EP0530635B1 - Neutral composition for dishwashing machine - Google Patents
Neutral composition for dishwashing machine Download PDFInfo
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- EP0530635B1 EP0530635B1 EP92114418A EP92114418A EP0530635B1 EP 0530635 B1 EP0530635 B1 EP 0530635B1 EP 92114418 A EP92114418 A EP 92114418A EP 92114418 A EP92114418 A EP 92114418A EP 0530635 B1 EP0530635 B1 EP 0530635B1
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- dishwashing
- dishwashing agent
- builder system
- salt
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
Definitions
- the invention relates to a neutral machine dishwashing detergent.
- acid dishwashing detergents which have a pH of 2-6, preferably 3-5, in 0.5-0.7% aqueous solution.
- These acidic dish detergents contain 5-80% by weight of hydroxypolycarboxylic acids such as citric acid and sodium citrate as framework substances. They also contain 0.5-5% by weight of at least one enzyme from the group of hydrolases, such as proteases and lipases, and preferably amylases.
- DE-PS 35 32 586 relates to phosphate-free, acidic detergent in powder form for dishwashers, which contain a polymeric organic carboxylic acid, a weakly acidic organic acid, such as citric acid, a nonionic surfactant, silica and fillers.
- DE-AS 1 151 627 discloses acidic cleaning agents, in particular for dishwashers, which contain poorly soluble mixed ethylene oxide and propylene oxide addition products with, for example, nonylphenol and additions of acidic agents, for example citric acid.
- DE-AS 1 628 632 discloses a method for machine washing dishes, whereby a pH value of 3-6 is set in the pre-cleaning liquor by means of appropriately acidic agents and a pH value of 4-6 in the rinse aid liquor.
- U.S. Patent 3,553,139 discloses dishwashing detergents containing an enzyme and a per compound.
- GB-PS 1 197 446 discloses dishwashing detergents, the invention being seen in that an amylolytic enzyme is added to them.
- dishwashing detergents have a pH of 7.0-9.0 and have a high phosphate content.
- these agents should contain 40-60% alkali phosphate.
- GB-PS 1 323 670 discloses washing and cleaning agents which are said to be phosphate-free and are said to contain a certain surface-active agent.
- the pH of these agents is completely uncritical and can range from 6-10.
- These known agents are detergents, especially for cleaning textiles.
- the compositions can also be used as detergents in dishwashing, it is obvious to the person skilled in the art that the disclosed compositions are not very suitable for dishwashing and in particular are completely unsuitable for machine dishwashing because they are much too foaming.
- DE-OS 1 792 359 relates to a multi-stage process for the automatic washing of dishes, with a soaking bath upstream which contains enzymes.
- This soaking bath can have a pH of 4-12.
- DE-OS 1 692 021 discloses dishwashing detergents which necessarily contain alkali phosphates.
- DE-OS 2 060 485 discloses enzymatic detergents with a pH of 6.5-6.8, which are to be used as hand-held detergents or rinse aids (rinse aids). Because of their high surfactant content, they are not suitable as automatic dishwashing detergents.
- dishwashing detergents also has some disadvantages. In part, they still largely consist of ingredients that are no longer caustic but still irritating to the skin or eyes. The bleaching effect of the oxygen system also lags behind that of the chlorine system.
- the acidic dishwashing detergents described in DE-OS 38 33 047 have advantages in that, for example, no regenerating salt has to be used, but they have to lose a distance in the acidic pH range accept certain types of soiling. Only a formulation with strong complexing agents such as NTA or EDTA was able to largely compensate for this disadvantage. Due to their potential for the remobilization of heavy metals from sludge or sediments, such compounds should not, according to current knowledge, be released into the environment in large quantities.
- neutral automatic dishwashing detergents of a certain composition not only offer better consumer safety and more favorable environmental behavior, but surprisingly also provide comparable or even better cleaning performance than conventional cleaners.
- the invention therefore relates to liquid or powdered, phosphate-free automatic dishwashing agents containing a builder system, which ensure a pH of 5-8 in 1.0% aqueous solution and which are free of NTA and EDTA.
- a builder system from the salt of a hydroxycarboxylic acid or from the mixture of a hydroxycarboxylic acid and the salt of a hydroxycarboxylic acid is particularly preferred.
- the preferred object of the invention is a liquid or powdered automatic dishwashing detergent which contains a builder or buffer system composed of a salt of a hydroxycarboxylic acid or a mixture of a hydroxycarboxylic acid with the salt of a hydroxycarboxylic acid and has a pH of more than 1.0% in aqueous solution 6-8, preferably 6.1-7.5. A pH of 6.2-6.5 is particularly preferred.
- the builder system preferably consists of the salt of a hydroxypolycarboxylic acid with 2-4 carboxyl groups, which can be mixed with a hydroxypolycarboxylic acid or acidic inorganic salts for pH adjustment.
- a suitable polymer e.g. Polyacrylate.
- Sodium citrate or a mixture of sodium citrate with citric acid is preferably used.
- Mixtures with a predominant proportion of sodium citrate, for example 10 parts of trisodium citrate dihydrate with 1 part of citric acid, are suitable for adjusting the pH value according to the invention, up to and including systems which consist exclusively of trisodium citrate.
- a system of 20-22 parts by weight of trisodium citrate per 1 part of citric acid is particularly preferred.
- the dishwashing detergent according to the invention generally contains 20-98% by weight of such a builder system.
- Liquid dishwashing detergent products generally contain 20-60% by weight, powdered dishwashing detergents naturally contain a higher proportion, generally in the range of 50-98% by weight.
- the water content of the liquid dishwashing detergent can be about 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 product name "Carbopol”, proved to be very useful.
- inorganic compounds in this product composition have thickening properties can 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 Pat. No. 4,933,101 or EP-A2-0 407 187.
- the liquid dishwashing detergents according to the invention are bleach-free.
- Powdered cleaners can contain an oxygen-based bleaching or oxidizing agent.
- bleaching or oxidizing agents come e.g. in question perborates, percarbonates, peroxymonosulfates, peroxydisulfates or peroxycarboxylic acid and their salts.
- Boron-free bleaches such as e.g. Caroate (Peroxymonosulfate).
- a small amount of bleach can be beneficial to prevent the formation of sulfide on silver.
- the dishwashing detergents according to the invention can also contain a low content of generally 0.2-5, preferably 0.5-2,% by weight of a nonionic surfactant. All non-ionic surfactants customary for this purpose, in particular fatty alcohol alkoxylates, are suitable for this purpose. Anionic surfactants should preferably not be used.
- the automatic dishwashing agents according to the invention preferably contain one or more enzymes, such as, for example, amylase, protease, lipase, cellulase.
- amylase such as, for example, amylase, protease, lipase, cellulase.
- protease such as, for example, amylase, protease, lipase, cellulase.
- the best cleaning results were achieved by the combined use of amylase and protease.
- These enzymes can be used particularly effectively in the pH ranges described here; For example, the temperature-stable amylase Termamyl (Novo) achieves the optimum of its spectrum of action at pH 7-8.
- the enzymes come in granular form or in solution with commercially available ones Concentrations or activities are used, the content of enzymes being 0.5-6, preferably 1-4% by weight.
- Liquid dishwashing detergents are particularly preferred according to the invention.
- the neutral dishwashing detergents according to the invention are neither caustic nor irritating because of their neutral pH and therefore do not require any particularly secure packaging. A good washing result can be achieved with a relatively low amount of 15-20 g powder or 20-50 ml liquid cleaner. All ingredients are after current knowledge is neither toxic nor otherwise harmful to health.
- the cleaning agents described here are therefore an environmentally and consumer-friendly alternative to conventional cleaners, which are also characterized by a surprisingly high cleaning ability.
- the types of soiling were prepared and applied in accordance with DIN 44990.
- the drying times of DIN 44990 were observed.
- the evaluation was carried out in accordance with DIN 44990 according to an internal evaluation procedure, with a rating of 5 for absolutely clean dishes after cleaning, a rating of 0 if no dirt is removed.
- rinsing with tap water of approximately 20 ° d was carried out, which was not softened in the machine.
- the amount of detergent was 20 g for the powder detergent. 40 ml (corresponds to approx. 50 g) were added to the liquid cleaner.
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Abstract
Description
Die Erfindung betrifft ein neutrales maschinelles Geschirrspülmittel.The invention relates to a neutral machine dishwashing detergent.
Aus der DE-OS 38 33 047 sind saure Geschirreinigungsmittel bekannt, die in 0,5-0,7 %iger wässriger Lösung einen pH-Wert von 2-6, vorzugsweise 3-5 aufweisen. Als Gerüstsubstanzen enthalten diese sauren Geschirreinigungsmittel 5-80 Gew.% an Hydroxypolycarbonsäuren wie beispielsweise Zitronensäure und Natriumcitrat. Sie enthalten ferner 0,5-5 Gew.% wenigstens eines Enzyms aus der Gruppe der Hydrolasen, wie Proteasen und Lipasen, sowie vorzugsweise Amylasen.From DE-OS 38 33 047 acid dishwashing detergents are known which have a pH of 2-6, preferably 3-5, in 0.5-0.7% aqueous solution. These acidic dish detergents contain 5-80% by weight of hydroxypolycarboxylic acids such as citric acid and sodium citrate as framework substances. They also contain 0.5-5% by weight of at least one enzyme from the group of hydrolases, such as proteases and lipases, and preferably amylases.
Die DE-PS 35 32 586 betrifft phosphatfreie, sauer eingestellte Spülmittel in Pulverform für Geschirrspülmaschinen, die eine polymere organische Carbonsäure, eine schwach sauer reagierende organische Säure, wie beispielsweise Zitronensäure, ein nichtionogenes Tensid, Kieselsäure und Füllstoffe enthalten.DE-PS 35 32 586 relates to phosphate-free, acidic detergent in powder form for dishwashers, which contain a polymeric organic carboxylic acid, a weakly acidic organic acid, such as citric acid, a nonionic surfactant, silica and fillers.
Die DE-AS 1 151 627 offenbart saure Reinigungsmittel, insbesondere für Geschirrspülmaschinen, die schwer lösliche gemischte Ethylenoxyd- und Propylenoxydanlagerungsprodukte an beispielsweise Nonylphenol sowie Zusätze von sauer wirkenden Mitteln wie beispielsweise Zitronensäure enthalten.DE-AS 1 151 627 discloses acidic cleaning agents, in particular for dishwashers, which contain poorly soluble mixed ethylene oxide and propylene oxide addition products with, for example, nonylphenol and additions of acidic agents, for example citric acid.
Die DE-AS 1 628 632 offenbart ein Verfahren zum maschinellen Spülen von Geschirr, wobei durch entsprechend saure Mittel in der Vorreinigungsflotte ein pH-Wert von 3-6 und in der Klarspülflotte ein pH-Wert von 4-6 eingestellt wird.DE-AS 1 628 632 discloses a method for machine washing dishes, whereby a pH value of 3-6 is set in the pre-cleaning liquor by means of appropriately acidic agents and a pH value of 4-6 in the rinse aid liquor.
In der US-PS 3 553 139 werden Geschirrspülmittel offenbart, die ein Enzym und eine Perverbindung enthalten.U.S. Patent 3,553,139 discloses dishwashing detergents containing an enzyme and a per compound.
Die GB-PS 1 197 446 offenbart Geschirrspülmittel, wobei die Erfindung darin gesehen wird, daß diesen ein amylolytisches Enzym zugesetzt wird. Diese bekannten Geschirrspülmittel besitzen einen pH-Wert von 7,0-9,0 und weisen einen hohen Phosphatgehalt auf. Insbesondere für maschinelles Geschirrspülen sollen diese Mittel 40-60 % Alkaliphosphat enthalten.GB-PS 1 197 446 discloses dishwashing detergents, the invention being seen in that an amylolytic enzyme is added to them. These known dishwashing detergents have a pH of 7.0-9.0 and have a high phosphate content. For machine dishwashing in particular, these agents should contain 40-60% alkali phosphate.
Die GB-PS 1 323 670 offenbart Wasch- und Reinigungsmittel, die phosphatfrei sein sollen und ein bestimmtes oberflächenaktives Mittel enthalten sollen. Der pH-Wert dieser Mittel ist völlig unkritisch und kann im weiten Bereich von 6-10 liegen. Diese bekannten Mittel sind Waschmittel, insbesondere zur Reinigung von Textilien. Trotz des Hinweises, daß die Zusammensetzungen auch als Reinigungsmittel beim Geschirrspülen verwendet werden können, ist es für den Fachmann offensichtlich, daß die offenbarten Zusammensetzungen zum Geschirrspülen wenig geeignet sind und insbesondere zum maschinellen Geschirrspülen völlig ungeeignet sind, weil sie viel zu stark schäumend sind.GB-PS 1 323 670 discloses washing and cleaning agents which are said to be phosphate-free and are said to contain a certain surface-active agent. The pH of these agents is completely uncritical and can range from 6-10. These known agents are detergents, especially for cleaning textiles. Despite the indication that the compositions can also be used as detergents in dishwashing, it is obvious to the person skilled in the art that the disclosed compositions are not very suitable for dishwashing and in particular are completely unsuitable for machine dishwashing because they are much too foaming.
Die DE-OS 1 792 359 betrifft ein mehrstufiges Verfahren zum maschinellen Spülen von Geschirr, wobei man ein Einweichbad vorschaltet, das Enzyme enthält. Dieses Einweichbad kann einen pH-Wert von 4-12 aufweisen.DE-OS 1 792 359 relates to a multi-stage process for the automatic washing of dishes, with a soaking bath upstream which contains enzymes. This soaking bath can have a pH of 4-12.
Die DE-OS 1 692 021 offenbart Geschirrspülmittel, die zwingend Alkaliphosphate enthalten.DE-OS 1 692 021 discloses dishwashing detergents which necessarily contain alkali phosphates.
Die DE-OS 2 060 485 offenbart enzymatische Spülmittel mit einem pH-Wert von 6,5-6,8, die als Handspülmittel oder Klarspülmittel (Glanzspülmittel) eingesetzt werden sollen. Wegen ihres hohen Tensidgehaltes sind sie als maschinelle Geschirrspülmittel nicht geeignet.DE-OS 2 060 485 discloses enzymatic detergents with a pH of 6.5-6.8, which are to be used as hand-held detergents or rinse aids (rinse aids). Because of their high surfactant content, they are not suitable as automatic dishwashing detergents.
Es wurde allgemein angenommen, daß maschinelle Geschirrspülmittel insbesondere zur Entfernung hartnäckiger und angetrockneter Verschmutzungen stark alkalisch sein müssen. Da man aber feststellte, daß stark alkalische Reinigungsmittel auch negative Effekte hinsichtlich Verbrauchersicherheit und Umweltverhalten aufweisen, ist man in neuerer Zeit dazu übergegangen, pH-Wert-reduzierte Geschirrspülmittel einzusetzen, die in der Reinigungsflotte nur noch pH-Werte von ca. 9-11 anstelle von früher 12-12,5 erreichen. Es konnte gezeigt werden, daß pH-Wert-reduzierte Reinigungsmittel durch den Einsatz von Enzymen, die erst durch das Ersetzen des Chlorbleichsystems durch ein Bleichsystem auf Sauerstoffbasis möglich wurden, eine vergleichbar gute Gesamtreinigungsleistung erzielen.It has been generally accepted that automatic dishwashing detergents, particularly for removing stubborn and dried-on soiling, must be strongly alkaline. However, since it was found that strongly alkaline cleaning agents also have negative effects with regard to consumer safety and environmental behavior, it has recently started to use pH-reduced dishwashing detergents which only have pH values of approx. 9-11 in the cleaning liquor reach 12-12.5 from earlier. It has been shown that pH-reduced cleaning agents can achieve a comparably good overall cleaning performance through the use of enzymes, which were only possible by replacing the chlorine bleaching system with an oxygen-based bleaching system.
Auch diese Gruppe von Geschirrspülmitteln besitzen noch einige Nachteile. Teilweise bestehen sie noch zu einem großen Teil aus Inhaltsstoffen, die zwar nicht mehr ätzend, aber immerhin noch reizend auf Haut oder Augen wirken. Auch die Bleichwirkung des Sauerstoffsystems bleibt hinter der des Chlorsystems zurück.This group of dishwashing detergents also has some disadvantages. In part, they still largely consist of ingredients that are no longer caustic but still irritating to the skin or eyes. The bleaching effect of the oxygen system also lags behind that of the chlorine system.
Die in DE-OS 38 33 047 beschriebenen sauren Geschirrspülmittel besitzen zwar Vorteile dahingehend, daß z.B. kein Regeneriersalz benutzt werden muß, sie müssen aber im sauren pH-Wert-Bereich eine Einbuße in der Entfernung bestimmter Anschmutzungen in Kauf nehmen. Lediglich durch eine Formulierung mit starken Komplexbildnern wie NTA oder EDTA konnte dieser Nachteil größtenteils kompensiert werden. Aufgrund ihres möglichen Potentials zur Remobilisierung von Schwermetallen aus Schlämmen oder Sedimenten sollten solche Verbindungen aber nach derzeitigem Wissen nicht in größeren Mengen in die Umwelt gelangen.The acidic dishwashing detergents described in DE-OS 38 33 047 have advantages in that, for example, no regenerating salt has to be used, but they have to lose a distance in the acidic pH range accept certain types of soiling. Only a formulation with strong complexing agents such as NTA or EDTA was able to largely compensate for this disadvantage. Due to their potential for the remobilization of heavy metals from sludge or sediments, such compounds should not, according to current knowledge, be released into the environment in large quantities.
Es wurde nun gefunden, daß neutrale maschinelle Geschirrspülmittel einer bestimmten Zusammensetzung nicht nur eine bessere Verbrauchersicherheit und ein günstigeres Umweltverhalten bieten, sondern überraschenderweise eine vergleichbare oder sogar bessere Reinigungsleistung als herkömmliche Reiniger erbringen.It has now been found that neutral automatic dishwashing detergents of a certain composition not only offer better consumer safety and more favorable environmental behavior, but surprisingly also provide comparable or even better cleaning performance than conventional cleaners.
Die Erfindung betrifft daher flüssige oder pulverförmige, ein Buildersystem enthaltende, phosphatfreie maschinelle Geschirrspülmittel, welche in 1,0 %iger wässriger Lösung einen pH-Wert von 5-8 sicherstellen und die frei sind von NTA und EDTA. Besonders bevorzugt wird ein Buildersystem aus dem Salz einer Hydroxycarbonsäure oder aus dem Gemisch aus einer Hydroxycarbonsäure und dem Salz einer Hydroxycarbonsäure.The invention therefore relates to liquid or powdered, phosphate-free automatic dishwashing agents containing a builder system, which ensure a pH of 5-8 in 1.0% aqueous solution and which are free of NTA and EDTA. A builder system from the salt of a hydroxycarboxylic acid or from the mixture of a hydroxycarboxylic acid and the salt of a hydroxycarboxylic acid is particularly preferred.
Bevorzugter Gegenstand der Erfindung ist ein flüssiges oder pulverförmiges maschinelles Geschirrspülmittel, welches ein Builder- oder Puffersystem aus einem Salz einer Hydroxycarbonsäure oder einem Gemisch aus einer Hydroxycarbonsäure mit dem Salz einer Hydroxycarbonsäure enthält und in 1,0 %iger wässriger Lösung einen pH-Wert von über 6-8, vorzugsweise 6,1-7,5 aufweist. Besonders bevorzugt wird ein pH-Wert von 6,2-6,5.The preferred object of the invention is a liquid or powdered automatic dishwashing detergent which contains a builder or buffer system composed of a salt of a hydroxycarboxylic acid or a mixture of a hydroxycarboxylic acid with the salt of a hydroxycarboxylic acid and has a pH of more than 1.0% in aqueous solution 6-8, preferably 6.1-7.5. A pH of 6.2-6.5 is particularly preferred.
Das Buildersystem besteht vorzugsweise aus dem Salz einer Hydroxypolycarbonsäure mit 2-4 Carboxylgruppen, das zur pH-Wert-Einstellung mit einer Hydroxypolycarbonsäure oder sauren anorganischen Salzen vermischt werden kann. Als Builderkomponente kann auch ein geeignetes Polymer, z.B. Polyacrylat, verwendet werden. Vorzugsweise wird Natriumcitrat oder ein Gemisch aus Natriumcitrat mit Zitronensäure verwendet. Zur Einstellung des erfindungsgemäß erforderlichen pH-Wertes eignen sich Gemische mit einem überwiegenden Anteil an Natriumcitrat, beispielsweise 10 Teile Trinatriumcitrat-Dihydrat mit 1 Teil Zitronensäure wasserfrei und darüber bis zu Systemen, die ausschließlich aus Trinatriumcitrat bestehen. Besonders bevorzugt wird ein System aus 20-22 Gewichtsteilen Trinatriumcitrat je 1 Teil Zitronensäure.The builder system preferably consists of the salt of a hydroxypolycarboxylic acid with 2-4 carboxyl groups, which can be mixed with a hydroxypolycarboxylic acid or acidic inorganic salts for pH adjustment. A suitable polymer, e.g. Polyacrylate. Sodium citrate or a mixture of sodium citrate with citric acid is preferably used. Mixtures with a predominant proportion of sodium citrate, for example 10 parts of trisodium citrate dihydrate with 1 part of citric acid, are suitable for adjusting the pH value according to the invention, up to and including systems which consist exclusively of trisodium citrate. A system of 20-22 parts by weight of trisodium citrate per 1 part of citric acid is particularly preferred.
Das erfindungsgemäße Geschirrspülmittel enthält im allgemeinen 20-98 Gew.% eines derartigen Buildersystems. Flüssige Geschirrspülmittelprodukte enthalten im allgemeinen 20-60 Gew.%, pulverförmige Geschirrspülmittel enthalten naturgemäß einen höheren Anteil, im allgemeinen im Bereich von 50-98 Gew.%.The dishwashing detergent according to the invention generally contains 20-98% by weight of such a builder system. Liquid dishwashing detergent products generally contain 20-60% by weight, powdered dishwashing detergents naturally contain a higher proportion, generally in the range of 50-98% by weight.
Der Wasseranteil der flüssigen Geschirrspülmittel kann etwa 40-80 Gew.% betragen.The water content of the liquid dishwashing detergent can be about 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. Carboxyvinyl Polymere, wie sie z.B. von B. F. Goodrich unter der Produktbezeichnung "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-Patent 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 composed of olefinically unsaturated carboxylic acids, are suitable as thickeners. Carboxyvinyl polymers, such as those marketed by BF Goodrich under the product name "Carbopol", proved to be very useful. Also inorganic compounds in this product composition have thickening properties can 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 Pat. No. 4,933,101 or EP-A2-0 407 187.
Die erfindungsgemäßen flüssigen Geschirrspülmittel sind bleichmittelfrei. Pulverförmige Reiniger können ein Bleich- oder Oxidationsmittel auf Sauerstoffbasis enthalten. Als Bleich- oder Oxidationsmittel kommen z.B. in Frage Perborate, Percarbonate, Peroxymonosulfate, Peroxydisulfate oder Peroxycarbonsäure und deren Salze. Bevorzugt sind borfreie Bleichmittel wie z.B. Caroate (Peroxymonosulfate). Eine geringe Menge Bleichmittel kann vorteilhaft sein, um der Bildung eines Sulfidbelages auf Silber vorzubeugen.The liquid dishwashing detergents according to the invention are bleach-free. Powdered cleaners can contain an oxygen-based bleaching or oxidizing agent. As bleaching or oxidizing agents come e.g. in question perborates, percarbonates, peroxymonosulfates, peroxydisulfates or peroxycarboxylic acid and their salts. Boron-free bleaches such as e.g. Caroate (Peroxymonosulfate). A small amount of bleach can be beneficial to prevent the formation of sulfide on silver.
Die erfindungsgemäßen Geschirrspülmittel können auch einen geringen Gehalt von im allgemeinen 0,2-5, vorzugsweise 0,5-2 Gew.% eines nichtionischen Tensids enthalten. Hierzu eignen sich alle für diesen Zweck üblichen nichtionischen Tenside, insbesondere Fettalkoholalkoxylate. Anionische Tenside sollen vorzugsweise nicht verwendet werden.The dishwashing detergents according to the invention can also contain a low content of generally 0.2-5, preferably 0.5-2,% by weight of a nonionic surfactant. All non-ionic surfactants customary for this purpose, in particular fatty alcohol alkoxylates, are suitable for this purpose. Anionic surfactants should preferably not be used.
Vorzugsweise enthalten die erfindungsgemäßen maschinellen Geschirrspülmittel ein oder mehrere Enzyme, wie beispielsweise Amylase, Protease, Lipase, 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 automatic dishwashing agents according to the invention preferably contain one or more enzymes, such as, for example, amylase, protease, lipase, cellulase. The best cleaning results were achieved by the combined use of amylase and protease. These enzymes can be used particularly effectively in the pH ranges described here; For example, the temperature-stable amylase Termamyl (Novo) achieves the optimum of its spectrum of action at pH 7-8. The enzymes come in granular form or in solution with commercially available ones Concentrations or activities are used, the content of enzymes being 0.5-6, preferably 1-4% by weight.
Weitere übliche Zusätze sind Farbstoffe und Duftstoffe und gegebenenfalls bei flüssigen Produkten Konservierungsmittel, wozu z.B. Verbindungen auf Isothiazolinon-Basis geeignet sind.Other common additives are dyes and fragrances and, if necessary, preservatives for liquid products, for which purpose e.g. Compounds based on isothiazolinone are suitable.
Erfindungsgemäß besonders bevorzugt werden flüssige Geschirrspülmittel.Liquid dishwashing detergents are particularly preferred according to the invention.
Ein besonders bevorzugtes flüssiges Geschirrspülmittel gemäß vorliegender Erfindung besteht im wesentlichen aus
- a) 20-60 Gew.% eines Buildersystems bestehend aus Natriumcitrat und Zitronensäure,
- b) 0,5-2 Gew.% eines nichtionischen Tensids,
- c) 0,5-2 Gew.% eines oder mehrerer Enzyme,
- d) 0,5-2 Gew.% eines Verdickers,
- e) 38-78 Gew.% Wasser.
- a) 20-60% by weight of a builder system consisting of sodium citrate and citric acid,
- b) 0.5-2% by weight of a nonionic surfactant,
- c) 0.5-2% by weight of one or more enzymes,
- d) 0.5-2% by weight of a thickener,
- e) 38-78% by weight of water.
Die erfindungsgemäßen neutralen Geschirrspülmittel sind wegen ihres neutralen pH-Wertes weder ätzend noch reizend 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 Inhaltsstoffe sind nach derzeitigem Wissen weder giftig noch anderweitig gesundheitsgefährdend. Die hier beschriebenen Reinigungsmittel stellen deshalb eine umwelt- und verbraucherfreundliche Alternative zu den herkömmlichen Reinigern dar, die sich darüber hinaus durch ein überraschend hohes Reinigungsvermögen auszeichnen.The neutral dishwashing detergents according to the invention are neither caustic nor irritating because of their neutral pH and therefore do not require any particularly secure packaging. A good washing result can be achieved with a relatively low amount of 15-20 g powder or 20-50 ml liquid cleaner. All ingredients are after current knowledge is neither toxic nor otherwise harmful to health. The cleaning agents described here are therefore an environmentally and consumer-friendly alternative to conventional cleaners, which are also characterized by a surprisingly high cleaning ability.
In den nachstehenden Vergleichsversuchen werden pulverförmige und flüssige Formulierung in Übereinstimmung mit der vorliegenden Erfindung bei verschiedenen pH-Werten verglichen. Während die Reinigungsleistung bei manchen Anschmutzungen erwartungsgemäß weniger pH-abhängig ist (Margarine), wird bei anderen Anschmutzungen die optimale Reinigungsleistung bei den vorliegenden Formulierungen schon bei einem pH-Wert um ca. 6 erreicht, die auch durch pH-Wert-Steigerung bis 9 nicht mehr steigerungsfähig ist (Eigelb, Hackfleisch). Bei bestimmten Anschmutzungen wird im pH-Wert-Bereich 6-7 bei den hier vorliegenden Zusammensetzungen ein Maximum durchlaufen (Tee), so daß in dem erfindungsgemäßen pH-Wert-Bereich in der Gesamtreinigungsleistung ein Optimum festzustellen ist.In the comparative experiments below, powdery and liquid formulations in accordance with the present invention are compared at different pH values. While the cleaning performance of some soiling is expected to be less pH-dependent (margarine), with other soiling the optimal cleaning performance of the present formulations is already achieved at a pH of around 6, which is also not possible by increasing the pH up to 9 is more capable of increasing (egg yolk, minced meat). For certain types of soiling, a maximum is run through in the pH range 6-7 in the compositions here (tea), so that in the pH range according to the invention an optimum can be determined in the overall cleaning performance.
Die Anschmutzungsarten wurden nach DIN 44990 zubereitet und aufgetragen.
Die Trocknungszeiten der DIN 44990 wurden eingehalten.
Die Auswertung erfolgte in Anlehnung an die DIN 44990 nach einem internen Auswertungsverfahren, wobei die Note 5 für absolut sauberes Geschirr nach der Reinigung vergeben wird, die Note 0 wird vergeben, wenn kein Schmutz entfernt wird.
Um die Reinigungsbedingungen zu erschweren und damit die Leistungsfähigkeit der erfindungsgemäßen Rezepturen unter harten Bedingungen zu prüfen, wurde mit Leitungswasser von ca. 20 °d gespült, welches in der Maschine nicht enthärtet wurde.The types of soiling were prepared and applied in accordance with DIN 44990.
The drying times of DIN 44990 were observed.
The evaluation was carried out in accordance with DIN 44990 according to an internal evaluation procedure, with a rating of 5 for absolutely clean dishes after cleaning, a rating of 0 if no dirt is removed.
In order to make the cleaning conditions more difficult and thus to test the performance of the formulations according to the invention under harsh conditions, rinsing with tap water of approximately 20 ° d was carried out, which was not softened in the machine.
Die Reinigermenge betrug 20 g beim Pulverreiniger. Beim Flüssigreiniger wurden 40 ml (entspricht ca. 50 g) dosiert.The amount of detergent was 20 g for the powder detergent. 40 ml (corresponds to approx. 50 g) were added to the liquid cleaner.
Unter diesen erschwerten Prüfbedingungen wurden die in den folgenden Tabellen aufgeführten Reinigungsergebnisse erzielt. Es wurde eine BOSCH-Spülmaschine Typ S 511 eingesetzt, wobei das Normalprogramm 65°C benutzt wurde.
Claims (14)
- Liquid or pulverulent mechanical dishwashing agents that are free of phosphate, NTA and EDTA, comprising a builder system, characterized in that they have a pH of 5 to 8 in 1.0% aqueous solution.
- A dishwashing agent as claimed in claim 1, characterized in that the builder system consists ofa) the salt of a hydroxycarboxylic acid, orb) the mixture of a hydroxycarboxylic acid and the salt of a hydroxycarboxylic acid, orc) the mixture of a hydroxycarboxylic acid and the salt of a hydroxycarboxylic acid and a polymer.
- A dishwashing agent as claimed in claim 2, characterized in that it has a pH of above 6 to 8, preferably from 6.1 to 7.5, and that it comprises a builder system comprising the salt of a hydroxycarboxylic acid or the mixture of a hydroxycarboxylic acid and the salt thereof.
- A dishwashing agent as claimed in any one of claims 1-3, characterized in that it comprises sodium citrate or a mixture of citric acid and sodium citrate as the builder system.
- A dishwashing agent as claimed in claim 4, characterized in that it comprises 20-98% by weight of sodium citrate or of the mixture of citric acid and sodium citrate.
- A liquid dishwashing agent as claimed in any one of claims 1-5, characterized in that it comprises 20-60% by weight of the builder system.
- A liquid dishwashing agent as claimed in any one of claims 1-6, characterized in that it comprises 0.2-5, preferably 0.5-2, % by weight of a thickener.
- A pulverulent dishwashing agent as claimed in any one of claims 1-5, characterized in that it comprises 1-20% by weight of a bleaching or oxidizing agent.
- A pulverulent dishwashing agent as claimed in any one of claims 1-5 and 8, characterized in that it comprises 50-98% by weight of the builder system.
- A dishwashing agent as claimed in any one of the preceding claims, characterized in that it comprises 0.2-5, preferably 0.5-2, % by weight of a nonionic surfactant.
- A dishwashing agent as claimed in any one of the preceding claims, characterized in that it comprises at least one enzyme.
- A dishwashing agent as claimed in claim 11, characterized in that it comprises an amylase and a protease.
- A liquid dishwashing agent as claimed in claim 1 consisting essentially ofa) 20-60% by weight of a builder system consisting of sodium citrate and citric acid,b) 0.5-2% by weight of a nonionic surfactant,c) 0.5-2% by weight of one or more enzymes,d) 0.5-2% by weight of a thickener,e) 38-78% by weight of water.
- The use of a liquid or pulverulent, phosphate-free dishwashing agent which comprises a builder system and in 1.0% aqueous solution has a pH of more than 6 to 8 and is free of NTA and EDTA, for mechanical dishwashing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4128767 | 1991-08-29 | ||
| DE4128767 | 1991-08-29 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0530635A2 EP0530635A2 (en) | 1993-03-10 |
| EP0530635A3 EP0530635A3 (en) | 1993-08-04 |
| EP0530635B1 true EP0530635B1 (en) | 1997-05-14 |
Family
ID=6439450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92114418A Revoked EP0530635B1 (en) | 1991-08-29 | 1992-08-24 | Neutral composition for dishwashing machine |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0530635B1 (en) |
| AT (1) | ATE153056T1 (en) |
| DE (1) | DE59208478D1 (en) |
| DK (1) | DK0530635T3 (en) |
| ES (1) | ES2100985T3 (en) |
| GR (1) | GR3023893T3 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8314056B2 (en) | 2008-10-31 | 2012-11-20 | Henkel Ag & Co. Kgaa | Automatic dishwashing agent |
| US9127235B2 (en) | 2013-10-09 | 2015-09-08 | Ecolab Usa Inc. | Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control |
| US9487738B2 (en) | 2013-10-09 | 2016-11-08 | Ecolab Usa Inc. | Solidification matrix comprising a carboxylic acid terpolymer |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0636170B1 (en) * | 1992-04-13 | 1997-08-06 | The Procter & Gamble Company | Thixotropic liquid automatic dishwashing composition with enzyme |
| US5898025A (en) * | 1992-09-25 | 1999-04-27 | Henkel Kommanditgesellschaft Auf Aktien | Mildly alkaline dishwashing detergents |
| DE4232170C2 (en) * | 1992-09-25 | 1999-09-16 | Henkel Kgaa | Weakly alkaline dish detergent |
| EP0726935B1 (en) * | 1993-11-03 | 2000-08-30 | The Procter & Gamble Company | Control of calcium carbonate precipitation in automatic dishwashing |
| EP0726934B1 (en) * | 1993-11-03 | 1998-09-02 | The Procter & Gamble Company | Control of calcium carbonate precipitation in automatic dishwashing |
| ATE189696T1 (en) * | 1995-08-25 | 2000-02-15 | Henkel Kgaa | USE OF LIPASES IN LOW ALKALINE AGENTS FOR MACHINE DISHWASHING |
| DE19708500A1 (en) * | 1997-03-03 | 1998-09-10 | Henkel Kgaa | Detergent with an acidic pH |
| DE10153553A1 (en) | 2001-07-07 | 2003-06-12 | Henkel Kgaa | Non-aqueous "3in1" dishwasher detergent II |
| DE10153554A1 (en) * | 2001-07-07 | 2003-05-15 | Henkel Kgaa | Aqueous "3in1" dishwasher detergent II |
| AU2002331215A1 (en) | 2001-08-17 | 2003-03-03 | Henkel Kommanditgesellschaft Auf Aktien | Dishwasher detergent with improved protection against glass corrosion |
| DE10311429A1 (en) * | 2003-03-13 | 2004-09-23 | Thomas Hartl | Combined washing-up agent for crockery and cutlery comprises a combination of a de-fatting and a de-scaling agent stored in a container |
| EP2126089A2 (en) | 2007-03-09 | 2009-12-02 | Danisco US, INC., Genencor Division | Alkaliphilic bacillus species a-amylase variants, compositions comprising a-amylase variants, and methods of use |
| DK2291526T3 (en) | 2008-06-06 | 2014-10-06 | Danisco Us Inc | SACCHARIFICATION OF ENZYME COMPOSITION WITH BACILLUS SUBTILIS ALPHA AMYLASE |
| CA2726803A1 (en) | 2008-06-06 | 2009-12-10 | Danisco Us Inc. | Variant alpha-amylases from bacillus subtilis and methods of use, thereof |
| EP2698434A1 (en) | 2008-06-06 | 2014-02-19 | Danisco US Inc. | Uses of an alpha-amylase from Bacillus subtilis |
| JP5419303B2 (en) | 2008-09-25 | 2014-02-19 | ダニスコ・ユーエス・インク | Alpha amylase mixture and method of using the mixture |
| MX356389B (en) | 2009-10-23 | 2018-05-28 | Danisco Us Inc | Methods for reducing blue saccharide. |
| ES2733300T3 (en) | 2014-12-17 | 2019-11-28 | Procter & Gamble | Detergent composition |
| EP3181671B1 (en) | 2015-12-17 | 2024-07-10 | The Procter & Gamble Company | Automatic dishwashing detergent composition |
| DE102022131908A1 (en) | 2022-12-01 | 2024-06-06 | Henkel Ag & Co. Kgaa | Dishwasher cleaner with improved limescale removal and additional grease removal |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1792359A1 (en) * | 1968-08-23 | 1973-02-08 | Henkel & Cie Gmbh | METHOD OF MACHINE WASHING OF DISHES |
| CA966751A (en) * | 1971-03-18 | 1975-04-29 | Charles R. Ries | Phosphorus-free detergent composition |
| CA981555A (en) * | 1972-05-12 | 1976-01-13 | William L. Groves (Jr.) | Phosphate and nitrilotriacetic acid-free, heavy-duty detergent powder |
| DE2230453A1 (en) * | 1972-06-22 | 1974-01-17 | Benckiser Gmbh Joh A | BASIC MATERIAL APPROACH FOR DETERGENTS AND DETERGENTS |
| DE3532586C1 (en) * | 1985-09-11 | 1986-09-11 | almaca Bioprodukte Herstellungs GmbH, 7901 Illerrieden | Phosphate-free, acidic detergent in powder form for dishwashers |
| US5030377A (en) * | 1988-11-11 | 1991-07-09 | Kao Corporation | Detergent compositions containing starch debranching enzymes |
-
1992
- 1992-08-24 DE DE59208478T patent/DE59208478D1/en not_active Revoked
- 1992-08-24 DK DK92114418.4T patent/DK0530635T3/en active
- 1992-08-24 ES ES92114418T patent/ES2100985T3/en not_active Expired - Lifetime
- 1992-08-24 AT AT92114418T patent/ATE153056T1/en not_active IP Right Cessation
- 1992-08-24 EP EP92114418A patent/EP0530635B1/en not_active Revoked
-
1997
- 1997-06-26 GR GR970401540T patent/GR3023893T3/en unknown
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8314056B2 (en) | 2008-10-31 | 2012-11-20 | Henkel Ag & Co. Kgaa | Automatic dishwashing agent |
| US9127235B2 (en) | 2013-10-09 | 2015-09-08 | Ecolab Usa Inc. | Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control |
| US9487738B2 (en) | 2013-10-09 | 2016-11-08 | Ecolab Usa Inc. | Solidification matrix comprising a carboxylic acid terpolymer |
| US9840683B2 (en) | 2013-10-09 | 2017-12-12 | Basf Se | Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control |
| US10364409B2 (en) | 2013-10-09 | 2019-07-30 | Ecolab Usa Inc. | Solidification matrix comprising a carboxylic acid terpolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0530635A3 (en) | 1993-08-04 |
| DE59208478D1 (en) | 1997-06-19 |
| EP0530635A2 (en) | 1993-03-10 |
| ATE153056T1 (en) | 1997-05-15 |
| ES2100985T3 (en) | 1997-07-01 |
| GR3023893T3 (en) | 1997-09-30 |
| DK0530635T3 (en) | 1997-09-29 |
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