EP0523681B1 - 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
EP0523681B1
EP0523681B1 EP92112124A EP92112124A EP0523681B1 EP 0523681 B1 EP0523681 B1 EP 0523681B1 EP 92112124 A EP92112124 A EP 92112124A EP 92112124 A EP92112124 A EP 92112124A EP 0523681 B1 EP0523681 B1 EP 0523681B1
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weight
acid
surfactant
water
thickener
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EP92112124A
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German (de)
French (fr)
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EP0523681A3 (en
EP0523681A2 (en
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Johannes Dr. Behrensdorf
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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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • the invention is based on a low-foaming surfactant and a dishwasher detergent containing polymeric polycarboxylic acid.
  • Dishes are cleaned in dishwashers today generally two or more stages in one main wash Use of a main cleaning agent and one or more rinse cycles using - at least in the last rinse - a rinse aid, that usually consists of a wetting, nonionic surfactant and a weak organic acid, generally citric acid and who has the task of wetting the dish surface well to ensure the formation of limescale or detergent deposits to prevent especially on glasses.
  • a rinse aid that usually consists of a wetting, nonionic surfactant and a weak organic acid, generally citric acid and who has the task of wetting the dish surface well to ensure the formation of limescale or detergent deposits to prevent especially on glasses.
  • the known dishwashing detergents of this type have a number considerable disadvantages.
  • a major disadvantage is the high content of alkalis with their strong caustic effects on skin and mucous membranes, which is the cause of the fact that the known dishwashing detergents on the one hand, cannot be classified as "childproof” and, on the other hand often cause damage to the decorations of the harness.
  • child safety today can generally be seen as one by the consumer as a self-evident property of all budget funds apply, just as today the consumer is hardly willing to stand alone because of the usability of a dishwasher on the use of to restrict machine-proof dishes.
  • the high, up to 50% and above the phosphate content of the known Dishwasher detergents are known to have a significant environmental impact Water eutrophication.
  • the dishwashing liquid is slightly acidic falls however, as a powdery product of high concentration and therefore causes Handling problems. Furthermore, arise great manufacturing difficulties.
  • Dishwasher detergent that has become known to help remove its strong corrosive effect is set slightly acidic, but powdery and the use of high proportions of environmentally harmful phosphate as a reinforcing agent can not do without.
  • EP-A-355 551 a pasty washing and Known cleaning agent, which essentially consists of a surfactant combination an alkyl glycoside as a nonionic surfactant and an alpha sulfofatty acid disalt contains as an anionic surfactant on an aqueous basis.
  • FR-B-1 545 299 is a cleaning phase and a dishwashing method comprising a rinsing phase has become known, which in the cleaning phase consists of an acidic mixture water-soluble monomeric and / or polymeric phosphates and complexing organic acids and / or water-soluble salts thereof Acids and weakly foaming wetting agents as an active substance in the rinsing phase and complex-forming organic acids as well as water-soluble Salts of these acids can be used. These agents are organic difficult to degrade and very irritating to the skin.
  • the present invention has for its object to provide a liquid dishwashing detergent, which is effective childproof, i.e. is absolutely non-toxic, good skin tolerance and does not cause environmental pollution.
  • the dishwashing detergent according to the invention contains no phosphates and toxic components and is otherwise fully biodegradable. It is therefore child-safe and environmentally compatible. It is also due its weakly acidic setting of good skin and mucous membrane tolerance with excellent effectiveness especially as Dishwasher detergent. It has been shown that by using the invention Dish detergent also removes tea and coffee stains can be, so that on the usual in the known standard cleaners Use of bleaching agents can be dispensed with.
  • the agent is produced in such a way that that first the powdery thickener with a liquid non-ionic water-free surfactant and the so formed dispersed mass is added to the liquid (dissolved) surfactant, whereupon the liquid line for the purpose of dissolving the thickener and Gelling with alkali to a pH between 4 and 6. preferably 5 is neutralized.
  • the invention provides a method by means of which using a powdery, non-water-soluble substance a liquid detergent of high effectiveness can be made can do so by adding water to any desired concentration can be brought. Due to the watery basis of the The use of fillers, such as sodium sulfate, which is another notable in terms of environmental sustainability Is an advantage.
  • the liquid or gel-like consistency of the By means of it facilitates its handling, especially its dosage in extraordinary way and thus comes to the habits of consumers contrary to experience, the dosing of a larger amount prefer to dose small amounts. It can be the most common powdery detergents observed overdose practically completely be excluded.
  • the agent because of its liquid consistency can be dosed from a spray bottle, so that skin contact with the agent is largely excluded can.
  • Automatic metering is also possible without further ado when using powdered agents, not or only with considerable technical effort is possible.
  • non-foaming or low-foaming, preferably readily biodegradable surfactants are used, in particular non-ionic surfactants of the type of fatty alcohols alkoxylated with ethylene oxide and propylene oxide or end groups capped, preferably terminally methylated fatty alcohol polyglycol ethers, moreover, anionic surfactants of the short-chain type Ether carboxylic acids to a large extent in the agent can be included. Due to high proportions of these substances the use of phosphates, their - in conventional Agents exercised - effect of the environmentally compatible surfactant is taken over.
  • Suitable acidifiers are the food acids, preferably citric acid, tartaric acid, acetic acid, gluconic acid or Malic acid, used singly or in a mixture with each other, while as water softener and dirt disperser with advantage polyacrylic acid and / or a copolymer of acrylic acid and maleic acid (sodium salt) be used.
  • the pasted Mass of the solution is added with constant stirring.
  • the triethanolamine is added until Reaching a pH of about 5 with first solving the solid Components of the mixture and subsequent gelation. It results - a clear, homogeneous and storage stable gel with a viscosity of 5000 mPas at 20 ° C in a rotary viscometer.
  • the operational concentration based on the total formulation is 6g / l in the main wash.
  • the production takes place analogously to example 1.
  • the product is a slightly cloudy, homogeneous gel.
  • the pH is adjusted to 5 with triethanolamine set.
  • the viscosity is 6000 mPas at 20 ° C in Rotational viscometer.
  • the use concentration in the main cleaning cycle the dishwasher is 5 g / l wash water.
  • the product is a clear, homogeneous and storage-stable gel.
  • the pH is adjusted to 5 with KOH.
  • the viscosity is approx. 10,000 mPas at 20 ° C in a rotary viscometer.
  • the concentration in the main wash cycle is 5 g / l.

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 ein schwachschäumendes Tensid sowie eine polymere Polycarbonsäure enthaltenden Maschinengeschirrspülmittel.The invention is based on a low-foaming surfactant and a dishwasher detergent containing polymeric polycarboxylic acid.

Die Reinigung 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.Dishes are cleaned in dishwashers today generally two or more stages in one main wash Use of a main cleaning agent and one or more rinse cycles using - at least in the last rinse - a rinse aid, that usually consists of a wetting, nonionic surfactant and a weak organic acid, generally citric acid and who has the task of wetting the dish surface well to ensure the formation of limescale or detergent deposits to prevent 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.Today, increased demands are placed on the means used Related to their skin and especially their environmental compatibility, the known main cleaning agents in particular are considerable Problems cause because of their high level of saponification of the edible fats serving, in the form of caustic soda or soda in the detergents present alkali content. In addition, the marketable Dishwashing detergent phosphates and silicates for cleaning reinforcement and binding of water hardness, dichloroisocyanurate as a bleaching agent Elimination or Coverage caused by tea and coffee Discoloration and finally a generally non-ionic surfactant Wetting agent and dispersant, with the help of which the dirt from the Dish surface detached and kept in suspension in the rinse water shall be.

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 Polyoxyethylenpolyoxypropylen-Blockpolymere eingesetzt werden, die nur ungenügend biologisch abbaubar sind und damit ebenfalls eine Umweltbelastung darstellen.The known dishwashing detergents of this type have a number considerable disadvantages. A major disadvantage is the high content of alkalis with their strong caustic effects on skin and mucous membranes, which is the cause of the fact that the known dishwashing detergents on the one hand, cannot be classified as "childproof" and, on the other hand often cause damage to the decorations of the harness. However, child safety today can generally be seen as one by the consumer as a self-evident property of all budget funds apply, just as today the consumer is hardly willing to stand alone because of the usability of a dishwasher on the use of to restrict machine-proof dishes. In addition, the high, up to 50% and above the phosphate content of the known Dishwasher detergents are known to have a significant environmental impact Water eutrophication. The same applies to those in the Bleaching chlorine compounds contained in agents. The used Dichloroisocyanurate itself is a toxic and caustic substance that moreover - escaping into the atmosphere - chlorine and beyond Cleaves chlorine radicals, which in turn toxic chlorine compounds can form. Finally there is that in dishwashing detergents Polyoxyethylene polyoxypropylene block polymers used as surfactants that are only insufficiently biodegradable and therefore also represent an environmental impact.

Es ist aus der DE-C-35 32 586 und des korrespondierenden EP-A-217732 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-C-35 32 586 and the corresponding EP-A-217732, in standard dishwashing detergents of this type to use polyacrylic acid instead of phosphate, however, what the use of high proportions of sodium sulfate as an adjusting agent required. This will not reduce the environmental impact reached. Apart from that, the high immission of sodium sulfate also represents a significant environmental impact in the case of polyacrylic acid, it is biologically extremely slow degradable substance. The strong caustic effect is not thereby mitigated.

Das Geschirrspülmittel ist zwar schwach sauer eingestellt fällt jedoch als pulverförmiges Produkt hoher Konzentration an und verursacht daher Probleme bei der Handhabung. Darüberhinaus ergeben sich große herstellungstechnische Schwierigkeiten.The dishwashing liquid is slightly acidic falls however, as a powdery product of high concentration and therefore causes Handling problems. Furthermore, arise great manufacturing difficulties.

Das entsprechende gleich gilt für das aus der DE-A-16 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 that from DE-A-16 28 632 Dishwasher detergent that has become known to help remove its strong corrosive effect is set slightly acidic, but powdery and the use of high proportions of environmentally harmful phosphate as a reinforcing agent can not do without.

Es ist weiterhin aus der EP-A-355 551 ein pastenförmiges Wasch- und Reinigunsmittel bekannt, das im wesentlichen eine Tensidkombination aus einem Alkylglykosid als nichtionisches Tensid und einem Alpha-Sulfofettsäuredisalz als anionisches Tensid auf wässriger Basis enthält.It is also from EP-A-355 551 a pasty washing and Known cleaning agent, which essentially consists of a surfactant combination an alkyl glycoside as a nonionic surfactant and an alpha sulfofatty acid disalt contains as an anionic surfactant on an aqueous basis.

Es ist schließlich aus der FR-B-1 545 299 ein eine Reinigungsphase und eine Spülphase umfassendes Geschirrspül-Verfahren bekannt geworden, bei dem in der Reinigungsphase eine sauer reagierende Mischung aus wasserlöslichen monomeren und/oder polymeren Phosphaten und komplexbildenden organischen Säuren und/oder wasseerlöslichen Salzen dieser Säuren und in der Spülphase als aktive Substanz schwachschäumende Netzmittel und komplexbildenden organische Säuren sowie wasserlösliche Salze dieser Säuren verwendet werden. Diese Mittel sind biologisch schwer abbaubar und stark hautreizend.Finally, FR-B-1 545 299 is a cleaning phase and a dishwashing method comprising a rinsing phase has become known, which in the cleaning phase consists of an acidic mixture water-soluble monomeric and / or polymeric phosphates and complexing organic acids and / or water-soluble salts thereof Acids and weakly foaming wetting agents as an active substance in the rinsing phase and complex-forming organic acids as well as water-soluble Salts of these acids can be used. These agents are organic difficult to degrade and very irritating to the skin.

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 effective childproof, i.e. is absolutely non-toxic, good skin tolerance and does not cause environmental pollution.

Diese Aufgabe wird mit einem Geschirrspülmittel mit folgenden Merkmalen gelöst.This task is done with a dishwashing liquid with the following Features resolved.

Das phosphatfreie Maschinengeschirrspülmittel mit einem schwachschäumenden Tensid sowie einer polymeren Polycarbonsäure ist durch folgende Zusammensetzung gekennzeichnet:

  • 5 - 20 Gew.-% schwachschäumendes Tensid
  • 2 - 10 Gew.-% organischen Säure
  • 3 - 8 Gew.-% polymeric Polycarbonsäure
  • 0 - 5 Gew.-% Nitrilotriacetat
  • 3 - 5 Gew.-% Emulgator
  • 2 - 5 Gew.-% Verdicker
  • 1 - 4 Gew. % Lauge
  • Rest Wasser
    • und weist einen pH-Wert zwischen 4 und 6, vorzugsweise etwa 5 auf.The phosphate-free dishwasher detergent with a low-foaming surfactant and a polymeric polycarboxylic acid is characterized by the following composition:
  • 5 - 20% by weight low-foaming surfactant
  • 2 - 10 wt .-% organic acid
  • 3 - 8% by weight polymeric polycarboxylic acid
  • 0 - 5% by weight nitrilotriacetate
  • 3 - 5% by weight emulsifier
  • 2 - 5% by weight thickener
  • 1 - 4 wt% lye
  • Rest of water
    • and has a pH between 4 and 6, preferably about 5.

    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 durch den Einsatz des erfindungsgemäßen Geschirrspülmittels auch Tee- und Kaffeeflecken 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 components and is otherwise fully biodegradable. It is therefore child-safe and environmentally compatible. It is also due its weakly acidic setting of good skin and mucous membrane tolerance with excellent effectiveness especially as Dishwasher detergent. It has been shown that by using the invention Dish detergent also removes tea and coffee stains can be, so that on the usual in the known standard cleaners Use of bleaching agents can be dispensed with.

    Die Herstellung des Mittels erfolgt erfindungsgemäß 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.According to the invention, the agent is produced in such a way that that first the powdery thickener with a liquid non-ionic water-free surfactant and the so formed dispersed mass is added to the liquid (dissolved) surfactant, whereupon the liquid line for the purpose of dissolving the thickener and Gelling with alkali to a pH between 4 and 6. preferably 5 is neutralized.

    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 beobachtende 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 detergent of high effectiveness can be made can do so by adding water to any desired concentration can be brought. Due to the watery basis of the The use of fillers, such as sodium sulfate, which is another notable in terms of environmental sustainability Is an advantage. The liquid or gel-like consistency of the By means of it facilitates its handling, especially its dosage in extraordinary way and thus comes to the habits of consumers contrary to experience, the dosing of a larger amount prefer to dose small amounts. It can be the most common powdery detergents observed overdose practically completely be excluded. In addition, the agent because of its liquid consistency can be dosed from a spray bottle, so that skin contact with the agent is largely excluded can. In addition, with appropriate technical equipment Automatic metering is also possible without further ado when using powdered agents, not or only with considerable technical effort is possible.

    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 are used, in particular non-ionic surfactants of the type of fatty alcohols alkoxylated with ethylene oxide and propylene oxide or end groups capped, preferably terminally methylated fatty alcohol polyglycol ethers, moreover, anionic surfactants of the short-chain type Ether carboxylic acids to a large extent in the agent can be included. Due to high proportions of these substances the use of phosphates, their - in conventional Agents exercised - effect of the environmentally compatible surfactant is taken over.

    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.Suitable acidifiers are the food acids, preferably citric acid, tartaric acid, acetic acid, gluconic acid or Malic acid, used singly or in a mixture with each other, while as water softener and dirt disperser with advantage polyacrylic acid and / or a copolymer of acrylic acid and maleic acid (sodium salt) be used.

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

    Beispiel 1example 1

    Ein phosphatfreies 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 rinsing gel consists of
  • 73% by weight of 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 mPas 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 pasted with the lauryl alcohol and the remaining surfactant, citric acid and the copolymer of acrylic acid and maleic acid dissolved in the water presented. Then the pasted Mass of the solution is added with constant stirring. After achieving one homogeneous mixture, the triethanolamine is added until Reaching a pH of about 5 with first solving the solid Components of the mixture and subsequent gelation. It results - a clear, homogeneous and storage stable gel with a viscosity of 5000 mPas at 20 ° C in a rotary viscometer. The operational concentration based on the total formulation is 6g / l in the main wash.

    Beipiel 2Example 2

    Phosphatfreies 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 Herstellung 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 mPas 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 set. The viscosity is 6000 mPas at 20 ° C in Rotational viscometer. The use concentration in the main cleaning cycle the dishwasher is 5 g / l 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.-% Laurylalkoholpolyethylenglykolether (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 (C 6 -C 8 ) polyethylene glycol ether (4 EO) methylene carboxylic acid)
  • 3% by weight lauryl alcohol polyethylene glycol 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 mPas 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 approx. 10,000 mPas at 20 ° C in a rotary viscometer. The concentration in the main wash cycle is 5 g / l.

    Claims (8)

    1. Phosphate-free dishwashing detergent composition with a low-foaming surfactant and a polymeric polycarboxylic acid, charactarised by the following composition
      5 - 20% by weight of low-foaming surfactant
      2 - 10% by weight of organic acid
      3 - 8% by weight of a polymeric 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 lye
      Residue water
      which has a pH value between 4 and 6, preferably about 5.
    2. Method of manufacturing a phosphate-free dishwashing detergent composition with a low-foaming surfactant and a polymeric polycarboxylic acid of 5 to 20% by weight low-foaming surfactant, 2 to 10% by weight organic acid 3 to 8% by weight of a polymeric polycarboxylic acid, 0 to 5% by weight of nitrilotriacetate, 3 to 5% by weight of emulsifier, 2 to 5% by weight of thickener, 1 to 4% by weight of lye as well as water water, which has a pH value of between 4 and 6, preferably about 5, characterised in that firstly the pulverulent thickner is mixed to a paste in a liquid non-ionogenic water-free surfactant, and the dispersed mass so formed is added to the liquid (dissolved) surfactant, whereupon the solution formed is neutralised for purposes of dissolution of the pulverulent thickener and gelification of the liquid by means of alkali, preferably triethanolamine, to a pH value of between 4 and 6, preferably 5.
    3. Method according to claim 2, characterised in that there are used as a low-foaming surfactant fatty alcohols alkoxylised with ethylene oxide and propylene oxide and/or terminal-group closed, preferably terminally methylised fatty alcohol polyglycol ethers and/or an anionic surfactant of the type of short-chained ethercarboxylic acids, for example (C6 - C8) - polyethyleneglycolethermethylene carboxylic acid.
    4. Method according to claim 2, characterised in that there are used as acidification agents a foodstuff acid, preferably citric acid, tartaric acid, gluconic acid or malic acid, individually or in admixture with one another.
    5. Method according to claim 2, characterised in that there are used as a water hardener and dirt dispersers polyacrylic acid and/or a copolymer of acrylic acid and maleic acid (sodium salt).
    6. Method according to claim 2, characterised in that there are used as a thickener a cross-linked 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.
    7. Method according to claim 2, characterised in that there are used as a neutralising agent triethanolamine and/or soda lye and/or potash lye.
    8. Method according to claim 6 and 7, characterised in that in order to reinforce the dissolution of the emulsifer, a further emulsifier is used, for example a non-ionogenic fatty alcoholethoxylate with 3 to 8 Mol ethylene oxide.
    EP92112124A 1991-07-17 1992-07-16 Automatic dishwashing detergent composition and method for producing the same Expired - Lifetime EP0523681B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE4123623 1991-07-17
    DE4123623 1991-07-17

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    EP0523681A3 EP0523681A3 (en) 1993-05-05
    EP0523681B1 true EP0523681B1 (en) 1998-11-04

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    AT (1) ATE173006T1 (en)
    DE (2) DE4223265A1 (en)

    Families Citing this family (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
    ES2120074T3 (en) * 1993-11-03 1998-10-16 Procter & Gamble CONTROL OF THE PRECIPITATION OF CALCIUM CARBONATE IN AUTOMATIC DISHWASHERS.
    AU8015094A (en) * 1993-11-03 1995-05-23 Procter & Gamble Company, The Control of calcium carbonate precipitation in automatic dishwashing
    DE4415804A1 (en) * 1994-05-05 1995-11-09 Henkel Kgaa Rinse aid with biodegradable polymers
    GB2311537A (en) * 1996-03-29 1997-10-01 Procter & Gamble Rinse composition for dishwashers
    DE19618725A1 (en) † 1996-05-09 1997-11-13 Weigert Chem Fab Method and kit for cleaning dishes
    DE19723616A1 (en) † 1997-06-05 1998-12-10 Henkel Kgaa Granular detergent
    ES2393673T3 (en) * 2002-11-22 2012-12-27 Basf Se Enzymatic synthesis of polyol acrylates
    ES2598402T5 (en) * 2009-12-30 2019-10-09 Ecolab Inc Phosphate substitutes for cleaning and / or detergent compositions compatible with membranes

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    * 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
    JPS4950004A (en) * 1972-09-13 1974-05-15
    DE3815291A1 (en) * 1988-05-05 1989-11-23 Basf Ag WAFER ACID CLEANSER FORMULATIONS
    DE3827778A1 (en) * 1988-08-16 1990-02-22 Henkel Kgaa PASTE-SHAPED DETERGENT AND CLEANING AGENT AND METHOD FOR PRODUCING THE SAME

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    DE4223265A1 (en) 1993-03-18
    DE59209547D1 (en) 1998-12-10
    EP0523681A2 (en) 1993-01-20
    ATE173006T1 (en) 1998-11-15

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