EP0267371B1 - Phosphate-free dishwashing agent - Google Patents

Phosphate-free dishwashing agent Download PDF

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Publication number
EP0267371B1
EP0267371B1 EP87110811A EP87110811A EP0267371B1 EP 0267371 B1 EP0267371 B1 EP 0267371B1 EP 87110811 A EP87110811 A EP 87110811A EP 87110811 A EP87110811 A EP 87110811A EP 0267371 B1 EP0267371 B1 EP 0267371B1
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weight
builder
sodium
dishwashing agent
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German (de)
French (fr)
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EP0267371A1 (en
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Hannsjörg Dr. Ulrich
Lothar Westermann
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Hoechst AG
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Hoechst AG
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    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the present invention relates to dishwashing detergents, in particular those for machine dishwashing, which contain sodium silicate as a builder and also co-builders and active chlorine carriers and which are free of phosphates.
  • dishwashing detergents for the automatic washing of household dishes or crockery and cutlery in commercial canteen kitchens contain, as components, builders, alkali carriers, active chlorine carriers, surfactants, perfumes and, if appropriate, fillers.
  • Polyphosphates preferably sodium triphosphate (NTPP), as alkali carriers of water-soluble silicates, preferably sodium metasilicate, caustic soda or sodium carbonate, as active chlorine carriers either chlorine bleach or products from the series of chloroisocyanurates and as surfactants are low-foaming, chlorine-stable block polymers with ethylene and propylene oxide groups modified fatty alcohol polyglycol ether used.
  • NTPP sodium triphosphate
  • alkali carriers of water-soluble silicates preferably sodium metasilicate, caustic soda or sodium carbonate
  • active chlorine carriers either chlorine bleach or products from the series of chloroisocyanurates and as surfactants are low-foaming, chlorine-stable block polymers with ethylene and propylene oxide groups modified fatty alcohol polyglycol ether used.
  • DE-A1-34 13 571 already describes crystalline layered sodium silicates for water softening, which have the composition NaMSi x 0 2x + 1 . y correspond to H20, where M is sodium or hydrogen, x is 1.9 to 4 and y is 0 to 20.
  • co-builder 0.1-3% by weight is used if this is preferably in dry, powdery form and 0.3-7.5% by weight if this co-builder is in liquid form.
  • Polycarboxylates such as polyacetal carboxylates or maleic anhydride-acrylic acid copolymers or maleic anhydride-methylene vinyl ether or their sodium salts, are preferably suitable as co-builders.
  • the other dishwashing components such as fillers, alkali carriers, surfactants and active chlorine carriers and, if appropriate, perfumes, can be substances which are already sufficiently known for these purposes.
  • sodium sulfate as fillers preferably in anhydrous form, sodium carbonate, caustic soda or water-soluble alkali silicates as alkali carrier, chlorine-stable block polymers of long-chain aliphatic alcohols with ethylene oxide or propylene oxide groups or modified fatty alcohol polyglycol ethers as surfactants and sodium dichloroisocyanurate or bleaching liquor as active chlorine carriers.
  • the phosphate-free mixtures according to the invention are notable for very good cleaning action, extremely low corrosion on the items to be washed or the machine and for high chlorine stability.
  • the powdery mixtures are free-flowing even after months of open storage in the laboratory air (see Table 2 below).
  • phyllosilicates used according to the invention have the favorable property of not or only slightly abrasive, which in particular enables gentle rinsing of glasses.
  • a comparison of the cleaning indices shows that, on average, standard cleaning successes are achieved, and the working pH can even be reduced by 0.5 to 1 step.
  • White porcelain plates and cups, stainless steel cutlery from various manufacturers and glasses of various compositions and shapes were tested as items to be washed.
  • a table divided into 5 damage levels is used to determine any damage, and after visual evaluation of the tests after 125, 250, 500 and 1,000 rinse cycles was used to make a judgment.
  • Formulations A, B, C, D and E were used for the corrosion test.
  • the average damage ratings found for 500 wash cycles are shown in Table 3.
  • An automatically operating household machine was used as the machine, which opens the machine door for 1 hour between each washing cycle so that the items to be washed dry completely.
  • the water hardness was between 2 ° and 7 ° d, the rinse temperature at 62 - 66 ° C, the total amount of water per rinse cycle is 28 I, of which approx. 6 I in the cleaning cycle with a dosage of 30 g detergent and 3 ml rinse aid in the rinse cycle .

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Glass Compositions (AREA)

Abstract

1. Claims for the Contracting States : AT, BE, CH, DE, FR, IT, LI, NL, SE A phosphate-free dishwashing agent containing, as a builder, sodium silicate and also, as a co-builder, a polymeric and/or copolymeric carboxylic acid or a salt of this polymeric carboxylic acid and an active chlorine carrier, which contains, as a sodium silicate builder, crystalline, sheet-like sodium silicate of the formula Na M Six O2x+1 .yH2 O in which M denotes sodium or hydrogen, x denotes a number from 1.9 to 4 and y denotes a number from 0 to 20. 1. Claims for the Contracting State : ES Process for producing phosphate-free dishwashing agent containing, as a builder, sodium silicate and also, as co-builder, a polymeric and/or copolymeric carboxylic acid and an active chlorine carrier, characterized in that, as a sodium silicate builder, crystalline, sheet-like sodium silicate of the general formula Na M Six O2x+1 .yH2 O in which M denotes sodium or hydrogen, x denotes a number from 1.9 to 4 and y denotes a number from 0 to 20, is worked into.

Description

Die vorliegende Erfindung betrifft Geschirrspülmittel, insbesondere solche für das maschinelle Spülen von Geschirr, die als Builder Natriumsilikat sowie Co-Builder und Aktivchlorträger enthalten und die frei von Phosphaten sind.The present invention relates to dishwashing detergents, in particular those for machine dishwashing, which contain sodium silicate as a builder and also co-builders and active chlorine carriers and which are free of phosphates.

Handelsübliche Geschirrspülmittel für das maschinelle Spülen von Haushaltsgeschirr oder Geschirr und Bestekken gewerblicher Großküchen enthalten als Komponenten Builder, Alkaliträger, Aktivchlorträger, Tenside, Parfüme und gegebenenfalls Füllmittel.Commercially available dishwashing detergents for the automatic washing of household dishes or crockery and cutlery in commercial canteen kitchens contain, as components, builders, alkali carriers, active chlorine carriers, surfactants, perfumes and, if appropriate, fillers.

Wichtig ist dabei, je nach Verwendungszweck, eine ausgewogene Mischung der einzelnen Komponenten. Als Builder werden üblicherweise Polyphosphate, vorzugsweise Natriumtriphosphat (NTPP), als Alkaliträger wasserlöslicher Silikate, vorzugsweise Natriummetasilikat, Ätznatron oder Natriumcarbonat, als Aktivchlorträger entweder Chlorbleichlauge oder Produkte aus der Reihe der Chlorisocyanurate und als Tenside schwach schäumende, möglichst chlorstabile Blockpolymerisate mit Ethylen-und Propylenoxidgruppen oder modifizierte Fettalkoholpolyglykolether verwendet.Depending on the intended use, it is important to have a balanced mixture of the individual components. Polyphosphates, preferably sodium triphosphate (NTPP), as alkali carriers of water-soluble silicates, preferably sodium metasilicate, caustic soda or sodium carbonate, as active chlorine carriers either chlorine bleach or products from the series of chloroisocyanurates and as surfactants are low-foaming, chlorine-stable block polymers with ethylene and propylene oxide groups modified fatty alcohol polyglycol ether used.

Alle genannten Produkte sind relativ leicht wasserlöslich und werden bei Temperaturen zwischen 50 und 70°C verwendet.All of the products mentioned are relatively easily water-soluble and are used at temperatures between 50 and 70 ° C.

Im Zuge der Entlastung der Abwässer von Phosphaten wurde schon versucht, das Buildersystem in Geschirrspülmitteln durch lösliche oder unlösliche Austauschstoffe zu ersetzen. Unter den löslichen Produkten wurden z.B. Citrate oder Polycarbonsäuren, wie z.B. Polyacrylsäure, aber auch Nitrilotriessigsäure (NTE) oder Ethylendiamintetraessigsäure (EDTE) sowie deren Salze, oder auch verschiedene Phosphonsäuren und Phosphonate probiert. Unter den unlöslichen Austauschstoffen stehen bisher Zeolith A und Bentonite zur Diskussion.In the course of relieving the waste water from phosphates, attempts have already been made to replace the builder system in dishwashing detergents with soluble or insoluble substitutes. Among the soluble products e.g. Citrates or polycarboxylic acids, e.g. Tried polyacrylic acid, but also nitrilotriacetic acid (NTE) or ethylenediaminetetraacetic acid (EDTE) and their salts, or various phosphonic acids and phosphonates. So far, zeolite A and bentonite have been discussed among the insoluble substitutes.

Alle erwähnten Austauschstoffe für NTPP haben aber bisher technische Nachteile aufgezeigt, die einem Einsatz in einem handelsüblichen Geschirrspülmittel entgegenstanden. Dieses waren z.T. schlechtere Reinigungswirkung, höhere Korrosion am Spülgut oder an den Maschinen, schlechte Lagerstabilität oder andere ungünstige Eigenschaften, wie Unverträglichkeit mit Aktivchlorträgern oder Neigung zum Verklumpen.So far, however, all of the substitutes mentioned for NTPP have shown technical disadvantages which prevented them from being used in a commercially available dishwashing detergent. Some of these were poorer cleaning effect, higher corrosion on the items to be washed or on the machines, poor storage stability or other unfavorable properties, such as incompatibility with active chlorine carriers or a tendency to clump.

In der DE-A1-34 13 571 sind bereits kristalline schichtförmige Natriumsilikate zur Wasserenthärtung beschrieben, welche der Zusammensetzung NaMSi x0 2x+1 . y H20 entsprechen, wobei M Natrium oder Wasserstoff bedeutet, x 1,9 bis 4 und y 0 bis 20 ist.DE-A1-34 13 571 already describes crystalline layered sodium silicates for water softening, which have the composition NaMSi x 0 2x + 1 . y correspond to H20, where M is sodium or hydrogen, x is 1.9 to 4 and y is 0 to 20.

Es wurde in diesem Zusammenhang auch schon vorgeschlagen, diese Produkte, beispielsweise zusammen mit Pentanatriumtriphosphat. Trinatriumnitrilotrisulfonat und/oder Zeolith A, oder auch mit Phosphonaten, Polycarboxylaten oder anderen amorphen oder kristallinen Silikaten, als Builder in Wasch-und Reinigungsmitteln, insbesondere Geschirrspülmitteln, einzusetzen.In this connection, it has also been proposed to use these products, for example together with pentasodium triphosphate. Use trisodium nitrilotrisulfonate and / or zeolite A, or also with phosphonates, polycarboxylates or other amorphous or crystalline silicates, as builders in washing and cleaning agents, in particular dishwashing agents.

Dieser Vorschlag ließ sich jedoch bisher nicht realisieren, da sich gezeigt hat, daß die genannten kristallinen, schichtförmigen Natriumsilikate zwar gute Wasserenthärter sind, sich aber als Builder in Geschirrspülmitteln nicht ohne weiteres eignen, da sie insbesondere auf Oberflächen von Gegenständen aus Glas oder Keramik, festhaftende Ablagerungen bilden, die auch durch Behandlung mit Säuren nicht wieder aufgelöst werden können.However, this proposal has not yet been able to be implemented, since it has been shown that the crystalline, layered sodium silicates mentioned are good water softeners, but are not readily suitable as builders in dishwashing detergents, since they adhere particularly to surfaces of glass or ceramic objects Form deposits that cannot be dissolved even by treatment with acids.

Überraschenderweise wurde nun gefunden, daß man diesen Nachteil überwinden kann, wenn man in phosphatfreien Geschirrspülmitteln, enthaltend als Builder Natriumsilikat sowie als Co-Builder eine polymere und/oder copolymere Carbonsäure oder ein Salz dieser polymeren Carbonsäure und Aktivchlorträger, als Natriumsilikat-Builder kristallines, schichtförmiges Natriumsilikat der allgemeinen Formel Na M Six02x+i ' yH20, in der M Natrium oder Wasserstoff, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 bedeuten, zugibt.Surprisingly, it has now been found that this disadvantage can be overcome if, in phosphate-free dishwashing detergents containing sodium silicate as a builder and as a co-builder, a polymeric and / or copolymeric carboxylic acid or a salt of this polymeric carboxylic acid and active chlorine carrier, as a sodium silicate builder, crystalline, layered Sodium silicate of the general formula Na M Six02x + i 'yH 2 0, in which M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20.

Vorzugsweise enthält ein erfindungsgemäßes Geschirrspülmittel:

  • 30-50 Gew.-% vorzugsweise 40 Gew.-%, des kristallinen Natriumschichtsilikates
  • 0,1-7,5 Gew.-% des Co-Builders
  • 0-45 Gew.-% eines Füllstoffs
  • 10-25 Gew.-% eines Alkaliträgers
  • 1-2 Gew.-% eines Tensides und
  • 1-5 Gew.-% des Aktivchlorträgers.
A dishwashing detergent according to the invention preferably contains:
  • 30-50% by weight, preferably 40% by weight, of the crystalline layered sodium silicate
  • 0.1-7.5% by weight of the co-builder
  • 0-45% by weight of a filler
  • 10-25% by weight of an alkali carrier
  • 1-2% by weight of a surfactant and
  • 1-5% by weight of the active chlorine carrier.

Dabei werden 0,1-3 Gew.-% Co-Builder eingesetzt, wenn dieser vorzugsweise in trockener, pulverförmiger Form vorliegt und 0,3-7,5 Gew.-%, wenn dieser Co-Builder in flüssiger Form vorliegt.0.1-3% by weight of co-builder is used if this is preferably in dry, powdery form and 0.3-7.5% by weight if this co-builder is in liquid form.

Als Co-Builder sind vorzugsweise geeignet Polycarboxylate, wie Polyacetalcarboxylate oder Maleinsäureanhydrid-acrylsäure-copolymerisate oder Maleinsäureanhydrid-methylen-vinylether bzw. deren Natriumsalze. Die übrigen Geschirrspülkomponenten, wie Füllstoffe, Alkaliträger, Tenside und Aktivchlorträger sowie gegebenenfalls Parfüme, können Stoffe sein, die für diese Zwecke bereits hinreichend bekannt sind.Polycarboxylates, such as polyacetal carboxylates or maleic anhydride-acrylic acid copolymers or maleic anhydride-methylene vinyl ether or their sodium salts, are preferably suitable as co-builders. The other dishwashing components, such as fillers, alkali carriers, surfactants and active chlorine carriers and, if appropriate, perfumes, can be substances which are already sufficiently known for these purposes.

So können z.B. als Füllstoffe Natriumsulfat, vorzugsweise in wasserfreier Form, als Alkaliträger Natriumcarbonat, Ätznatron oder wasserlösliche Alkalisilikate, als Tenside chlorstabile Blockpolymerisate langkettiger aliphatischer Alkohole mit Ethylenoxid- oder Propylenoxidgruppen oder modifizierte Fettalkoholpolyglykolether und als Aktivchlorträger Natriumdichlorisocyanurat oder Bleichlauge eingesetzt werden.For example, sodium sulfate as fillers, preferably in anhydrous form, sodium carbonate, caustic soda or water-soluble alkali silicates as alkali carrier, chlorine-stable block polymers of long-chain aliphatic alcohols with ethylene oxide or propylene oxide groups or modified fatty alcohol polyglycol ethers as surfactants and sodium dichloroisocyanurate or bleaching liquor as active chlorine carriers.

Die erfindungsgemäßen, phosphatfreien Mischungen zeichnen sich durch sehr gute Reinigungswirkung, äußerst geringe Korrosion am Spülgut oder der Maschine und durch hohe Chlorstabilität aus. Die pulverförmigen Gemische sind auch nach monatelanger offener Lagerung an der Laborluft gut rieselfähig (siehe nachfolgende Tabelle 2).The phosphate-free mixtures according to the invention are notable for very good cleaning action, extremely low corrosion on the items to be washed or the machine and for high chlorine stability. The powdery mixtures are free-flowing even after months of open storage in the laboratory air (see Table 2 below).

Im Vergleich zu dem ebenfalls unlöslichen Phosphataustauschstoff Zeolith haben erfindungsgemäß eingesetzte Schichtsilikate die günstige Eigenschaft, nicht oder nur wenig abrasiv zu wirken, was besonders eine schonende Spülung von Gläsern ermöglicht.In comparison to the likewise insoluble phosphate exchange zeolite, phyllosilicates used according to the invention have the favorable property of not or only slightly abrasive, which in particular enables gentle rinsing of glasses.

Folgende Beispiele sollen die vorteilhaften Eigenschaften der erfindungsgemäßen Mischungen unter Beweis stellen. Als Vergleich gelten marktübliche Spülmittel auf Phosphatbasis und Versuchsmischungen mit Zeolith A oder Schichtsilikat in Abwesenheit der erfindungsgemäß eingesetzten Co-Builder. Als Tensid wurde in allen Fällen ein Blockpolymerisat linearer C12 - C15 Alkohole mit 4 Propylenoxid- und 7 Ethylenoxidgruppen verwendet. Als Schichtsilikat diente ein Silikat, das der Zusammensetzung Na2Si2O5 entsprach und sich durch die folgenden charakteristischen Röntgenbeugungsreflexe auszeichnete:

  • d(10-8 cm)relative Intensitäten
  • 4,92 (± 0,10)schwach
  • 3,97 (± 0,08)sehr stark
  • 3,79 (± 0,08)mittel bis stark
  • 3,31 (± 0,07)schwach
  • 3,02 (± 0,06)schwach bis mittel
  • 2,85 (± 0,06)schwach
  • 2,65 (± 0,05)schwach
  • 2,49 (± 0,05)schwach
  • 2,43 (± 0,05)mittel
The following examples are intended to demonstrate the advantageous properties of the mixtures according to the invention. As a comparison, commercially available detergents based on phosphate and test mixtures with zeolite A or layered silicate are used in the absence of the co-builders used according to the invention. A block polymer of linear C 12 -C 15 alcohols with 4 propylene oxide and 7 ethylene oxide groups was used as the surfactant in all cases. A silicate which corresponded to the composition Na 2 Si 2 O 5 and which was distinguished by the following characteristic X-ray diffraction reflections served as layered silicate:
  • d (10 -8 cm) relative intensities
  • 4.92 (± 0.10) weak
  • 3.97 (± 0.08) very strong
  • 3.79 (± 0.08) medium to strong
  • 3.31 (± 0.07) weak
  • 3.02 (± 0.06) weak to medium
  • 2.85 (± 0.06) weak
  • 2.65 (± 0.05) weak
  • 2.49 (± 0.05) weak
  • 2.43 (± 0.05) medium

Beispiel 1 (Reinigungswirkung)Example 1 (cleaning effect)

Es wurden folgende Mischungen eingesetzt:

  • A) 30Gew% granuliertes Natriumtriphosphat, teilhydratisiert
    • 57Gew% Natriummetasilikat wasserfrei
    • 10Gew% Soda wasserfrei
    • 2Gew% Natriumdichlorisocyanurat · 2 H20
    • 1 Gew% Tensid
  • B) 50Gew% Zeolith A
    • 40Gew% Natriummetasilikat wasserfrei
    • 5,75Gew% Natriumsulfat wasserfrei
    • 2,25Gew% Natiumdichlorisocyanurat · 2 H20
    • 2Gew% Tensid
  • C) 50Gew% Schichtsilikat
    • 40Gew% Natriumsilikat wasserfrei
    • 5,75Gew% Natriumsulfat wasserfrei
    • 2,25Gew% Natriumdichlorisocyanurat · 2 H20
    • 2Gew% Tensid

    erfindungsgemäß
  • D) 40Gew% Schichtsilikat
    • 1 0Gew% Soda wasserfrei
    • 41 Gew% Natriumsulfat wasserfrei
    • 5Gew% Maleinsäureanhydrid-methylen-vinylester, flüssig (35 % Wirksubstanz)
    • 2Gew% Natriumdichlorisocyanurat · 2 H20
    • 2Gew% Tensid
  • E) 40Gew% Schichtsilikat
    • 25Gew% Soda wasserfrei
    • 28,85Gew% Natriumsulfat wasserfrei
    • 1,9Gew% Maleinsäureanhydrid-methylen-vinylester, Pulver (92 % Wirksubstanz)
    • 2,25Gew% Natriumdichlorisocyanurat · 2 H20
    • 2Gew% Tensid
  • F) 30Gew% Schichtsilikat
    • 20Gew% Soda wasserfrei
    • 44,75Gew% Natriumsulfat wasserfrei
    • 2Gew% Maleinsäureanhydrid-acrylsäure-copolymerisat, Pulver (92 % Wirksubstanz)
    • 2,25Gew% Natriumdichlorisocyanurat · 2 H20
    • 2Gew% Tenside.
  • G) 40Gew% Schichtsilikat
    • 10Gew% Soda wasserfrei
    • 15Gew% Ätznatron
    • 47Gew% Natriumsulfat wasserfrei
    • 4Gew% Maleinsäureanhydrid-methylen-vinylester, flüssig (35 % Wirksubstanz)
    • 2Gew% Natriumdichlorisocyanurat · 2 H20
    • 2Gew% Tensid
  • H) 40Gew% Schichtsilikat
    • 10Gew% Soda wasserfrei
    • 2Gew% Polyacetalcarboxylat, Na-Salz
    • 2Gew% Natriumdichlorisocyanurat · 2 H20
    • 2Gew% Tensid
    • 44Gew% Natriumsulfat wasserfrei
The following mixtures were used:
  • A) 30% by weight granulated sodium triphosphate, partially hydrated
    • 57% by weight sodium metasilicate anhydrous
    • 10% water soda anhydrous
    • 2% by weight sodium dichloroisocyanurate.2 H 2 0
    • 1 wt% surfactant
  • B) 50 wt% zeolite A
    • 40% by weight sodium metasilicate anhydrous
    • 5.75% by weight sodium sulfate anhydrous
    • 2.25% w / w sodium dichloroisocyanurate.2 H20
    • 2% by weight surfactant
  • C) 50% by weight layered silicate
    • 40% by weight sodium silicate anhydrous
    • 5.75% by weight sodium sulfate anhydrous
    • 2.25% by weight sodium dichloroisocyanurate.2 H 2 0
    • 2% by weight surfactant

    according to the invention
  • D) 40% by weight layered silicate
    • 1 0% water soda anhydrous
    • 41% by weight sodium sulfate anhydrous
    • 5% by weight maleic anhydride methylene vinyl ester, liquid (35% active substance)
    • 2% by weight sodium dichloroisocyanurate.2 H 2 0
    • 2% by weight surfactant
  • E) 40% by weight layered silicate
    • 25% water soda anhydrous
    • 28.85% by weight sodium sulfate anhydrous
    • 1.9% by weight maleic anhydride methylene vinyl ester, powder (92% active substance)
    • 2.25% by weight sodium dichloroisocyanurate · 2 H20
    • 2% by weight surfactant
  • F) 30% by weight layered silicate
    • 20% water soda anhydrous
    • 44.75% by weight sodium sulfate anhydrous
    • 2% by weight maleic anhydride-acrylic acid copolymer, powder (92% active substance)
    • 2.25% by weight sodium dichloroisocyanurate · 2 H20
    • 2% by weight surfactants.
  • G) 40% by weight layered silicate
    • 10% water soda anhydrous
    • 15% by weight caustic soda
    • 47% by weight sodium sulfate anhydrous
    • 4% by weight maleic anhydride methylene vinyl ester, liquid (35% active substance)
    • 2% by weight sodium dichloroisocyanurate.2 H20
    • 2% by weight surfactant
  • H) 40% by weight layered silicate
    • 10% water soda anhydrous
    • 2% by weight polyacetal carboxylate, Na salt
    • 2% by weight sodium dichloroisocyanurate.2 H 2 0
    • 2% by weight surfactant
    • 44% by weight sodium sulfate anhydrous

Die genannten Rezepturen wurden nach DIN-Norm-Entwurf 44 990 in zwei verschiedenen Maschinen bei Wasserhärten um 7° d auf ihre Reinigungswirkung geprüft. Als Maschine standen Produkte der Firma Miele und Bosch zur Verfügung. Es zeigte sich, daß maschinengebundene Einwirkungen kaum ausschlaggebend sind. In folgender Tabelle 1 sind die Ergebnisse der Versuche zusammengestellt, wobei auch der Einfluß der pH-Werte der Spülflotte verglichen wird.

Figure imgb0001
The formulations mentioned were tested for their cleaning effect in two different machines with water hardness of 7 ° d according to DIN standard draft 44 990. Products from Miele and Bosch were available as machines. It was shown that machine-bound effects are hardly decisive. The results of the tests are summarized in Table 1 below, the influence of the pH values of the washing liquor also being compared.
Figure imgb0001

Ein Vergleich der Reinigungsindices zeigt, daß im Durchschnitt marktübliche Reinigungserfolge erreicht werden, wobei sogar der Arbeits-pH-Wert um 0,5 bis 1 Stufe gesenkt werden kann.A comparison of the cleaning indices shows that, on average, standard cleaning successes are achieved, and the working pH can even be reduced by 0.5 to 1 step.

Beispiel 2 (Chlorstabilität)Example 2 (chlorine stability)

Proben der Rezepturen A, B, F und G wurden ca. 4 Monate im Labor offen an der Luft gelagert. Danach wurde der Verlust an Aktivchlor im Vergleich zum Gehalt nach Herstellung der Mischung bestimmt. Die prozentuale Abnahme ist in Tabelle 2 aufgeführt.

Figure imgb0002
Samples of formulations A, B, F and G were stored in the open air in the laboratory for approx. 4 months. The loss of active chlorine compared to the content after the mixture had been prepared was then determined. The percentage decrease is shown in Table 2.
Figure imgb0002

Hier zeigt sich eine besondere Lagerstabilität der erfindungsgemäßen Geschirrspülmittelmischungen, die den handelsüblichen Produkten deutlich überlegen ist.This shows a particular storage stability of the dishwashing agent mixtures according to the invention, which is clearly superior to the commercially available products.

Beispiel 3 (Korrosionsverhalten gegenüber Spülgut)Example 3 (Corrosion Behavior towards Washware)

Als Spülgut wurden weiße Porzellanteller und Tassen, Edelstahlbestecke verschiedener Herstellung und Gläser verschiedener Zusammensetzung und Form geprüft. Zur Feststellung eines eventuellen Schadens dient eine in 5 Schadensstufen unterteilte Tabelle, die nach visueller Auswertung der Versuche nach 125, 250, 500 und 1 000 Spülgängen zur Urteilsfindung herangezogen wurde. Die Tabelle erlaubt die Festsetzung von Zwischenstufen in 0,5er Schritten. (0 = ungeschädigt, 4,0 = Totalschaden)White porcelain plates and cups, stainless steel cutlery from various manufacturers and glasses of various compositions and shapes were tested as items to be washed. A table divided into 5 damage levels is used to determine any damage, and after visual evaluation of the tests after 125, 250, 500 and 1,000 rinse cycles was used to make a judgment. The table allows intermediate levels to be set in increments of 0.5. (0 = undamaged, 4.0 = total loss)

Zur Korrosionsprüfung wurden die Rezepturen A, B, C, D und E herangezogen. Die gefundenen durchschnittlichen Schadensbewertungen sind bei 500 Spülgängen in Tabelle 3 zusammengestellt. Als Maschine wurde eine automatisch arbeitende Haushaltsmaschine benutzt, die zwischen jeden Spülzyklus 1 Stunde die Maschinentür öffnet, damit das Spülgut vollständig abtrocknet. Die Wasserhärte lag zwischen 2° und 7° d, die Spültemperatur bei 62 - 66°C, die Wassermenge pro Spülzyklus beträgt in Summe 28 I, davon ca. 6 I im Reinigungsgang bei einer Dosierung von 30 g Spülmittel und 3 ml Klarspüler im Klarspülgang.

Figure imgb0003
Formulations A, B, C, D and E were used for the corrosion test. The average damage ratings found for 500 wash cycles are shown in Table 3. An automatically operating household machine was used as the machine, which opens the machine door for 1 hour between each washing cycle so that the items to be washed dry completely. The water hardness was between 2 ° and 7 ° d, the rinse temperature at 62 - 66 ° C, the total amount of water per rinse cycle is 28 I, of which approx. 6 I in the cleaning cycle with a dosage of 30 g detergent and 3 ml rinse aid in the rinse cycle .
Figure imgb0003

Diese Belagsbildung verhindert die kommerzielle Verwertung der Rezeptur.This deposit formation prevents the commercial use of the recipe.

Die Befunde der Rezepturen D + E zeigen dagegen deutlich die korrosionshemmenden Eigenschaften der erfindungsgemäßen Kombination von Schichtsilikaten und Co-Buildern.The results of the formulations D + E, on the other hand, clearly show the corrosion-inhibiting properties of the combination of sheet silicates and co-builders according to the invention.

Claims (9)

1. A phosphate-free dishwashing agent containing, as a builder, sodium silicate and also, as a co-builder, a polymeric and/or copolymeric carboxylic acid or a salt of this polymeric carboxylic acid and an active chlorine carrier, which contains, as a sodium silicate builder, crystalline, sheet-like sodium silicate of the formula Na M SixO2x+1 · yH20 in which M denotes sodium or hydrogen, x denotes a number from 1.9 to 4 and y denotes a number from 0 to 20.
2. A dishwashing agent as claimed in claim 1, containing
30-50% by weight of the crystalline sodium sheet silicate,
0.1-7.5% by weight of the co-builder,
0-45% by weight of a filler,
10-25% by weight of an alkali carrier,
1-2% by weight of a surfactant and
1-5% by weight of the active chlorine carrier.
3. A dishwashing agent as claimed in claim 1 or 2, which contains 0.1-3% by weight of co-builder, provided that the latter is in a pulverulent form.
4. A dishwashing agent as claimed in claim 1 or 2, which contains 0.3-7.5% by weight of co-builder, provided that the latter is in a liquid form.
5. A dishwashing agent as claimed in any of claims 1 to 4, which contains, as a co-builder, polyacetate- carboxylates, maleic anhydride/methylene vinyl ethers or maleic anhydride/acrylic acid copolymers or sodium salts thereof.
6. A dishwashing agent as claimed in any of claims 1 to 5, which contains sodium dichloroisocyanurate or chlorine bleach liquor as the active chlorine carrier.
7. A dishwashing agent as claimed in any of claims 2 to 6, which contains sodium sulfate as the filler.
8. A dishwashing agent as claimed in any of claims 2 to 6, which contains sodium carbonate, caustic soda or water-soluble alkali metal silicates as the alkali carrier.
9. A dishwashing agent as claimed in any of claims 2 to 8, which contains as surfactants, block polymers, stable to chlorine, of long-chain aliphatic alcohols with ethylene oxide groups and/or propylene oxide groups or modified fatty alcohol polyglycol ethers.
EP87110811A 1986-08-16 1987-07-25 Phosphate-free dishwashing agent Expired - Lifetime EP0267371B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87110811T ATE51018T1 (en) 1986-08-16 1987-07-25 PHOSPHATE-FREE DISHWASHER DETERGENT.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863627773 DE3627773A1 (en) 1986-08-16 1986-08-16 PHOSPHATE-FREE DISHWASHER
DE3627773 1986-08-16

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EP0267371A1 EP0267371A1 (en) 1988-05-18
EP0267371B1 true EP0267371B1 (en) 1990-03-14

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EP (1) EP0267371B1 (en)
JP (1) JPS6348399A (en)
AT (1) ATE51018T1 (en)
CA (1) CA1305007C (en)
DE (2) DE3627773A1 (en)
DK (1) DK165882C (en)
ES (1) ES2014283B3 (en)
NO (1) NO169599C (en)
PT (1) PT85539B (en)

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DE3931871A1 (en) * 1989-09-23 1991-04-04 Henkel Kgaa GRANULAR, PHOSPHATE-FREE WATER DISINFECTANT
NL9000272A (en) * 1990-02-05 1991-09-02 Sara Lee De Nv MAIN DETERGENT.
US5273675A (en) * 1990-02-16 1993-12-28 Rohm And Haas Company Phosphate-free liquid cleaning compositions containing polymer
DE4034131C2 (en) * 1990-10-26 1999-08-26 Henkel Kgaa Builders for detergents
DE4102743A1 (en) * 1991-01-30 1992-08-06 Henkel Kgaa PHOSPHATE-FREE DETERGENT
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NO169599C (en) 1992-07-15
DK425387D0 (en) 1987-08-14
EP0267371A1 (en) 1988-05-18
DK165882C (en) 1993-06-21
NO169599B (en) 1992-04-06
US4959170A (en) 1990-09-25
NO873410D0 (en) 1987-08-13
PT85539A (en) 1987-09-01
DK425387A (en) 1988-02-17
DE3761909D1 (en) 1990-04-19
JPS6348399A (en) 1988-03-01
ES2014283B3 (en) 1990-07-01
CA1305007C (en) 1992-07-14
PT85539B (en) 1990-06-29
DE3627773A1 (en) 1988-02-18
NO873410L (en) 1988-02-17
ATE51018T1 (en) 1990-03-15
DK165882B (en) 1993-02-01

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