EP0906407B1 - Low-alkaline mgda-containing dishwasher rinsing agent - Google Patents

Low-alkaline mgda-containing dishwasher rinsing agent Download PDF

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Publication number
EP0906407B1
EP0906407B1 EP97928266A EP97928266A EP0906407B1 EP 0906407 B1 EP0906407 B1 EP 0906407B1 EP 97928266 A EP97928266 A EP 97928266A EP 97928266 A EP97928266 A EP 97928266A EP 0906407 B1 EP0906407 B1 EP 0906407B1
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EP
European Patent Office
Prior art keywords
mgda
acid
detergent
salts
agents
Prior art date
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Revoked
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EP97928266A
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German (de)
French (fr)
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EP0906407A1 (en
Inventor
Guido Wäschenbach
Paul William Robinson
Laurence Geret
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Reckitt Benckiser NV
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Reckitt Benckiser NV
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Application filed by Reckitt Benckiser NV filed Critical Reckitt Benckiser NV
Priority to EP01105118A priority Critical patent/EP1113070B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds

Definitions

  • the invention relates to machine dishwashing detergents Alkalinity, methylglycinediacetic acid (MGDA) or a salt of which contain and which preferably have a reduced content of Have bleach.
  • MGDA methylglycinediacetic acid
  • US-A 3 673 098 discloses caustic compositions without Bleaching agents based on KOH and nitrilotriacetic acid (NTA) based.
  • Fr-A 1 590 416 also discloses caustic compositions without bleach based on alkali hydroxides, Pyrophosphates and NTA based.
  • EP-A-530 635 discloses acidic to mildly alkaline Compositions (pH 5-9) that do not contain complexing agents contain and on builders, enzymes and optionally Oxygen bleaching is based.
  • DE-A-3 833 047 discloses acidic compositions (pH 2-6) with hydrolases and builders or complexing agents.
  • the Examples disclose high NTA or EDTA share (up to 30%). While these compositions can e.g. Eliminate tea residues well, there is milk residue their effect, measured on a scale from 0 to 10, however always under 5.
  • biodegradable complexing agents such as ⁇ -alanine diacetic acid ( ⁇ -ADA) and iso-serine diacetic acid (ISDA), in detergents is in the DE-A-3 829 847 and DE-A-4 036 995. If those Publications Application examples for dishwasher detergents contained, it is machine dishwashing detergent, which in about 0.5% aqueous solution has a pH of more than 10.5.
  • DE-A-4 319 935 describes the use of MGDA in Dishwasher detergents disclosed without an example specify.
  • MGDA methylglycinediacetic acid
  • MGDA is supposed to be a better one, especially for blood-soiled laundry Have effect, as phosphonates and with tea soiled Laundry have about the same effect as phosphonates.
  • the same publication discloses that MGDA in a dishwashing detergent, similar to NTA, a very good one Deposit inhibition on glass, metal and porcelain shows, whereby a dishwashing detergent is disclosed which in solution provides pH of more than 10.5. It will too suggested MGDA in very strongly alkaline conditions to use for dairy cleaning.
  • a dishwashing detergent excellent cleaning performance for dishes have both milk and milk Tea residue is contaminated.
  • This task is accomplished by a Dishwasher detergent dissolved, the methylglycinediacetic acid or their salts as complexing agents and is characterized in that it is approximately 0.5% aqueous solution does not exceed a pH of 10.4 with which Provided that the dishwasher detergent more than 10 wt .-% of Contains methylglycine diacetic acid.
  • Milk residues consist of a mixture of denatured proteins (casein), fats, sugars and mineral deposits and consist of around 70% calcium phosphate (Ca 3 (PO 4 ) 2 ).
  • Complexing agents therefore have a significant influence on the removal of milk residues because they dissolve calcium phosphates by complexing the calcium ions.
  • Tea residues are also based on Ca deposits, that arise when brewing tea with hard water.
  • tea residues are usually different Requirements for a dishwasher detergent as Milk residues, which can be seen from the fact that the detergent disclosed in DE-A 3 833 047 in the acidic range (pH 2-6) Tea residues removed satisfactorily, at Milk residues cannot convince.
  • the ability (based on the weight of the complexing agent) to complex calcium ions at a certain pH value depends on the stability constant of the calcium complex (pK c ), the acidic character of the complexing agent (pK 3 ) and its molecular weight.
  • the theoretical is at pH 10.4 Degree of complexation for calcium phosphates when using NTA at 360 mg / g and when using MGDA at 340 mg / g, and at pH 8 the theoretical values are 510 mg / g for NTA and 490 mg / g for MGDA.
  • MGDA was only used in dishwashing detergents used in about 0.5% aqueous solution have a pH of more than 10.4.
  • Dishwashing detergents that contain MGDA and one of them 0.5% aqueous solution with a pH of up to 10.4 deliver better both tea residues and milk residues can remove and overall a better washing result have as dishwashing detergent, which instead of MGDA another Contain complexing agents such as the common NTA.
  • the sufficient Amount of complexing agent MGDA has the amount of Oxygen bleach can be reduced without changing thereby the flushing performance and in particular the ability Remove milk residues and tea residues, worsened. This surprising finding even opens up the possibility of using a sufficiently large amount of complexing agents completely on the use of To avoid oxygen bleach.
  • the dishwashing detergent according to the invention can be liquid or be powdery and also in the form of a single layer or multi-layer tablet. Appropriate Dosage forms and methods of obtaining them are the Known specialist.
  • the dishwasher detergents according to the invention preferably contain one or more enzymes such as Amylase, protease, lipase or cellulase. Through the combined application of amylase and protease were the best cleaning results.
  • the ones here are particularly suitable for the pH ranges described use effectively; for example, the temperature stable amylase Termamyl (Novo) at pH 7-8 das Optimal of your spectrum of activity.
  • the enzymes come in Granulate form or in solution with commercially available Concentrations or activities are used, the Enzyme content is 0.5-6, preferably 1-4% by weight can.
  • Suitable builders are homo- and copolymers Polycarboxylic acids and their partially or completely neutralized salts, monomeric polycarboxylic acids and Hydroxycarboxylic acids and their salts, carbonates, bicarbonates, Borates, phosphates, silicates, aluminosilicates and mixtures such substances.
  • Preferred salts of the above compounds are the ammonium and / or alkali salts, i.e. the lithium, Sodium, potassium and rubidium salts and particularly preferred the sodium salt used.
  • Suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic and aromatic carboxylic acids, these contain at least two carboxy groups, each through preferably no more than two carbon atoms from each other are separated.
  • Polycarboxylates containing two carboxy groups include for example water-soluble salts of succinic acid, Malonic acid, (ethylenedioxy) diacetic acid, maleic acid, Diglycolic acid, tartaric acid, tartronic acid and fumaric acid.
  • Polycarboxylates containing three carboxy groups include for example, water-soluble citrates.
  • Corresponding is suitable as a hydroxycarboxylic acid, for example Citric acid.
  • one of aspartic acid can also be used HOOC-CH (NH 2 ) -CH 2 -COOH derived polymer with monomer units of the formula to be named.
  • the homopolymer of is also suitable as the polycarboxylic acid Acrylic acid.
  • borate builders can also such builders are used, the borates among the Detergent storage conditions or rinsing conditions release.
  • Suitable phosphates are polyphosphates such as tripolyphosphate, Pyrophosphate, orthophosphate and the polymeric metaphosphate.
  • polyphosphates such as tripolyphosphate, Pyrophosphate, orthophosphate and the polymeric metaphosphate.
  • Suitable silicates are sodium silicates such as sodium disilicate, Sodium metasilicate and crystalline layered silicates. Sodium aluminosilicates are also suitable (Zeolite).
  • a builder system from the salt of one is particularly preferred Hydroxycarboxylic acid or from the mixture of one Hydroxycarboxylic acid and the salt of a hydroxycarboxylic acid.
  • Both the hydroxycarboxylic acid and the salt of Hydroxycarboxylic acid can be completely or partially Tripolyphosphate can be replaced, although this is not preferred becomes.
  • the builder system preferably consists of a Hydroxypolycarboxylic acid with 2-4 carboxyl groups (or acidic inorganic salts), which are used to adjust the pH value with their Salt can be mixed.
  • Citric acid is preferred or a mixture of sodium citrate with citric acid used.
  • the required pH value is suitable depending on the others Components of the mixture e.g. Mix with one predominant proportion of citric acid.
  • the water content of liquid dishwashing detergent can be 40-80 % By weight.
  • the liquid dishwashing detergents also contain 0.2-5.0% by weight, preferably 0.5-2% by weight, of a thickener.
  • a thickener preferably 0.5-2% by weight
  • Carboxyvinyl polymers such as those marketed by BF Goodrich under the production name "Carbopol”, proved to be very useful.
  • Inorganic compounds which have thickening properties in this product composition can also be used. Examples of this are natural or synthetic thickeners based on differently structured silicate structures. Their use is described in various patents, for example in US-A-4 933 101 or EP-A2-0 407 187.
  • nonionic surfactants are suitable as surfactants. These include, for example, water-soluble ethoxylated C 6-16 fatty alcohols and C 6-16 mixed ethoxylated / propoxylated fatty alcohols and mixtures thereof, and also polyglucosides.
  • Another class of non-ionic surfactants includes polyhydroxy fatty acid amides.
  • the dishwasher detergent according to the invention can further contain one or more foam control agents. All those used in this area are suitable for this Foam control agents such as silicones and Paraffin oil.
  • the foam control agents are in the invention Machine dishwashing detergent preferably with less than 5% by weight of the total weight of the detergent.
  • the machine dishwashing detergents according to the invention can be used as Bleaching agents prefer chlorine-free, active oxygen releasing bleaches such as inorganic perhydrates or contain organic peracids and their salts.
  • inorganic perhydrates are perborates, Percarbonates and persulfates such as peroxymonopersulfate.
  • the inorganic perhydrates are usually alkali metal salts, such as lithium, sodium, potassium or rubidium salts, especially the sodium salts.
  • the inorganic perhydrates can in the detergent as crystalline solids without protection. For certain perhydrates however, it is advantageous to use them as granular To use compositions with a coating are provided, the better the granular products Gives storage stability.
  • the preferred perborate is sodium perborate, which can be present as a monohydrate with the formula NaBO 2 H 2 O 2 or as a tetrahydrate with the formula NaBO 2 H 2 O 2 .3H 2 O.
  • the preferred percarbonate is sodium percarbonate with the formula 2Na 2 CO 3 3H 2 O 2 .
  • the percarbonate is preferably used in a coated form to increase its stability.
  • Organic peracids all conventionally include bleaching agents used organic peracids, including for example perbenzoic acid and peroxycarboxylic acids such as Mono- or diperoxyphthalic acid, 2-octydiperoxysuccinic acid, Diperoxydodecanedicarboxylic acid, Diperoxyazelaic acid and Imidoperoxycarboxylic acid and optionally its salts.
  • perbenzoic acid and peroxycarboxylic acids such as Mono- or diperoxyphthalic acid, 2-octydiperoxysuccinic acid, Diperoxydodecanedicarboxylic acid, Diperoxyazelaic acid and Imidoperoxycarboxylic acid and optionally its salts.
  • the dishwasher detergent according to the invention can continue to contain one or more bleach activators. These are preferred in detergents for dishwashing operations at temperatures below 60 ° C used to achieve a sufficient bleaching effect.
  • N- and O-acyl compounds are particularly suitable such as acylated amines, acylated glycolurils or acylated sugar compounds.
  • TAED N, N ', N'-tetraacetylethylenediamine
  • PAG pentaacetylglucose
  • TAGU tetraacetylglycoluril
  • Dishwasher detergent is an oxygen bleach an amount of less than 1% by weight, based on the active Oxygen on. The amount of bleach activator used will be adjusted accordingly.
  • the machine dishwashing detergent s a large percentage of MGDA, like 25% or more, preferably 30% or more, in each case based on the free acid, and an oxygen bleach is not used.
  • the dishwasher detergent according to the invention can also contain a silver / copper anti-corrosion agent.
  • This term includes funds that start up Non-ferrous metals, especially silver and copper, prevent or mitigate.
  • Preferred silver / copper anti-corrosion agents are benzotriazole or bis-benzotriazoles as well as their substituted derivatives.
  • Suitable agents are organic and / or inorganic redox-active substances and paraffin oil.
  • Benzotriazole derivatives are those compounds in which the available substitution sites of the aromatic ring are partially or completely substituted.
  • Suitable substituents are linear or branched C 1- 20 alkyl groups are suitable as well as hydroxy, thio, phenyl or halogen such as fluorine, chlorine, bromine and iodine.
  • Preferred substituted benzotriazole is tolyltriazole.
  • Suitable bis-benzotriazoles are those in which the benzotriazole groups are each connected in the 6-position by a group X, in which X is a bond, a straight-chain alkylene group which is optionally substituted by one or more C 1-4 alkyl groups and preferably has 1-6 carbon atoms , a cycloalkyl radical having at least 5 carbon atoms, a carbonyl group, a sulfuryl group, an oxygen or a sulfur atom.
  • the aromatic rings of the bis-benzotriazoles can be substituted as defined above for the benzotriazole.
  • Suitable organic redox-active substances are, for example, ascorbic acid, indole, methionine, an N-mono- (C 1 -C 4 alkyl) glycine, an N, N-di (C 1 -C 4 alkyl) glycine, 2- phenylglycine or a coupler and / or developer compound chosen from the group of diaminopyridines, aminohydroxypyridines, dihydroxypyridines, heterocyclic hydrazones, aminohydroxypyrimidines, dihydroxypyrimidines, tetraaminopyrimidines, triaminohydroxypyrimidines, Diaminodihydroxypyrimidine, Dihydroxynaphtaline, naphthols, pyrazolones, hydroxyquinolines, aminoquinolines, primary aromatic amines, which in ortho, meta or para position have a further free or with C 1 -C 4 alkyl or C 2 -C 4 hydroxyalkyl groups substituted hydroxy or amino
  • Suitable inorganic redox-active substances are for example, metal salts and / or metal complexes selected from the group of manganese, titanium, zirconium, hafnium, Vanadium, cobalt and cerium salts and / or complexes, wherein the metals in one of the oxidation states II, III, IV, V or VI are available.
  • Organic and inorganic redox-active substances which as Silver / copper anti-corrosion agents are suitable also mentioned in WO 94/26860 and WO 94/26859, on the Content hereby referred.
  • Suitable paraffin oil are predominantly branched aliphatic hydrocarbons with a number of carbon atoms in the range from 20 to 50.
  • the paraffin oil is preferably selected from predominantly branched chain C 25-45 species with a ratio of cyclic to noncyclic hydrocarbons of 1:10 to 2: 1 , preferably from 1: 5 to 1: 1.
  • a silver / copper anticorrosive in the machine dishwashing detergent according to the invention is present, it is preferably 0.01 to 5% by weight, particularly preferably with 0.1 to 2 wt .-% of the total weight.
  • the proportion of MGDA on the dishwasher detergent is high enough, such as 25% or more, preferably 30% or more, each based on is the free acid, so that there is no bleaching agent can also be used on a silver / copper anti-corrosion agent to be dispensed with.
  • the machine dishwashing detergents according to the invention are not caustic and therefore do not require a specially secured one Packaging. A good washing result can be achieved with one relatively low use of 15-20 g powder or 20-50 ml of liquid detergent can be achieved. All ingredients are according to current knowledge, neither toxic nor otherwise harmful to health.
  • the cleaning agents described here therefore also represent an environmentally and consumer-friendly Alternative to conventional cleaners with Complexing agents in the strongly basic area work.
  • the methylglycinediacetic acid used according to the invention has the following structural formula:
  • Methylglycinediacetic acid is particularly preferred as free acid or used as sodium or potassium salt and is preferably in an amount of 3% to 90%, based on the free acid, contained in the detergent.
  • the amount of MGDA is preferably at least 5%, based on the free acid.
  • an approximately 0.5% aqueous solution of the detergent has a pH of no more than 10.4.
  • the pH is preferably about 0.5% aqueous solution of the detergent according to the invention more than 6 to 10.4, particularly preferably from 7 to 10.0.
  • the table below shows the quantities of each Components in g and%.
  • the ingredients were in one Liters of water of 10 ° hardness dissolved, and the pH of the solution was determined in each case.
  • the total amount of ingredients (100%) is 4 g each, corresponding to a 0.4% Concentration as disclosed in Figure 14 of the article.
  • MGDA is not commercially available in its pure form and therefore a 77% solution in water was used. A larger amount of the commercially available product had to be used, as shown in the table. Two values are given in the table for MGDA. The first value indicates the amount in g of the commercial product, and the second value corresponds to the corresponding amount of pure substance (100%). S ⁇ FW Journal 122, 1996, 392-397 Ex. 1 Ex. 2 Quantities in g. (%) Ex.
  • the following example shows that when replacing part of the builder of a dishwasher detergent with methylglycinediacetic acid at low pH values excellent washing performance can be achieved and especially contrary to theoretical expectations Ability to remove milk residues and tea residues higher than other common complexing agents such as NTA.
  • the example illustrates the invention.
  • Liquid dishwashing detergents with a Composition as shown in Table 1 is made (both according to the invention using MGDA and using the NTA used in the prior art), and their washing performance was measured using dishes that both Contained milk and tea residues, determined. In this Test was essentially the DIN standard No. 44990, part 2 followed. It became a Bosch SMS 5062 dishwasher used. The water had a hardness of 19 ° dH (3.39 mmol Calcium carbonate), the temperature of the water was 65 ° C and 20 ml of detergent were used in each case. The results The flushing performance was assessed on a scale of 1-5 (5 for 100% clean dishes are rated) and are also listed in Table 1.
  • the non-ionic surfactant is a common, low-foaming ethoxylated and propoxylated fatty alcohol. Common proteases and amylases are used.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Detergent Compositions (AREA)

Abstract

A mechanical dishwasher rinsing agent contains, as complexing agent, methyl glycine diacetic acid (I) (or one of its salts), the rinsing agent has pH not more than 10.4 (preferably 6-10.4) as a 0.5% aqueous solution. Use of (I) (or its salt) is claimed as partial or complete substitute for builders or complexing agents in such rinsing agents in order to improve removal of milk and tea residues.

Description

Die Erfindung betrifft Maschinengeschirrspülmittel niederer Alkalität, die Methylglycindiessigsäure (MGDA) oder ein Salz davon enthalten und die bevorzugt einen veringerten Gehalt an Bleichmittel aufweisen.The invention relates to machine dishwashing detergents Alkalinity, methylglycinediacetic acid (MGDA) or a salt of which contain and which preferably have a reduced content of Have bleach.

Hochalkalische Maschinengeschirrspülmittel ohne Bleichmittel mit einem hohen Anteil an Komplexierungsmittel sind im Stand der Technik bekannt. In der Vergangenheit verkaufte man sie als Mittel für Haushaltsgeschirrspülmaschinen und noch heute werden sie für Industriegeräte verwendet.Highly alkaline dishwasher detergent without bleach with a high proportion of complexing agents are in the state known in the art. They were sold in the past as a means for household dishwashers and still today they are used for industrial devices.

US-A 3 673 098 offenbart kaustische Zusammensetzungen ohne Bleichmittel, die auf KOH und Nitrilotriessigsäure (NTA) basieren.US-A 3 673 098 discloses caustic compositions without Bleaching agents based on KOH and nitrilotriacetic acid (NTA) based.

Fr-A 1 590 416 offenbart ebenfalls kaustische Zusammensetzungen ohne Bleichmittel, die auf Alkalihydroxiden, Pyrophosphaten und NTA basieren. Fr-A 1 590 416 also discloses caustic compositions without bleach based on alkali hydroxides, Pyrophosphates and NTA based.

Später wurden solche Mittel ohne kaustische Alkalien formuliert, und der Leistungsverlust wurde durch Hinzufügen von Chlorbleiche, wie es in US-A- 3 826 748 beispielhaft ausgeführt ist, ausgeglichen. Diese Mittel ohne kaustische Alkalien hatten immer noch einen hohen pH-Wert von mehr als 11.Such agents later became without caustic alkalis was formulated, and the loss of performance was added by of chlorine bleach, as exemplified in US-A-3,826,748 is balanced. This means without caustic Alkaline still had a high pH greater than 11.

Der Trend zu sichereren und umweltfreundlicheren Mitteln führte zunächst zum Ersatz von starken Komplexierungsmitteln durch Builder und später zu einer neuen Generation von mild alkalischen Geschirrspülmitteln mit einem pH-Wert von 9 bis 11,5, deren Chlorbleichen durch Sauerstoffbleichen und Enzyme ersetzt wurden.The trend towards safer and more environmentally friendly means initially led to the replacement of strong complexing agents through builder and later to a new generation of mild alkaline dishwashing detergents with a pH of 9 to 11.5, whose chlorine bleaching by oxygen bleaching and enzymes have been replaced.

Gute Beispiele für derartige Mittel findet man in der EP-A- 135 226, der EP-A- 135 227 und der EP-A- 414 197. Bei diesen Mitteln sind Komplexierungsmittel normalerweise, wenn überhaupt, nur in geringen Mengen vorhanden.Good examples of such means can be found in the EP-A-135 226, EP-A-135 227 and EP-A-414 197. Bei These agents are usually complexing agents if at all, only available in small quantities.

EP-A- 530 635 offenbart saure bis mild alkalische Zusammensetzungen (pH 5-9), die keine Komplexierungsmittel enthalten und auf Buildern, Enzymen und gegebenenfalls Sauerstoffbleichen basieren.EP-A-530 635 discloses acidic to mildly alkaline Compositions (pH 5-9) that do not contain complexing agents contain and on builders, enzymes and optionally Oxygen bleaching is based.

DE-A- 3 833 047 offenbart saure Zusammensetzungen (pH 2-6) mit Hydrolasen und Buildern oder Komplexierungsmitteln. Die Beispiele offenbaren Zusammensetzungen mit hohem NTA- oder EDTA-Anteil (bis zu 30%). Diese Zusammensetzungen können zwar z.B. Teerückstände gut beseitigen, bei Milchrückständen liegt ihre Wirkung, auf einer Skala von 0 bis 10 gemessen, aber immer unter 5.DE-A-3 833 047 discloses acidic compositions (pH 2-6) with hydrolases and builders or complexing agents. The Examples disclose high NTA or EDTA share (up to 30%). While these compositions can e.g. Eliminate tea residues well, there is milk residue their effect, measured on a scale from 0 to 10, however always under 5.

Die Verwendung anderer biologisch abbaubarer Komplexierungsmittel, wie β-Alanindiessigsäure (β-ADA) und Iso-serindiessigsäure (ISDA), in Reinigungsmitteln ist in der DE-A- 3 829 847 und der DE-A- 4 036 995 offenbart. Wenn diese Druckschriften Anwendungsbeispiele für Maschinengeschirrspülmittel enthalten, handelt es sich um Maschinengeschirrspülmittel, die in etwa 0,5%-iger wäßriger Lösung einen pH-Wert von mehr als 10,5 aufweisen.The use of other biodegradable complexing agents, such as β-alanine diacetic acid (β-ADA) and iso-serine diacetic acid (ISDA), in detergents is in the DE-A-3 829 847 and DE-A-4 036 995. If those Publications Application examples for dishwasher detergents contained, it is machine dishwashing detergent, which in about 0.5% aqueous solution has a pH of more than 10.5.

Darüber hinaus wirken diese Verbindungen wesentlich weniger komplexierend als NTA und können dieses in dem fertigen Mittel nur mangelhaft ersetzen.In addition, these connections work much less complexing as NTA and can do this in the finished Only insufficiently replace funds.

In der DE-A- 4 319 935 wird die Verwendung von MGDA in Maschinengeschirrspülmitteln offenbart, ohne ein Beispiel anzugeben. In einem GDCH-Vortrag am 30. Mai 1995 veröffentlicht einer der Erfinder der DE-A- 4 319 935 die Verwendung von Methylglycindiessigsäure (MGDA) als Komplexierungsmittel zur Reinigung von Ausrüstungsteilen der Milchindustrie im industriellen Maßstab und in Geschirrspülmitteln mit einem pH-Wert in Lösung von mehr als 10,5.DE-A-4 319 935 describes the use of MGDA in Dishwasher detergents disclosed without an example specify. In a GDCH lecture on May 30, 1995 published one of the inventors of DE-A-4 319 935 Use of methylglycinediacetic acid (MGDA) as Complexing agent for cleaning equipment parts of the Dairy industry on an industrial scale and in Dishwashing detergents with a pH in solution of more than 10.5.

Die gleiche Information kann auch der "Vorläufige technische Information, Trilon® ES 9964", April 1995 , der BASF AG entnommen werden. Die dort offenbarten Geschirreiniger enthalten 5-30% MGDA und 1.12% aktiven Sauerstoff, wobei MGDA bei der Belagshemmung (Bildung von Calciumcarbonatablagerungen) ein vergleichbares Ergebnis erzielt wie NTA. Die Wirksamkeit der Geschirreiniger bei Milchrückständen oder Teerückständen wird nicht erwähnt. MGDA soll jedoch bei der Molkereireinigung Caiciumphosphatrückstände besser auflösen als NTA. Bei der Moikereireinigung wird üblicherweise im stark alkalischen Bereich gearbeitet.The same information can also be found in the "Preliminary technical Information, Trilon® ES 9964 ", April 1995, from BASF AG be removed. The dishwashers disclosed there contain 5-30% MGDA and 1.12% active oxygen, with MGDA in the inhibition of deposits (formation of calcium carbonate deposits) achieved a result comparable to that of NTA. The effectiveness of dishwashers on milk residues or Tea residues are not mentioned. MGDA is said to be at Better dissolve dairy residues of calcium phosphate as an NTA. When cleaning the Moikerei is usually in strongly alkaline range worked.

In einem Artikel im SÖFW-Journal 122, 1996, 392 wird der Einsatz von MGDA in Wäschewaschmitteln vorgeschlagen. MGDA soll insbesondere bei blutverschmutzter Wäsche eine bessere Wirkung aufweisen, als Phosphonate und bei teeverschmutzter Wäsche in etwa die gleiche Wirkung aufweisen wie Phosphonate. In der gleichen Druckschrift wird offenbart, daß MGDA in einem Geschirrspülmittel, ähnlich wie NTA, eine sehr gute Belagsinhibierung auf Glas, Metall und Porzellan zeigt, wobei ein Geschirrspülmittel offenbart wird, das in Lösung einen pH-Wert von mehr als 10,5 liefert. Es wird ebenfalls vorgeschlagen, MGDA bei sehr stark alkalischen Bedingungen zur Molkereireinigung zu verwenden.In an article in SÖFW Journal 122, 1996, 392 the Use of MGDA in laundry detergents suggested. MGDA is supposed to be a better one, especially for blood-soiled laundry Have effect, as phosphonates and with tea soiled Laundry have about the same effect as phosphonates. The same publication discloses that MGDA in a dishwashing detergent, similar to NTA, a very good one Deposit inhibition on glass, metal and porcelain shows, whereby a dishwashing detergent is disclosed which in solution provides pH of more than 10.5. It will too suggested MGDA in very strongly alkaline conditions to use for dairy cleaning.

Die bisher vorgeschlagenen Maschinengeschirrspülmittel, die Komplexbildner einsetzen, weisen daher den Nachteil auf, daß sie entweder bei höheren pH-Werten arbeiten oder keine ausreichende Reinigungskraft für bestimmte Speiserückstände, insbesondere für Milchrückstände und Teerückstände, aufweisen.The previously proposed machine dishwashing liquid, the Use complexing agents therefore have the disadvantage that they either work at higher pH values or none sufficient cleaning power for certain food residues, especially for milk residues and tea residues, exhibit.

Es ist eine Aufgabe der Erfindung, ein Maschinengeschirrspülmittel zur Verfügung zu stellen, das nicht nur bei einem niedrigen pH-Wert arbeitet, sondern darüber hinaus auch schwierig zu entfernende Speisereste entfernt, die üblicherweise bei einem solchen pH-Wert arbeitende Maschinengeschirrspülmittel nicht zufriedenstellend entfernen. Insbesondere soll ein solches Geschirrspülmittel eine ausgezeichnete Reinigungsleistung bei Geschirr aufweisen, das sowohl durch Milch- als auch durch Teerückstände verunreinigt ist. Diese Aufgabe wird durch ein Maschinengeschirrspülmittel gelöst, das Methylglycindiessigsäure oder deren Salze als Komplexierungsmittel enthält und dadurch gekennzeichnet ist, daß es in etwa 0,5%-iger wäßriger Lösung einen pH-Wert von 10,4 nicht übersteigt, mit der Maßgabe, daß das Maschinengeschirrspülmittel mehr als 10 Gew.-% der Methylglycindiessigsaüre enthält.It is an object of the invention to provide a dishwasher detergent to provide that not only works at a low pH but beyond also removes food remnants that are difficult to remove usually working at such a pH Dishwasher detergent unsatisfactory remove. In particular, such a dishwashing detergent excellent cleaning performance for dishes have both milk and milk Tea residue is contaminated. This task is accomplished by a Dishwasher detergent dissolved, the methylglycinediacetic acid or their salts as complexing agents and is characterized in that it is approximately 0.5% aqueous solution does not exceed a pH of 10.4 with which Provided that the dishwasher detergent more than 10 wt .-% of Contains methylglycine diacetic acid.

Milchrückstände setzen sich aus einer Mischung aus denaturierten Proteinen (Kasein), Fetten, Zuckern und mineralischen Ablagerungen zusammen und bestehen zu rund 70% aus Calciumphosphat (Ca3(PO4)2). Komplexierungsmittel haben daher einen wesentlichen Einfluß auf die Entfernung von Milchrückständen, weil sie Calciumphosphate durch Komplexieren der Calciumionen auflösen.Milk residues consist of a mixture of denatured proteins (casein), fats, sugars and mineral deposits and consist of around 70% calcium phosphate (Ca 3 (PO 4 ) 2 ). Complexing agents therefore have a significant influence on the removal of milk residues because they dissolve calcium phosphates by complexing the calcium ions.

Auch Teerückstände beruhen unter anderem auf Ca-Ablagerungen, die beim Aufbrühen von Tee mit hartem Wasser entstehen. Teerückstände stellen jedoch üblicherweise andere Anforderungen an ein Maschinengeschirrspülmittel als Milchrückstände, was schon daran gesehen werden kann, daß das in der DE-A 3 833 047 offenbarte Spülmittel im sauren Bereich (pH 2-6) Teerückstände zufriedenstellend entfernt, bei Milchrückständen aber nicht überzeugen kann.Tea residues are also based on Ca deposits, that arise when brewing tea with hard water. However, tea residues are usually different Requirements for a dishwasher detergent as Milk residues, which can be seen from the fact that the detergent disclosed in DE-A 3 833 047 in the acidic range (pH 2-6) Tea residues removed satisfactorily, at Milk residues cannot convince.

Die Fähigkeit (bezogen auf das Gewicht des Komplexierungsmittels), Calciumionen bei einem bestimmten pH-Wert zu komplexieren, hängt von der Stabilitätskonstanten des Calciumkomplexes (pKc), dem sauren Charakter des Komplexierungsmittels (pK3) und von dessen Molekulargewicht ab.The ability (based on the weight of the complexing agent) to complex calcium ions at a certain pH value depends on the stability constant of the calcium complex (pK c ), the acidic character of the complexing agent (pK 3 ) and its molecular weight.

Obwohl MGDA für Calciumcarbonat bei einem pH-Wert von 11 einen höheren theoretischen Komplexierungsgrad aufweist als NTA (wie in dem vorstehend erwähnten GDCH-Vortrag offenbart wurde und was theoretisch berechnet werden kann) ergibt sich bei einem pH-Wert von 7 und 10,4 und für Calciumphosphate ein anderes Resultat.Although MGDA for calcium carbonate at pH 11 has a higher theoretical degree of complexation than NTA (as disclosed in the aforementioned GDCH lecture and what can be calculated theoretically) results at pH 7 and 10.4 and for calcium phosphates different result.

Tatsächlich liegt bei einem pH-Wert von 10,4 der theoretische Komplexierungsgrad für Calciumphosphate bei Verwendung von NTA bei 360 mg/g und bei Verwendung von MGDA bei 340 mg/g, und bei einem pH-Wert von 8 sind die theoretischen Werte 510 mg/g für NTA und 490 mg/g für MGDA.In fact, the theoretical is at pH 10.4 Degree of complexation for calcium phosphates when using NTA at 360 mg / g and when using MGDA at 340 mg / g, and at pH 8 the theoretical values are 510 mg / g for NTA and 490 mg / g for MGDA.

Daher folgt anhand dieser theoretischen Überlegungen, daß MGDA bei einem Geschirrspülmittel, das in etwa 0,5%-iger wäßriger Lösung einen pH-Wert von weniger als 10,4 liefert auf Calciumphosphate schlechter komplexierend wirkt und somit Milchrückstände schlechter entfernen sollte, als das gebräuchliche NTA.Therefore, based on these theoretical considerations, it follows that MGDA for a dishwashing detergent that is approximately 0.5% aqueous solution provides a pH of less than 10.4 has a less complexing effect on calcium phosphates and thus Milk residues should be removed worse than that common NTA.

MGDA wurde im Stand der Technik auch nur in Geschirrspülmitteln eingesetzt, die in etwa 0,5%-iger wäßriger Lösung einen pH-Wert von mehr als 10,4 aufweisen.In the prior art, MGDA was only used in dishwashing detergents used in about 0.5% aqueous solution have a pH of more than 10.4.

Bei niedrigeren pH-Werten bietet sich eher der Einsatz von NTA an, das bei solchen pH-Werten auf Calciumphosphate besser komplexierend wirken sollte als MGDA und zudem im sauren Bereich (pH 2-6) Teerückstände zufriedenstellend entfernt (DE-A 38 33 047).At lower pH values, the use of NTA on that better at such pH values on calcium phosphates should have a complexing effect as MGDA and also in acid Range (pH 2-6) Tea residues removed satisfactorily (DE-A 38 33 047).

Erfindungsgemäß wurde jedoch überraschend gefunden, daß Geschirrspülmittel, die MGDA enthalten und die eine etwa 0,5%-ige wäßrige Lösung mit einem pH-Wert von bis zu 10,4 liefern sowohl Teerückstände als auch Milchrückstände besser entfernen können und insgesamt ein besseres Spülergebnis aufweisen als Geschirrspülmittel, die statt MGDA ein anderes Komplexierungsmittel wie das gebräuchliche NTA enthalten.According to the invention, however, it was surprisingly found that Dishwashing detergents that contain MGDA and one of them 0.5% aqueous solution with a pH of up to 10.4 deliver better both tea residues and milk residues can remove and overall a better washing result have as dishwashing detergent, which instead of MGDA another Contain complexing agents such as the common NTA.

Ferner wurde überraschend gefunden, daß bei einem erfindungsgemäßen Geschirrspülmittel, das eine ausreichende Menge an Komplexierungsmittel MGDA aufweist, die Menge an Sauerstoffbleichmittel verringert werden kann, ohne daß sich hierdurch die Spülleistung und insbesondere die Fähigkeit, Milchrückstände und Teerückstände zu entfernen, verschlechtert. Dieser überraschende Befund eröffnet sogar die Möglichkeit, bei Verwendung einer genügend großen Menge an Komplexierungsmittel vollständig auf den Einsatz von Sauerstoffbleichmittel zu verzichten.It was also surprisingly found that one Dishwashing detergent according to the invention, the sufficient Amount of complexing agent MGDA has the amount of Oxygen bleach can be reduced without changing thereby the flushing performance and in particular the ability Remove milk residues and tea residues, worsened. This surprising finding even opens up the possibility of using a sufficiently large amount of complexing agents completely on the use of To avoid oxygen bleach.

Das erfindungsgemäße Geschirrspülmittel kann flüssig oder pulverförmig sein und ebenfalls in Form einer einschichtigen oder mehrschichtigen Tablette vorliegen. Entsprechende Dosierungsformen und Verfahren wie man sie erhält sind dem Fachmann bekannt.The dishwashing detergent according to the invention can be liquid or be powdery and also in the form of a single layer or multi-layer tablet. Appropriate Dosage forms and methods of obtaining them are the Known specialist.

Vorzugsweise enthalten die erfindungsgemäßen Maschinengeschirrspülmittel ein oder mehrere Enzyme wie beispielsweise Amylase, Protease, Lipase oder Cellulase. Durch die kombinierte Anwendung von Amylase und Protease wurden die besten Reinigungsergebnisse erzielt. Bei den hier beschriebenen pH-Bereichen lassen sich diese Enzyme besonders effektiv einsetzen; so erreicht zum Beispiel die temperaturstabile Amylase Termamyl (Novo) bei pH 7-8 das Optimum ihres Wirkungsspektrums. Die Enzyme kommen in Granulatform oder in Lösung mit handelsüblichen Konzentrationen bzw. Aktivitäten zum Einsatz, wobei der Gehalt an Enzymen bei 0,5-6, vorzugsweise 1-4 Gew.% liegen kann.The dishwasher detergents according to the invention preferably contain one or more enzymes such as Amylase, protease, lipase or cellulase. Through the combined application of amylase and protease were the best cleaning results. The ones here These enzymes are particularly suitable for the pH ranges described use effectively; for example, the temperature stable amylase Termamyl (Novo) at pH 7-8 das Optimal of your spectrum of activity. The enzymes come in Granulate form or in solution with commercially available Concentrations or activities are used, the Enzyme content is 0.5-6, preferably 1-4% by weight can.

Als Builder eignen sich beispielsweise homo- und copolymere Polycarbonsäuren sowie deren teilweise oder vollständig neutralisierten Salze, monomere Polycarbonsäuren und Hydroxycarbonsäuren und deren Salze, Carbonate, Bicarbonate, Borate, Phosphate, Silicate, Aluminosilicate sowie Mischungen solcher Substanzen.Examples of suitable builders are homo- and copolymers Polycarboxylic acids and their partially or completely neutralized salts, monomeric polycarboxylic acids and Hydroxycarboxylic acids and their salts, carbonates, bicarbonates, Borates, phosphates, silicates, aluminosilicates and mixtures such substances.

Als Salze der oben genannten Verbindungen werden bevorzugt die Ammonium- und/oder Alkalisalze, d.h. die Lithium-, Natrium-, Kalium- und Rubidiumsalze und besonders bevorzugt das Natriumsalz eingesetzt.Preferred salts of the above compounds are the ammonium and / or alkali salts, i.e. the lithium, Sodium, potassium and rubidium salts and particularly preferred the sodium salt used.

Als Polycarbonsäuren eignen sich acyclische, alicyclische, heterocyclische und aromatische Carbonsäuren, wobei diese mindestens zwei Carboxygruppen enthalten, die jeweils durch vorzugsweise nicht mehr als zwei Kohlenstoffatome voneinander getrennt sind.Suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic and aromatic carboxylic acids, these contain at least two carboxy groups, each through preferably no more than two carbon atoms from each other are separated.

Polycarboxylate, die zwei Carboxygruppen enthalten, schließen beispielsweise wasserlösliche Salze der Bernsteinsäure, Malonsäure, (Ethylendioxy)diessigsäure, Maleinsäure, Diglycolsäure, Weinsäure, Tartronsäure und Fumarsäure ein. Polycarboxylate, die drei Carboxygruppen enthalten, schließen beispielsweise wasserlösliche Citrate ein. Entsprechend eignet sich als Hydroxycarbonsäure beispielsweise Citronensäure.Polycarboxylates containing two carboxy groups include for example water-soluble salts of succinic acid, Malonic acid, (ethylenedioxy) diacetic acid, maleic acid, Diglycolic acid, tartaric acid, tartronic acid and fumaric acid. Polycarboxylates containing three carboxy groups include for example, water-soluble citrates. Corresponding is suitable as a hydroxycarboxylic acid, for example Citric acid.

Als spezieller Builder für Maschinengeschirrspülmittel kann auch ein von der Asparaginsäure HOOC-CH(NH2)-CH2-COOH abgeleitetes Polymer mit Monomereinheiten der Formel

Figure 00080001
genannt werden.As a special builder for dishwasher detergents, one of aspartic acid can also be used HOOC-CH (NH 2 ) -CH 2 -COOH derived polymer with monomer units of the formula
Figure 00080001
to be named.

Als Polycarbonsäure eignet sich weiterhin das Homopolymer der Acrylsäure.The homopolymer of is also suitable as the polycarboxylic acid Acrylic acid.

Als Boratbuilder können neben Boraten wie Natriumborat auch solche Builder verwendet werden, die Borate unter den Reinigungsmittellagerbedingungen oder Spülbedingungen freisetzen.In addition to borates such as sodium borate, borate builders can also such builders are used, the borates among the Detergent storage conditions or rinsing conditions release.

Als Phosphate eignen sich Polyphosphate wie Tripolyphosphat, Pyrophosphat, Orthophosphat und das polymere Metaphosphat. Beispielsweise seien Alkalitripolyphosphate, Natrium-, Kalium- und Ammoniumpyrophosphat, Natrium- und Kaliumorthophosphat sowie Natriumpolymetaphosphat genannt, worin der Polymerisationsgrad bevorzugt von 5 bis 21 reicht.Suitable phosphates are polyphosphates such as tripolyphosphate, Pyrophosphate, orthophosphate and the polymeric metaphosphate. For example, alkali tripolyphosphates, sodium, Potassium and ammonium pyrophosphate, sodium and potassium orthophosphate as well as sodium polymetaphosphate, wherein the degree of polymerization preferably ranges from 5 to 21.

Als Silicate eignen sich Natriumsilicate wie Natriumdisilicat, Natriummetasilicat und kristalline Schichtsilicate. Weiterhin eignen sich Natriumaluminosilicate (Zeolite).Suitable silicates are sodium silicates such as sodium disilicate, Sodium metasilicate and crystalline layered silicates. Sodium aluminosilicates are also suitable (Zeolite).

Weitere geeignete Builder werden in der WO 95/01416 offenbart, auf deren Inhalt hiermit ausdrücklich Bezug genommen wird.Further suitable builders are described in WO 95/01416 hereby expressly refers to the content thereof is taken.

Besonders bevorzugt wird ein Buildersystem aus dem Salz einer Hydroxycarbonsäure oder aus dem Gemisch aus einer Hydroxycarbonsäure und dem Salz einer Hydroxycarbonsäure. Sowohl die Hydroxycarbonsäure als auch das Salz der Hydroxycarbonsäure können ganz oder teilweise durch Tripolyphosphat ersetzt werden, obwohl dies nicht bevorzugt wird.A builder system from the salt of one is particularly preferred Hydroxycarboxylic acid or from the mixture of one Hydroxycarboxylic acid and the salt of a hydroxycarboxylic acid. Both the hydroxycarboxylic acid and the salt of Hydroxycarboxylic acid can be completely or partially Tripolyphosphate can be replaced, although this is not preferred becomes.

Das Buildersystem besteht vorzugsweise aus einer Hydroxypolycarbonsäure mit 2-4 Carboxylgruppen (oder sauren anorganischen Salzen), die zur pH-Wert-Einstellung mit ihrem Salz vermischt werden kann. Vorzugsweise wird Citronensäure oder ein Gemisch aus Natriumcitrat mit Citronensäure verwendet. Zur Einstellung des erfindungsgemäßen erforderlichen pH-Wertes eignen sich abhängig von den übrigen Bestandteilen des Gemischs z.B. Gemische mit einem überwiegenden Anteil an Citronensäure.The builder system preferably consists of a Hydroxypolycarboxylic acid with 2-4 carboxyl groups (or acidic inorganic salts), which are used to adjust the pH value with their Salt can be mixed. Citric acid is preferred or a mixture of sodium citrate with citric acid used. To adjust the invention The required pH value is suitable depending on the others Components of the mixture e.g. Mix with one predominant proportion of citric acid.

Der Wasseranteil der flüssigen Geschirrspülmittel kann 40-80 Gew.% betragen.The water content of liquid dishwashing detergent can be 40-80 % By weight.

Die flüssigen Geschirrspülmittel enthalten darüber hinaus 0,2-5,0 Gew.%, bevorzugt 0,5-2 Gew.% eines Verdickers. Als Verdicker eignen sich hochmolekulare organische Polymere mit Molekulargewichten von 5 x 105 bis ca. 5 x 106, die aus olefinisch ungesättigten Carbonsäuren aufgebaut sind. Carboxyvinylpolymere, wie sie z.B. von B. F. Goodrich unter der Produktionsbezeichnung "Carbopol" auf dem Markt sind, erwiesen sich als gut einsetzbar. Auch anorganische Verbindungen, die bei dieser Produktzusammensetzung verdickende Eigenschaften besitzen, können eingesetzt werden. Beispiele hierfür sind natürliche oder synthetische Verdicker, die auf verschieden aufgebauten Silikatgerüsten basieren. Ihr Einsatz wird in verschiedenen Patenten beschrieben, z.B. in US-A- 4 933 101 oder EP-A2- 0 407 187.The liquid dishwashing detergents also contain 0.2-5.0% by weight, preferably 0.5-2% by weight, of a thickener. High-molecular organic polymers with molecular weights of 5 × 10 5 to approx. 5 × 10 6 , which are made up of olefinically unsaturated carboxylic acids, are suitable as thickeners. Carboxyvinyl polymers, such as those marketed by BF Goodrich under the production name "Carbopol", proved to be very useful. Inorganic compounds which have thickening properties in this product composition can also be used. Examples of this are natural or synthetic thickeners based on differently structured silicate structures. Their use is described in various patents, for example in US-A-4 933 101 or EP-A2-0 407 187.

Als oberflächenaktive Mittel eignen sich beispielsweise nichtionische oberflächenaktive Mittel. Hierzu zählen beispielsweise wasserlösliche ethoxylierte C6-16 Fettsäurealkohole und C6-16 gemischte ethoxylierte/propoxylierte Fettsäurealkohole und Mischungen davon sowie Polyglucoside. For example, nonionic surfactants are suitable as surfactants. These include, for example, water-soluble ethoxylated C 6-16 fatty alcohols and C 6-16 mixed ethoxylated / propoxylated fatty alcohols and mixtures thereof, and also polyglucosides.

Eine weiter Klasse nichtionischer oberflächenaktiver Mittel umfaßt Polyhydroxyfettsäureamide.Another class of non-ionic surfactants includes polyhydroxy fatty acid amides.

Weitere geeignete oberflächenaktive Mittel werden in der WO 95/01416 offenbart, auf deren Inhalt hiermit ausdrücklich Bezug genommen wird.Further suitable surface-active agents are described in WO 95/01416, the content of which is hereby expressly disclosed Reference is made.

Das erfindungsgemäße Maschinengeschirrspülmittel kann weiterhin ein oder mehrere Schaumkontrollmittel enthalten. Hierzu eignen sich alle in diesem Bereich eingesetzten Schaumkontrollmittel wie beispielsweise Silicone und Paraffinöl.The dishwasher detergent according to the invention can further contain one or more foam control agents. All those used in this area are suitable for this Foam control agents such as silicones and Paraffin oil.

Die Schaumkontrollmittel sind in dem erfindungsgemäßen Maschinengeschirrspülmittel bevorzugt mit weniger als 5 Gew.% des Gesamtgewichts des Spülmittels enthalten.The foam control agents are in the invention Machine dishwashing detergent preferably with less than 5% by weight of the total weight of the detergent.

Die erfindungsgemäßen Maschinengeschirrspülmittel können als Bleichmittel bevorzugt chlorfreie, aktiven Sauerstoff freisetzende Bleichmittel wie anorganische Perhydrate oder organische Persäuren und deren Salze enthalten.The machine dishwashing detergents according to the invention can be used as Bleaching agents prefer chlorine-free, active oxygen releasing bleaches such as inorganic perhydrates or contain organic peracids and their salts.

Beispiele für anorganische Perhydrate sind Perborate, Percarbonate und Persulfate wie Peroxymonopersulfat. Die anorganischen Perhydrate sind normalerweise Alkalimetallsalze, wie Lithium-, Natrium-, Kalium- oder Rubidiumsalze, insbesondere die Natriumsalze. Die anorganischen Perhydrate können in dem Spülmittel als kristalline Feststoffe ohne einen weiteren Schutz vorliegen. Für bestimmte Perhydrate ist es allerdings vorteilhaft, sie als granuläre Zusammensetzungen zu verwenden, die mit einem Überzug versehen sind, der den granulären Produkten eine bessere Lagerstabilität verleiht.Examples of inorganic perhydrates are perborates, Percarbonates and persulfates such as peroxymonopersulfate. The inorganic perhydrates are usually alkali metal salts, such as lithium, sodium, potassium or rubidium salts, especially the sodium salts. The inorganic perhydrates can in the detergent as crystalline solids without protection. For certain perhydrates however, it is advantageous to use them as granular To use compositions with a coating are provided, the better the granular products Gives storage stability.

Das bevorzugte Perborat ist Natriumperborat, das als Monohydrat mit der Formel NaBO2H2O2 oder als Tetrahydrat mit der Formel NaBO2H2O2.3H2O vorliegen kann. The preferred perborate is sodium perborate, which can be present as a monohydrate with the formula NaBO 2 H 2 O 2 or as a tetrahydrate with the formula NaBO 2 H 2 O 2 .3H 2 O.

Das bevorzugte Percarbonat ist Natriumpercarbonat mit der Formel 2Na2CO33H2O2. Bevorzugt wird das Percarbonat zur Erhöhung seiner Stabilität in einer überzogenen Form eingesetzt.The preferred percarbonate is sodium percarbonate with the formula 2Na 2 CO 3 3H 2 O 2 . The percarbonate is preferably used in a coated form to increase its stability.

Organische Persäuren schließen alle herkömmlich als Bleichmittel verwendeten organischen Persäuren ein, einschließlich beispielsweise Perbenzoesäure und Peroxycarbonsäuren wie Mono- oder Diperoxyphtalsäure, 2-Octydiperoxybernsteinsäure, Diperoxydodecandicarbonsäure, Diperoxyazelainsäure und Imidoperoxycarbonsäure sowie gegebenenfalls deren Salze.Organic peracids all conventionally include bleaching agents used organic peracids, including for example perbenzoic acid and peroxycarboxylic acids such as Mono- or diperoxyphthalic acid, 2-octydiperoxysuccinic acid, Diperoxydodecanedicarboxylic acid, Diperoxyazelaic acid and Imidoperoxycarboxylic acid and optionally its salts.

Das erfindungsgemäße Maschinengeschirrspülmittel kann weiterhin einen oder mehrere Bleichaktivatoren enthalten. Diese werden bevorzugt in Spülmitteln für Geschirrspülvorgänge bei Temperaturen im Bereich unterhalb 60°C eingesetzt, um eine ausreichende Bleichwirkung zu erzielen. Insbesondere eignen sich beispielsweise N- und O-Acylverbindungen wie acylierte Amine, acylierte Glycolurile oder acylierte Zuckerverbindungen. Bevorzugt werden N,N,N',N'-Tetraacetylethylendiamin (TAED), Pentaacetylglucose (PAG) und Tetraacetylglycoluril (TAGU). Weiterhin eignen sich aber auch katalytisch aktive Metallkomplexe und bevorzugt Übergangsmetallkomplexe als Bleichaktivatoren. Am meisten bevorzugt wird TAED.The dishwasher detergent according to the invention can continue to contain one or more bleach activators. These are preferred in detergents for dishwashing operations at temperatures below 60 ° C used to achieve a sufficient bleaching effect. N- and O-acyl compounds, for example, are particularly suitable such as acylated amines, acylated glycolurils or acylated sugar compounds. To be favoured N, N, N ', N'-tetraacetylethylenediamine (TAED), pentaacetylglucose (PAG) and tetraacetylglycoluril (TAGU). Are also suitable but also catalytically active metal complexes and preferred Transition metal complexes as bleach activators. The most TAED is preferred.

Weitere geeignete Bleichaktivatoren werden in der WO 95/01416 offenbart, auf deren Inhalt hiermit ausdrücklich Bezug genommen wird.Further suitable bleach activators are described in WO 95/01416 hereby expressly refers to the content thereof is taken.

Durch die Verwendung von MGDA bei verhältnismäßig niedrigen pH-Werten kann aber der Einsatz von Bleichmitteln verringert werden und bevorzugt weisen die erfindungsgemäßen Maschinengeschirrspülmittel ein Sauerstoffbleichmittel in einer Menge von weniger als 1 Gew.%, bezogen auf den aktiven Sauerstoff auf. Die Menge an verwendetem Bleichaktivator wird entsprechend angepaßt. By using MGDA at relatively low However, the use of bleaching agents can reduce pH values are and preferably have the invention Dishwasher detergent is an oxygen bleach an amount of less than 1% by weight, based on the active Oxygen on. The amount of bleach activator used will be adjusted accordingly.

In einer Ausführungsform weisen die Maschinengeschirrspülmittel einen großen Anteil an MGDA auf, wie 25% oder mehr, bevorzugt 30% oder mehr, jeweils bezogen auf die freie Säure, und es wird auf ein Sauerstoffbleichmittel verzichtet.In one embodiment, the machine dishwashing detergents a large percentage of MGDA, like 25% or more, preferably 30% or more, in each case based on the free acid, and an oxygen bleach is not used.

Das erfindungsgemäße Maschinengeschirrspülmittel kann weiterhin ein Silber-/Kupferkorrosionsschutzmittel enthalten. Unter diesen Begriff fallen Mittel, die das Anlaufen von Nichteisenmetallen, insbesondere von Silber und Kupfer, verhindern oder mindern sollen. Bevorzugte Silber-/Kupferkorrosionsschutzmittel sind Benzotriazol oder Bis-Benzotriazole sowie deren substituierte Derivate.The dishwasher detergent according to the invention can also contain a silver / copper anti-corrosion agent. This term includes funds that start up Non-ferrous metals, especially silver and copper, prevent or mitigate. Preferred silver / copper anti-corrosion agents are benzotriazole or bis-benzotriazoles as well as their substituted derivatives.

Weitere geeignete Mittel sind organische und/oder anorganische redoxaktive Substanzen und Paraffinöl.Other suitable agents are organic and / or inorganic redox-active substances and paraffin oil.

Benzotriazol-Derivate sind solche Verbindungen, in denen die verfügbaren Substitutionsstellen des aromatischen Rings teilweise oder vollständig substituiert sind. Als Substituenten eignen sich lineare oder verzweigtkettige C1- 20-Alkylgruppen sowie Hydroxy, Thio, Phenyl oder Halogen wie Fluor, Chlor, Brom und Jod. Bevorzugtes substituiertes Benzotriazol ist Tolyltriazol.Benzotriazole derivatives are those compounds in which the available substitution sites of the aromatic ring are partially or completely substituted. Suitable substituents are linear or branched C 1- 20 alkyl groups are suitable as well as hydroxy, thio, phenyl or halogen such as fluorine, chlorine, bromine and iodine. Preferred substituted benzotriazole is tolyltriazole.

Geeignete Bis-Benzotriazole sind solche, in denen die Benzotriazolgruppen jeweils in 6-Stellung durch eine Gruppe X verbunden sind, worin X eine Bindung, eine geradkettige, gegebenenfalls mit einer oder mehreren C1-4-Alkylgruppen substituierte Alkylengruppe mit bevorzugt 1-6 Kohlenstoffatomen, ein Cycloalkylrest mit mindestens 5 Kohlenstoffatomen, eine Carbonylgruppe, eine Sulfurylgruppe, ein Sauerstoff- oder ein Schwefelatom sein kann. Die aromatischen Ringe der Bis-Benzotriazole können, wie oben für das Benzotriazol definiert, substituiert sein.Suitable bis-benzotriazoles are those in which the benzotriazole groups are each connected in the 6-position by a group X, in which X is a bond, a straight-chain alkylene group which is optionally substituted by one or more C 1-4 alkyl groups and preferably has 1-6 carbon atoms , a cycloalkyl radical having at least 5 carbon atoms, a carbonyl group, a sulfuryl group, an oxygen or a sulfur atom. The aromatic rings of the bis-benzotriazoles can be substituted as defined above for the benzotriazole.

Geeignete organische redoxaktive Substanzen sind beispielsweise Ascorbinsäure, Indol, Methionin, ein N-Mono-(C1-C4-alkyl)-glycin, ein N,N-Di-(C1-C4-alkyl)-glycin, 2-Phenylglycin oder eine Kuppler- und/oder Entwicklerverbindung ausgewählt aus der Gruppe der Diaminopyridine, Aminohydroxypyridine, Dihydroxypyridine, heterocyclischen Hydrazone, Aminohydroxypyrimidine, Dihydroxypyrimidine, Tetraaminopyrimidine, Triaminohydroxypyrimidine, Diaminodihydroxypyrimidine, Dihydroxynaphtaline, Naphtole, Pyrazolone, Hydroxychinoline, Aminochinoline, der primären aromatischen Amine, die in ortho-, meta- oder para-Position eine weitere freie oder mit C1-C4-Alkyl oder C2-C4-Hydroxyalkylgruppen substituierte Hydroxy- oder Aminogruppen haben und der Di- oder Trihydroxybenzole.Suitable organic redox-active substances are, for example, ascorbic acid, indole, methionine, an N-mono- (C 1 -C 4 alkyl) glycine, an N, N-di (C 1 -C 4 alkyl) glycine, 2- phenylglycine or a coupler and / or developer compound chosen from the group of diaminopyridines, aminohydroxypyridines, dihydroxypyridines, heterocyclic hydrazones, aminohydroxypyrimidines, dihydroxypyrimidines, tetraaminopyrimidines, triaminohydroxypyrimidines, Diaminodihydroxypyrimidine, Dihydroxynaphtaline, naphthols, pyrazolones, hydroxyquinolines, aminoquinolines, primary aromatic amines, which in ortho, meta or para position have a further free or with C 1 -C 4 alkyl or C 2 -C 4 hydroxyalkyl groups substituted hydroxy or amino groups and the di- or trihydroxybenzenes.

Geeignete anorganische redoxaktive Substanzen sind beispielsweise Metallsalze und/oder Metallkomplexe ausgewählt aus der Gruppe der Mangan-, Titan-, Zirkonium-, Hafnium-, Vanadium-, Cobalt- und Cer-Salze und/oder -Komplexe, worin die Metalle in einer der Oxidationsstufen II, III, IV, V oder VI vorliegen.Suitable inorganic redox-active substances are for example, metal salts and / or metal complexes selected from the group of manganese, titanium, zirconium, hafnium, Vanadium, cobalt and cerium salts and / or complexes, wherein the metals in one of the oxidation states II, III, IV, V or VI are available.

Insbesondere geeignet sind Metallsalze und/oder Metallkomplexe, ausgewählt aus der Gruppe MnSO4, Mn(II)-citrat, Mn(II)-stearat, Mn(II)-acetylacetonat, Mn(II)-[1-Hydroxyethan-1,1-diphosphonat], V2O5, V2O4, VO2, TiOSO4, K2TiF6, K2ZrF6, CoSO4, Co(NO3)2, Ce(NO3)3.Metal salts and / or metal complexes selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1 are particularly suitable -diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , CoSO 4 , Co (NO 3 ) 2 , Ce (NO 3 ) 3 .

Organische und anorganische redoxaktive Substanzen, die als Silber-/Kupferkorrosionsschutzmittel geeignet sind, werden auch in der WO 94/26860 und WO 94/26859 genannt, auf deren Inhalt hiermit Bezug genommen wird.Organic and inorganic redox-active substances, which as Silver / copper anti-corrosion agents are suitable also mentioned in WO 94/26860 and WO 94/26859, on the Content hereby referred.

Als Paraffinöl eignen sich überwiegend verzweigte aliphatische Kohlenwasserstoffe mit einer Anzahl von Kohlenstoffatomen im Bereich von 20 bis 50. Bevorzugt wird das Paraffinöl ausgewählt aus überwiegend verzweigtkettigen C25-45-Spezies mit einem Verhältnis von cyclischen zu nichtcyclischen Kohlenwasserstoffen von 1:10 bis 2:1, bevorzugt von 1:5 bis 1:1. Suitable paraffin oil are predominantly branched aliphatic hydrocarbons with a number of carbon atoms in the range from 20 to 50. The paraffin oil is preferably selected from predominantly branched chain C 25-45 species with a ratio of cyclic to noncyclic hydrocarbons of 1:10 to 2: 1 , preferably from 1: 5 to 1: 1.

Wenn ein Silber-/Kupferkorrosionsschutzmittel in dem erfindungsgemäßen Maschinengeschirrspülmittel vorhanden ist, liegt es bevorzugt mit 0,01 bis 5 Gew.-%, besonders bevorzugt mit 0,1 bis 2 Gew.-% des Gesamtgewichts vor.If a silver / copper anticorrosive in the machine dishwashing detergent according to the invention is present, it is preferably 0.01 to 5% by weight, particularly preferably with 0.1 to 2 wt .-% of the total weight.

In der Ausführungsform der Erfindung, in der der Anteil an MGDA an dem Maschinengeschirrspülmittel ausreichend hoch, wie 25% oder mehr, bevorzugt 30% oder mehr, jeweils bezogen auf die freie Säure ist, so daß auf Bleichmittel verzichtet werden kann, kann auch auf ein Silber-/Kupferkorrosionsschutzmittel verzichtet werden.In the embodiment of the invention in which the proportion of MGDA on the dishwasher detergent is high enough, such as 25% or more, preferably 30% or more, each based on is the free acid, so that there is no bleaching agent can also be used on a silver / copper anti-corrosion agent to be dispensed with.

Weitere übliche Zusätz sind z.B. Farbstoffe und Duftstoffe und gegebenenfalls bei flüssigen Produkten Konservierungsmittel, wozu z.B. Verbindungen auf Isothiazolinon-Basis geeignet sind.Other common additions are e.g. Dyes and fragrances and if necessary preservatives for liquid products, why e.g. Isothiazolinone based compounds are suitable.

Die erfindungsgemäßen Maschinengeschirrspülmittel sind nicht ätzend und benötigen deshalb keine besonders gesicherte Verpackung. Ein gutes Spülergebnis kann schon bei einer relativ niedrigen Einsatzmenge von 15-20 g Pulver bzw. 20-50 ml Flüssigreiniger erzielt werden. Alle Inhaltstoffe sind nach derzeitigem Wissen weder giftig noch anderweitig gesundheitsgefährdend. Die hier beschriebenen Reinigungsmittel stellen deshalb auch eine umwelt- und verbraucherfreundliche Alternative zu den herkömmlichen Reinigern mit Komplexierungsmitteln, die im stark basischen Bereich arbeiten, dar.The machine dishwashing detergents according to the invention are not caustic and therefore do not require a specially secured one Packaging. A good washing result can be achieved with one relatively low use of 15-20 g powder or 20-50 ml of liquid detergent can be achieved. All ingredients are according to current knowledge, neither toxic nor otherwise harmful to health. The cleaning agents described here therefore also represent an environmentally and consumer-friendly Alternative to conventional cleaners with Complexing agents in the strongly basic area work.

Die erfindungsgemäß eingesetzte Methylglycindiessigsäure hat folgende Strukturformel:

Figure 00140001
The methylglycinediacetic acid used according to the invention has the following structural formula:
Figure 00140001

Besonders bevorzugt wird die Methylglycindiessigsäure als freie Säure oder als Natrium- oder Kaliumsalz eingesetzt und ist bevorzugt in einer Menge von 3% bis 90%, bezogen auf die freie Säure, in dem Geschirrspülmittel enthalten.Methylglycinediacetic acid is particularly preferred as free acid or used as sodium or potassium salt and is preferably in an amount of 3% to 90%, based on the free acid, contained in the detergent.

In bleichmittelfreien Maschinengeschirrspülmitteln, die auf Phosphaten als hauptsächlichem Bestandteil des Buildersystems basieren, beträgt die Menge an MGDA vorzugsweise zumindest 5%, bezogen auf die freie Säure.In bleach-free dishwasher detergents that are Phosphates as the main component of the builder system based, the amount of MGDA is preferably at least 5%, based on the free acid.

Erfindungsgemäß ist es wesentlich, daß eine etwa 0,5%-ige wäßrige Lösung des Spülmittels einen pH-Wert von nicht mehr als 10,4 aufweist. Bevorzugt ist der pH-Wert einer etwa 0,5%-igen wäßrigen Lösung des erfindungsgemäßen Spülmittels von mehr als 6 bis 10,4, besonders bevorzugt von 7 bis 10,0.According to the invention it is essential that an approximately 0.5% aqueous solution of the detergent has a pH of no more than 10.4. The pH is preferably about 0.5% aqueous solution of the detergent according to the invention more than 6 to 10.4, particularly preferably from 7 to 10.0.

Der folgende Vergleichsversuch belegt, daß die in dem Artikel im SÖFW-Journal 122, 1996, 392-397 vorgeschlagenen Geschirrspülmittel in 0,5%-igen wäßrigen Lösungen einen pH-Wert von mehr als 10,4 aufweisen. Die Offenbarung dieses Artikels ist daher im Einklang mit der theoretischen Erwartung, daß MGDA bei pH-Werten von mehr als 10,4 ein ausgezeichnete Komplexbildner ist, bei pH-Werten von 10,4 oder darunter aber dem gebräuchlichen NTA unterlegen ist.The following comparison test proves that the in the article in the SÖFW Journal 122, 1996, 392-397 Dishwashing detergent in 0.5% aqueous solutions have a pH value of more than 10.4. The revelation of this Article is therefore in line with the theoretical Expectation that MGDA will occur at pH greater than 10.4 is excellent complexing agent, at pH values of 10.4 or but is inferior to the usual NTA.

VergleichsversuchComparison test

Im Einklang mit der Offenbarung des Artikels im SÖFW-Journal 122, 1996, 392-397 werden Geschirrspülmittel aus folgenden Bestandteilen hergestellt:

  • Natriumcitratdihydrat
  • Natriumcarbonat
  • Natriumhydrogencarbonat
  • Natriumperboratmonohydrat
  • TAED
  • C13C15 Oxoalkohol + 4 Mol PO + 2 Mol EO
  • MGDA (Trinatriumsalz von Methylglycindiessigsäure) (77%-ige Lösung in Wasser) = TRILON ES 9964 erhältlich von der BASF-AG
    • In accordance with the disclosure of the article in SÖFW-Journal 122, 1996, 392-397, dishwashing detergents are made from the following ingredients:
  • Sodium citrate dihydrate
  • sodium
  • Sodium bicarbonate
  • Sodium perborate monohydrate
  • TAED
  • C 13 C 15 oxo alcohol + 4 moles PO + 2 moles EO
  • MGDA (trisodium salt of methylglycinediacetic acid) (77% solution in water) = TRILON ES 9964 available from BASF-AG

    • Die nachstehende Tabelle zeigt die Mengen der jeweiligen Bestandteile in g und %. Die Bestandteile wurden in einem Liter Wasser von 10° Härte gelöst, und der pH-Wert der Lösung wurde jeweils bestimmt. Die Gesamtmenge der Bestandteile (100%) beträgt jeweils 4 g, entsprechend einer 0,4%-igen Konzentration, wie sie in Figur 14 des Artikels offenbart ist.The table below shows the quantities of each Components in g and%. The ingredients were in one Liters of water of 10 ° hardness dissolved, and the pH of the solution was determined in each case. The total amount of ingredients (100%) is 4 g each, corresponding to a 0.4% Concentration as disclosed in Figure 14 of the article.

    MGDA ist nicht in Reinform im Handel erhältlich, und daher wurde eine 77%-ige Lösung in Wasser verwendet. Es mußte somit eine größere Menge des käuflich erhältlichen Produktes eingesetzt werden, wie es in der Tabelle gezeigt ist. Für MGDA sind in der Tabelle jeweils zwei Werte angegeben. Der erste Wert gibt die Menge in g des kommerziellen Produktes an, und der zweite Wert entspricht der entsprechenden Menge an reiner Substanz (100%). SÖFW-Journal 122, 1996, 392-397 Beisp. 1 Beisp. 2
    Mengen in g. (%)     Beisp. 3     Citrat 2 (50%) 1,6 (40%) 1 (25%) Carbonat 1 (25%) 1 (25%) 1 (25%) Hydrogencarbonat 0,36 (9%) 0,36 (9%) 0,36 (9%) Perborat 0,28 (7%) 0,28 (7%) 0,28 (7%) TAED 0,08 (2%) 0,08 (2%) 0,08 (2%) nichtionisches oberflächenaktives Mittel 0,08 (2%) 0,08 (2%) 0,08 (2%) MGDA (77% Lös.)/ (100%) 0,26/0,2 (5%) 0,78/0,6 (15%) 1,56/1,2 (30%) Gesamt 4,06   4 4,18   4 4,36   4 pH 10,64 10,79 10,82     MGDA is not commercially available in its pure form and therefore a 77% solution in water was used. A larger amount of the commercially available product had to be used, as shown in the table. Two values are given in the table for MGDA. The first value indicates the amount in g of the commercial product, and the second value corresponds to the corresponding amount of pure substance (100%). SÖFW Journal 122, 1996, 392-397 Ex. 1 Ex. 2
    Quantities in g. (%)     Ex. 3     Citrate 2 (50%) 1.6 (40%) 1 (25%) Carbonate 1 (25%) 1 (25%) 1 (25%) Bicarbonate 0.36 (9%) 0.36 (9%) 0.36 (9%) Perborate 0.28 (7%) 0.28 (7%) 0.28 (7%) TAED 0.08 (2%) 0.08 (2%) 0.08 (2%) nonionic surfactant 0.08 (2%) 0.08 (2%) 0.08 (2%) MGDA (77% Sol.) / (100%) 0.26 / 0.2 (5%) 0.78 / 0.6 (15%) 1.56 / 1.2 (30%) total 4.06 4 4.18 4 4.36 4 pH 10.64 10.79 10.82

    Obwohl der pH-Wert von 0,5%-igen Lösungen der Mittel nicht direkt bestimmt wurde, wurde der pH-Wert von 0,4%-igen Lösungen bestimmt. Bei einer höheren Konzentration des Reinigers werden die Lösungen des Reinigers selbstverständlich die gleichen oder, wahrscheinlicher, höhere pH-Werte aufweisen.Although the pH of 0.5% solutions of the agent is not was determined directly, the pH was 0.4% Solutions determined. At a higher concentration of the Detergent solutions are a matter of course the same or, more likely, higher pH values exhibit.

    Anhand des folgenden Beispiels wird gezeigt, daß bei Ersatz eines Teils des Builders eines Maschinengeschirrspülmittels durch Methylglycindiessigsäure bei niederigen pH-Werten eine hervorragende Spülleistung erzielt werden kann und insbesondere entgegen den theoretischen Erwartungen die Fähigkeit Milchrückstände und Teerückstände zu entfernen höher ist als bei anderen gebräuchlichen Komplexbildnern wie NTA. Das Beispiel veranschaulicht die Erfindung.The following example shows that when replacing part of the builder of a dishwasher detergent with methylglycinediacetic acid at low pH values excellent washing performance can be achieved and especially contrary to theoretical expectations Ability to remove milk residues and tea residues higher than other common complexing agents such as NTA. The example illustrates the invention.

    Beispielexample

    Es wurden flüssige Geschirrspülmittel mit einer Zusammensetzung wie sie in Tabelle 1 gezeigt ist hergestellt (sowohl gemäß der Erfindung unter Verwendung von MGDA als auch unter Verwendung des im Stand der Technik gebräuchlichen NTA), und ihre Spülleistung wurde mittels Geschirr, das sowohl Milch- als auch Teerückstände enthielt, bestimmt. In diesem Versuch wurde im wesentlichen dem DIN-Standard Nr. 44990, Teil 2 gefolgt. Es wurde eine Bosch SMS 5062 Spülmaschine verwendet. Das Wasser hatte eine Härte von 19° dH (3.39 mmol Calciumcarbonat), die Temperatur des Wassers betrug 65°C und es wurden jeweils 20 ml Spülmittel eingesetzt. Die Ergebnisse der Spülleistung wurden auf einer Skala von 1-5 (wobei 5 für 100%-ig sauberes Geschirr steht) bewertet und sind ebenfalls in Tabelle 1 aufgeführt.Liquid dishwashing detergents with a Composition as shown in Table 1 is made (both according to the invention using MGDA and using the NTA used in the prior art), and their washing performance was measured using dishes that both Contained milk and tea residues, determined. In this Test was essentially the DIN standard No. 44990, part 2 followed. It became a Bosch SMS 5062 dishwasher used. The water had a hardness of 19 ° dH (3.39 mmol Calcium carbonate), the temperature of the water was 65 ° C and 20 ml of detergent were used in each case. The results The flushing performance was assessed on a scale of 1-5 (5 for 100% clean dishes are rated) and are also listed in Table 1.

    Bei dem nicht-ionischen Tensid handelt es sich um einen üblichen, nieder schäumenden ethoxylierten und propoxylierten Fettalkohol. Es werden übliche Proteasen und Amylasen verwendet.

    Figure 00180001
    The non-ionic surfactant is a common, low-foaming ethoxylated and propoxylated fatty alcohol. Common proteases and amylases are used.
    Figure 00180001

    Aus den Ergebnissen der Tabelle 1 wird ersichtlich, daß in einem pH-Bereich unter 10,4 Spülmittel, die MGDA enthalten, überraschenderweise sowohl bei der Entfernung von Milchrückständen als auch bei der Entfernung von Teerückständen bessere Ergebnisse erzielen als die entsprechenden Spülmittel, die statt MGDA das gebräuchliche NTA enthalten.From the results of Table 1 it can be seen that in a pH range below 10.4 detergents containing MGDA, surprisingly both in the removal of Milk residues as well as in the removal of Tea residues get better results than that appropriate detergent, which is the usual instead of MGDA NTA included.

    Claims (4)

    1. A dishwasher detergent comprising methylglycinediacetic acid or salts thereof as complexing agent, wherein the composition, in about 0.5% strength aqueous solution, does not exceed a pH of 10.4, with the proviso that the dishwasher detergent comprises more than 10% by weight of methylglycinediacetic acid.
    2. The dishwasher detergent as claimed in claim 1 which comprises an oxygen bleach in an amount of less than 1% based on the weight of active oxygen.
    3. The dishwasher detergent as claimed in claim 1 or 2, wherein the composition, in about 0.5% strength aqueous solution, has a pH of from 6 to 10.4.
    4. The use of methylglycinediacetic acid or salts thereof as the complete or partial replacement for builders or complexing agents in dishwasher detergents with a pH of no more than 10.4 in about 0.5% strength aqueous solution to improve its ability to remove milk residues and also tea residues.
    EP97928266A 1996-06-21 1997-06-20 Low-alkaline mgda-containing dishwasher rinsing agent Revoked EP0906407B1 (en)

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    MX2015017866A (en) * 2013-06-25 2016-08-11 Unilever Nv Hygroscopic detergent formulation comprising water, aminocarboxylate chelant and moisture-sensitive ingredients.
    EP2821471A1 (en) * 2013-07-02 2015-01-07 Basf Se Aqueous solutions containing a complexing agent in high concentration
    DE102013214780A1 (en) * 2013-07-29 2015-01-29 Henkel Ag & Co. Kgaa Care products for automatic dishwashers
    EP3228686B1 (en) 2016-04-08 2021-10-27 The Procter & Gamble Company Automatic dishwashing
    DE102019219812A1 (en) * 2019-12-17 2021-06-17 Henkel Ag & Co. Kgaa Agent for machine dishwashing with improved cleaning performance for bleachable soiling

    Family Cites Families (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE4036695C2 (en) * 1990-11-17 1994-08-25 Henkel Kgaa Use of beta-alanine derivatives as builders in phosphate-free dishwashing detergents
    JPH05105900A (en) * 1991-08-27 1993-04-27 Kao Corp Cleaning agent for cleaning apparatus
    DE4319798A1 (en) * 1993-06-15 1994-12-22 Henkel Kgaa Dishwashing detergent with reduced tendency to scale up
    DE4319935A1 (en) * 1993-06-16 1994-12-22 Basf Ag Use of glycine-N, N-diacetic acid derivatives as complexing agents for alkaline earth and heavy metal ions
    US5481018A (en) * 1995-03-31 1996-01-02 The Dow Chemical Company Amino nitrile intermediate for the preparation of alanine diacetic acid
    GB2311536A (en) * 1996-03-29 1997-10-01 Procter & Gamble Dishwashing and laundry detergents

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    US7879154B2 (en) 2007-02-06 2011-02-01 Henkel Ag & Co. Kgaa Phosphate-free dishwashing detergents comprising builder, bleaching agent, nonionic surfactant, copolymer and a phosphonate
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    WO2011051419A1 (en) 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Dishwasher detergent
    DE102009046216A1 (en) 2009-10-30 2011-05-12 Henkel Ag & Co. Kgaa Machine dishwashing detergent
    DE102013019269A1 (en) 2013-11-15 2015-06-03 Weylchem Switzerland Ag Dishwashing detergent and its use
    WO2018007298A1 (en) 2016-07-05 2018-01-11 Henkel Ag & Co. Kgaa Dishwasher agent containing saccharic acid and amino carboxylic acid
    DE102016212248A1 (en) 2016-07-05 2018-01-11 Henkel Ag & Co. Kgaa Dishwashing detergent containing sugar acid and aminocarboxylic acid
    EP3623456A1 (en) 2018-09-12 2020-03-18 CLARO Products GmbH Silver protection agent

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    EP1113070B1 (en) 2008-03-19
    ATE389709T1 (en) 2008-04-15
    ES2160355T3 (en) 2001-11-01
    EP0906407A1 (en) 1999-04-07
    DE59704543D1 (en) 2001-10-11
    CA2258218A1 (en) 1997-12-31
    ES2300287T3 (en) 2008-06-16
    DE59712930D1 (en) 2008-04-30
    EP1113070A2 (en) 2001-07-04
    ATE205250T1 (en) 2001-09-15
    WO1997049792A1 (en) 1997-12-31
    EP1113070A3 (en) 2002-01-02

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