EP0523681A2 - Automatic dishwashing detergent composition and method for producing the same - Google Patents

Automatic dishwashing detergent composition and method for producing the same Download PDF

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Publication number
EP0523681A2
EP0523681A2 EP92112124A EP92112124A EP0523681A2 EP 0523681 A2 EP0523681 A2 EP 0523681A2 EP 92112124 A EP92112124 A EP 92112124A EP 92112124 A EP92112124 A EP 92112124A EP 0523681 A2 EP0523681 A2 EP 0523681A2
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Prior art keywords
acid
weight
surfactant
thickener
liquid
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EP92112124A
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German (de)
French (fr)
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EP0523681A3 (en
EP0523681B1 (en
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Johannes Dr. Behrensdorf
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2079Monocarboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2086Hydroxy carboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • the invention is based on a dishwasher detergent according to the preamble of claim 1.
  • the cleaning of dishes in dishwashers is now generally carried out in two or more stages in a main wash cycle using a main detergent and one or more wash cycles using - at least in the last wash cycle - a rinse aid, which usually consists of a wetting, nonionic surfactant and a weak one organic acid, generally citric acid, and which has the task of ensuring good wetting of the dish surface in order to prevent the formation of limescale or detergent deposits, especially on glasses.
  • a rinse aid which usually consists of a wetting, nonionic surfactant and a weak one organic acid, generally citric acid, and which has the task of ensuring good wetting of the dish surface in order to prevent the formation of limescale or detergent deposits, especially on glasses.
  • the known main cleaning agents in particular, causing considerable problems because of their high alkali content, for example in the form of sodium hydroxide solution or soda, which is present in the detergents in the form of sodium hydroxide solution or soda.
  • the common dishwashing detergents contain phosphates and silicates to enhance cleaning and bind water hardness, dichloroisocyanurate as a bleaching agent Elimination or Coverage of discoloration caused by tea and coffee and finally a non-ionic surfactant as a wetting agent and dispersant in the RE, with the help of which the dirt should be removed from the surface of the dishes and kept in suspension in the rinse water.
  • the known dishwashing detergents of this type have a number of significant disadvantages.
  • a major disadvantage is the high content of alkalis with their strong caustic effect on the skin and mucous membrane, which is the reason why the known dishwashing detergents on the one hand cannot be classified as "child-safe" and on the other hand often cause damage to the decorations of the dishes.
  • child safety today can generally be seen as a self-evident property of all household funds, just as consumers today are hardly willing to limit themselves to the use of machine-proof dishes solely because of the usability of a dishwasher.
  • the high, up to 50% and above, phosphate content of the known dishwashing detergents is known to cause considerable environmental pollution through eutrophication of the water.
  • the dichloroisocyanurate used itself is a toxic and caustic substance, which also escapes chlorine and escapes into the atmosphere, as well as chlorine radicals, which in turn can form toxic chlorine compounds.
  • the surfactants known as "PLURONICS" in dishwashing detergents Block polymers of ethylene oxide and propylene oxide are used which are only insufficiently biodegradable and thus also represent an environmental burden.
  • a dishwashing detergent has become known from EP-OS 217 732, which is adjusted to be slightly acidic, but which is obtained as a powdery product of high concentration and therefore causes problems in handling. In addition, there are great manufacturing difficulties.
  • the present invention has for its object to provide a liquid dishwashing detergent which is childproof with good effectiveness, i.e. is absolutely non-toxic, has good skin tolerance and does not cause environmental pollution.
  • the dishwashing detergent according to the invention contains no phosphates and toxic constituents and is otherwise fully biodegradable. It is therefore child-safe and environmentally compatible. Furthermore, due to its weakly acidic setting, it is well tolerated by the skin and mucous membranes with excellent effectiveness, in particular as a machine dishwashing detergent. It has been shown that tea and coffee stains can also be removed by using the dishwashing detergent according to the invention, so that the use of bleaching agents customary in the known standard cleaners can be dispensed with.
  • the preparation of the agent is carried out according to the invention in such a way that first the powdery thickener is pasted with a (liquid) nonionic anhydrous surfactant and the dispersed mass thus formed is added to the liquid (dissolved) surfactant, whereupon the liquid conduit for the purpose of dissolving the thickener and gelling is neutralized by means of alkali to a pH of between 4 and 6, preferably 5.
  • the invention provides a method by means of which, using a powdery, non-water-soluble substance, a liquid cleaning agent of high effectiveness can be produced, which can be brought to any desired concentration by adding water as required. Due to the aqueous basis of the agent, the use of fillers, such as sodium sulfate, is unnecessary, which can be regarded as a further considerable advantage in terms of environmental compatibility.
  • the liquid or gel-like consistency of the agent facilitates its handling, in particular its dosage in an extraordinary way and thus complies with the habits of the consumer, who experience has shown that the dosage of a larger quantity is preferred to the dosage of very small quantities. This means that the overdosing that can often be observed with powdery detergents can be practically completely ruled out.
  • the agent can be dosed from a spray bottle, so that skin contact with the agent can be largely ruled out.
  • automatic metering is also readily possible, which is not possible or only possible with considerable technical effort when using powdered agents.
  • non-foaming or low-foaming, preferably readily biodegradable surfactants can be used as low-foaming surfactants, in particular non-ionic surfactants of the type of fatty alcohols alkoxylated with ethylene oxide and propylene oxide or end group-capped, preferably terminally methylated fatty alcohol polyglycol ethers, moreover, anionic surfactants of the short-chain ether carboxylic acid type, which may be present in the agent in a high proportion. Due to the high proportions of these substances, the use of phosphates can be dispensed with, the effect of which - carried out in conventional means - is also taken over by the environmentally compatible surfactant.
  • the acidifying agents used are advantageously the food acids, preferably citric acid, tartaric acid, acetic acid, gluconic acid or malic acid, individually or in a mixture with one another, while polyacrylic acid and / or a copolymer of acrylic acid and maleic acid (sodium salt) can advantageously be used as water softener and soil dispersant.
  • a phosphate-free washing gel consists of 73 wt% water 8% by weight of a surfactant consisting of a lauryl alcohol with 4 moles of ethylene oxide and 3 moles of propylene oxide 3% by weight of citric acid 4% by weight of a copolymer of acrylic acid and maleic acid.
  • the polymeric glucose acrylic acid ester together with the nitriloacetate is mixed with the lauryl alcohol and the remaining surfactant, citric acid and the copolymer of acrylic acid and maleic acid are dissolved in the water. Then the pasted mass of the solution is added with constant stirring. After achieving a homogeneous mixture, the triethanolamine is added until a pH of approximately 5 is reached, with the solid constituents of the mixture first being dissolved and then gelling. The result - a clear, homogeneous and storage-stable gel with a viscosity of 5000 (mPa x s) at 20 ° C in a rotary viscometer. The concentration in relation to the total formulation is 6g / l in the main wash.
  • Phosphate-free washing gel consisting of 57% by weight of water 10% by weight of a nonionic surfactant of the composition myristyl alcohol with 4 moles of propylene oxide. 5% by weight tartaric acid 5% by weight polyacrylic acid.
  • the production takes place analogously to example 1.
  • the product is a slightly cloudy, homogeneous gel.
  • the pH is adjusted to 5 with triethanolamine.
  • the viscosity is 6000 (mPa xs) at 20 ° C in a rotary viscometer.
  • the concentration used in the main cleaning cycle of the dishwasher is 5 g / l of wash water.
  • Detergent in gel form consisting of 68% by weight of water 6% by weight citric acid 6% by weight copolymer of acrylic acid and maleic acid.
  • Na salt 9% by weight ether carboxylic acid (alkyl (C6-C8) polyethylene glycol ether (4 EO) methylene carboxylic acid) 3% by weight lauryl alcohol polyglycol ether (6 EO) 2% by weight copolymer of acrylic acid and acrylamide (thickener) 5 wt% KOH. 50% by weight 1% by weight of perfume.
  • Preservative Preservative.
  • the product is a clear, homogeneous and storage stable gel.
  • the pH is adjusted to 5 with KOH.
  • the viscosity is approximately 10,000 (mPa.s) at 20 ° C in a rotary viscometer.
  • the concentration in the main wash cycle is 5 g / l.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

The composition consists of a low-foam surfactant and, where appropriate, of a polycarboxylic acid and has the composition 5 - 20 % by weight of low-foam surfactant 2 - 10 % by weight of an organic acid 3 - 8 % by weight of a polycarboxylic acid 0 - 5 % by weight of nitrilotriacetate 3 - 5 % by weight of emulsifier 2 - 5 % by weight of thickener 1 - 4 % by weight of alkali remainder water which has a pH between 4 and 6, preferably about 5. The composition is produced by initially making a paste of the powdered thickener in a (liquid) non-ionic anhydrous surfactant, and adding the resulting dispersion to the liquid (dissolved) surfactant, after which the resulting solution is neutralised to a pH between 4 and 6, preferably 5, with alkali, preferably triethanolamine, for the purpose of dissolving the powdered thickener and gelling the liquid.

Description

Die Erfindung geht aus von einem Maschinengeschirrspülmittel gemäß dem Oberbegriff des Patentanspruches 1.The invention is based on a dishwasher detergent according to the preamble of claim 1.

Die Reinigug von Geschirr in Geschirrspülmaschinen erfolgt heute generell zwei- oder mehrstufig in zunächst einem Hauptwaschgang unter Einsatz eines Hauptreinigungsmittels und einem oder mehreren Spülgängen unter Verwendung - zumindest im letzten Spülgang - eines Klarspülmittels, das in der Regel aus einem netzenden, nichtionogenen Tensid und einer schwachen organischen Säure, im allgemeinen Zitronensäure, besteht und dem die Aufgabe zufällt, für eine gute Benetzung der Geschirroberfläche zu sorgen, um die Bildung von Kalk- oder Reinigungsmittelablagerungen insbesondere auf Gläsern zu verhindern.The cleaning of dishes in dishwashers is now generally carried out in two or more stages in a main wash cycle using a main detergent and one or more wash cycles using - at least in the last wash cycle - a rinse aid, which usually consists of a wetting, nonionic surfactant and a weak one organic acid, generally citric acid, and which has the task of ensuring good wetting of the dish surface in order to prevent the formation of limescale or detergent deposits, especially on glasses.

An die eingesetzten Mittel werden heute erhöhte Anforderungen in Bezug auf ihre Haut- und insbesondere ihre Umweltverträglichkeit gestellt , wobei insbesondere die bekannten Hauptreinigungsmittel erhebliche Probleme verursachen wegen ihres hohen der Verseifung der Speisefette dienenden, in Form etwa von Natronlauge oder Soda in den Spülmitteln vorliegenden Alkaligehaltes. Daneben enthalten die marktgängigen Geschirrspülmittel Phosphate und Silikate zur Reinigungsverstärkung und Bindung von Wasserhärte, Dichlorisocyanurat als Bleichmittel zur Beseitigung bezw. Überdeckung von durch Tee und Kaffee verursachten Verfärbungen und schließlich ein in der REgel nichtionogenes Tensid als Netzmittel und Dispergator, mit dessen Hilfe der Schmutz von der Geschirroberfläche abgelöst und im Spülwasser in Schwebe gehalten werden soll.Increased demands are made on the agents used with regard to their skin and in particular their environmental compatibility, the known main cleaning agents, in particular, causing considerable problems because of their high alkali content, for example in the form of sodium hydroxide solution or soda, which is present in the detergents in the form of sodium hydroxide solution or soda. In addition, the common dishwashing detergents contain phosphates and silicates to enhance cleaning and bind water hardness, dichloroisocyanurate as a bleaching agent Elimination or Coverage of discoloration caused by tea and coffee and finally a non-ionic surfactant as a wetting agent and dispersant in the RE, with the help of which the dirt should be removed from the surface of the dishes and kept in suspension in the rinse water.

Die bekannten Geschirrspülmittel dieser Art weisen eine Reihe erheblicher Nachteile auf. Ein wesentlicher Nachteil ist der hohe Gehalt an Alkalien mit ihrer stark ätzenden Wirkung auf Haut und Schleimhaut, die die Ursache dafür ist, daß die bekannten Geschirrspülmittel einerseits nicht als "kindersicher" eingestuft werden können und andererseits häufig eine Schädigung der Dekors der Geschirre verursachen. Kindersicherheit kann jedoch heute generell als eine vom Verbraucher als selbstverständlich vorausgesetzte Eigenschaft aller Haushaltsmittel gelten, ebenso ist der Verbraucher heute kaum noch bereit, sich alleine wegen der Nutzbarkeit einer Geschirrspülmaschine auf die Verwendung von maschinenfestem Geschirr zu beschränken. Darüberhinaus verursacht der hohe, bis zu 50% und darüber liegende Phosphatgehalt der bekannten Geschirrspülmittel bekanntlich eine erhebliche Umweltbelastung durch Eutrophierung der Gewässer. Das entsprechende gilt für die in den Mitteln enthaltenen bleichenden Chlorverbindungen. Das eingesetzte Dichlorisocyanurat selbst ist eine toxische und ätzende Substanz, die darüberhinaus - in die Atmosphäre entweichens - Chlor und darüberhinaus Chlorradikale abspaltet, die ihrerseits wiederum toxische Chlorverbindungen bilden können. Hinzu kommt schließlich, daß in Geschirrspülmitteln als Tenside die unter der Bezeichnung "PLURONICS" bekannten Blockpolymerisate aus Ethylenoxid und Propylenoxid eingesetzt werden, die nur ungenügend biologisch abbaubar sind und damit ebenfalls eine Umweltbelastung darstellen.The known dishwashing detergents of this type have a number of significant disadvantages. A major disadvantage is the high content of alkalis with their strong caustic effect on the skin and mucous membrane, which is the reason why the known dishwashing detergents on the one hand cannot be classified as "child-safe" and on the other hand often cause damage to the decorations of the dishes. However, child safety today can generally be seen as a self-evident property of all household funds, just as consumers today are hardly willing to limit themselves to the use of machine-proof dishes solely because of the usability of a dishwasher. In addition, the high, up to 50% and above, phosphate content of the known dishwashing detergents is known to cause considerable environmental pollution through eutrophication of the water. The same applies to the bleaching chlorine compounds contained in the agents. The dichloroisocyanurate used itself is a toxic and caustic substance, which also escapes chlorine and escapes into the atmosphere, as well as chlorine radicals, which in turn can form toxic chlorine compounds. In addition, there is the fact that the surfactants known as "PLURONICS" in dishwashing detergents Block polymers of ethylene oxide and propylene oxide are used which are only insufficiently biodegradable and thus also represent an environmental burden.

Es ist aus der DE-OS 35 32 586 bekannt, in Standard-Geschirrspülmitteln dieser Art an Stelle von Phosphat Polyacrylsäure einzusetzen, was jedoch den Einsatz hoher Anteile an Natriumsulfat als Stellmittel erfordert. Eine Verringerung der Umweltbelastung wird hierdurch nicht erreicht. Abgesehen davon, daß die hohe Immission von Natriumsulfat ebenfalls eine erhebliche Umweltbelastung darstellt, handelt es sich bei der Polyacrylsäure um eine biologisch nur außerordentlich langsam abbaubare Substanz. Die stark ätzende Wirkung wird hierdurch nicht gemildert.It is known from DE-OS 35 32 586 to use polyacrylic acid instead of phosphate in standard dishwashing detergents of this type, but this requires the use of high proportions of sodium sulfate as an adjusting agent. This will not reduce the environmental impact. In addition to the fact that the high immissions of sodium sulfate also represent a considerable environmental burden, polyacrylic acid is a substance that is only extremely slowly biodegradable. The strong caustic effect is not reduced by this.

Es ist aus der EP-OS 217 732 ein Geschirrspülmittel bekannt geworden, das zwar schwach sauer eingestellt ist, das jedoch als pulverförmiges Produkt hoher Konzentration anfällt und daher Probleme bei der Handhabung verursacht. Darüberhinaus ergeben sich große herstellungs-technische Schwierigkeiten.A dishwashing detergent has become known from EP-OS 217 732, which is adjusted to be slightly acidic, but which is obtained as a powdery product of high concentration and therefore causes problems in handling. In addition, there are great manufacturing difficulties.

Das entsprechende gleich gilt für das aus der DE-PS 15 28 632 bekannt gewordene Geschirrspülmittel, das zur Beseitigung seiner stark ätzenden Wirkung schwach sauer eingestellt wird, jedoch pulverförmig anfällt und auf den Einsatz hoher Anteile an umweltbelastendem Phosphat als Verstärkungsmittel nicht verzichten kann.The corresponding applies equally to the dishwashing detergent known from DE-PS 15 28 632, which is adjusted to be slightly acidic to eliminate its strongly caustic effect, but is obtained in powder form and cannot do without the use of high proportions of environmentally harmful phosphate as reinforcing agent.

Der vorliegenden Erfindung liegt als Aufgabe die Schaffung eines flüssigen Geschirrspülmittels zugrunde, das bei guter Wirksamkeit kindersicher, d.h. absolut untoxisch ist, eine gute Hautverträglichkeit aufweist und keine Umweltbelastung verursacht.The present invention has for its object to provide a liquid dishwashing detergent which is childproof with good effectiveness, i.e. is absolutely non-toxic, has good skin tolerance and does not cause environmental pollution.

Diese Aufgabe wird mit einem Geschirrspülmittel mit den im Patentanspruch 1 wiedergegebenen Merkmalen gelöst.This object is achieved with a dishwashing detergent with the features set out in claim 1.

Das erfindungsgemäße Geschirrspülmittel enthält keine Phosphate und toxischen Bestandteile und ist im übrigen biologisch voll abbaubar. Es ist daher kindersicher und umweltvertäglich. Es ist darüberhinaus aufgrund seiner schwach saueren Einstellung von guter Haut- und Schleimhautverträglichkeit bei ausgezeichneter Wirksamkeit insbesondere als Maschinenspülmittel. Es hat sich gezeigt, daß durchden Einsatz des erfindungsgemäßen Geschirrspülmittels auch Tee- und Kaffeflecken entfernt werden können, so daß auf den bei den bekannten Standardreinigern üblichen Einsatz von Bleichmitteln verzichtet werden kann.The dishwashing detergent according to the invention contains no phosphates and toxic constituents and is otherwise fully biodegradable. It is therefore child-safe and environmentally compatible. Furthermore, due to its weakly acidic setting, it is well tolerated by the skin and mucous membranes with excellent effectiveness, in particular as a machine dishwashing detergent. It has been shown that tea and coffee stains can also be removed by using the dishwashing detergent according to the invention, so that the use of bleaching agents customary in the known standard cleaners can be dispensed with.

Die Herstellung des Mittels erfolgt erfindungsgemäße in der Weise, daß zunächst der pulverförmige Verdicker mit einem (flüssigen) nichtionogenen wasserfreien Tensid angeteigt und die so gebildete dispergierte Masse dem flüssigen (gelösten) Tensid zugegeben wird, worauf die Flüssigleit zum Zwecke der Lösung des Verdickers und Gelierung mittels Alkali bis auf einen PH-Wert von zwischen 4 und 6, vorzugsweise 5 neutralisiert wird.The preparation of the agent is carried out according to the invention in such a way that first the powdery thickener is pasted with a (liquid) nonionic anhydrous surfactant and the dispersed mass thus formed is added to the liquid (dissolved) surfactant, whereupon the liquid conduit for the purpose of dissolving the thickener and gelling is neutralized by means of alkali to a pH of between 4 and 6, preferably 5.

Durch die Erfindung ist ein Verfahren geschaffen, mit dessen Hilfe unter Verwendung einer pulverförmigen, nicht wasserlöslichen Substanz ein flüssiges Reinigungsmittel hoher Wirksamkeit hergestellt werden kann, das nach Bedarf durch Zugabe von Wasser in jede gewünschte Konzentration gebracht werden kann. Aufgrund der wässrigen Grundlage des Mittels erübrigt sich der Einsatz von Füllstoffen, etwa Natriumsulfat, was in Bezug auf die Umweltverträglichkeit als ein weiterer beachtlicher Vorteil anzusehen ist. Die flüssige bzw. gelartige Konsistenz des Mittels erleichtert seine Handhabung, insbesondere seine Dosierung in außerordentlicher Weise und kommt damit den Gewohnheiten der Verbraucher entgegen, die erfahrungsgemäß die Dosierung einer größeren menge der Dosierung von Kleinstmengen vorziehen. Es kann damit die häufig bei pulvrigen Spülmitteln zu beoachtende Überdosierung praktisch vollständig ausgeschlossen werden. Hinzu kommt, daß das Mittel aufgrund seiner flüssigen Konsistenz aus einer Sprühflasche dosiert werden kann, so daß der Hautkontakt mit dem Mittel weitestgehend ausgeschlossen werden kann. Darüberhinaus ist bei entsprechender technischer Ausrüstung der Maschine ohne weiteres auch eine automatische Dosierung möglich, die bei Verwendung von pulverförmigen Mitteln nicht oder nur mit erheblichem technischem Aufwand möglich ist.The invention provides a method by means of which, using a powdery, non-water-soluble substance, a liquid cleaning agent of high effectiveness can be produced, which can be brought to any desired concentration by adding water as required. Due to the aqueous basis of the agent, the use of fillers, such as sodium sulfate, is unnecessary, which can be regarded as a further considerable advantage in terms of environmental compatibility. The liquid or gel-like consistency of the agent facilitates its handling, in particular its dosage in an extraordinary way and thus complies with the habits of the consumer, who experience has shown that the dosage of a larger quantity is preferred to the dosage of very small quantities. This means that the overdosing that can often be observed with powdery detergents can be practically completely ruled out. In addition, because of its liquid consistency, the agent can be dosed from a spray bottle, so that skin contact with the agent can be largely ruled out. In addition, with the appropriate technical equipment of the machine, automatic metering is also readily possible, which is not possible or only possible with considerable technical effort when using powdered agents.

Als schwachschäumende Tenside können alle bekannten nicht- oder schwachschäumenden, vorzugsweise biologisch gut abbaubaren Tenside eingesetzt werden, so insbesondere nicht ionogene Tenside des Typs der mit Ethylenoxid und Propylenoxid alkoxylierten Fettalkohole oder endgruppenverschlossene, vorzugsweise endständig methylierte Fettalkoholpolyglykolether, darüberhinaus anionische Tenside des Typs der kurzkettigen Etherkarbonsäuren, die zu einem hohen Anteil in dem Mittel enthalten sein können. Aufgrund hoher Anteile dieser Substanzen kann auf den Einsatz von Phosphaten verzichtet werden, deren - in herkömmlichen Mitteln ausgeübte - Wirkung von dem umweltverträglichen Tensid mit übernommen wird.All known non-foaming or low-foaming, preferably readily biodegradable surfactants can be used as low-foaming surfactants, in particular non-ionic surfactants of the type of fatty alcohols alkoxylated with ethylene oxide and propylene oxide or end group-capped, preferably terminally methylated fatty alcohol polyglycol ethers, moreover, anionic surfactants of the short-chain ether carboxylic acid type, which may be present in the agent in a high proportion. Due to the high proportions of these substances, the use of phosphates can be dispensed with, the effect of which - carried out in conventional means - is also taken over by the environmentally compatible surfactant.

Als Säuerungsmittel finden zweckmäßig die Lebensmittelsäuren, vorzugsweise Citronensäure, Weinsäure, Essigsäure, Gluconsäure oder Apfelsäure, einzeln oder in Mischung miteinander Verwendung, während als Wasserenthärter und Schmutzdispergator mit Vorteil Polyacrylsäure und/oder ein Copolymer aus Acrylsäure und Maleinsäure (Natriumsalz) eingesetzt werden können.The acidifying agents used are advantageously the food acids, preferably citric acid, tartaric acid, acetic acid, gluconic acid or malic acid, individually or in a mixture with one another, while polyacrylic acid and / or a copolymer of acrylic acid and maleic acid (sodium salt) can advantageously be used as water softener and soil dispersant.

Es werden nachstehend einige Beispiele für die Formulierung eines Geschirrspülmittels gegeben:Some examples of the formulation of a dishwashing detergent are given below:

Beispiel 1example 1

Ein phospahtfreies Spülgel besteht aus
   73 Gew.-% Wasser
   8 Gew.-% eines Tensides bestehend aus einem Laurylalkohol mit 4 Mol Ethylenoxid und 3 Molen Propylenoxid
   3 Gew.-% Citronensäure
   4 Gew.-% eines Copolymers der Acrylsäure und der Maleinsäure. Na-Salz
   4 Gew.-% Laurylalkohol mit 5 Molen Ethylenoxid
   2 Gew.-% polymerer Glucoseacrylsäureester, sauer
   1 Gew.-% Nitrilotriacetat Trinatriumsalz
   4 Gew.-% Triethanolamin
   1 Gew.-% Parfüm, Konservierungsmittel, Farbstofflösung
A phosphate-free washing gel consists of
73 wt% water
8% by weight of a surfactant consisting of a lauryl alcohol with 4 moles of ethylene oxide and 3 moles of propylene oxide
3% by weight of citric acid
4% by weight of a copolymer of acrylic acid and maleic acid. Na salt
4% by weight lauryl alcohol with 5 moles of ethylene oxide
2% by weight of polymeric glucose acrylic acid ester, acidic
1% by weight of nitrilotriacetate trisodium salt
4% by weight of triethanolamine
1% by weight of perfume, preservative, dye solution

Es werden zunächst der polymere Glucoseacrylsäureester zusammen mit dem Nitriloacetat mit dem Laurylalkohol angeteigt und das restliche Tensid, die Zitronensäure sowie das Copolymer der Acrylsäure und der Maleinsäure in dem vorgelegten Wasser gelöst. Hierauf wird die angeteigte Masse der Lösung unter ständigem Rühren zugegeben. Nach Erzielung einer homogenen Mischung erfolgt die Zugabe des Triethanolamins bis zur Erreichung eines pH-Wertes von etwa 5 unter zunächst Lösung der festen Bestandteile der Mischung und anschließender Gelierung. Es resultiert - ein klares, homogenes und lagerstabiles Gel mit einer Viskosität von 5000 (mPa x s) bei 20 °C im Rotationsviskosimeter. Die Einsatzkonzentration bezogen auf die Gesamtformulierung beträgt 6g/l im Hauptspülgang.First the polymeric glucose acrylic acid ester together with the nitriloacetate is mixed with the lauryl alcohol and the remaining surfactant, citric acid and the copolymer of acrylic acid and maleic acid are dissolved in the water. Then the pasted mass of the solution is added with constant stirring. After achieving a homogeneous mixture, the triethanolamine is added until a pH of approximately 5 is reached, with the solid constituents of the mixture first being dissolved and then gelling. The result - a clear, homogeneous and storage-stable gel with a viscosity of 5000 (mPa x s) at 20 ° C in a rotary viscometer. The concentration in relation to the total formulation is 6g / l in the main wash.

Beipiel 2Example 2

Phospahtfreies Spülgel bestehend aus
   57 Gew.-% Wasser
   10 Gew.-% eines Nichtionogenen Tensides der Zusammensetzung Myristylalkohol mit 4 Molen Propylenoxid.
   5 Gew.-% Weinsäure
   5 Gew.-% Polyacrylsäure. Na-Salz
   2 Gew. -% Laurylalkohol. 3 Mol Ethylenoxid
   15 Gew.-% der Dispersion einer hochmolekularen Polyacrylsäure
   4 Gew.-% Triethanolamin
   1 Gew.-% Nitrilotriacetat. Trinatriumsalz
   1 Gew.-% Parfüm Konservierungsmittel, Farbstofflösung
Phosphate-free washing gel consisting of
57% by weight of water
10% by weight of a nonionic surfactant of the composition myristyl alcohol with 4 moles of propylene oxide.
5% by weight tartaric acid
5% by weight polyacrylic acid. Na salt
2% by weight lauryl alcohol. 3 moles of ethylene oxide
15% by weight of the dispersion of a high molecular weight polyacrylic acid
4% by weight of triethanolamine
1% by weight nitrilotriacetate. Trisodium salt
1% by weight perfume preservative, dye solution

Die Hersatellung erfolgt analog zum Beispiel 1. Das Produkt ist ein leicht trübes, homogenes Gel. Der pH-Wert wird mit Triethanolamin auf 5 eingestellt. Die Viskosität beträgt 6000 (mPa x s) bei 20 °C im Rotationsviskosimeter. Die Einsatzkonzentration im Hauptreinigungsgang der Geschirrspülmaschine beträgt 5 g/l Waschlauge.The production takes place analogously to example 1. The product is a slightly cloudy, homogeneous gel. The pH is adjusted to 5 with triethanolamine. The viscosity is 6000 (mPa xs) at 20 ° C in a rotary viscometer. The concentration used in the main cleaning cycle of the dishwasher is 5 g / l of wash water.

Beispiel 3Example 3

Spülmittel in Gelform bestehend aus
   68 Gew.-% Wasser
   6 Gew.-% Citronensäure
   6 Gew.-% Copolymer der Acrylsäure und der Maleinsäure. Na-Salz
   9 Gew.-% Ethercarbonsäure (Alkyl (C₆-C₈) polyethylenglykolether (4 EO) methylencarbonsäure )
   3 Gew.-% Laurylalkoholpolyethylewnglykolether (6 EO)
   2 Gew.-% Copolymer der Acrylsäure und des Acrylamid (Verdicker)
   5 Gew.-% KOH. 50 Gew.-%
   1 Gew.-% Parfüm. Konservierungsmittel.
Detergent in gel form consisting of
68% by weight of water
6% by weight citric acid
6% by weight copolymer of acrylic acid and maleic acid. Na salt
9% by weight ether carboxylic acid (alkyl (C₆-C₈) polyethylene glycol ether (4 EO) methylene carboxylic acid)
3% by weight lauryl alcohol polyglycol ether (6 EO)
2% by weight copolymer of acrylic acid and acrylamide (thickener)
5 wt% KOH. 50% by weight
1% by weight of perfume. Preservative.

Das Produkt ist ein klares, homogenes und lagerstabiles Gel. Der pH-Wert wird mit KOH auf 5 eingestellt. Die Viskosität beträgt ca. 10.000 (mPa.s) bei 20 °C im Rotationsviskosimeter.
Die Einsatzkonzentration im Hauptspülgang beträgt 5 g/l.
The product is a clear, homogeneous and storage stable gel. The pH is adjusted to 5 with KOH. The viscosity is approximately 10,000 (mPa.s) at 20 ° C in a rotary viscometer.
The concentration in the main wash cycle is 5 g / l.

Claims (8)

Maschinengeschirrspülmittel, bestehend aus einem schwachschäumenden Tensid sowie gegebenenfalls einer Polycarbonsäure, gekennzeichnet durch folgende Zusammensetzung:
   5 - 20 Gew.-% schwachschäumendes Tensid
   2 - 10 Gew.-% einer organischen Säure
   3 - 8 Gew.-% einer Polycarbonsäure
   0 - 5 Gew.-% Nitrilotriacetat
   3 - 5 Gew.-% Emulgator
   2 - 5 Gew.-% Verdicker
   1 - 4 Gew. % Lauge
   Rest Wasser
das einen pH-Wert zwischen 4 und 6, vorzugsweise etwa 5 aufweist.
Dishwasher detergent, consisting of a low-foaming surfactant and optionally a polycarboxylic acid, characterized by the following composition:
5 - 20% by weight low-foaming surfactant
2 - 10% by weight of an organic acid
3 - 8% by weight of a polycarboxylic acid
0 - 5% by weight nitrilotriacetate
3 - 5% by weight emulsifier
2 - 5% by weight thickener
1 - 4 wt% lye
Rest of water
which has a pH between 4 and 6, preferably about 5.
Verfahren zur Herstellung eines Maschinengeschirrspülmittels, bestehend aus einem schwachschäumenden Tensid sowie gegebenenfalls einer Polycarbonsäure, dadurch gekennzeichnet, daß zunächst der pulverförmige Verdicker in einem (flüssigen) nichtionogenen wasserfreien Tensid angeteigt und die so gebildete dispergierte Masse dem flüssigen (gelösten) Tensid zugegeben wird, worauf die sich bildende Lösung zum Zwecke der Lösung des pulverförmigen Verdickers und Gelierung der Flüssigkeit mittels Alkali, vorzugsweise Tri-ethanolamin, bis auf einen PH-Wert von zwischen 4 und 6, vorzugsweise 5 neutralisiert wird.A process for producing a machine dishwashing detergent consisting of a low-foaming surfactant and optionally a polycarboxylic acid, characterized in that first the powdery thickener is pasted in a (liquid) nonionic anhydrous surfactant and the dispersed mass thus formed is added to the liquid (dissolved) surfactant, after which the Solution which is formed for the purpose of dissolving the powdered thickener and gelling the liquid by means of alkali, preferably triethanolamine, is neutralized to a pH of between 4 and 6, preferably 5. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß als schwachschäumendes Tensid mit Ethylenoxid und Propylenoxid alkoxylierte Fettalkohole und/oder endgruppenverschlossene, vorzugsweise endständig methylierte Fettalkoholpolyglykolether und/oder kurzkettige Etherkarbonsäuren Verwendung finden.A method according to claim 2, characterized in that the low-foaming surfactant alkoxylated with ethylene oxide and propylene oxide and / or end group-capped, preferably terminally methylated fatty alcohol polyglycol ethers and / or short-chain ether carboxylic acids are used. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß als Säuerungsmittel eine Lebensmittelsäure, vorzugsweise Citronensäure, Weinsäure, Essigsäure, Gluconsäure oder Apfelsäure, einzeln oder in Mischung miteinander Verwendung findet.Process according to Claim 2, characterized in that a food acid, preferably citric acid, tartaric acid, acetic acid, gluconic acid or malic acid, is used individually or as a mixture with one another as acidifying agent. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß als Wasserenthärter und Schmutzdispergator Polyacrylsäure und/oder ein Copolymer aus Acrylsäure und Maleinsäure (Natriumsalz) Verwendung findet.Process according to Claim 2, characterized in that polyacrylic acid and / or a copolymer of acrylic acid and maleic acid (sodium salt) is used as the water softener and soil dispersant. Verfahren nach Anspruch 2, dadurch gekenzeichnet, daß als Verdicker ein vernetzter polymerer Acrylsäureester der Glucose oder ein Ethoxylat hiervon und/oder eine hochmolekulare Polyacrylsäure und/oder ein Copolymer der Acrylsäure mit Acrylamid Verwendung findet.A method according to claim 2, characterized in that a crosslinked polymeric acrylic acid ester of glucose or an ethoxylate thereof and / or a high molecular weight polyacrylic acid and / or a copolymer of acrylic acid with acrylamide is used as the thickener. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß als Neutralisierungsmittel Triethanolamin und/oder Natronlauge und/oder Kalilauge Verwendung finden.Process according to Claim 2, characterized in that triethanolamine and / or sodium hydroxide solution and / or potassium hydroxide solution are used as neutralizing agents. Verfahren nach Anspruch 6 und 7, dadurch gekennzeichnet, daß zur Unterstützung der Lösung des Emulgators ein weiterer Emulgator, beispielsweise ein nichtionogenes Fettalkoholethoxylat mit 3 - 8 Mol Ethylenoxid Verwendung findet.Process according to Claims 6 and 7, characterized in that a further emulsifier, for example a non-ionic fatty alcohol ethoxylate with 3-8 mol ethylene oxide, is used to support the solution of the emulsifier.
EP92112124A 1991-07-17 1992-07-16 Automatic dishwashing detergent composition and method for producing the same Expired - Lifetime EP0523681B1 (en)

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DE4123623 1991-07-17

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995010590A1 (en) * 1993-10-14 1995-04-20 Ecolab Inc. Rinse agents that form clear coatings on ware
WO1995030732A1 (en) * 1994-05-05 1995-11-16 Henkel Kommanditgesellschaft Auf Aktien Clear rinse agents with biologically degradable polymers
US5786315A (en) * 1993-11-03 1998-07-28 The Procter & Gamble Company Control of calcium carbonate precipitation in automatic dishwashing
US5786314A (en) * 1993-11-03 1998-07-28 The Procter & Gamble Company Control of calcium precipitation in automatic dishwashing
EP0889946A1 (en) * 1996-03-29 1999-01-13 The Procter & Gamble Company Rinsing compositions
WO2004048585A3 (en) * 2002-11-22 2004-08-05 Basf Ag Enzymatic synthesis of polyol acrylates
EP0806472B2 (en) 1996-05-09 2004-10-13 Chemische Fabrik Dr. Weigert GmbH & Co KG Cleaning kit for crockery and process therefor
EP0986629B2 (en) 1997-06-05 2007-05-16 Henkel Kommanditgesellschaft auf Aktien Granular detergent
EP2519623A1 (en) * 2009-12-30 2012-11-07 Ecolab Inc. Phosphate substitutes for membrane-compatible cleaning and/or detergent compositions

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FR1545299A (en) * 1966-11-26 1968-11-08 Henkel & Cie Gmbh Mechanical dishwashing process
DE2345834A1 (en) * 1972-09-13 1974-03-21 Kao Corp Buffered cleaning agents - contg anionic or nonionic surface active agent and weak acid buffer, cause less skin roughness
EP0340704A2 (en) * 1988-05-05 1989-11-08 BASF Aktiengesellschaft Aqueous acid detergent compositions
EP0355551A2 (en) * 1988-08-16 1990-02-28 Henkel Kommanditgesellschaft auf Aktien Pasty washing and cleaning agent, and method for its preparation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1545299A (en) * 1966-11-26 1968-11-08 Henkel & Cie Gmbh Mechanical dishwashing process
DE2345834A1 (en) * 1972-09-13 1974-03-21 Kao Corp Buffered cleaning agents - contg anionic or nonionic surface active agent and weak acid buffer, cause less skin roughness
EP0340704A2 (en) * 1988-05-05 1989-11-08 BASF Aktiengesellschaft Aqueous acid detergent compositions
EP0355551A2 (en) * 1988-08-16 1990-02-28 Henkel Kommanditgesellschaft auf Aktien Pasty washing and cleaning agent, and method for its preparation

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995010590A1 (en) * 1993-10-14 1995-04-20 Ecolab Inc. Rinse agents that form clear coatings on ware
US5786315A (en) * 1993-11-03 1998-07-28 The Procter & Gamble Company Control of calcium carbonate precipitation in automatic dishwashing
US5786314A (en) * 1993-11-03 1998-07-28 The Procter & Gamble Company Control of calcium precipitation in automatic dishwashing
WO1995030732A1 (en) * 1994-05-05 1995-11-16 Henkel Kommanditgesellschaft Auf Aktien Clear rinse agents with biologically degradable polymers
EP0889946A1 (en) * 1996-03-29 1999-01-13 The Procter & Gamble Company Rinsing compositions
EP0889946A4 (en) * 1996-03-29 1999-07-21 Procter & Gamble Rinsing compositions
EP0806472B2 (en) 1996-05-09 2004-10-13 Chemische Fabrik Dr. Weigert GmbH & Co KG Cleaning kit for crockery and process therefor
EP0986629B2 (en) 1997-06-05 2007-05-16 Henkel Kommanditgesellschaft auf Aktien Granular detergent
WO2004048585A3 (en) * 2002-11-22 2004-08-05 Basf Ag Enzymatic synthesis of polyol acrylates
EP2519623A1 (en) * 2009-12-30 2012-11-07 Ecolab Inc. Phosphate substitutes for membrane-compatible cleaning and/or detergent compositions
EP2519623A4 (en) * 2009-12-30 2013-06-05 Ecolab Inc Phosphate substitutes for membrane-compatible cleaning and/or detergent compositions

Also Published As

Publication number Publication date
DE4223265A1 (en) 1993-03-18
ATE173006T1 (en) 1998-11-15
DE59209547D1 (en) 1998-12-10
EP0523681A3 (en) 1993-05-05
EP0523681B1 (en) 1998-11-04

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