EP0171007A2 - Dish cleaning agent - Google Patents

Dish cleaning agent Download PDF

Info

Publication number
EP0171007A2
EP0171007A2 EP85109465A EP85109465A EP0171007A2 EP 0171007 A2 EP0171007 A2 EP 0171007A2 EP 85109465 A EP85109465 A EP 85109465A EP 85109465 A EP85109465 A EP 85109465A EP 0171007 A2 EP0171007 A2 EP 0171007A2
Authority
EP
European Patent Office
Prior art keywords
weight
alkali
chain
alkanols
optionally
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP85109465A
Other languages
German (de)
French (fr)
Other versions
EP0171007B1 (en
EP0171007A3 (en
Inventor
Eric Dr. Sung
Peter Dr. Jeschke
Klaus Dr. Schumann
Theodor Dr. Altenschöpfer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT85109465T priority Critical patent/ATE61398T1/en
Publication of EP0171007A2 publication Critical patent/EP0171007A2/en
Publication of EP0171007A3 publication Critical patent/EP0171007A3/en
Application granted granted Critical
Publication of EP0171007B1 publication Critical patent/EP0171007B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only

Definitions

  • the invention relates to dishwashing detergents, in particular for the automatic washing of dishes at low temperatures, which are distinguished by a high level of cleaning ability, in particular also in relation to stubborn and normally difficult to remove soiling, such as sebum / grease soiling, and by an extraordinarily low foaming ability.
  • alkaline cleaning agent mixtures are used for the automatic cleaning of dishes, which essentially consist of inorganic salts such as alkali phosphates, alkali silicates and alkali carbonates and of active chlorine carriers and which, in order to improve the wetting effect, may also contain minor additions of a low-foaming nonionic surfactant. These mixtures have a good cleaning ability against all stains at generally normal working temperatures of 55 to 65 ° C.
  • the invention therefore relates to agents for the mechanical cleaning of dishes based on polymeric alkali phosphates and / or their substitutes, alkali silicates, alkali carbonates and, if appropriate, compounds which release active oxygen and low-foaming nonionic surfactants, which are characterized in that they contain enzymes and primary, straight-chain or branched-chain C. 8 -C 10 alkanols, which may optionally be propoxylated, contain.
  • Suitable polymeric alkali metal phosphates are the condensed phosphates which are usually used in washing-up and cleaning agent mixtures and which can be present in the form of their alkaline neutral or acidic sodium or potassium salts. Examples include: tetrasodium pyrophosphate, disodium dihydrogen pyrophosphate, pentasodium triphosphate, sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • the water-soluble organic complexing agents for calcium are essentially found among the polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, carboxyalkyl ethers, polyanionic polymeric carboxylic acids and the phosphonic acids, these compounds mostly being used in the form of their water-soluble salts.
  • Specific but not exhaustive examples are citric acid, carboxymethyl tartronic acid, mellitic acid, polyacrylic acid, poly-or-hydroxyacrylic acid, carboxymethyl malic acid, nitrilotriacetic acid and 1-hydroxyethane-1,1-diphosphonic acid.
  • Water-soluble sodium or potassium metasilicates are used as alkali metal silicates. You can free of water, or anhydrate kristallwasserhalti g and containing from 5 to 9 moles of water.
  • Water glass is understood as meaning water-soluble sodium or potassium silicates in which the ratio of alkali oxide to silicon dioxide is approximately 1: 2 to 1: 4. They can be used as anhydrous solid substances or as liquid, approximately 50% solutions.
  • Such enzymes are those of animal and vegetable origin, in particular active substances obtained from digestive ferment, yeast and bacterial strains. They usually represent a complex mixture of different enzymatic active ingredients. Of particular interest are starch, protein or fat-cleaving enzymes, such as amylases, proteases and lipases.
  • the enzymes are obtained from a variety of processes from bacterial strains, fungi, yeasts or animal organs and are sold under different names. Most of these are enzyme mixtures that have a combined effect on starch, protein and fats have.
  • the enzyme preparations obtained from Bacillus subtilis have the particular advantage for practical use that they are relatively resistant to alkalis. The temperature sensitivity of the enzymes no longer plays a significant role here.
  • the manufacturers set the enzymes to a certain degree of activity, possibly with the addition of blending agents such as sodium sulfate, sodium chloride, alkali phosphates or alkali polyphosphates.
  • blending agents such as sodium sulfate, sodium chloride, alkali phosphates or alkali polyphosphates.
  • LVE / g Löhlein-Volhard units per gram
  • IU international units
  • DE / g Devices per gram
  • the activity is often stated in LVE / g.
  • the proteolytic enzyme activity should be 100 to 5,000, preferably 200 to 2,000 LVE / g.
  • Amylolytic activity is generally reported in SKB / g (Sandstedt-Kneen-Blish units per gram). It should be about 5 to 1,000, preferably 15 to 250, SKB / g in the detergent mixture. The amount of the Geschirreinigun sstoffn g enzymes to be used, is determined by these values.
  • the primary, straight or branched chain alkanols contain 8 to 10 carbon atoms in the alkyl radical. They can be propoxylated with 1 to 2, preferably 2, moles per mole of alkanol propylene oxide. These include in particular n-octanol, 2-ethylhexanol, isononanyl alcohol, n-decanol, isodecanol and preferably n-octanol + 2 moles of propylene oxide (PO).
  • PO propylene oxide
  • alkali perborates, persulfates and percarbonate which can be activated by activators such as tetraacetylethylenediamine, tetraacetylglycoluril, pentaacetylglucose, but also compounds such as magnesium monoperphthalate, can be used as compounds which release active oxygen, but also compounds such as magnesium monoperphthalate, it being possible to dispense with the addition of activator.
  • activators such as tetraacetylethylenediamine, tetraacetylglycoluril, pentaacetylglucose, but also compounds such as magnesium monoperphthalate, can be used as compounds which release active oxygen, but also compounds such as magnesium monoperphthalate, it being possible to dispense with the addition of activator.
  • Suitable nonionic low-foaming surfactants are preferably ethylene oxide adducts with higher molecular weight polypropylene glycols with a molecular weight of 900 to 4,000, and ethylene oxide or ethylene oxide and propylene oxide adducts with C 12 -C 18 alkanols and nonylphenol.
  • the preparation is carried out in a known manner by addition of the alkylene oxides in question in the presence of mostly alkaline catalysts, if appropriate under pressure and at elevated temperatures, it being possible to add up to three times the amount by weight of the starting compounds on alkylene oxides.
  • Suitable addition products are the adduct of 10% by weight of ethylene oxide with a polyoxypropylene glycol of molecular weight 1750, and the adduct of 9 mol of ethylene oxide and 10 mol of propylene oxide with nonylphenol, and the like.
  • the useful nonionic surfactants also include the surface-active amine oxides, which are usually derived from tertiary amines with a hydrophobic C 10 -C 20 alkyl group and two shorter alkyl and / or alkylol groups each containing up to 4 C atoms.
  • Typical representatives are, for example, the compounds N-dodecyl-N, N-dimethylamine oxide, N-tetradecyl-N, N-dihydroxyethylamine oxide or N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide.
  • inorganic salts such as sodium sulfate
  • inorganic salts such as sodium sulfate
  • acidic or alkaline or buffering inorganic or organic compounds can be used to establish a pH value which is advantageous for the enzyme action.
  • the pH values are between 4 and 12, depending on the type of enzyme.
  • enzyme-activating additives such as ammonium chloride, sodium chloride, dyes, perfumes and the like can also be added to the mixtures.
  • the claimed agents are generally used as mixtures of granular or powdery individual substances or as granulated, agglomerated or prilled products.
  • the claimed cleaning agent combinations are characterized by a high wetting effect and an extraordinarily good low-temperature cleaning ability, especially in relation to stubborn stains, such as grease, protein and starch deposits.
  • the application takes place by adding the powdery, granulated, agglomerated or prilled agents by hand into the dishwashing liquor or preferably by means of automatic dosing devices.
  • the application concentrations in the cleaning liquor should be about 2 to 7 g / 1, temperatures of about 40 to 45 C being used.
  • the test soils consisted of oatmeal porridge and starch in the form of mashed potatoes, which were placed on plates and scraped off. The dishes were then left to stand in the air for 6 hours at room temperature and then placed in the dishwasher.
  • Rindertalganschmutzung was pre-gen as follows, g: 0.5 to 0.8 g of beef tallow were heated until liquefied and stirred for about 2% of titanium dioxide. Then the still warm mass was spread evenly onto red plastic plates using a brush.
  • a conventional standard cleaning agent (A) was used, which had the following composition:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)
  • Washing And Drying Of Tableware (AREA)

Abstract

Dishwashing composition for the machine washing of crockery at around 40 DEG C. which contain, in addition to polymeric alkali phosphates (di-, triphosphates), water-soluble complexing zeolites of the NaA or NaX type or organic complexing agents for calcium, alkali metasilicate, sodium carbonate, sodium hydrogen carbonate, waterglass, active oxygen donors and a low-foaming nonionic surfactant from the group of alkylene oxide adducts with C12-C18 alkanols, nonylphenol or with polypropylene glycols having a molecular weight of from 900 to 4000, (1) form about 0.1 to 5% by weight of a hydrolase enzyme (amylases, proteases, lipases) and, (2) as cleansing boosters, from about 0.1 to 10% by weight of C8-C10 primary, straight-chain or branched-chain alkanols which may optionally be propoxylated with from 1 to 2 moles of propylene oxide.

Description

Die Erfindung betrifft Geschirreinigungsmittel, insbesondere für das maschinelle Spülen von Geschirr bei niedrigen Temperaturen, die sich durch ein hohes Reinigungsvermögen, insbesondere auch gegenüber hartnäckigen und normalerweise schwer zu entfernenden Anschmutzungen wie etwa Talg - Fettanschmutzungen, sowie durch ein außerordentlich geringes Schäumvermögen auszeichnen.The invention relates to dishwashing detergents, in particular for the automatic washing of dishes at low temperatures, which are distinguished by a high level of cleaning ability, in particular also in relation to stubborn and normally difficult to remove soiling, such as sebum / grease soiling, and by an extraordinarily low foaming ability.

Zum maschinellen Reinigen von Geschirr werden bekanntlich alkalische Reinigungsmittelgemische verwendet, die im wesentlichen aus anorganischen Salzen wie Alkaliphosphaten, Alkalisilikaten und Alkalicarbonaten sowie aus Aktivchlorträgern bestehen und die zur Verbesserung der Benetzungswirkung gegebenenfalls noch geringe Zusätze eines schwachschäumenden nichtionogenen Tensids enthalten. Diese Gemische besitzen ein gutes Reinigungsvermögen gegenüber allen Anschmutzungen bei im allgemeinen üblichen Arbeitstemperaturen von 55 bis 65 °C. Zur Verhinderung von dünnen Belägen, die sich im Laufe der Zeit auf den Geschirroberflächen absetzen können, die im wesentlichen aus Stärke und eventuell Eiweißspuren bestehen und die das Aussehen des gespülten Geschirrs unter Umständen erheblich beeinträchtigen, wurden verbesserte, enzymhaltige Geschirrspülmittel angewendet, wie sie beispielsweise in der DE-OS 17 67 567 beschrieben sind.It is known that alkaline cleaning agent mixtures are used for the automatic cleaning of dishes, which essentially consist of inorganic salts such as alkali phosphates, alkali silicates and alkali carbonates and of active chlorine carriers and which, in order to improve the wetting effect, may also contain minor additions of a low-foaming nonionic surfactant. These mixtures have a good cleaning ability against all stains at generally normal working temperatures of 55 to 65 ° C. In order to prevent thin deposits, which can settle over time on the surface of the dishes, which consist essentially of starch and possibly traces of protein and which may significantly impair the appearance of the washed dishes, improved, enzyme-containing dishwashing detergents have been used, as described, for example, in DE- OS 17 67 567 are described.

Dem Zwang zum Energiesparen folgend haben viele Hersteller bereits Geschirrspülmaschinen als energiesparsame Modelle auf den Markt gebracht, bei denen der Wasserverbrauch der Reinigungsflotte nicht nur von 10 auf 6 bis 7 Liter gesenkt wurde, sondern die auch ein Sparprogramm mit stark herabgesetzter Temperatur anbieten. Eine von der Firma AEG in den Handel gebrachte Haushaltsgeschirrspülmaschine vom Typ "Favorit de Luxe Elektronik i" benötigt für die Reinigungsflotte beispielsweise nur etwa 6 Liter Wasser. Der Stromverbrauch des Programms "40 °C Normal" (Klarspültemperatur: 55 °C) beträgt, im Gegensatz zum bisher üblichen Verbrauch von 1,9 bis 2,2 kW/h bei 65 °C,lediglich nur noch 1,1 kW/h. Beim Arbeiten mit dieser Maschine hat es sich jedoch gezeigt, daß die Reinigungsleistung von - wie bisher üblich - 30 g Standardreiniger (~5 g/l) beim Übergang vom 65 °C-Programm auf das 40 °C-Programm bei 8 Testanschmutzungen um durchschnittlich 1,4 Bewertungspunkte abfiel.Following the pressure to save energy, many manufacturers have already launched dishwashers on the market as energy-saving models in which the water consumption of the cleaning fleet has not only been reduced from 10 to 6 to 7 liters, but also offer a savings program with a greatly reduced temperature. For example, a "Favorit de Luxe Elektronik i" household dishwashing machine put on the market by AEG only needs about 6 liters of water for the cleaning liquor. The power consumption of the "40 ° C Normal" program (rinse aid temperature: 55 ° C) is only 1.1 kW / h, in contrast to the usual consumption of 1.9 to 2.2 kW / h at 65 ° C . When working with this machine, however, it has been shown that the cleaning performance of - as usual - 30 g standard cleaner (~ 5 g / l) during the transition from the 65 ° C program to the 40 ° C program with 8 test stains by average 1.4 evaluation points dropped.

Während ein Zusatz von 1 % eines Amylase-Protease-Gemisches im Reinigungsgang zwar die Entfernung von Haferflocken- und Stärkerückständen verbesserte, war ein Lipasezusatz zum Reiniger zur Steigerung der Fettentfernung wenig wirksam. Talgfettanschmutzungen ließen sich bei Temperaturen um 40 °C nur noch schwer entfernen.While adding 1% of an amylase-protease mixture in the cleaning cycle improved the removal of oatmeal and starch residues, adding a lipase to the cleaner to increase fat removal was not very effective. Sebum grease stains were difficult to remove at temperatures around 40 ° C.

Überraschenderweise wurde nun gefunden, daß die Entfernung besonders von hartnäckigen Fettanschmutzungen, wie z.B. Rindertalg bei Reinigungstemperaturen um 40 °C über das normale bekannte 65 °C-Ergebnis hinaus verbessert wird, wenn man dem Geschirrspülmittel außer einem Enzymgemisch als Peinigungsverstärker primäre, gerad- oder verzweigtkettige C8-C10-Alkanole, die gegebenenfalls noch propoxyliert sein können, zusetzt.Surprisingly, it now has been found that the distance is improved particularly stubborn fatty soils such as beef tallow at Cleaner with g stemperaturen to 40 ° C above the normal known 65 ° C result also when primary the dishwashing except an enzyme mixture as Peinigungsverstärker, straight or branched-chain C 8 -C 10 -alkanols, which may optionally also be propoxylated.

Die Erfindung betrifft daher Mittel zum maschinellen Reinigen von Geschirr auf Basis von polymeren Alkaliphosphaten und/oder deren Austauschstoffen, Alkalisilikaten, Alkalicarbonaten sowie gegebenenfalls Aktivsauerstoff abspaltenden Verbindungen und schwachschäumenden nichtionischen Tensiden, die dadurch gekennzeichnet sind, daß sie Enzyme und primäre, gerad-oder verzweigtkettige C8-C10-Alkanole, die gegebenenfalls propoxyliert sein können, enthalten.The invention therefore relates to agents for the mechanical cleaning of dishes based on polymeric alkali phosphates and / or their substitutes, alkali silicates, alkali carbonates and, if appropriate, compounds which release active oxygen and low-foaming nonionic surfactants, which are characterized in that they contain enzymes and primary, straight-chain or branched-chain C. 8 -C 10 alkanols, which may optionally be propoxylated, contain.

Die erfindungsgemäßen Reinigungsmittel bestehen im einzelnen aus einer Kombination aus

  • O bis 50, vorzugsweise 10 bis 40 Gew.-%, eines polymeren Alkaliphosphates aus der Gruppe der Alkalidiphosphate und Alkalitriphosphate,
  • O bis 60, vorzugsweise 5 bis 50 Gew.-% an wasserunlöslichen, komplexbildenden Zeolithen vom Typ NaA oder NaX bzw. deren Gemischen oder wasserlöslichen organischen Komplexierungsmitteln für Calcium, wobei wenigstens eine dieser Verbindungen oder eines der polymeren Alkaliphosphate anwesend sein muß,
  • 10 bis 60, vorzugsweise 20 bis 50 Gew.-% Alkalimetasilikat,
  • 2 bis 40, vorzugsweise 5 bis 30 Gew.-% Natriumcarbonat,
  • O bis 20, vorzugsweise 5 bis 20 Gew.-% Natriumhydrogencarbonat,
  • 1 bis 20, vorzugsweise 1 bis 15 Gew.-% Wasserglas,
  • 0,1 bis 5, vorzugsweise 0,5 bis 3 Gew.-% eines Enzyms oder Enzymgemisches aus der Gruppe der Hydrolasen, vorzugsweise Amylasen, Proteasen und Lipasen,
  • 0,1 bis 10, vorzugsweise 0,5 bis 5 Gew.-% an primären, gerad- oder verzweigtkettigen C8-C10-Alkanole, die gegebenenfalls noch mit 1 bis 2 Mol Propylenoxid pro Mol Alkanol propoxyliert sein können,
  • O bis 10, vorzugsweise 0,5 bis 5 Gew.-% an aktivsauerstoffabspaltenden Verbindungen, gegebenenfalls auch Aktivatoren für diese,
    und
  • O bis 5, vorzugsweise 0,5 bis 2 Gew.-% eines schwachschäumenden nichtionogenen Tensids aus der Gruppe der Alkylenoxidaddukte an C12-C18 Alkanole, Nonylphenol oder an Polypropylenglykole der Molgewichte 900 bis 4 000.
The cleaning agents according to the invention consist of a combination of
  • 0 to 50, preferably 10 to 40% by weight of a polymeric alkali metal phosphate from the group of the alkali metal diphosphates and alkali metal triphosphates,
  • 0 to 60, preferably 5 to 50% by weight of water-insoluble, complex-forming zeolites of the NaA or NaX type or their mixtures or water-soluble organic complexing agents for calcium, at least one of these compounds or one of the polymeric alkali metal phosphates must be present,
  • 10 to 60, preferably 20 to 50% by weight alkali metasilicate,
  • 2 to 40, preferably 5 to 30% by weight sodium carbonate,
  • 0 to 20, preferably 5 to 20% by weight sodium hydrogen carbonate,
  • 1 to 20, preferably 1 to 15% by weight of water glass,
  • 0.1 to 5, preferably 0.5 to 3% by weight of an enzyme or enzyme mixture from the group of the hydrolases, preferably amylases, proteases and lipases,
  • 0.1 to 10, preferably 0.5 to 5% by weight of primary, straight-chain or branched-chain C 8 -C 10 -alkanols, which can optionally also be propoxylated with 1 to 2 moles of propylene oxide per mole of alkanol,
  • 0 to 10, preferably 0.5 to 5% by weight of active oxygen-releasing compounds, optionally also activators for these,
    and
  • 0 to 5, preferably 0.5 to 2% by weight of a low-foaming nonionic surfactant from the group of the alkylene oxide adducts with C12-C18 alkanols, nonylphenol or with polypropylene glycols with a molecular weight of 900 to 4,000.

Als polymere Alkaliphosphate kommen die üblicherweise in Spül- und Reinigungsmittelgemischen verwendeten kondensierten Phosphate in Betracht, die in Form ihrer alkalischen neutralen oder sauren Natrium- oder Kaliumsalze vorliegen können. Beispiele hierfür sind: Tetranatriumpyrophosphat, Dinatriumdihydrogenpyrophosphat, Pentanatriumtriphosphat, Natriumhexametaphosphat sowie die entsprechenden Kaliumsalze bzw. Gemische aus Natrium- und Kaliumsalzen.Suitable polymeric alkali metal phosphates are the condensed phosphates which are usually used in washing-up and cleaning agent mixtures and which can be present in the form of their alkaline neutral or acidic sodium or potassium salts. Examples include: tetrasodium pyrophosphate, disodium dihydrogen pyrophosphate, pentasodium triphosphate, sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.

Nun wird bekanntlich der Phosphatgehalt von Waschmitteln allgemein von der Fachwelt und der öffentlichkeit in zunehmendem Maße für die Gewässereutrophierung verantwortlich gemacht und deshalb als ein Nachteil angesehen. Man hat daher ein Reihe von Substanzen als Ersatz für die bisher üblichen Waschmittelphosphate vorgeschlagen. Am besten bewährt und durchgesetzt haben sich offensichtlich Natriumaluminiumsilikate in Form der synthetisch hergestellten Zeolithe vom Typ NaA und NaX , wie sie beispielsweise in den US-amerikanischen Patentschriften 2 882 243 und 2 882 244 beschrieben sind. Die Zeolithe werden in ihrer hydratisierten Form eingesetzt.As is well known, the phosphate content of detergents in general is increasingly being held responsible for water reutrophication by experts and the public and is therefore regarded as a disadvantage. A number of substances have therefore been proposed as a replacement for the detergent phosphates which have been customary to date. Sodium aluminum silicates in the form of the synthetically produced zeolites of the NaA and NaX type, as are described, for example, as described, for example, in the US Pat. The zeolites are used in their hydrated form.

Die wasserlöslichen organischen Komplexierungsmittel für Calcium finden sich im wesentlichen unter den Polycarbonsäuren, Hydroxycarbonsäuren, Aminocarbonsäuren, Carboxyalkylethern, polyanionischen polymeren Carbonsäuren und den Phosphonsäuren, wobei diese Verbindungen meist in Form ihrer wasserlöslichen Salze eingesetzt werden. Spezifische, aber nicht vollständige Beispiele sind Citronensäure, Carboxymethyltartronsäure, Mellithsäure, Polyacrylsäure, Poly-or--hydroxyacrylsäure, Carboxymethyl- äpfelsäure, Nitrilotriessigsäure und 1-Hydroxy-äthan-1,1-diphosphonsäure.The water-soluble organic complexing agents for calcium are essentially found among the polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, carboxyalkyl ethers, polyanionic polymeric carboxylic acids and the phosphonic acids, these compounds mostly being used in the form of their water-soluble salts. Specific but not exhaustive examples are citric acid, carboxymethyl tartronic acid, mellitic acid, polyacrylic acid, poly-or-hydroxyacrylic acid, carboxymethyl malic acid, nitrilotriacetic acid and 1-hydroxyethane-1,1-diphosphonic acid.

Als Alkalimetasilikate werden wasserlösliche Natrium-oder Kaliummetasilikate verwendet. Sie können wasserfrei, anhydratisiert oder kristallwasserhaltig sein und 5 bis 9 Mol Wasser enthalten.Water-soluble sodium or potassium metasilicates are used as alkali metal silicates. You can free of water, or anhydrate kristallwasserhalti g and containing from 5 to 9 moles of water.

Unter Wasserglas werden wasserlösliche Natrium- oder Kaliumsilikate verstanden, bei denen das Verhältnis von Alkalioxid zu Siliciumdioxid etwa 1 : 2 bis 1 : 4 beträgt. Sie können als wasserfreie feste Substanzen oder als flüssige, etwa 50%ige Lösungen eingesetzt werden.Water glass is understood as meaning water-soluble sodium or potassium silicates in which the ratio of alkali oxide to silicon dioxide is approximately 1: 2 to 1: 4. They can be used as anhydrous solid substances or as liquid, approximately 50% solutions.

Als Enzyme kommen solche tierischen und pflanzlichen Ursprungs, insbesondere aus Verdauungsfermenten, Hefen und Bakterienstämmen gewonnene Wirkstoffe in Frage. Sie stellen meist ein kompliziert zusammengesetztes Gemisch verschiedener enzymatischer Wirkstoffe dar. Von besonderem Interesse sind Stärke, Eiweiß oder Fette spaltende Enzyme, wie Amylasen, Proteasen und Lipasen. Die Enzyme werden nach den verschiedensten Verfahren aus Bakterienstämmen, Pilzen, Hefen oder tierischen Organen gewonnen und unter unterschiedlichen Namen im Handel angeboten. Meist handelt es sich dabei um Enzymgemische, die eine kombinierte Wirkung gegenüber Stärke, Eiweiß und Fetten besitzen. Die aus Bacillus subtilis gewonnenen Enzympräparate besitzen den für die praktische Verwendung besonderen Vorteil, daß sie gegenüber Alkalien relativ beständig sind. Die Temperaturempfindlichkeit der Enzyme spielt hier keine nennenswerte Rolle mehr.Such enzymes are those of animal and vegetable origin, in particular active substances obtained from digestive ferment, yeast and bacterial strains. They usually represent a complex mixture of different enzymatic active ingredients. Of particular interest are starch, protein or fat-cleaving enzymes, such as amylases, proteases and lipases. The enzymes are obtained from a variety of processes from bacterial strains, fungi, yeasts or animal organs and are sold under different names. Most of these are enzyme mixtures that have a combined effect on starch, protein and fats have. The enzyme preparations obtained from Bacillus subtilis have the particular advantage for practical use that they are relatively resistant to alkalis. The temperature sensitivity of the enzymes no longer plays a significant role here.

Die Enzyme werden von den Herstellern,gegebenenfalls unter Zusatz von Verschnittmitteln wie Natriumsulfat, Natriumchlorid, Alkaliphosphaten oder Alkalipolyphospha- ten,auf einen bestimmten Aktivitätsgrad eingestellt. Üblich sind die Angaben in LVE/g (Löhlein-Volhard-Einheiten pro Gramm), IU (Internationale Einheiten) und DE/g (Delfter Einheiten pro Gramm) für proteolytische Enzyme. Wegen der einfachen Analysenmethode wird vielfach die Aktivität in LVE/g angegeben. In den erfindungsgemäßen Geschirrspülmitteln soll die proteolytische Enzymaktivität 100 bis 5 000, vorzugsweise 200 bis 2 000 LVE/g betragen. Die amylolytische Aktivität wird im allgemeinen in SKB/g (Sandstedt-Kneen-Blish-Einheiten pro Gramm) angegeben. Sie soll im Reinigergemisch etwa 5 bis 1 000, vorzugsweise 15 bis 250 SKB/g betragen. Die Menge,der in den Geschirreinigungsmitteln zu verwendenden Enzyme,richtet sich nach diesen Werten.The manufacturers set the enzymes to a certain degree of activity, possibly with the addition of blending agents such as sodium sulfate, sodium chloride, alkali phosphates or alkali polyphosphates. The data in LVE / g (Löhlein-Volhard units per gram), IU (international units) and DE / g (Delft units per gram) are common for proteolytic enzymes. Because of the simple analysis method, the activity is often stated in LVE / g. In the dishwashing detergents according to the invention, the proteolytic enzyme activity should be 100 to 5,000, preferably 200 to 2,000 LVE / g. Amylolytic activity is generally reported in SKB / g (Sandstedt-Kneen-Blish units per gram). It should be about 5 to 1,000, preferably 15 to 250, SKB / g in the detergent mixture. The amount of the Geschirreinigun smitteln g enzymes to be used, is determined by these values.

Die primären, gerad- oder verzweigtkettigen Alkanole enthalten 8 bis 10 Kohlenstoffatome im Alkylrest. Sie können mit 1 bis 2, vorzugsweise 2 Mol pro Mol Alkanol Propylenoxid propoxyliert sein. Hierzu gehören insbesondere n-Octanol, 2-Ethylhexanol, Isononanylalkohol, n-Decanol, Isodecanol und bevorzugt n-Octanol + 2 Mol Propylenoxid (PO).The primary, straight or branched chain alkanols contain 8 to 10 carbon atoms in the alkyl radical. They can be propoxylated with 1 to 2, preferably 2, moles per mole of alkanol propylene oxide. These include in particular n-octanol, 2-ethylhexanol, isononanyl alcohol, n-decanol, isodecanol and preferably n-octanol + 2 moles of propylene oxide (PO).

Als Aktivsauerstoff abspaltende Verbindungen können die bekannten Alkaliperborate, -persulfate und -percarbonat dienen, die durch Aktivatoren wie Tetraacetylethylendiamin, Tetraacetylglykoluril, Pentaacetylglukose aktiviert werden können, aber auch Verbindungen wie Magnesiummonoperphthalat, wobei auf Aktivatorzusatz verzichtet werden kann.The known alkali perborates, persulfates and percarbonate, which can be activated by activators such as tetraacetylethylenediamine, tetraacetylglycoluril, pentaacetylglucose, but also compounds such as magnesium monoperphthalate, can be used as compounds which release active oxygen, but also compounds such as magnesium monoperphthalate, it being possible to dispense with the addition of activator.

Als nichtionogene schwachschäumende Tenside kommen vorzugsweise Ethylenoxidaddukte an höhermolekulare Polypropylenglykole der Molgewichte 900 bis 4 000, sowie Ethylenoxid- bzw. Ethylenoxid- und Propylenoxidaddukte an C12-C18-Alkanole und Nonylphenol in Betracht. Die Herstellung erfolgt in bekannter Weise durch Anlagerung der betreffenden Alkylenoxide in Gegenwart meist alkalischer Katalysatoren, gegebenenfalls unter Druck und bei erhöhten Temperaturen, wobei bis zur dreifachen Gewichtsmenge der Ausgangsverbindungen an Alkylenoxiden angelagert werden kann. Beispiele für geeignete Anlagerungsprodukte sind das Addukt von 10 Gewichtsprozent Ethylenoxid an ein Polyoxypropylenglykol des Molgewichtes 1750, sowie das Addukt von 9 Mol Ethylenoxid und 10 Mol Propylenoxid an Nonylphenol, und dergleichen.Suitable nonionic low-foaming surfactants are preferably ethylene oxide adducts with higher molecular weight polypropylene glycols with a molecular weight of 900 to 4,000, and ethylene oxide or ethylene oxide and propylene oxide adducts with C 12 -C 18 alkanols and nonylphenol. The preparation is carried out in a known manner by addition of the alkylene oxides in question in the presence of mostly alkaline catalysts, if appropriate under pressure and at elevated temperatures, it being possible to add up to three times the amount by weight of the starting compounds on alkylene oxides. Examples of suitable addition products are the adduct of 10% by weight of ethylene oxide with a polyoxypropylene glycol of molecular weight 1750, and the adduct of 9 mol of ethylene oxide and 10 mol of propylene oxide with nonylphenol, and the like.

Zu den brauchbaren nichtionischen Tensiden gehören auch die oberflächenaktiven Aminoxide, die sich meist von tertiären Aminen mit einer hydrophoben C10-C20-Alkylgruppe und zwei kürzeren, bis zu je 4 C-Atome enthaltenden Alkyl- und/oder Alkylolgruppen ableiten. Typische Vertreter sind beispielsweise die Verbindungen N-Dodecyl-N,N-dimethylaminoxid, N-Tetradecyl-N,N-dihydroxyethyl- aminoxid bzw. N-Hexadecyl-N,N-bis(2,3-dihydroxypropyl)-aminoxid.The useful nonionic surfactants also include the surface-active amine oxides, which are usually derived from tertiary amines with a hydrophobic C 10 -C 20 alkyl group and two shorter alkyl and / or alkylol groups each containing up to 4 C atoms. Typical representatives are, for example, the compounds N-dodecyl-N, N-dimethylamine oxide, N-tetradecyl-N, N-dihydroxyethylamine oxide or N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide.

Außer den genannten Bestandteilen können die beanspruchten. Gemische weitere Komponenten, insbesondere anorganische Salze wie Natriumsulfat als Verschnittmittel enthalten. Weiterhin kommen sauer oder alkalisch reagierende bzw. puffernde anorganische oder organische Verbindungen zur Einstellung eines für die Enzymwirkung vorteilhaften pH-Wertes in Betracht. Bevorzugt werden hierfür die auch als Komplexbildner verwendeten organischen Hydroxycarbonsäuren, wie Zitronensäure oder Weinsäure, sowie Phosphorsäure oder saure Alkaliorthophosphate. Im allgemeinen liegen die pH-Werte - je nach Art des Enzyms - zwischen 4 und 12. Schließlich können den Gemischen noch enzymaktivierende Zusätze, wie Ammoniumchlorid, Natriumchlorid, Farbstoffe, Parfüms und dergleichen zugesetzt werden.In addition to the components mentioned, the claimed. Mixtures of other components, especially inorganic salts such as sodium sulfate, contain as a blending agent. In addition, acidic or alkaline or buffering inorganic or organic compounds can be used to establish a pH value which is advantageous for the enzyme action. For this purpose, preference is given to the organic hydroxycarboxylic acids, such as citric acid or tartaric acid, which are also used as complexing agents, and also phosphoric acid or acidic alkali orthophosphates. In general, the pH values are between 4 and 12, depending on the type of enzyme. Finally, enzyme-activating additives such as ammonium chloride, sodium chloride, dyes, perfumes and the like can also be added to the mixtures.

Die beanspruchten Mittel werden im allgemeinen als Mischungen von gekörnten oder pulverförmigen Einzelsubstanzen oder als granulierte, agglomerierte oder geprillte Produkte angewendet.The claimed agents are generally used as mixtures of granular or powdery individual substances or as granulated, agglomerated or prilled products.

Die beanspruchten Reinigungsmittelkombinationen zeichnen sich durch eine hohe Benetzungswirkung sowie ein außerordentlich gutes Niedrigtemperatur-Reinigungsvermögen, insbesondere gegenüber hartnäckigen Anschmutzungen, wie Fett-, Eiweiß- und Stärkebelägen aus.The claimed cleaning agent combinations are characterized by a high wetting effect and an extraordinarily good low-temperature cleaning ability, especially in relation to stubborn stains, such as grease, protein and starch deposits.

Die Anwendung erfolgt durch Zugabe der pulverförmigen, granulierten, agglomerierten oder geprillten Mittel von Hand in die Geschirreinigungsflotte oder vorzugsweise mittels automatischer Dosiervorrichtungen. Die Anwendungskonzentrationen in der Reinigungsflotte sollen etwa 2 bis 7 g/1 betragen, wobei Temperaturen von etwa 40 bis 45 C angewendet werden.The application takes place by adding the powdery, granulated, agglomerated or prilled agents by hand into the dishwashing liquor or preferably by means of automatic dosing devices. The application concentrations in the cleaning liquor should be about 2 to 7 g / 1, temperatures of about 40 to 45 C being used.

Zur Prüfung des Reiniaungsergebnisses der erfindungsgemäßen Reinigungsmittel wurden Teller mit Kartoffelstärke-und Haferbreianschmutzungen sowie mit Fettstift- und Rindertalgbelägen, Schalen mit Milch-, Pudding- und Hackfleischanschmutzungen und weiterhin Tassen mit angetrockneten Teeresten gereinigt. Die Versuche wurden in einer Haushaltsgeschirrspülmaschine (HGSM) vom Typ AEG "Favorit de Luxe Elektronik i" mit Düsseldorfer Stadtwasser (16 °d) durchgeführt, die folgende Programmschritte aufwies:

Figure imgb0001
To test the cleaning result of the cleaning agents according to the invention, plates with potato starch and porridge soiling as well as with grease stick and beef tallow toppings, bowls with milk, pudding and minced meat soiling and furthermore cups with dried-on tea residues were cleaned. The experiments were carried out in one Household dishwasher (HGSM) type AEG "Favorite de Luxe Electronics i" with Düsseldorf city water (16 ° d) carried out, which had the following program steps:
Figure imgb0001

Im Reinigungsgang wurden 30 g Reinigungsmittel, entsprechend 5 g/l Flotte, eingesetzt. Im Klarspülgang wurde kein Klarspüler zudosiert, um die Reinigungsergebnisse nicht zu verfälschen. Nach Beendigung des gesamten Programms erfolgte jeweils die visuelle Beurteilung des Reinigungsvermögens der eingesetzten Reinigungsmittel. Die einzelnen Bewertungen erfolgten nach einem Punktsystem, das von O bis 10 reichte, wobei 0 Punkte "ohne erkennbare Reinigungswirkung" und 10 Punkte "restlose Beseitigung der Testanschmutzungen" bedeutete. Es ergab sich hieraus eine Anzahl von Zwischenwerten, die eine differenzierte Aussage ermöglichten. Die Ergebnisse stellen Mittelwerte aus 4 Parallelbeurteilungen von 4 Testpersonen dar.30 g of detergent, corresponding to 5 g / l of liquor, were used in the cleaning cycle. No rinse aid was added in the rinse aid in order not to falsify the cleaning results. At the end of the entire program, the cleaning ability of the cleaning agents used was visually assessed. The individual evaluations were carried out according to a point system which ranged from 0 to 10, with 0 points meaning "without any recognizable cleaning effect" and 10 points meaning "complete removal of the test soiling". This resulted in a number of intermediate values that made it possible to make a differentiated statement. The results represent mean values from 4 parallel assessments by 4 test subjects.

Die Testanschmutzungen bestanden aus Haferflockenbrei und Stärke in Form von Kartoffelpürree, die auf Teller aufgebracht und abgekratzt wurden. Danach wurde das Geschirr 6 Stunden lang bei Raumtemperatur an der Luft stehengelassen und dann in die Geschirrspülmaschine eingebracht. Bei der Rindertalganschmutzung wurde wie folgt vorgegan- gen: 0,5 bis 0,8 g Rindertalg wurden bis zur Verflüssigung erwärmt und ca. 2 % Titandioxid eingerührt. Dann wurde die noch warme Masse mittels eines Pinsels gleichmäßig auf rote Kunststoffteller verstrichen. Zunächst wurde mit einem herkömmlichen Standardreinigungsmittel (A) gespült, das folgende Zusammensetzung aufwies:The test soils consisted of oatmeal porridge and starch in the form of mashed potatoes, which were placed on plates and scraped off. The dishes were then left to stand in the air for 6 hours at room temperature and then placed in the dishwasher. In the Rindertalganschmutzung was pre-gen as follows, g: 0.5 to 0.8 g of beef tallow were heated until liquefied and stirred for about 2% of titanium dioxide. Then the still warm mass was spread evenly onto red plastic plates using a brush. First, a conventional standard cleaning agent (A) was used, which had the following composition:

Reiniger A:Cleaner A:

  • 40 Gew.-% Natriumtriphosphat, wasserfrei,40% by weight sodium triphosphate, anhydrous,
  • 45 Gew.-% Natriummetasilikat, wasserfrei,45% by weight sodium metasilicate, anhydrous,
  • 5 Gew.-% Natriumcarbonat, wasserfrei, Rest Wasser5% by weight sodium carbonate, anhydrous, the rest water

Es wurden weitere Reinigungsmittelzusammensetzungen unter Verwendung anderer anorganischer Komplexbildner, wie z. B. Natriumaluminiumsilikate_vom Typ NaA oder NaX oder organischer Komplexbildner, wie z. B. des Na-Salzes der Nitrilotriessigsäure als Teil- bzw. Vollphosphatersatz mit in die Untersuchungen einbezogen. Diese Reiniger hatten folgende Zusammensetzungen:There have been other detergent compositions using other inorganic complexing agents, such as. B. sodium aluminum silicates of type NaA or NaX or organic complexing agents, such as. B. the sodium salt of nitrilotriacetic acid as a partial or full phosphate substitute included in the studies. These cleaners had the following compositions:

Reiniger B:Cleaner B:

  • 20 Gew.-% Natriumtriphosphat, wasserfrei,20% by weight sodium triphosphate, anhydrous,
  • 20 Gew.-% Zeolith NaA, (als wasserfreie Substanz berechnet),20% by weight of zeolite NaA, (calculated as anhydrous substance),
  • 45 Gew.-% Natriummetasilikat, wasserfrei,45% by weight sodium metasilicate, anhydrous,
  • 5 Gew.-% Natriumcarbonat, wasserfrei, Rest Wasser5% by weight sodium carbonate, anhydrous, the rest water
Reiniger C:Cleaner C:

  • 40 Gew.-% Zeolith NaA, (als wasserfreie Substanz berechnet),40% by weight of zeolite NaA (calculated as anhydrous substance),
  • 45 Gew.-% Natriummetasilikat, wasserfrei,45% by weight sodium metasilicate, anhydrous,
  • 5 Gew.-% Natriumcarbonat, wasserfrei, Rest Wasser5% by weight sodium carbonate, anhydrous, the rest water
Reiniger D:Cleaner D:

  • 20 Gew.-% Natriumtriphosphat, wasserfrei,20% by weight sodium triphosphate, anhydrous,
  • 20 Gew.-% Nitrilotriessigsäure, Na-Salz,20% by weight nitrilotriacetic acid, sodium salt,
  • 45 Gew.-% Natriummetasilikat, wasserfrei,45% by weight sodium metasilicate, anhydrous,
  • 5 Gew.-% Natriumcarbonat, wasserfrei, Rest Wasser5% by weight sodium carbonate, anhydrous, the rest water
Reiniger E:Cleaner E:

  • 40 Gew.-% Nitrilotriessigsäure, Na-Salz,40% by weight nitrilotriacetic acid, sodium salt,
  • 45 Gew.-% Natriummetasilikat, wasserfrei,45% by weight sodium metasilicate, anhydrous,
  • 5 Gew.-% Natriumcarbonat, wasserfrei Rest Wasser5% by weight sodium carbonate, anhydrous remainder water

Die Reinigungsergebnisse sind der nachfolgenden Tabelle 1 zu entnehmen. Sie zeigt, daß der Einsatz von Reinigungsmitteln der vorstehend angegebenen konventionell variierten Rezepturen bei Reduzierung der Reinigungstemperatur um 25 °C zu erheblich verminderter Reinigungsleistung führt.

Figure imgb0002
The cleaning results are shown in Table 1 below. It shows that the use of cleaning agents of the conventionally varied recipes given above leads to a considerably reduced cleaning performance when the cleaning temperature is reduced by 25 ° C.
Figure imgb0002

Bei den nachfolgenden Beispielen wurden 4 Gew.-%, entsprechend 1,2 g, des Natriummetasilikats der Standardrezeptur A durch 1 Gew.-%, entsprechend 0,3 g, eines 1 : 1 Gemisches aus Amylase und Protease (Maxamyl (R) bzw. Maxatase (R) der Firma Koninklijke Nederlandsche Gist en Spiritus-Fabriek N.V., Delft) und 3 Gew.-%, entsprechend 0,9 g, der in der vorliegenden Tabelle angegebenen Verbindungen ersetzt.In the following examples, 4% by weight, corresponding to 1.2 g, of the sodium metasilicate of standard formulation A was replaced by 1% by weight, corresponding to 0.3 g, of a 1: 1 mixture of amylase and protease (Maxamyl (R) or Maxatase (R) from Koninklijke Nederlandsche Gist en Spiritus-Fabriek NV, Delft) and 3% by weight, corresponding to 0.9 g, of the compounds listed in the table below.

Figure imgb0003
Figure imgb0003
Figure imgb0004
Figure imgb0004
Figure imgb0005
Figure imgb0005
Figure imgb0006
Figure imgb0006
Figure imgb0007
Figure imgb0007
Figure imgb0008
Figure imgb0008

Claims (2)

1. Geschirreinigungsmittel auf Basis von polymeren Alkaliphosphaten und/oder deren Austauschstoffen, Alkalisilikaten, Alkalicarbonaten sowie gegebenenfalls Aktivsauerstoff abspaltenden Verbindungen und schwach schäumenden nichtionischen Tensiden, dadurch gekennzeichnet, daß sie Enzyme und primäre, gerad-oder verzweigtkettige C8-C10-Alkanole, die gegebenenfalls propoxyliert sein können, enthalten.1. Dishwashing detergent based on polymeric alkali phosphates and / or their substitutes, alkali silicates, alkali carbonates and optionally active oxygen-releasing compounds and low-foaming nonionic surfactants, characterized in that they contain enzymes and primary, straight-chain or branched-chain C 8 -C 10 alkanols may optionally be propoxylated. 2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß sie aus einer Kombination aus 0 bis 50, vorzugsweise 10-bis 40 Gew.-% eines polymeren Alkaliphosphates aus der Gruppe der Alkalidiphosphate und Alkalitriphosphate, O bis 60, vorzugsweise 5 bis 50 Gew.-% an wasserunlöslichen, komplexbildenden Zeolithen vom Typ NaA oder NaX bzw. deren Gemischen oder wasserlöslichen organischen Komplexierungsmittel für Calcium, wobei wenigstens eine dieser Verbindungen oder eines der polymeren Alkaliphosphate anwesend sein muß, 10 bis 60, vorzugsweise 20 bis 50 Gew.-% Alkalimetasilikat, 2 bis 40, vorzugsweise 5 bis 30 Gew.-% Natriumcarbonat, 0 bis 20, vorzugsweise 5 bis 20 Gew.-% Natriumhydrogencarbonat, 1 bis 20, vorzugsweise 1 bis 15 Gew.-% Wasserglas, 0,1 bis 5, vorzugsweise 0,5 bis 3 Gew.-% eines Enzyms oder Enzymgemisches aus der Gruppe der Hydrolasen, vorzugsweise Amylasen, Proteasen und Lipasen, 0,1 bis 10, vorzugsweise 0,5 bis 5 Gew.-% an primären, gerad- oder verzweigtkettigen C8-C10-Alkanolen, die gegebenenfalls noch mit 1 - 2 Mol Propylenoxid pro Mol Alkanol propoxyliert sein können, 0 bis 10, vorzugsweise 0,5 bis 5 Gew.-% an aktivsauerstoffabspältenden Verbindungen, gegebenenfalls auch Aktivatoren für diese, und 0 bis 5, vorzugsweise 0,5 bis 2 Gew.-% eines schwachschäumenden nichtionogenen Tensids aus der Gruppe der Alkylenoxidaddukte an C12-C18-Alkanole, Konylphenol oder an Polypropylenglykole der Molgewichte 900 bis 4 000 bestehen. 2. Composition according to claim 1, characterized in that it consists of a combination of 0 to 50, preferably 10 to 40% by weight of a polymeric alkali metal phosphate from the group of the alkali metal diphosphates and alkali metal triphosphates, 0 to 60, preferably 5 to 50% by weight of water-insoluble, complex-forming zeolites of the NaA or NaX type or their mixtures or water-soluble organic complexing agents for calcium, at least one of these compounds or one of the polymeric alkali metal phosphates must be present, 10 to 60, preferably 20 to 50% by weight alkali metasilicate, 2 to 40, preferably 5 to 30% by weight sodium carbonate, 0 to 20, preferably 5 to 20% by weight sodium hydrogen carbonate, 1 to 20, preferably 1 to 15% by weight of water glass, 0.1 to 5, preferably 0.5 to 3% by weight of an enzyme or enzyme mixture from the group of the hydrolases, preferably amylases, proteases and lipases, 0.1 to 10, preferably 0.5 to 5% by weight of primary, straight-chain or branched-chain C 8 -C 10 -alkanols, which can optionally be propoxylated with 1 to 2 moles of propylene oxide per mole of alkanol, 0 to 10, preferably 0.5 to 5% by weight of compounds releasing active oxygen, optionally also activators for these, and 0 to 5, preferably 0.5 to 2 wt .-% of a low-foaming nonionic surfactant from the group of alkylene oxide adducts with C 12 -C 18 alkanols, Konylphenol or with polypropylene glycols with a molecular weight of 900 to 4,000.
EP85109465A 1984-08-04 1985-07-27 Dish cleaning agent Expired - Lifetime EP0171007B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85109465T ATE61398T1 (en) 1984-08-04 1985-07-27 DISHWASHER CLEANER.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843428834 DE3428834A1 (en) 1984-08-04 1984-08-04 DISHWASHER
DE3428834 1984-08-04

Publications (3)

Publication Number Publication Date
EP0171007A2 true EP0171007A2 (en) 1986-02-12
EP0171007A3 EP0171007A3 (en) 1989-05-03
EP0171007B1 EP0171007B1 (en) 1991-03-06

Family

ID=6242387

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85109465A Expired - Lifetime EP0171007B1 (en) 1984-08-04 1985-07-27 Dish cleaning agent

Country Status (4)

Country Link
US (1) US4692260A (en)
EP (1) EP0171007B1 (en)
AT (1) ATE61398T1 (en)
DE (2) DE3428834A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0239379A2 (en) * 1986-03-26 1987-09-30 Amway Corporation Water spot control and dish-washing compositions
EP0256679A1 (en) * 1986-08-05 1988-02-24 Imperial Chemical Industries Plc Dishwashing compositions
EP0271155A2 (en) † 1986-12-10 1988-06-15 Unilever N.V. Enzymatic dishwashing and rinsing process
US4931217A (en) * 1987-11-26 1990-06-05 Lever Brothers Company Automatic dishwashing detergent comprising quaternary ammonium salt
EP0518720A1 (en) * 1991-05-31 1992-12-16 Colgate-Palmolive Company Nonaqueous liquid automatic dishwashing composition containing enzymes
EP0518721A1 (en) * 1991-05-31 1992-12-16 Colgate-Palmolive Company Nonaqueous liquid, phosphate-free automatic dishwashing composition containing enzymes
WO2012131390A3 (en) * 2011-03-31 2012-11-29 Reckitt Benckiser N.V. Detergent composition

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5269960A (en) * 1988-09-25 1993-12-14 The Clorox Company Stable liquid aqueous enzyme detergent
US5256327A (en) * 1991-08-01 1993-10-26 Shaklee Corporation Method of preparing a sequestering agent for a non-phosphate cleaning composition
US5429765A (en) * 1993-04-29 1995-07-04 Amway Corporation Detergent and method for producing the same
TR28788A (en) 1993-05-25 1997-03-25 Henkel Ecolab Gmbh & Co Ohg Methods and equipment for machine-dishwashing cleaning.
DE4416303A1 (en) * 1994-05-09 1995-11-16 Bayer Ag Low-foaming wetting agent and its use
US5861366A (en) * 1994-08-31 1999-01-19 Ecolab Inc. Proteolytic enzyme cleaner
US5876514A (en) * 1997-01-23 1999-03-02 Ecolab Inc. Warewashing system containing nonionic surfactant that performs both a cleaning and sheeting function and a method of warewashing
US7415983B2 (en) * 2003-12-18 2008-08-26 Ecolab Inc. Method of cleaning articles in a dish machine using an acidic detergent
CN101448399B (en) * 2006-04-21 2013-06-05 花王株式会社 Composition of biofilm control agent
JP5322400B2 (en) * 2006-04-21 2013-10-23 花王株式会社 Biofilm control agent composition
WO2014200658A1 (en) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase from promicromonospora vindobonensis
WO2014200656A1 (en) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase from streptomyces umbrinus
WO2014200657A1 (en) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase from streptomyces xiamenensis
EP3011020A1 (en) 2013-06-17 2016-04-27 Danisco US Inc. Alpha-amylase from bacillaceae family member
WO2015050724A1 (en) 2013-10-03 2015-04-09 Danisco Us Inc. Alpha-amylases from a subset of exiguobacterium, and methods of use, thereof
EP3060659B1 (en) 2013-10-03 2019-05-29 Danisco US Inc. Alpha-amylases from exiguobacterium, and methods of use, thereof
EP3071691B1 (en) 2013-11-20 2019-10-23 Danisco US Inc. Variant alpha-amylases having reduced susceptibility to protease cleavage, and methods of use, thereof
WO2017173190A2 (en) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions & methods
WO2017173324A2 (en) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions & methods
EP3399013B1 (en) * 2017-05-05 2022-08-03 The Procter & Gamble Company Laundry detergent compositions with improved grease removal

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1600256A (en) * 1968-05-24 1970-07-20
US3557002A (en) * 1967-11-15 1971-01-19 Procter & Gamble Stabilized aqueous enzyme preparation
DE2062465A1 (en) * 1970-12-18 1972-06-22 Henkel & Cie. GmbH, 4000 Düsseldorf Scouring agent - for dish washing machines, contg aminopolycarboxylic acid and alkali silicate
US4101457A (en) * 1975-11-28 1978-07-18 The Procter & Gamble Company Enzyme-containing automatic dishwashing composition
US4125475A (en) * 1974-12-23 1978-11-14 Texaco Inc. Detergents containing a fatty alcohol builder and a water-insoluble inorganic absorbent
FR2518567A1 (en) * 1981-12-23 1983-06-24 Colgate Palmolive Co DETERGENT COMPOSITION FOR DISHWASHER
WO1984004324A1 (en) * 1983-05-03 1984-11-08 Eka Ab Machine dishwashing composition
EP0135227A2 (en) * 1983-08-15 1985-03-27 Unilever N.V. Machine-dishwashing compositions

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2882244A (en) * 1953-12-24 1959-04-14 Union Carbide Corp Molecular sieve adsorbents
US2882243A (en) * 1953-12-24 1959-04-14 Union Carbide Corp Molecular sieve adsorbents
US3882038A (en) * 1968-06-07 1975-05-06 Union Carbide Corp Cleaner compositions
US3925224A (en) * 1973-04-17 1975-12-09 Church & Dwight Co Inc Detergent additive composition
AR208392A1 (en) * 1973-05-07 1976-12-27 Henkel & Cie Gmbh COMPOSITION TO WASH, WHITE OR CLEAN RESISTANT MATERIALS, ESPECIALLY TEXTILES ADDITIONAL TO PATENT NO 201687 ADDITIONAL TO NO 253286
DE2918826A1 (en) * 1979-05-10 1980-11-27 Basf Ag USE OF ALCOXYLATED ALCOHOLS AS BIODEGRADABLE, LOW-FOAM SURFACES IN DETERGENTS AND CLEANERS

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3557002A (en) * 1967-11-15 1971-01-19 Procter & Gamble Stabilized aqueous enzyme preparation
FR1600256A (en) * 1968-05-24 1970-07-20
DE2062465A1 (en) * 1970-12-18 1972-06-22 Henkel & Cie. GmbH, 4000 Düsseldorf Scouring agent - for dish washing machines, contg aminopolycarboxylic acid and alkali silicate
US4125475A (en) * 1974-12-23 1978-11-14 Texaco Inc. Detergents containing a fatty alcohol builder and a water-insoluble inorganic absorbent
US4101457A (en) * 1975-11-28 1978-07-18 The Procter & Gamble Company Enzyme-containing automatic dishwashing composition
FR2518567A1 (en) * 1981-12-23 1983-06-24 Colgate Palmolive Co DETERGENT COMPOSITION FOR DISHWASHER
WO1984004324A1 (en) * 1983-05-03 1984-11-08 Eka Ab Machine dishwashing composition
EP0135227A2 (en) * 1983-08-15 1985-03-27 Unilever N.V. Machine-dishwashing compositions

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0239379A2 (en) * 1986-03-26 1987-09-30 Amway Corporation Water spot control and dish-washing compositions
EP0239379A3 (en) * 1986-03-26 1989-05-24 Amway Corporation Water spot control and dish-washing compositions
EP0256679A1 (en) * 1986-08-05 1988-02-24 Imperial Chemical Industries Plc Dishwashing compositions
EP0271155A2 (en) † 1986-12-10 1988-06-15 Unilever N.V. Enzymatic dishwashing and rinsing process
EP0271155B2 (en) † 1986-12-10 2000-09-06 Unilever N.V. Enzymatic dishwashing and rinsing process
US4931217A (en) * 1987-11-26 1990-06-05 Lever Brothers Company Automatic dishwashing detergent comprising quaternary ammonium salt
EP0518720A1 (en) * 1991-05-31 1992-12-16 Colgate-Palmolive Company Nonaqueous liquid automatic dishwashing composition containing enzymes
EP0518721A1 (en) * 1991-05-31 1992-12-16 Colgate-Palmolive Company Nonaqueous liquid, phosphate-free automatic dishwashing composition containing enzymes
WO2012131390A3 (en) * 2011-03-31 2012-11-29 Reckitt Benckiser N.V. Detergent composition
US9540591B2 (en) 2011-03-31 2017-01-10 Reckitt Benckiser Finish B.V. Detergent composition
AU2016202223B2 (en) * 2011-03-31 2017-12-07 Reckitt Benckiser Finish B.V. Detergent composition
US10017721B2 (en) 2011-03-31 2018-07-10 Reckitt Benckiser Finish B.V. Detergent composition

Also Published As

Publication number Publication date
EP0171007B1 (en) 1991-03-06
ATE61398T1 (en) 1991-03-15
US4692260A (en) 1987-09-08
EP0171007A3 (en) 1989-05-03
DE3581978D1 (en) 1991-04-11
DE3428834A1 (en) 1986-02-13

Similar Documents

Publication Publication Date Title
EP0171007B1 (en) Dish cleaning agent
DE4232170C2 (en) Weakly alkaline dish detergent
DE2038103A1 (en) Dish-washing concentrates - contg enzymes, stabilised with sugar alcohols, monosaccharides or disaccharides
DE68925560T3 (en) Enzyme-containing detergent composition
DE69433032T2 (en) LIQUIDIFYING - [alpha] -AMYLASE, METHOD FOR THE PRODUCTION THEREOF, AND DETERGENT COMPOSITION CONTAINING THE SAME
DE1767142A1 (en) Surfactant combinations which can be used as laundry detergents and detergents or washing auxiliaries containing them
EP0530635B1 (en) Neutral composition for dishwashing machine
DE102007029643A1 (en) cleaning supplies
EP1000136B1 (en) Cleaning agent for hard surfaces, containing glucanase
DE2101508A1 (en) Dishwashing liquid
DE2062465A1 (en) Scouring agent - for dish washing machines, contg aminopolycarboxylic acid and alkali silicate
EP3342846B1 (en) Self-dissoluble capsule for preparation of washing solutions
EP0171006B1 (en) Dish cleaning agent
EP0171008B1 (en) Dish cleaning agent
US4333771A (en) Detergent composition with a mechanical cleaning effect
DE2153460A1 (en) DISHWASHING LIQUID
DE2435479A1 (en) Cleansing compsns for use in dish-washing machines - contg. water-soluble alkali metal silicate and water-soluble alkali metal polyacrylate
US6362150B1 (en) Detergent composition in the form of a solid detergent containing surfactant and bleaching peroxide
DE1767567A1 (en) Dishwashing liquid
DE2149251C3 (en) Dishwashing liquid
EP0569365B1 (en) Phosphate-free cleaning agent
EP0256679A1 (en) Dishwashing compositions
DE4036695C2 (en) Use of beta-alanine derivatives as builders in phosphate-free dishwashing detergents
DE2259201A1 (en) Cleansers for protein and starch-soiled surfaces - contg protease and amylase enzymes and use for cleaning solid surfaces in food, brewery and dairy inds
CH704560A2 (en) Detergents for dishwashers and methods therefor.

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE FR GB IT LI NL

RHK1 Main classification (correction)

Ipc: C11D 3/386

17P Request for examination filed

Effective date: 19891023

17Q First examination report despatched

Effective date: 19900405

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB IT LI NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19910306

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 19910306

Ref country code: GB

Effective date: 19910306

Ref country code: FR

Effective date: 19910306

Ref country code: BE

Effective date: 19910306

REF Corresponds to:

Ref document number: 61398

Country of ref document: AT

Date of ref document: 19910315

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3581978

Country of ref document: DE

Date of ref document: 19910411

EN Fr: translation not filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19910727

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19910731

Ref country code: CH

Effective date: 19910731

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19920401