can be achieved in the cleaning liquor of the dishwashing detergent according to the invention is primarily dependent on the concentration ratio of layered sodium silicate to proton donor. It would now be obvious to combine free layered silica with alkalis in order to maintain the same pH value in the cleaning liquor. It has been found, however, that despite the same pH value in the cleaning liquor in the case of the combination of layered silica / alkalis, the cleaning success achieved with the dishwashing detergent according to the invention cannot be achieved.

Der pH-Wert von wäßrigen Lösungen der Geschirrspülmittel wurde wie folgt ermittelt:
10 g des Geschirrspülmittels wurden in einen 100 ml Meßkol­ben eingewogen, 80 ml entmineralisiertes Wasser zugesetzt und während 1 Stunde mit einem Magnetrührer bei Raumtempe­ratur kräftig, aber unter Vermeidung von Schaumbildung ge­rührt. Nach Entfernen des Magnetrührers wurde der Meßkolben bis zur Marke mit entmineralisiertem Wasser aufgefüllt, die Lösung durchmischt und sofort zentrifugiert. Die pH-Wert-­Messungen wurden unmittelbar danach mit einer Glaselektrode vorgenommen.The pH of aqueous dishwashing detergent solutions was determined as follows:
10 g of the dishwashing detergent were weighed into a 100 ml volumetric flask, 80 ml of demineralized water were added and the mixture was stirred vigorously for 1 hour using a magnetic stirrer at room temperature but avoiding foaming. After removing the magnetic stirrer, the volumetric flask was filled to the mark with demineralized water, the solution was mixed and immediately centrifuged. The pH measurements were carried out immediately afterwards with a glass electrode.

Der pH-Wert der Reinigungsflotten wurde nach Abzentrifugie­ren des Feststoffes auch unmittelbar danach mit Hilfe einer Glaselektrode ermittelt.After the solid had been centrifuged off, the pH of the cleaning liquors was determined immediately afterwards with the aid of a glass electrode.

Um die vorteilhaften Eigenschaften des erfindungsgemäßen Geschirrspülmittel unter Beweis zu stellen, wurden die fol­genden Mischungen A bis M hergestellt und geprüft, wobei die Mischungen A bis D Geschirrspülmittel gemäß dem Stand der Technik entsprechen, während die Mischungen E bis M Ge­schirrspülmittel gemäß der Erfindung sind:

  • A 30 Gewichts% Natriumtriphosphat, teilhydratisiert
    57 Gewichts% Natriummetasilikat, wasserfrei
    10 Gewichts% Soda, wasserfrei
    2 Gewichts% Natriumdichlorisocyanurat · 2 H₂O
    1 Gewichts% modifizierter Fettalkoholpolyglykolether
  • B 50 Gewichts% Zeolith A
    40 Gewichts% Natriummetasilikat, wasserfrei
    6 Gewichts% Natriumsulfat, wasserfrei
    2 Gewichts% Natriumdichlorisocyanurat · 2 H₂O
  • C 50 Gewichts% kristallines Natriumschichtsilikat
    40 Gewichts% Natriummetasilikat, wasserfrei
    6 Gewichts% Natriumsulfat, wasserfrei
    2 Gewichts% Natriumdichlorisocyanurat · 2 H₂O
    2 Gewichts% modifizierter Fettalkoholpolyglycolether
  • D 40 Gewichts% kristallines Natriumschichtsilikat
    28 Gewichts% Natriumsulfat, wasserfrei
    10 Gewichts% Soda, wasserfrei
    15 Gewichts% Natriumhydroxid
    2 Gewichts% modifizierter Fettalkoholpolyglycolether
    1 Gewichts% Natriumdichlorisocyanurat · 2 H₂O
    4 Gewichts% Maleinsäureanhydrid-Methylvinylether-­Copolymerisat, Natriumsalz (z.B. ® Soka­lan CP 2 der Fa. BASF AG)
  • E 30 Gewichts% kristallines Natriumschichtsilikat
    33 Gewichts% Natriumhydrogencarbonat
    30 Gewichts% Natriumtriphosphat
    4 Gewichts% Copolymer auf Basis Maleinsäureanhydrid, Natriumsalz (ca. 55 % Wirksubstanz; z.B. ® Sokalan PM 10 der Fa. BASF AG)
    2 Gewichts% modifizierter Fettalkoholpolyglycolether
    1 Gewichts% Natriumdichlorisocyanurat · 2 H₂O
  • F 30 Gewichts% kristallines Natriumschichtsilikat
    20 Gewichts% Dinatrium-dihydrogen-diphosphat
    10 Gewichts% Natriumtriphosphat
    4 Gewichts% modifizierte Polyacrylsäure (Molgewicht = 20 000, 35 % Wirksubstanz; z.B. ® Sokalan CP 13 S der Fa. BASF AG)
    2 Gewichts% modifizierter Fettalkoholpolyglycolether
    1 Gewichts% Natriumdichlorisocyanurat · 2 H₂O
    33 Gewichts% Natriumsulfat, wasserfrei
  • G 30 Gewichts% kristallines Natriumschichtsilikat
    16 Gewichts% Butyl/Ethylenglykol-Phosphorsäureester (z.B. Knapsack-Reinigerkomponente GB der Fa. Hoechst AG)
    15 Gewichts% Natriumtriphosphat
    4 Gewichts% modifizierte Polyacrylsäure, Natriumsalz (Molgewicht = 70 000, 40 % Wirksubstanz; z.B. ® Sokalan CP 5 der Fa. BASF AG)
    2 Gewichts% modifizierter Fettalkoholpolyglycolether
    1 Gewichts% Natriumdichlorisocyanurat · 2 H₂O
    32 Gewichts% Natriumsulfat, wasserfrei
  • H 60 Gewichts% kristallines Natriumschichtsilikat
    35 Gewichts% Natriumhydrogencarbonat
    2 Gewichts% modifizierter Fettalkoholpolyglycolether
    3 Gewichts% Natriumdichlorisocyanurat · 2 H₂O
  • I 40 Gewichts% kristallines Natriumschichtsilikat
    27 Gewichts% Natriumhydrogensulfat
    20 Gewichts% Natriumtriphosphat
    1 Gewichts% modifizierter Fettalkoholpolyglycolether
    12 Gewichts% Natriumpercarbonat
  • J 40 Gewichts% kristallines Natriumschichtsilikat
    26 Gewichts% 2-Phosphono-butan-1,2,4-tricarbonsäure (50 % Wirksubstanz ; z.B. ® Bayhibit-AM der Fa. Bayer AG)
    31 Gewichts% Natriumsulfat, wasserfrei
    2 Gewichts% modifizierter Fettalkoholpolyglycolether
    1 Gewichts% Natriumdichlorisocyanurat · 2 H₂O
  • K 30 Gewichts% kristallines Natriumschichtsilikat
    30 Gewichts% Natriumtriphosphat
    14 Gewichts% Citronensäure-monohydrat
    2 Gewichts% modifizierter Fettalkoholpolyglycolether
    1 Gewichts% Natriumdichlorisocyanurat · 2 H₂O
    23 Gewichts% Natriumsulfat, wasserfrei
  • L 40 Gewichts% kristallines Natriumschichtsilikat
    14 Gewichts% Phosphorsäure 85 %ig
    40 Gewichts% Natriumsulfat, wasserfrei
    2 Gewichts% modifizierte Polyacrylsäure (Natriumsalz; z.B. ® Sokalan CP 10 der Fa. BASF AG)
    2 Gewichts% Natriumdichlorisocyanurat · 2 H₂O
    2 Gewichts% modifizierter Fettalkoholpolyglycolether
  • M 30 Gewichts% kristallines Natriumschichtsilikat
    30 Gewichts% Natriumtriphosphat
    14 Gewichts% eines Gemisches aus max. 33 % Adipin-, max. 50 % Glutar- und max. 31 % Bern­steinsäure (® Sokalan DCS der Fa. BASF AG)
    2 Gewichts% modifizierter Fettalkoholpolyglycolether
    2 Gewichts% Natriumdichlorisocyanurat · 2 H₂O
    22 Gewichts% Natriumsulfat
To the advantageous properties of the invention To demonstrate dishwashing detergents, the following mixtures A to M were produced and tested, mixtures A to D corresponding to dishwashing detergents according to the prior art, while mixtures E to M are dishwashing detergents according to the invention:
  • A 30% by weight sodium triphosphate, partially hydrated
    57% by weight sodium metasilicate, anhydrous
    10% by weight soda, anhydrous
    2% by weight sodium dichloroisocyanurate · 2 H₂O
    1% by weight modified fatty alcohol polyglycol ether
  • B 50% by weight of zeolite A
    40% by weight sodium metasilicate, anhydrous
    6% by weight sodium sulfate, anhydrous
    2% by weight sodium dichloroisocyanurate · 2 H₂O
  • C 50% by weight crystalline layered sodium silicate
    40% by weight sodium metasilicate, anhydrous
    6% by weight sodium sulfate, anhydrous
    2% by weight sodium dichloroisocyanurate · 2 H₂O
    2% by weight modified fatty alcohol polyglycol ether
  • D 40% by weight crystalline layered sodium silicate
    28% by weight sodium sulfate, anhydrous
    10% by weight soda, anhydrous
    15% by weight sodium hydroxide
    2% by weight modified fatty alcohol polyglycol ether
    1% by weight sodium dichloroisocyanurate · 2 H₂O
    4% by weight maleic anhydride-methyl vinyl ether copolymer, sodium salt (for example ® Sokalan CP 2 from BASF AG)
  • E 30% by weight crystalline layered sodium silicate
    33% by weight sodium hydrogen carbonate
    30% by weight sodium triphosphate
    4% by weight copolymer based on maleic anhydride, sodium salt (approx. 55% active substance; e.g. ® Sokalan PM 10 from BASF AG)
    2% by weight modified fatty alcohol polyglycol ether
    1% by weight sodium dichloroisocyanurate · 2 H₂O
  • F 30% by weight crystalline layered sodium silicate
    20% by weight disodium dihydrogen diphosphate
    10% by weight sodium triphosphate
    4% by weight modified polyacrylic acid (molecular weight = 20,000, 35% active substance; for example ® Sokalan CP 13 S from BASF AG)
    2% by weight modified fatty alcohol polyglycol ether
    1% by weight sodium dichloroisocyanurate · 2 H₂O
    33% by weight sodium sulfate, anhydrous
  • G 30% by weight crystalline layered sodium silicate
    16% by weight butyl / ethylene glycol phosphoric acid ester (eg Knapsack cleaner component GB from Hoechst AG)
    15% by weight sodium triphosphate
    4% by weight of modified polyacrylic acid, sodium salt (molecular weight = 70,000, 40% active substance; for example ® Sokalan CP 5 from BASF AG)
    2% by weight modified fatty alcohol polyglycol ether
    1% by weight sodium dichloroisocyanurate · 2 H₂O
    32% by weight sodium sulfate, anhydrous
  • H 60% by weight crystalline layered sodium silicate
    35% by weight sodium hydrogen carbonate
    2% by weight modified fatty alcohol polyglycol ether
    3% by weight sodium dichloroisocyanurate · 2 H₂O
  • I 40% by weight crystalline layered sodium silicate
    27% by weight sodium hydrogen sulfate
    20% by weight sodium triphosphate
    1% by weight modified fatty alcohol polyglycol ether
    12% by weight sodium percarbonate
  • J 40% by weight crystalline layered sodium silicate
    26% by weight 2-phosphonobutane-1,2,4-tricarboxylic acid (50% active substance; e.g. ® Bayhibit-AM from Bayer AG)
    31% by weight sodium sulfate, anhydrous
    2% by weight modified fatty alcohol polyglycol ether
    1% by weight sodium dichloroisocyanurate · 2 H₂O
  • K 30% by weight crystalline layered sodium silicate
    30% by weight sodium triphosphate
    14% by weight citric acid monohydrate
    2% by weight modified fatty alcohol polyglycol ether
    1% by weight sodium dichloroisocyanurate · 2 H₂O
    23% by weight sodium sulfate, anhydrous
  • L 40% by weight crystalline layered sodium silicate
    14% by weight phosphoric acid 85%
    40% by weight sodium sulfate, anhydrous
    2% by weight modified polyacrylic acid (sodium salt; e.g. ® Sokalan CP 10 from BASF AG)
    2% by weight sodium dichloroisocyanurate · 2 H₂O
    2% by weight modified fatty alcohol polyglycol ether
  • M 30% by weight crystalline layered sodium silicate
    30% by weight sodium triphosphate
    14% by weight of a mixture of max. 33% adipine, max. 50% glutar and max. 31% succinic acid (® Sokalan DCS from BASF AG)
    2% by weight modified fatty alcohol polyglycol ether
    2% by weight sodium dichloroisocyanurate · 2 H₂O
    22% by weight sodium sulfate

Beispiel 1example 1

Die Mischungen A bis M wurden in Haushaltsgeschirrspülma­schinen der Fa. MIELE auf ihre Reinigungswirkung unter Mit­verwendung eines Klarspülers geprüft. In der Tabelle 1 sind die Ergebnisse der Prüfung angegeben, wobei in der ersten Zeile der pH-Wert einer 10 %igen wäßrigen Lösung der Mi­schung, in der zweiten Zeile der pH-Wert der Reinigungs­flotte (5 g Mischung/l Wasser) und der Reinigungsindex nach DIN 44 990, Teil 2 (Entwurf, Dezember 1980) angegeben sind. Tabelle 1 Stand der Technik Gemäß der Erfindung Mischung A B C D E F G H I J K L M pH (10 g/100 ml) 13,1 13,1 12,3 13,3 10,4 10,3 10,2 10,3 10,4 10,3 10,1 10,4 10,4 pH (5 g/l) 12,2 11,9 11,2 11,9 9,9 9,6 9,6 9,9 9,5 9,4 9,7 9,9 9,8 Reinigungsindex 4,2 4,0 4,4 4,4 4,3 4,0 3,9 4,3 4,4 4,2 3,8 4,0 4,0 The mixtures A to M were tested in household dishwashers from MIELE for their cleaning action using a rinse aid. Table 1 shows the results of the test, the first line being the pH of a 10% aqueous solution of the mixture, the second line being the pH of the cleaning liquor (5 g of mixture / l of water) and the cleaning index according to DIN 44 990, Part 2 (draft, December 1980). Table 1 State of the art According to the invention mixture A B C. D E F G H I. J K L M pH (10 g / 100 ml) 13.1 13.1 12.3 13.3 10.4 10.3 10.2 10.3 10.4 10.3 10.1 10.4 10.4 pH (5 g / l) 12.2 11.9 11.2 11.9 9.9 9.6 9.6 9.9 9.5 9.4 9.7 9.9 9.8 Cleaning index 4.2 4.0 4.4 4.4 4.3 4.0 3.9 4.3 4.4 4.2 3.8 4.0 4.0

Ein Vergleich der Reinigungsindices zeigt, daß die erfin­dungsgemäßen Geschirrspülmittel im Vergleich zu Rezepturen nach dem Stand der Technik trotz erheblicher Senkung des pH-Wertes in den Spülflotten vergleichbare Reinigungserfol­ge aufweisen.A comparison of the cleaning indices shows that the dishwashing detergents according to the invention have comparable cleaning successes in comparison to recipes according to the prior art, despite a considerable reduction in the pH in the washing liquors.

Beispiel 2Example 2

An Edelstahlbestecken und Gläsern verschiedener Provenienz, Zusammensetzung und Form wurde die korrosive Schädigung geprüft. Porzellanteller und -tassen dienten als Ballast zur Auffüllung der vorgeschriebenen Spülgutmenge von 12 Maßgedecken nach DIN 44 990, Teil 100 (Entwurf, Dezember 1981).The corrosive damage was tested on stainless steel cutlery and glasses of different provenance, composition and shape. Porcelain plates and cups served as ballast for filling the prescribed amount of 12 items to be washed according to DIN 44 990, part 100 (draft, December 1981).

Zur Schadensbeurteilung diente eine in 5 Stufen unterteilte Skala, nach der die visuelle Auswertung der Versuche nach 125, 250, 500 und 1000 Spülgängen vorgenommen wurde. Die Skala erlaubte die Festsetzung von Zwischenstufen in Ein­heiten von 0,5 (0 = ungeschädigt; 4 - Totalschaden).A scale divided into 5 levels was used to assess the damage, according to which the tests were evaluated visually after 125, 250, 500 and 1000 rinse cycles. The scale allowed the setting of intermediate levels in units of 0.5 (0 = undamaged; 4 - total loss).

Zur Korrosionsprüfung wurden die Mischungen nach dem Stand der Technik A und B sowie die erfindungsgemäßen Geschirr­spülmittel gemäß E, F, H und K herangezogen. Die ermittel­ten durchschnittlichen Schadensbewertungen nach 1000 Spül­gängen sind in Tabelle 2 zusammengestellt. Es wurde eine automatisch arbeitende Haushaltsgeschirrspülmaschine be­nutzt, die nach jedem Spülzyklus die Maschinentür für 30 Minuten öffnet, damit das Spülgut abkühlt. Im Reinigungs­gang wurden 5 g Mischung/l Spülflotte und im Klarspülgang 3 ml handelsüblicher Klarspüler dosiert. Es wurde nichtan­geschmutztes Spülgut eingesetzt. Tabelle 2 Stand der Technik Gemäß der Erfindung Mischung A B E F H K Glas 0,6 1,8 0,6 0,8 0,5 0,7 Besteck 1,5 0,7 0,4 0,1 0,0 0,5 Summe 2,1 2,5 1,0 0,9 0,5 1,2 The mixtures according to the prior art A and B and the dishwashing detergents according to the invention according to E, F, H and K were used for the corrosion test. The determined average damage ratings after 1000 rinses are summarized in Table 2. An automatic household dishwasher was used, which opens the machine door for 30 minutes after each wash cycle so that the dishes cool down. 5 g of mixture / l of rinsing liquor were metered into the cleaning cycle and 3 ml of commercially available rinse aid into the rinse cycle. Unwashed dishes were used. Table 2 State of the art According to the invention mixture A B E F H K Glass 0.6 1.8 0.6 0.8 0.5 0.7 cutlery 1.5 0.7 0.4 0.1 0.0 0.5 total 2.1 2.5 1.0 0.9 0.5 1.2

Beispiel 3Example 3

Die Mischungen nach dem Stand der Technik A und B sowie die erfindungsgemäßen Geschirrspülmittel gemäß E, F, H, I und K wurden 3 Monate im Labor offen an der Luft gelagert. Danach wurde der Verlust an Aktivchlor bzw. Aktivsauerstoff im Vergleich zum Gehalt unmittelbar nach Herstellung der Mi­schungen bestimmt. Die prozentuale Abnahme ist in Tabelle 3 aufgezeigt. Tabelle 3 Stand der Technik Gemäß der Erfindung Mischung A B E F H I K Verlust an Aktivchlor in % 39,0 41,5 15,1 9,5 19,0 - 12,1 Verlust an Aktivsauerstoff in % - - - - - 19,5 - The mixtures according to the prior art A and B and the dishwashing detergents according to the invention according to E, F, H, I and K were stored in the open air in the laboratory for 3 months. The loss of active chlorine or active oxygen compared to the content immediately after the mixtures had been prepared was then determined. The percentage decrease is shown in Table 3. Table 3 State of the art According to the invention mixture A B E F H I. K Active chlorine loss in% 39.0 41.5 15.1 9.5 19.0 - 12.1 Loss of active oxygen in% - - - - - 19.5 -

Hieraus ergibt sich, daß die Lagerstabilität der erfin­dungsgemäßen Geschirrspülmittel in bezug auf Aktivchlor bzw. Aktivsauerstoff größer ist als bei entsprechenden Mi­schungen nach dem Stand der Technik.It follows from this that the storage stability of the dishwashing detergents according to the invention with respect to active chlorine or active oxygen is greater than with corresponding mixtures according to the prior art.

Claims (5)

1. Geschirrspülmittel auf der Basis eines kristallinen Al­kalischichtsilikates, dadurch gekennzeichnet, daß es ein kristallines, weitgehend wasserunlösliches Natrium­schichtsilikat mit einem Molverhältnis SiO₂/Na₂O von (1,9 bis 3,5) : 1 in Kombination mit einem Protonendona­tor enthält, dessen 0,5 gewichtsprozentige wäßrige Lö­sung einen pH-Wert von weniger als 10 aufweist.1. Dishwashing detergent based on a crystalline alkali layer silicate, characterized in that it contains a crystalline, largely water-insoluble sodium layer silicate with a SiO₂ / Na₂O molar ratio of (1.9 to 3.5): 1 in combination with a proton donor, the 0.5 weight percent aqueous solution has a pH of less than 10. 2. Geschirrspülmittel nach Anspruch 1, enthaltend
20 bis 60 Gewichts% des kristallinen Schichtsilikates
10 bis 40 Gewichts% des Protonendonators
1 bis 2 Gewichts% eines Tensides
1 bis 30 Gewichts% eines Aktivchlor- oder Aktivsau­erstoffträgers
0 bis 7 Gewichts% eines Dispergiermittels
0 bis 50 Gewichts% eines Alkaliphosphates und/oder eines Alkalipolyphosphates und
0 bis 40 Gewichts% eines Füllstoffes.2. Dishwashing detergent according to claim 1, containing
20 to 60% by weight of the crystalline layered silicate
10 to 40% by weight of the proton donor
1 to 2% by weight of a surfactant
1 to 30% by weight of an active chlorine or active oxygen carrier
0 to 7% by weight of a dispersant
0 to 50% by weight of an alkali phosphate and / or an alkali polyphosphate and
0 to 40% by weight of a filler. 3. Geschirrspülmittel nach Anspruch 1 oder 2, dadurch ge­kennzeichnet, daß als Protonendonator Mineralsäuren und/oder Polycarbonsäuren und/oder Hydroxypolycarbonsäu­ren und/oder Phosphonsäuren und/oder deren saure Salze bzw. Ester enthalten sind.3. Dishwashing detergent according to claim 1 or 2, characterized in that mineral acids and / or polycarboxylic acids and / or hydroxypolycarboxylic acids and / or phosphonic acids and / or their acidic salts or esters are contained as proton donors. 4. Geschirrspülmittel nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es 25 bis 35 Ge­wichts% kristallines Alkalischichtsilikat enthält.4. Dishwashing detergent according to at least one of claims 1 to 3, characterized in that it contains 25 to 35% by weight of crystalline alkali layer silicate. 5. Geschirrspülmittel nach Anspruch 2, dadurch gekennzeich­net, daß es 10 bis 30 Gewichts% Alkaliphosphat und/oder Alkalipolyphosphat enthält.5. Dishwashing detergent according to claim 2, characterized in that it contains 10 to 30% by weight of alkali metal phosphate and / or alkali metal polyphosphate.
EP90115975A 1989-09-08 1990-08-21 Dishwashing composition comprising layered silicates Expired - Lifetime EP0416366B1 (en)

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WO1992018594A1 (en) * 1991-04-23 1992-10-29 The Procter & Gamble Company Particulate detergent compositions
EP0550077A1 (en) * 1992-01-03 1993-07-07 The Procter & Gamble Company Granular laundry bleaching composition
WO1994016045A1 (en) * 1993-01-18 1994-07-21 Unilever N.V. Machine dishwashing composition containing a corrosion inhibitor
WO1996012783A1 (en) * 1994-10-20 1996-05-02 Henkel Kommanditgesellschaft Auf Aktien Crystalline layered silicates in washing agents for use in dish washers
EP0753568A2 (en) * 1995-07-11 1997-01-15 Hoechst Aktiengesellschaft Granular builder for detergent compositions
WO1998002515A1 (en) * 1996-07-16 1998-01-22 Rhodia Chimie Dishwasher detergent composition containing an anticorrosive agent
FR2751340A1 (en) * 1996-07-16 1998-01-23 Rhone Poulenc Chimie New detergent composition for dishwashers
WO1999057237A1 (en) * 1998-04-30 1999-11-11 Henkel Kommanditgesellschaft Auf Aktien Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates
US6463939B1 (en) 1999-02-05 2002-10-15 Unilever Home & Personal Care, Usa, Division Of Conopco, Inc. Dish washing process

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US5663136A (en) * 1992-06-15 1997-09-02 The Procter & Gamble Company Process for making compact detergent compositions
US6391839B1 (en) * 1992-08-01 2002-05-21 The Procter & Gamble Company Detergent bleach compositions containing layered silicate builder and percarbonate stabilized by EDDS
GB9216410D0 (en) * 1992-08-01 1992-09-16 Procter & Gamble Detergent compositions
US5378242A (en) * 1992-12-22 1995-01-03 Apollo Chemical Company Liquid alkali for soaping off reactive dyes
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CA2161083C (en) * 1993-04-27 2000-06-13 Eugene Steven Sadlowski Liquid or granular automatic dishwashing detergent compositions
DE4327884A1 (en) * 1993-08-19 1995-02-23 Hoechst Ag Process for the preparation of a mixture of sodium silicates and other salts and the use of the mixture
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WO1996009367A1 (en) * 1994-09-22 1996-03-28 Crosfield Limited Silicates granules and method for manufacturing the same
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US6835702B2 (en) 2000-11-07 2004-12-28 Ecolab Inc. Compositions and methods for mitigating corrosion of applied color designs
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EP1853690A1 (en) * 2005-03-04 2007-11-14 The Procter and Gamble Company Automatic dishwashing composition with corrosion inhibitors
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WO1992018594A1 (en) * 1991-04-23 1992-10-29 The Procter & Gamble Company Particulate detergent compositions
EP0550077A1 (en) * 1992-01-03 1993-07-07 The Procter & Gamble Company Granular laundry bleaching composition
WO1994016045A1 (en) * 1993-01-18 1994-07-21 Unilever N.V. Machine dishwashing composition containing a corrosion inhibitor
WO1996012783A1 (en) * 1994-10-20 1996-05-02 Henkel Kommanditgesellschaft Auf Aktien Crystalline layered silicates in washing agents for use in dish washers
EP0753568A3 (en) * 1995-07-11 1998-01-28 Clariant GmbH Granular builder for detergent compositions
EP0753568A2 (en) * 1995-07-11 1997-01-15 Hoechst Aktiengesellschaft Granular builder for detergent compositions
US5874397A (en) * 1995-07-11 1999-02-23 Hoechst Aktiengesellschaft Granular detergent builder
FR2751340A1 (en) * 1996-07-16 1998-01-23 Rhone Poulenc Chimie New detergent composition for dishwashers
FR2751341A1 (en) * 1996-07-16 1998-01-23 Rhone Poulenc Chimie DETERGENT COMPOSITION FOR DISHWASHER, ITS USE IN DISHWASHER AGAINST CORROSION OF THE DISHES AND METHOD FOR NON-CORROSIVE WASHING OF THE DISHWASHER
WO1998002515A1 (en) * 1996-07-16 1998-01-22 Rhodia Chimie Dishwasher detergent composition containing an anticorrosive agent
US6299701B1 (en) 1996-07-16 2001-10-09 Rhone-Poulenc Chimie Dishwasher detergent composition containing an anticorrosive agent
WO1999057237A1 (en) * 1998-04-30 1999-11-11 Henkel Kommanditgesellschaft Auf Aktien Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates
US6462006B1 (en) 1998-04-30 2002-10-08 Henkel Kommanditgesellschaft Auf Aktien Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates
US6463939B1 (en) 1999-02-05 2002-10-15 Unilever Home & Personal Care, Usa, Division Of Conopco, Inc. Dish washing process

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CA2023240A1 (en) 1991-03-09
CA2023240C (en) 2000-04-11
PT95225A (en) 1991-06-25
EP0416366A3 (en) 1992-04-01
ATE130027T1 (en) 1995-11-15
ES2079408T3 (en) 1996-01-16
US5066415A (en) 1991-11-19
DE3929896A1 (en) 1991-03-14
PT95225B (en) 1997-06-30
JPH03100100A (en) 1991-04-25
DE59009851D1 (en) 1995-12-14
JP2886645B2 (en) 1999-04-26
EP0416366B1 (en) 1995-11-08
DK0416366T3 (en) 1996-03-04

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