EP0008059A1 - Process for mechanical dish-washing using polyalcohols, carboxylic acids and/or esters thereof as rinsing agents - Google Patents

Process for mechanical dish-washing using polyalcohols, carboxylic acids and/or esters thereof as rinsing agents Download PDF

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Publication number
EP0008059A1
EP0008059A1 EP79102708A EP79102708A EP0008059A1 EP 0008059 A1 EP0008059 A1 EP 0008059A1 EP 79102708 A EP79102708 A EP 79102708A EP 79102708 A EP79102708 A EP 79102708A EP 0008059 A1 EP0008059 A1 EP 0008059A1
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Prior art keywords
alcohols
carboxylic acids
esters
acid
hydroxy
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EP79102708A
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German (de)
French (fr)
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EP0008059B1 (en
Inventor
Johannes Dr. Dipl.-Chem. Perner
Dieter Stoeckigt
Paul Diessel
Franz Dr. Dipl.-Chem. Merger
Jürgen Dr. Dipl.-Chem. Paetsch
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BASF SE
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BASF SE
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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
    • C11D3/2086—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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • 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
    • C11D3/2093—Esters; Carbonates

Definitions

  • the invention relates to a method for machine washing dishes, which takes place in one or more cleaning and rinse cycles, special alcohols, carboxylic acids and / or esters thereof being used as rinse aids, which above all involve a greater wetting (outflow of the washing liquor), Stain and haze removal ability compared to previously used substances of this type.
  • alkaline agents are used to detach and emulsify the food residues.
  • special rinse aids are used to achieve clear, stain-free and veil-free dishes.
  • Such agents are known in large numbers and, for example, wetting agents such as ethylene and / or propylene oxide adducts with alcohols, phenols or amines and ethylene oxide / propylene oxide block copolymers may be mentioned. In many cases, however, these agents alone are not sufficient in themselves to achieve a complete rinse aid effect, and organic acids such as citric acid or dicarboxylic acids such as adipic acid and possibly mono- or polyhydric alcohols such as isopropanol, ethanol, ethylene glycol are therefore used or butyl diglycol as a solubilizer, which led to improvements. Aryl sulfonates such as sodium cumene sulfonate have also been used for this purpose.
  • the aim of the invention was to develop a method which is based on the previous knowledge, which leads to even better rinse aid effects and which nevertheless does not increase the cost of the process.
  • the substances which are active according to the invention are the alcohols according to the definition, (hydroxy) carboxylic acids, the esters which are obtained from the alcohols and carboxylic acids as starting substances and above all their mixtures, and - of very special interest - the combination of three, which additionally has an unexpected synergistic effect with regard to the improved rinse aid.
  • the alcohols are 2- to 4-valent and contain 5 to 9 carbon atoms, one of which is quaternary.
  • the alcoholic hydroxyl groups are said to be primary in nature.
  • neopentyl glycol, trimethylolpropane, pentaerythritol and their homologs may be mentioned, which carry methylol groups or methyl groups, ethyl groups or hydroxyethyl groups instead of the quaternary carbon atom; the latter, as stated, must carry primary OH groups.
  • the (hydroxy) carboxylic acids have the same construction principle; they are also said to contain 5 to 9 carbon atoms, one of which is quaternary. They contain a carboxyl group that is attached to the quaternary carbon atom. They can also contain up to 3 hydroxyl groups, preferably one which is primary in nature.
  • pivalic acid and, more preferably, hydroxypivalic acid are mentioned, which the latter is an oxidation product of neopentyl glycol.
  • esters of alcohols and acids are also effective, and of these neopentylglycol, trimethylolpropane and pentaerythritol (hydroxy) pivalic acid esters are preferred.
  • the esters can be partial esters or full esters, but preference is given to fully esterified alcohols or carboxylic acids.
  • the esters should not be polymeric - which would be conceivable if dicarboxylic acids were used - i.e. the esterification should be controlled so that the resulting ester is monomeric.
  • connection types are effective on their own and clearly result in improved rinse aid effects.
  • alcohols and acids, alcohols and esters as well as acids and esters can be combined and - as the most effective combination - all three components.
  • the quantitative ratios for combinations of two can be chosen as desired, but it is advisable for alcohol or ester relative to the acid to be at least 50% by weight.
  • a preferred combination of three is a mixture of neopentyl glycol, hydroxypivalic acid and neopentyl glycol L 1 hydroxypivalic acid esters in the proportions mentioned.
  • the latter mixture is particularly easy to access technically.
  • agents or combinations of agents to be used according to the invention can be added to the rinse aid liquor concentrates in amounts of up to 30% by weight (larger amounts are possible but have no additional advantages).
  • the agents are expediently added in amounts of 0.2 to 10% by weight, based on the concentrate weight. An optimal effect is achieved by adding 3 to 8% by weight.
  • the rinse aid liquors otherwise contain the surface-active substances known for this purpose, which should be as little foam as possible.
  • These are the adducts of ethylene oxide and / or propylene oxide with alkylphenols already mentioned, longer-chain aliphatic primary or secondary alcohols, longer-chain amines, fatty acids or fatty acid (alkylol) amides. To list all of them would go beyond the scope of the description - for example, refer to Schönfeld's monograph "Surface-active addition products of ethylene oxide".
  • C 10 to C 20 alcohols which have a low degree of alkoxylation, ie which contain about 2 to 10 ethylene oxide groups, have proven particularly useful - they are very low-foaming products.
  • the fleet concentrates generally contain 1.5 to 50% by weight of the liquor concentrates.
  • solubilizers previously used such as toluene or cumene sulfonate
  • alcohols such as isopropanol, ethanol, glycols, such as ethylene glycol, Bu tyldiglycol, 1,4-butanediol etc. in percentages up to 30% by weight, and especially if the surfactants used have too low cloud points (60 ° C), ie if a hot rinse is carried out.
  • acids known hitherto for this purpose such as phosphoric acid, citric acid, tartaric acid or dicarboxylic acids such as glutaric acid, succinic acid, adipic acid or mixtures thereof, can also be used in percentages of up to 10% by weight - but their use is no longer absolutely necessary.
  • the finished concentrates contain 30 to 70% by weight of water. and can be diluted in such a way that there are approx. 0.1 to 0.5 g of concentrate for 1 liter of water.
  • agents according to the invention now makes it possible to dispense entirely with solubilizers (to increase the cloud point), since the rinse aid effect occurs in a completely satisfactory manner even at temperatures between 30 and 40 ° C. In hot rinsing processes, they also work optimally in combination with the other additives.
  • the rinse aid liquor (10 l) contained 3 g of concentrate (0.3 gl -1 ).
  • the duration of the rinse aid was 9 minutes.
  • the following table shows the composition of the rinse aid concentrates. The numbers represent percentages by weight.
  • the marks range from 1 (very bad) to 5 (very good).

Abstract

Verfahren zum mechanischen Geschirrspülen bei dem eine Klarspülflotte eingesetzt wird, die 2-bis 4 wertige Alkohole, einbasige (Hydroxy)carbonsäuren und/oder Ester aus den Alkoholen und (Hydroxy)carbonsäuren enthält, wobei die Alkohole und Carbonsäuren 5 bis 9 C-Atome enthalten, von denen eines quartärer Natur ist, die alkoholischen Hydroxylgruppen ausschließlich primär und die Carboxylgruppe am quartären C-Atom gebunden ist. Besonders vorteilhaft sind Gemische aus Alkohol, (Hydroxy)carbonsäure und der Ester daraus. Besonders bevorzugt sind Gemische aus Neopentylglykol, Hydroxypivalinsäure und Neopentylglykolhydroxypivalinsäureester. Mit diesen Mitteln gelingt es, klares, fleck- und schleierfreies Geschirr zu erhalten.Process for mechanical dishwashing in which a rinse aid liquor is used which contains 2 to 4 polyhydric alcohols, monobasic (hydroxy) carboxylic acids and / or esters from the alcohols and (hydroxy) carboxylic acids, the alcohols and carboxylic acids containing 5 to 9 carbon atoms , one of which is quaternary in nature, the alcoholic hydroxyl groups are exclusively primary and the carboxyl group is bonded to the quaternary carbon atom. Mixtures of alcohol, (hydroxy) carboxylic acid and the ester thereof are particularly advantageous. Mixtures of neopentyl glycol, hydroxypivalic acid and neopentyl glycol hydroxypivalic acid esters are particularly preferred. With these means it is possible to obtain clear, stain-free and veil-free dishes.

Description

Die Erfindung betrifft ein Verfahren zum maschinellen Spülen von Geschirr, das in einem oder mehreren Reinigungs- und Klarspülgängen abläuft, wobei spezielle Alkohole, Carbonsäuren und/oder Ester daraus als Klarspülmittel eingesetzt werden, die vor allem ein größeres Benetzungs- (Ablauf der Spülflotte), Fleck- und Schleierentfernungsvermögen gegenüber bisher eingesetzten Stoffen dieser Art besitzen.The invention relates to a method for machine washing dishes, which takes place in one or more cleaning and rinse cycles, special alcohols, carboxylic acids and / or esters thereof being used as rinse aids, which above all involve a greater wetting (outflow of the washing liquor), Stain and haze removal ability compared to previously used substances of this type.

Nach den Erfahrungen der Praxis müssen beim maschinellen Geschirrspülen im allgemeinen zwei aufeinanderfolgende, meist durch einen Zwischenspülgang mit Wasser getrennte - Spülgänge mit verschiedenartigen Produkten eingesetzt werden.Experience has shown in practice that machine dishwashing generally requires two successive rinsing cycles with different types of products, usually separated by an intermediate rinsing cycle with water.

In der eigentlichen Reinigungsflotte kommen alkalisch reagierende Mittel zur Ablösung und Emulgierung der Speisereste zum Einsatz. In der Nach- oder Klarspülflotte werden dagegen spezielleoKlarspülmittel zur Erzielung eines klaren, fleck- und schleierfreien Geschirrs verwendet.In the actual cleaning liquor, alkaline agents are used to detach and emulsify the food residues. In the rinse or rinse liquor, on the other hand, special rinse aids are used to achieve clear, stain-free and veil-free dishes.

Diese Mittel müssen eine gute Netzwirkung besitzen, damit das Spülwasser filmartig vom Geschirr abläuft und keine sichtbare Rückstände hinterläßt. 'These agents must have a good wetting effect so that the rinsing water runs off the dishes like a film and none leaves visible residues. '

Solche Mittel sind in großer Zahl bekannt und es seien beispielsweise Netzmittel wie Äthylen- und/oder Propylenoxid- addukte an Alkohole, Phenole oder Amine und Äthylenoxid/Propylenoxidblockcopolymerisate genannt. Diese Mittel reichen aber für sich allein in vielen Fällen noch nicht aus, um einen vollständigen Klarspüleffekt zu erzielen, und man setzte daher noch organische Säuren, wie Citronensäure oder Dicarbonsäuren wie Adipinsäure und ggf. ein- oder mehrwertige Alkohole, wie Isopropanol, Äthanol, Äthylenglykol oder Butyldiglykol als Lösungsvermittler ein, was zu Verbesserungen führte. Auch Arylsulfonate, wie Natriumcumolsulfonat wurden für diesen Zweck verwendet.Such agents are known in large numbers and, for example, wetting agents such as ethylene and / or propylene oxide adducts with alcohols, phenols or amines and ethylene oxide / propylene oxide block copolymers may be mentioned. In many cases, however, these agents alone are not sufficient in themselves to achieve a complete rinse aid effect, and organic acids such as citric acid or dicarboxylic acids such as adipic acid and possibly mono- or polyhydric alcohols such as isopropanol, ethanol, ethylene glycol are therefore used or butyl diglycol as a solubilizer, which led to improvements. Aryl sulfonates such as sodium cumene sulfonate have also been used for this purpose.

Jedoch auch diese Maßnahmen genügen noch nicht in allen Fällen, vor allem beim Klarspülen von feinem Porzellan oder von Gläsern - Materialien also, auf denen der geringste Fleck oder Streifen sichtbar ist.However, even these measures are not sufficient in all cases, especially when rinsing fine porcelain or glasses - materials on which the slightest stain or streak is visible.

Das Ziel der Erfindung bestand darin ein Verfahren zu entwickeln, das auf den bisherigen Erkenntnissen aufgebaut ist, das zu noch besseren Klarspüleffekten führt, und das trotzdem keine Verteuerung des Prozesses mit sich bringt.The aim of the invention was to develop a method which is based on the previous knowledge, which leads to even better rinse aid effects and which nevertheless does not increase the cost of the process.

Dieses Ziel wurde überraschenderweise mit einem Verfahren erreicht, das wie bisher über mehrere Reinigungs- und Klarspülgänge abläuft, und bei dem beim Klarspülgang in die Flotte neben den bisher bekannten oben aufgeführten Stoffen spezielle Alkohole, Carbonsäuren und/oder Ester daraus zugesetzt werden, wie in den Patentansprüchen beschrieben wird.This goal was surprisingly achieved with a process that continues to run over several cleaning and rinse cycles, and in which, in the rinse cycle into the liquor, in addition to the previously known substances listed above, special alcohols, carboxylic acids and / or esters are added therefrom, as in the Claims is described.

Durch den Zusatz dieser Mittel gelingt es nunmehr gegenüber den bisherigen Formulierungen in den meisten Fällen hinsichtlich Ablauf der Klarspülflotte, Schleier, Streifen und Flecken zu besseren Ergebnissen zu kommen, wie später im einzelnen erläutert wird.The addition of these agents now works in most cases compared to the previous formulations the course of the rinse aid liquor, veils, stripes and stains to achieve better results, as will be explained in detail later.

Die erfindungsgemäß wirksamen Substanzen sind die definitionsgemäßen Alkohole, (Hydroxy)carbonsäuren, die Ester, die aus den Alkoholen und Carbonsäuren als Ausgangssubstanzen erhalten werden und vor allem deren Mischungen, und - von ganz speziellem Interesse - die Dreierkombination, die noch zusätzlich einen unerwarteten synergistischen Effekt hinsichtlich der verbesserten Klarspülwirkung erbringt.The substances which are active according to the invention are the alcohols according to the definition, (hydroxy) carboxylic acids, the esters which are obtained from the alcohols and carboxylic acids as starting substances and above all their mixtures, and - of very special interest - the combination of three, which additionally has an unexpected synergistic effect with regard to the improved rinse aid.

Die Alkohole sind 2- bis 4-wertig und enthalten 5 bis 9 C-Atome, von denen eines quartärer Natur ist. Außerdem sollen die alkoholischen Hydroxylgruppen primärer Natur sein.The alcohols are 2- to 4-valent and contain 5 to 9 carbon atoms, one of which is quaternary. In addition, the alcoholic hydroxyl groups are said to be primary in nature.

Von diesen Alkoholen seien Neopentylglykol, Trimethylolpropan, Pentaerythrit und deren Homologen zu nennen, die anstelle der am quartären C-Atom gebundenen Methylolgruppen oder Methylgruppen, Äthylgruppen bzw. Hydroxyäthylgruppen tragen; letztere müssen, wie gesagt, primäre OH-Gruppen ' tragen. Im Sinne der Erfindung bevorzugt werden Neopentylglykol, Trimethylolpropan und Pentaerythrit oder Gemische daraus.Of these alcohols, neopentyl glycol, trimethylolpropane, pentaerythritol and their homologs may be mentioned, which carry methylol groups or methyl groups, ethyl groups or hydroxyethyl groups instead of the quaternary carbon atom; the latter, as stated, must carry primary OH groups. For the purposes of the invention, preference is given to neopentyl glycol, trimethylolpropane and pentaerythritol or mixtures thereof.

Die (Hydroxy)carbonsäuren weisen dasselbe Bauprinzip auf; sie sollen ebenfalls 5 bis 9 C-Atome enthalten, wovon eines quartärer Natur ist. Sie enthalten eine Carboxylgruppe, die am quartären-C-Atom gebunden ist. Weiter können sie bis zu 3 Hydroxylgruppen enthalten, vorzugsweise eine, die primärer Natur sind.The (hydroxy) carboxylic acids have the same construction principle; they are also said to contain 5 to 9 carbon atoms, one of which is quaternary. They contain a carboxyl group that is attached to the quaternary carbon atom. They can also contain up to 3 hydroxyl groups, preferably one which is primary in nature.

Von diesen Säuren sind vor allem Pivalinsäure und in noch bevorzugterem Maße Hydroxypivalinsäure zu nennen, welch letztere ein Oxidationsprodukt des Neopentylglykols darstellt.Of these acids, especially pivalic acid and, more preferably, hydroxypivalic acid are mentioned, which the latter is an oxidation product of neopentyl glycol.

Wirksam sind auch die Ester der Alkohole und Säuren, und von diesen sind Neopentylglykol-, Trimethylolpropan- und Pentaerythrit-(hydroxy)pivalinsäureester bevorzugt zu nennen. Die Ester können Partialester oder Vollester sein, bevorzugt sind jedoch vollständig veresterte Alkohole bzw. Carbonsäuren. Die Ester sollen ferner nicht polymer sein - was im Falle des Einsatzes von Dicarbonsäuren denkbar wäre -, d.h. die Veresterung soll so gelenkt werden, daß der entstehende Ester monomer ist.The esters of alcohols and acids are also effective, and of these neopentylglycol, trimethylolpropane and pentaerythritol (hydroxy) pivalic acid esters are preferred. The esters can be partial esters or full esters, but preference is given to fully esterified alcohols or carboxylic acids. Furthermore, the esters should not be polymeric - which would be conceivable if dicarboxylic acids were used - i.e. the esterification should be controlled so that the resulting ester is monomeric.

Die drei möglichen Verbindungsarten sind für sich allein gut wirksam und ergeben eindeutig verbesserte Klarspüleffekte.The three possible connection types are effective on their own and clearly result in improved rinse aid effects.

Bedeutend wirksamer - und dies ist besonders überraschend - sind Mischungen aus den definitionsgemäßen Alkoholen, Säuren und Estern.Mixtures of the alcohols, acids and esters defined by definition are significantly more effective - and this is particularly surprising.

Hierbei können Alkohole und Säuren, Alkohole und Ester sowie Säuren und Ester miteinander kombiniert werden, und - als wirksamste Kombination - alle drei Komponenten.Here alcohols and acids, alcohols and esters as well as acids and esters can be combined and - as the most effective combination - all three components.

Die Mengenverhältnisse bei Zweierkombinationen können beliebig gewählt werden, doch sollten zweckmäßigerweise Alkohol bzw. Ester gegenüber der Säure zu mindestens 50 Gew.% anwesend sein.The quantitative ratios for combinations of two can be chosen as desired, but it is advisable for alcohol or ester relative to the acid to be at least 50% by weight.

Bei der Dreierkombination wählt man zweckmäßigerweise 30 bis 50 Gewichtsteile Alkohol, 5 bis 15 Gewichtsteile (Hydroxy)carbonsäure und 40 bis 60 Gewichtsteile des Esters. Eine bevorzugte Dreierkombination stellt eine Mischung aus Neopentylglykol, Hydroxypivalinsäure und Neopentylglykol-L 1 hydroxypivalinsäureester in den genannten Mengenverhältnissen dar.In the combination of three, 30 to 50 parts by weight of alcohol, 5 to 15 parts by weight (hydroxy) carboxylic acid and 40 to 60 parts by weight of the ester are expediently selected. A preferred combination of three is a mixture of neopentyl glycol, hydroxypivalic acid and neopentyl glycol L 1 hydroxypivalic acid esters in the proportions mentioned.

Letztere Mischung ist technisch besonders leicht zugänglich.The latter mixture is particularly easy to access technically.

Die erfindungsgemäß einzusetzenden Mittel oder Mittelkombinationen können den Klarspülflottenkonzentraten in Mengen bis zu 30 Gew.% zugesetzt werden (größere Mengen sind möglich, bringen aber keine zusätzlichen Vorteile).The agents or combinations of agents to be used according to the invention can be added to the rinse aid liquor concentrates in amounts of up to 30% by weight (larger amounts are possible but have no additional advantages).

Zweckmäßigerweise setzt man die Mittel in Mengen von - bezogen auf Konzentratgewicht - 0,2 bis 10 Gew.% zu. Eine optimale Wirkung erreicht man bei einem Zusatz von 3 bis 8 Gew.%.The agents are expediently added in amounts of 0.2 to 10% by weight, based on the concentrate weight. An optimal effect is achieved by adding 3 to 8% by weight.

Die Klarspülflotten enthalten ansonsten die für diesen Zweck bekannten oberflächenaktiven Substanzen, die möglichst schaumarm sein sollen. Es sind dies die bereits erwähnten Addukte des Äthylenoxids und/oder Propylenoxids an Alkylphenole, längerkettige aliphatische primäre oder sekundäre Alkohole, längerkettige Amine, Fettsäuren oder Fettsäure(alkylol)-amide. Sie alle aufzuzählen würde den Rahmen der Beschreibung sprengen - es sei z.B. auf die Monographie von Schönfeld "Oberflächenaktive Anlagerungsprodukte des Äthylenoxids" verwiesen. Besonders bewährt haben sich C10- bis C20-Alkohole erwiesen, die einen niedrigen Alkoxylierungsgrad aufweisen, d.h., die ca. 2 bis 10 Äthylenoxidgruppen angelagert enthalten - sie sind sehr schaumarme Produkte. Die Tenside sind.in den Flottenkonzentraten im allgemeinen zu 1,5 bis 50 Gew.% enthalten.The rinse aid liquors otherwise contain the surface-active substances known for this purpose, which should be as little foam as possible. These are the adducts of ethylene oxide and / or propylene oxide with alkylphenols already mentioned, longer-chain aliphatic primary or secondary alcohols, longer-chain amines, fatty acids or fatty acid (alkylol) amides. To list all of them would go beyond the scope of the description - for example, refer to Schönfeld's monograph "Surface-active addition products of ethylene oxide". C 10 to C 20 alcohols which have a low degree of alkoxylation, ie which contain about 2 to 10 ethylene oxide groups, have proven particularly useful - they are very low-foaming products. The fleet concentrates generally contain 1.5 to 50% by weight of the liquor concentrates.

Des weiteren können auch die bisher verwendeten Lösungsvermittler, wie Toluol- oder Cumolsulfonat, sodann Alkohole wie Isopropanol, Äthanol, Glykole, wie Äthylenglykol, Butyldiglykol, 1,4-Butandiol etc. in Prozentsätzen bis zu ' 30 Gew.% enthalten sein, und vor allem dann, wenn die verwendeten Tenside zu niedrige Trübungspunkte ( 60°C) aufweisen, d.h. wenn eine heiße Nachspülung durchgeführt wird.Furthermore, the solubilizers previously used, such as toluene or cumene sulfonate, then alcohols such as isopropanol, ethanol, glycols, such as ethylene glycol, Bu tyldiglycol, 1,4-butanediol etc. in percentages up to 30% by weight, and especially if the surfactants used have too low cloud points (60 ° C), ie if a hot rinse is carried out.

Schließlich können auch die bisher zu diesem Zweck bekannten Säuren, wie Phosphorsäure, Citronensäure, Weinsäure oder Dicarbonsäuren wie Glutarsäure, Bernsteinsäure, Adipinsäure oder deren Mischungen in Prozentsätzen bis zu 10 Gew.% - ihr Einsatz ist aber nicht mehr zwingend erforderlich - eingesetzt werden.Finally, the acids known hitherto for this purpose, such as phosphoric acid, citric acid, tartaric acid or dicarboxylic acids such as glutaric acid, succinic acid, adipic acid or mixtures thereof, can also be used in percentages of up to 10% by weight - but their use is no longer absolutely necessary.

Die fertigen Konzentrate enthalten 30 bis 70 Gew.% Wasser . und können derart verdünnt werden, daß auf 1 1 Wasser ca. 0,1 bis 0,5 g Konzentrat kommen.The finished concentrates contain 30 to 70% by weight of water. and can be diluted in such a way that there are approx. 0.1 to 0.5 g of concentrate for 1 liter of water.

Der Zusatz der erfindungsgemäßen Mittel ermöglicht es nun auf Lösungsvermittler (zur Erhöhung des Trübungspunktes) ganz zu verzichten, da der Klarspüleffekt schon bei Temperaturen zwischen 30 und 40°C in völlig befriedigender Weise auftritt. Bei Heißspülprozessen wirken sie aber auch in Verbindungen mit den anderen Zusatzstoffen optimal.The addition of the agents according to the invention now makes it possible to dispense entirely with solubilizers (to increase the cloud point), since the rinse aid effect occurs in a completely satisfactory manner even at temperatures between 30 and 40 ° C. In hot rinsing processes, they also work optimally in combination with the other additives.

überraschend ist es, daß z.B. ein Zusatz von 1,4-Butandiol gegenüber Neopentylglykol überhaupt keine Wirkung erbringt, und daß auch Citronensäure, die ja ebenfalls eine Hydroxycarbonsäure darstellt in ihrer Wirkung nicht an Hydroxypivalinsäure herankommt, vor allem, wenn letztere in Kombination mit erfindungsgemäßem Alkohol und Ester zum Einsatz gelangen.It is surprising that e.g. An addition of 1,4-butanediol has no effect at all compared to neopentyl glycol, and that citric acid, which is also a hydroxycarboxylic acid, has no effect on hydroxypivalic acid, especially if the latter is used in combination with the alcohol and ester according to the invention.

In den folgenden Beispielen soll die Erfindung erläutert werden.The invention is illustrated in the following examples.

BeispieleExamples

In einer Spülmaschine, die 10 1 Wasser faßt, wurden Kristallgläser bei 45°C einem Klarspültest unterworfen.In a dishwasher holding 10 liters of water, crystal glasses were subjected to a rinse aid test at 45 ° C.

Die Klarspülflotte (10 1) enthielt 3 g Konzentrat (0,3 gl-1).The rinse aid liquor (10 l) contained 3 g of concentrate (0.3 gl -1 ).

Die Dauer der Klarspülgänge betrug jeweils 9 Minuten.The duration of the rinse aid was 9 minutes.

Die Zusammensetzung der Klarspülkonzentrate ist aus folgender Tabelle ersichtlich. Die Zahlen geben Gewichtsprozente wieder.The following table shows the composition of the rinse aid concentrates. The numbers represent percentages by weight.

Die Benotung reicht von 1 (sehr schlecht) bis 5 (sehr gut).

Figure imgb0001
The marks range from 1 (very bad) to 5 (very good).
Figure imgb0001

Claims (4)

1. Verfahren zum maschinellen Spülen von Geschirr unter Anwendung mehrerer Reinigungs- und Klarspülgänge, wobei zum Klarspülen alkoxylierte, aktive Wasserstoffatome tragende Verbindungen, Solubilisatoren, anorganische und/oder organische Säuren und ggf. ein- oder mehrwertige Alkohole eingesetzt werden, dadurch gekennzeichnet, daß man eine Klarspülflotte einsetzt, die 2- bis 4-wertige Alkohole, einbasige (Hydroxy)-carbonsäuren und/oder Ester aus den Alkoholen und (Hydroxy)carbonsäuren enthält, wobei die Alkohole und Carbonsäuren 5 bis 9 C-Atome enthalten, von denen eines quartärer Natur ist, die alkoholischen Hydroxylgruppen ausschließlich primär und die Carboxylgruppe am quartären C-Atom gebunden ist.1. A method for machine washing dishes using multiple cleaning and rinse cycles, alkoxylated compounds carrying active hydrogen atoms, solubilizers, inorganic and / or organic acids and optionally mono- or polyhydric alcohols being used for rinsing, characterized in that uses a rinse aid liquor which contains 2- to 4-valent alcohols, monobasic (hydroxy) carboxylic acids and / or esters from the alcohols and (hydroxy) carboxylic acids, the alcohols and carboxylic acids containing 5 to 9 carbon atoms, one of which is quaternary It is natural that the alcoholic hydroxyl groups are exclusively primary and the carboxyl group is bound to the quaternary carbon atom. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man eine Mischung einsetzt, die aus 30 bis 50 Gewichtsteilen des Alkohols, 5 bis 15 Gewichtsteilen der (Hy- droxy)carbonsäure und 40 bis 60 Gewichtsteilen des Esters aus dem Alkohol und der Hydroxycarbonsäure besteht.2. The method according to claim 1, characterized in that a mixture is used which consists of 30 to 50 parts by weight of the alcohol, 5 to 15 parts by weight of the (hydroxy) carboxylic acid and 40 to 60 parts by weight of the ester from the alcohol and the hydroxycarboxylic acid . 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß als Alkohole Neopentylglykol, Trimethylolpropan und/oder Pentaerythrit, als Säuren Pivalinsäure und/oder Hydroxypivalinsäure und Ester aus den genannten Alkoholen und Säuren eingesetzt werden.3. The method according to claim 1 or 2, characterized in that as alcohols neopentyl glycol, trimethylolpropane and / or pentaerythritol, as acids pivalic acid and / or hydroxypivalic acid and esters from the alcohols and acids mentioned are used. 4. Verfahren nach Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß eine Mischung aus Neopentylglykol, Hydroxypivalinsäure und Neopentyglykolhydroxypivalinsäureester eingesetzt wird.4. Process according to Claims 1 to 3, characterized in that a mixture of neopentyl glycol, hydroxypivalic acid and neopentyglycol hydroxypivalic acid ester is used.
EP79102708A 1978-08-03 1979-07-30 Process for mechanical dish-washing using polyalcohols, carboxylic acids and/or esters thereof as rinsing agents Expired EP0008059B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79102708T ATE51T1 (en) 1978-08-03 1979-07-30 METHOD OF AUTOMATIC WASHING OF DISHWASHES USING POLY-ALCOHOLS, CARBON ACIDS AND/OR ESTERS THEREOF AS RINSE RIDERS.

Applications Claiming Priority (2)

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DE2833991 1978-08-03
DE19782833991 DE2833991A1 (en) 1978-08-03 1978-08-03 METHOD FOR MECHANICALLY RINSING DISHES USING MULTI-VALUE ALCOHOLS, CARBONIC ACIDS AND / OR ESTERS THEREOF AS A RINSE AID

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EP0008059A1 true EP0008059A1 (en) 1980-02-20
EP0008059B1 EP0008059B1 (en) 1981-04-29

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US (1) US4239552A (en)
EP (1) EP0008059B1 (en)
AT (1) ATE51T1 (en)
DE (2) DE2833991A1 (en)

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US5066568A (en) * 1985-08-05 1991-11-19 Hoehst Celanese Corporation Method of developing negative working photographic elements
EP3842510A1 (en) * 2019-12-17 2021-06-30 Henkel AG & Co. KGaA Rinse aid for automatic dishwashers

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US4517025A (en) * 1982-05-17 1985-05-14 Amchem Products, Inc. Method for removing sealant contamination
US4529525A (en) * 1982-08-30 1985-07-16 Colgate-Palmolive Co. Stabilized enzyme-containing detergent compositions
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US5427707A (en) * 1985-06-14 1995-06-27 Colgate Palmolive Co. Thixotropic aqueous compositions containing adipic or azelaic acid stabilizer
US4935158A (en) * 1986-10-30 1990-06-19 Aszman Harry W Solid detergent cleaning composition, reusable cleaning pad containing same and method of manufacture
DE3930028A1 (en) * 1989-09-08 1991-03-21 Kaw Kiehl Kg Hydrophobising agent contg. ester of mono or di:carboxylic acid - used in last rinse in vehicle washing machine being free of hydrocarbon(s) and biologically degradable
US5286300A (en) * 1991-02-13 1994-02-15 Man-Gill Chemical Company Rinse aid and lubricant
US5221362A (en) * 1991-08-23 1993-06-22 E. I. Du Pont De Nemours And Company Non-halogenated aqueous cleaning systems
US5925606A (en) * 1996-11-01 1999-07-20 Amway Corporation Concentrated acidic liquid detergent composition
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US5066568A (en) * 1985-08-05 1991-11-19 Hoehst Celanese Corporation Method of developing negative working photographic elements
EP3842510A1 (en) * 2019-12-17 2021-06-30 Henkel AG & Co. KGaA Rinse aid for automatic dishwashers

Also Published As

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DE2960312D1 (en) 1981-08-06
DE2833991A1 (en) 1980-02-21
ATE51T1 (en) 1981-05-15
US4239552A (en) 1980-12-16
EP0008059B1 (en) 1981-04-29

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