EP0267371A1 - Phosphate-free dishwashing agent - Google Patents

Phosphate-free dishwashing agent Download PDF

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Publication number
EP0267371A1
EP0267371A1 EP87110811A EP87110811A EP0267371A1 EP 0267371 A1 EP0267371 A1 EP 0267371A1 EP 87110811 A EP87110811 A EP 87110811A EP 87110811 A EP87110811 A EP 87110811A EP 0267371 A1 EP0267371 A1 EP 0267371A1
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Prior art keywords
weight
builder
dishwashing detergent
gew
sodium
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German (de)
French (fr)
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EP0267371B1 (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, low-foaming, chlorine-stable block polymers with ethylene and propylene oxide groups are usually used as builders 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, low-foaming, chlorine-stable block polymers with ethylene and propylene oxide groups are usually used as builders modified fatty alcohol polyglycol ether used.
  • the soluble products include, for example, citrates or polycarboxylic acids, such as polyacrylic acid, but also tried nitrilotriacetic acid (NTE) or ethylenediaminetetraacetic acid (EDTE) and their salts, or also various phosphonic acids and phosphonates. So far, zeolite A and bentonite have been discussed among the insoluble substitutes.
  • DE-A1-34 13 571 already describes crystalline layered sodium silicates for water softening, which correspond to the composition NaMSi x O 2x + 1 .y H2O, where M is sodium or hydrogen, x 1.9 to 4 and y 0 to 20 is.
  • a dishwashing detergent according to the invention preferably contains: 30-50% by weight, preferably 40% by weight, of the crystalline sodium layer 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.
  • 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 oxymethylene 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 dishwasher detergent 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 preferably in anhydrous form, as an alkali carrier, sodium carbonate, caustic soda or water-soluble alkali silicates as fillers, and long-chain chlorine-stable block polymers as surfactants aliphatic alcohols with ethylene oxide or propylene oxide groups or modified fatty alcohol polyglycol ethers and sodium dichloroisocyanurate or bleaching solution as active chlorine carrier.
  • 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.
  • 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 automatic household machine was used as the machine, opening the machine door for 1 hour between each wash cycle so that the washware dries completely.
  • the water hardness was between 2 ° and 7 ° d, the rinsing temperature at 62 - 66 ° C, the The total amount of water per rinse cycle is 28 l, of which approx. 6 l in the cleaning cycle with a dosage of 30 g detergent and 3 ml rinse aid in the rinse cycle.

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  • 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)
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Abstract

Die Erfindung betrifft ein phosphatfreies Geschirrspülmittel, das als Builder ein kristallines, schichtförmiges Natriumsilikat, der allgemeinen Formel NaMSi xO 2x+1 · y H2O, in der M Natrium oder Wasserstoff, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 bedeuten, in Verbindung mit einem Co-Builder enthält, der eine polymere und/oder copolymere Carbonsäure oder ein Salz dieser Polymerisate ist.The invention relates to a phosphate-free dishwashing liquid which, as a builder, comprises a crystalline, layered sodium silicate, of the general formula NaMSi xO 2x + 1 .y H2O, 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, in conjunction with a co-builder which is a polymeric and / or copolymeric carboxylic acid or a salt of these polymers.

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.
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.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.
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, low-foaming, chlorine-stable block polymers with ethylene and propylene oxide groups are usually used as builders 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. The soluble products include, for example, citrates or polycarboxylic acids, such as polyacrylic acid, but also tried nitrilotriacetic acid (NTE) or ethylenediaminetetraacetic acid (EDTE) and their salts, or also 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 xO 2x+1 · y H₂O 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 correspond to the composition NaMSi x O 2x + 1 .y H₂O, where M is sodium or hydrogen, x 1.9 to 4 and y 0 to 20 is.

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 non gefunden, daß man diesen Nachteil überwinden kann, wenn man in Geschirrspülmitteln ein kristallines, schichtförmiges Natriumsilikat der allgemeinen Formel NaMSi xO 2x+1 · y H₂O in der M Natrium oder Wasserstoff, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist, in Verbindung mit einem Co-Builder einsetzt, der eine polymere und/oder copolymere Carbonsäure oder ein Salz, insbesondere Alkalisalz, dieser Polymerisate ist.Surprisingly, it was found that you can overcome this disadvantage if you use a crystalline, layered sodium silicate of the general formula NaMSi x O 2x + 1 · y H₂O in the M sodium or hydrogen, x a number from 1.9 to 4 and y is a number from 0 to 20, used in conjunction with a co-builder which is a polymeric and / or copolymeric carboxylic acid or a salt, in particular an alkali metal salt, of these polymers.

Vorzugsweise enthält ein erfindungsgemäßes Geschirrspülmittel:
30 - 50      Gew% vorzugsweise 40 Gew%, des kristallinen N atriumschichtsilikates
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 sodium layer 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 Oxymethylencarboxylate oder Maleinsäureanhydridacrylsäure-copolymerisate oder Maleinsäureanhydrid-methylen-vinylether bzw. deren Natriumsalze. Die übrigen Geschirrspülmittelkomponenten, wie Füllstoffe, Alkaliträger, Tenside und Aktivchlorträger sowie gegebenenfalls Parfüme, können Stoffe sein, die für diese Zwecke bereits hinreichend bekannt sind.Polycarboxylates, such as oxymethylene 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 dishwasher detergent 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, preferably in anhydrous form, as an alkali carrier, sodium carbonate, caustic soda or water-soluble alkali silicates as fillers, and long-chain chlorine-stable block polymers as surfactants aliphatic alcohols with ethylene oxide or propylene oxide groups or modified fatty alcohol polyglycol ethers and sodium dichloroisocyanurate or bleaching solution as active chlorine carrier.

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 zeolite phosphate substitute, 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)      mittelThe 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. As a surfactant, a block polymer of linear C₁₂ - C₁₅ alcohols with 4 propylene oxide and 7 ethylene oxide groups was used in all cases. A silicate that corresponded to the composition Na₂Si₂O₅ and 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) 30      Gew% granuliertes Natriumtriphosphat, teilhydratisiert
    57      Gew% Natriummetasilikat wasserfrei
    10      Gew% Soda wasserfrei
    2      Gew% Natriumdichlorisocyanurat · 2 H₂O
    1      Gew% Tensid
  • B) 50      Gew% Zeolith A
    40      Gew% Natriummetasilikat wasserfrei
    5,75      Gew% Natriumsulfat wasserfrei
    2,25      Gew% Natiumdichlorisocyanurat · 2 H₂O
    2      Gew% Tensid
  • C) 50      Gew% Schichtsilikat
    40      Gew% Natriumsilikat wasserfrei
    5,75      Gew% Natriumsulfat wasserfrei
    2,25      Gew% Natriumdichlorisocyanurat · 2 H₂O
    2      Gew% Tensid
    erfindungsgemäß
  • D) 40      Gew% Schichtsilikat
    10      Gew% Soda wasserfrei
    41      Gew% Natriumsulfat wasserfrei
    5      Gew% Maleinsäureanhydrid-methylen-vinylester, flüssig (35 % Wirksubstanz)
    2      Gew% Natriumdichlorisocyanurat · 2 H₂O
    2      Gew% Tensid
  • E) 40      Gew% Schichtsili kat
    25      Gew% Soda wasserfrei
    28,85      Gew% Natriumsulfat wasserfrei
    1,9      Gew% Maleinsäureanhydrid-methylen-vinylester, Pulver (92 % Wirksubstanz)
    2,25      Gew% Natriumdichlorisocyanurat · 2 H₂O
    2      Gew% Tensid
  • F) 30      Gew% Schichtsilikat
    20      Gew% Soda wasserfrei
    44,75      Gew% Natriumsulfat wasserfrei
    2      Gew% Maleinsäureanhydrid-acrylsäure-copolymerisat, Pulver (92 % Wirksubstanz)
    2,25      Gew% Natriumdichlorisocyanurat · 2 H₂O
    2      Gew% Tenside.
  • G) 40      Gew% Schichtsilikat
    10      Gew% Soda wasserfrei
    15      Gew% Ätznatron
    47      Gew% Natriumsulfat wasserfrei
    4      Gew% Maleinsäureanhydrid-methylen-vinylester, flüssig (35 % Wirksubstanz)
    2      Gew% Natriumdichlorisocyanurat · 2 H₂O
    2      Gew% Tensid
  • H) 40      Gew% Schichtsilikat
    10      Gew% Soda wasserfrei
    2      Gew% Oxymethylencarboxylat, Na-Salz
    2      Gew% Natriumdichlorisocyanurat · 2 H₂O
    2      Gew% Tensid
    44      Gew% Natriumsulfat wasserfrei
The following mixtures were used:
  • A) 30% by weight of granulated sodium triphosphate, partially hydrated
    57% by weight sodium metasilicate anhydrous
    10% by weight soda anhydrous
    2% by weight sodium dichloroisocyanurate · 2 H₂O
    1 wt% surfactant
  • B) 50% by weight of zeolite A
    40% by weight sodium metasilicate anhydrous
    5.75% by weight sodium sulfate anhydrous
    2.25% by weight sodium dichloroisocyanurate · 2 H₂O
    2 wt% surfactant
  • C) 50% by weight of layered silicate
    40% by weight sodium silicate anhydrous
    5.75% by weight sodium sulfate anhydrous
    2.25% by weight sodium dichloroisocyanurate · 2 H₂O
    2 wt% surfactant
    according to the invention
  • D) 40% by weight layered silicate
    10% by weight 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 H₂O
    2 wt% surfactant
  • E) 40% by weight layer silicate cat
    25% by weight 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 H₂O
    2 wt% surfactant
  • F) 30% by weight of layered silicate
    20% by weight 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 H₂O
    2% by weight surfactants.
  • G) 40% by weight layered silicate
    10% by weight 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 H₂O
    2 wt% surfactant
  • H) 40% by weight layered silicate
    10% by weight soda anhydrous
    2% by weight oxymethylene carboxylate, Na salt
    2% by weight sodium dichloroisocyanurate · 2 H₂O
    2 wt% 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 serves to determine a possible damage, which was used for the judgment after a visual evaluation of the tests after 125, 250, 500 and 1,000 rinse cycles. 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 l, davon ca. 6 l 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 automatic household machine was used as the machine, opening the machine door for 1 hour between each wash cycle so that the washware dries completely. The water hardness was between 2 ° and 7 ° d, the rinsing temperature at 62 - 66 ° C, the The total amount of water per rinse cycle is 28 l, of which approx. 6 l 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. Geschirrspülmittel enthaltend als Builder Natriumsilikat sowie Co-Builder und Aktivchlorträger, dadurch gekennzeichnet , daß es als phosphatfreies Geschirrspülmittel als Builder ein kristallines, schichtförmiges Natriumsilikat der allgemeinen Formel NaMSi xO 2x+1 · y H₂O, in der M Natrium oder Wasserstoff, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 bedeuten, in Verbindung mit einem Co-Builder enthält, der eine polymere und/oder copolymere Carbonsäure oder ein Salz dieser Polymerisate ist.1. Dishwashing detergent containing sodium silicate as a builder and co-builder and active chlorine carrier, characterized in that it is a phosphate-free dishwashing detergent as a builder, a crystalline, layered sodium silicate of the general formula NaMSi x O 2x + 1 · y H₂O, in which M sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, in conjunction with a co-builder which is a polymeric and / or copolymeric carboxylic acid or a salt of these polymers. 2. Geschirrspülmittel nach Anspruch 1, enthaltend
30 - 50      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.2. Dishwashing detergent according to claim 1, containing
30 - 50% 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. 3. Geschirrspülmittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es 0,1 - 3 Gew% Co-Builder enthält, wenn dieser in pulverförmiger Form vorliegt.3. Dishwashing detergent according to claim 1 or 2, characterized in that it contains 0.1-3% by weight of co-builder if it is in powder form. 4. Geschirrspülmittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es 0,3 - 7,5 Gew% Co-Builder enthält, wenn dieser in flüssiger Form vorliegt.4. Dishwashing detergent according to claim 1 or 2, characterized in that it contains 0.3 - 7.5% by weight of co-builder when it is in liquid form. 5. Geschirrspülmittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es als Co-Builder Oxymethylencarboxylate, Maleinsäureanhydrid-methylenvinylether oder Maleinsäureanhydrid-acrylsäure-Copolymerisate bzw. deren Natriumsalze enthält.5. Dishwashing detergent according to one of claims 1 to 4, characterized in that it contains as co-builder oxymethylene carboxylates, maleic anhydride-methylene vinyl ether or maleic anhydride-acrylic acid copolymers or their sodium salts. 6. Geschirrspülmittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es als Aktivchlorträger Natriumdichlorisocyanurat oder Chlorbleichlauge enthält.6. Dishwashing detergent according to one of claims 1 to 5, characterized in that it contains sodium dichloroisocyanurate or chlorine bleach as the active chlorine carrier. 7. Geschirrspülmittel nach einem der Ansprüche 2 bis 6, dadurch gekennzeichnet, daß es als Füllstoff Natriunsulfat enthält.7. Dishwashing liquid according to one of claims 2 to 6, characterized in that it contains sodium sulfate as a filler. 8. Geschirrspülmittel nach einem der Ansprüche 2 bis 6, dadurch gekennzeichnet, daß es als Alkaliträger Natriumcarbonat, Ätznatron oder wasserlösliche Alkalisilikate enthält.8. Dishwashing liquid according to one of claims 2 to 6, characterized in that it contains sodium carbonate, caustic soda or water-soluble alkali silicates as alkali carrier. 9. Geschirrspülmittel nach einem der Ansprüche 2 bis 8, dadurch gekennzeichnet, daß es als Tenside chlorstabile Blockpolymerisate langkettiger aliphatischer Alkohole mit Ethylenoxid- und/oder Propylenoxidgruppen oder modifizierte Fettalkoholpolyglykolether enthält.9. Dishwashing detergent according to one of claims 2 to 8, characterized in that it contains chlorine-stable block polymers of long-chain aliphatic alcohols with ethylene oxide and / or propylene oxide groups or modified fatty alcohol polyglycol ethers as surfactants.
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.

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DE19863627773 DE3627773A1 (en) 1986-08-16 1986-08-16 PHOSPHATE-FREE DISHWASHER
DE3627773 1986-08-16

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EP0267371B1 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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GB2234980A (en) * 1989-07-25 1991-02-20 Unilever Plc Detergent composition for machine dishwashers
EP0416366A2 (en) * 1989-09-08 1991-03-13 Hoechst Aktiengesellschaft Dishwashing composition comprising layered silicates
EP0419970A2 (en) * 1989-09-23 1991-04-03 Henkel KGaA Granular, phosphate free water softening agent
WO1992013935A1 (en) * 1991-01-30 1992-08-20 Henkel Kommanditgesellschaft Auf Aktien Phosphate-free cleaning agent
EP0563631A1 (en) * 1992-03-28 1993-10-06 Hoechst Aktiengesellschaft Sodium silicate and aluminosilicate cogranulates, process for the preparation thereof and use thereof
WO1993025651A1 (en) * 1992-06-18 1993-12-23 Unilever N.V. Machine dishwashing composition
EP0653480A1 (en) * 1993-11-11 1995-05-17 The Procter & Gamble Company Softening through the wash compositions
EP0668344A2 (en) 1994-02-11 1995-08-23 BK LADENBURG GmbH, Gesellschaft für chemische Erzeugnisse Detergent composition containing polyepoxy succinic acid

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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
GB9108639D0 (en) * 1991-04-23 1991-06-12 Procter & Gamble Particulate detergent compositions
US5540855A (en) * 1991-04-23 1996-07-30 The Procter & Gamble Company Particulate detergent compositions
US5308532A (en) * 1992-03-10 1994-05-03 Rohm And Haas Company Aminoacryloyl-containing terpolymers
US5643358A (en) * 1994-06-10 1997-07-01 Pq Corporation Crystalline hydrated layered sodium and potassium silicates and method of producing same
US5739098A (en) * 1994-07-05 1998-04-14 Pq Corporation Crystalline sodium potassium silicates
US5614160A (en) * 1994-06-10 1997-03-25 Pq Corporation Composite silicate materials
US6403548B1 (en) 1998-10-27 2002-06-11 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Wrinkle reduction laundry product compositions
DE19854960A1 (en) 1998-11-29 2000-05-31 Clariant Gmbh Dishwasher detergent
US6701940B2 (en) 2001-10-11 2004-03-09 S. C. Johnson & Son, Inc. Hard surface cleaners containing ethylene oxide/propylene oxide block copolymer surfactants
JP2010280796A (en) * 2009-06-04 2010-12-16 Kao Corp Detergent composition for dishwasher
WO2015101448A1 (en) * 2013-12-30 2015-07-09 Unilever N.V. Hard surface cleaning composition

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Cited By (11)

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Publication number Priority date Publication date Assignee Title
GB2234980A (en) * 1989-07-25 1991-02-20 Unilever Plc Detergent composition for machine dishwashers
EP0416366A2 (en) * 1989-09-08 1991-03-13 Hoechst Aktiengesellschaft Dishwashing composition comprising layered silicates
EP0416366A3 (en) * 1989-09-08 1992-04-01 Hoechst Aktiengesellschaft Dishwashing agent
EP0419970A2 (en) * 1989-09-23 1991-04-03 Henkel KGaA Granular, phosphate free water softening agent
EP0419970A3 (en) * 1989-09-23 1991-06-26 Henkel Kommanditgesellschaft Auf Aktien Granular, phosphate free water softening agent
WO1992013935A1 (en) * 1991-01-30 1992-08-20 Henkel Kommanditgesellschaft Auf Aktien Phosphate-free cleaning agent
EP0563631A1 (en) * 1992-03-28 1993-10-06 Hoechst Aktiengesellschaft Sodium silicate and aluminosilicate cogranulates, process for the preparation thereof and use thereof
WO1993025651A1 (en) * 1992-06-18 1993-12-23 Unilever N.V. Machine dishwashing composition
EP0653480A1 (en) * 1993-11-11 1995-05-17 The Procter & Gamble Company Softening through the wash compositions
EP0668344A2 (en) 1994-02-11 1995-08-23 BK LADENBURG GmbH, Gesellschaft für chemische Erzeugnisse Detergent composition containing polyepoxy succinic acid
EP0668344A3 (en) * 1994-02-11 1997-04-02 Benckiser Knapsack Ladenburg Detergent composition containing polyepoxy succinic acid.

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DE3627773A1 (en) 1988-02-18
EP0267371B1 (en) 1990-03-14
NO873410L (en) 1988-02-17
ES2014283B3 (en) 1990-07-01
DK425387A (en) 1988-02-17
NO169599B (en) 1992-04-06
NO169599C (en) 1992-07-15
US4959170A (en) 1990-09-25
DE3761909D1 (en) 1990-04-19
DK165882B (en) 1993-02-01
JPS6348399A (en) 1988-03-01
DK165882C (en) 1993-06-21
CA1305007C (en) 1992-07-14
PT85539A (en) 1987-09-01
PT85539B (en) 1990-06-29
DK425387D0 (en) 1987-08-14
NO873410D0 (en) 1987-08-13
ATE51018T1 (en) 1990-03-15

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