EP0694606B1 - Mixtures of alkoxylates as foam depressing agent and use thereof - Google Patents

Mixtures of alkoxylates as foam depressing agent and use thereof Download PDF

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Publication number
EP0694606B1
EP0694606B1 EP95111558A EP95111558A EP0694606B1 EP 0694606 B1 EP0694606 B1 EP 0694606B1 EP 95111558 A EP95111558 A EP 95111558A EP 95111558 A EP95111558 A EP 95111558A EP 0694606 B1 EP0694606 B1 EP 0694606B1
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Prior art keywords
weight
foam
mixture
cleaning
mixtures
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EP95111558A
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German (de)
French (fr)
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EP0694606A3 (en
EP0694606A2 (en
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Norbert Schmitt
Manuela Hingerl
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the invention relates to mixtures of alkoxylates as foam suppressant and its use in Cleaning liquors.
  • nonionic surfactants foam suppressing (foam suppressing) agents in aqueous Use cleaning liquors.
  • foam suppressing agents foam suppressing agents
  • These are in particular Addition products of ethylene oxide and / or propylene oxide Amines, longer-chain fatty alcohols or alkylphenols, Polyglycol ether formals or acetals or Block copolymers of ethylene and propylene oxide.
  • Such surfactant systems can be modified appropriately Ethylene oxide and propylene oxide proportions to the lowest possible Foam tendency and increased cleaning effect set be, an excess weight of propylene oxide the former Property, an excess weight of ethylene oxide the latter Property favors.
  • such represents Setting these properties is always a compromise and it would be desirable to have more of one property received without having to give up shares in the other.
  • In machine cleaning processes for bottles, dishes and the like in the industrial field which under high mechanical movement, is for a trouble-free Operation - as mentioned above - especially low foam Cleaning liquors (cleaning baths) required.
  • WO 91/09925 and WO 92/14808 are mixtures of alkoxylates as foam suppressants the mechanical cleaning of hard surfaces described.
  • the agent described in WO 91/09925 exists essentially from at least one fatty alcohol ethoxylate with 2 to 12 ethylene oxide units and at least one Fatty alcohol ethoxylate propoxylate with 2 to 10 ethylene oxide units and 2 to 8 propylene oxide units in Weight ratio of 10: 1 to 1:10 and that according to WO 92/14808 from 2 fatty alcohol ethoxylate propoxylates in Weight ratio of 10:90 to 90:10, one being Fatty alkyl radical 8 to 18 carbon atoms and the other 10 to Has 20 C atoms, with the proviso that the two Fatty alkyl residues in the average number of carbon atoms differ by at least 0.5. These too Leave fatty alcohol alkoxylates alone based mixtures still to be desired, especially with regard to foam behavior left.
  • the alkyl radicals and alkenyl radicals, R 1 and R 2 can be straight or branched, with preference being given to straight.
  • the alkenyl radicals preferably have 1 to 3 double bonds.
  • the numbers given for x, y and m plus n are statistical averages (average values), i.e. x, y, m and n can each be an integer or fractional number.
  • Component A) is therefore a reaction product of a fatty alcohol with first x mol ethylene oxide and then y mol propylene oxide, which can be of the type -CH 2 -CH (CH 3 ) O- or -CH (CH 3 ) -CH 2 O- , the latter being preferred.
  • Component B) is a fatty amine (primary amine) with the specified alkyl or alkenyl groups or preferably a reaction product of such a fatty amine with m plus n mol of ethylene oxide.
  • the fatty amine ethoxylates according to formula II are therefore preferred as component B).
  • alkyl and alkenyl radicals in formulas I and II are n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, iso-nonyl, n-decyl, iso-decyl, n-dodecyl, stearyl, n-eikosyl, Oleyl, cocoalkyl and tallow alkyl as well as alkyl or alkenyl mixtures, for example a mixture of C 12 alkyl to C 14 alkyl (C 12/14 ). All of the compounds according to component A) and B) are known and commercially available.
  • the production of the foam-suppressant according to the invention Means are made simply by mixing the Components A) and B) and optionally further expedient components and additives at one temperature from 15 to 50 ° C, preferably 20 to 30 ° C, and advantageously with stirring.
  • the mixtures according to the invention can be used in undiluted form Form, that is as such or, for example, for the purpose of better Dosage in the form of aqueous concentrates used are, optionally with the addition of an organic Solvent.
  • components A) and B) also added separately to the aqueous cleaning liquor become.
  • the application concentration in the aqueous liquors is advantageously 0.05 to 10 g of the mixture according to the invention per liter Cleaning liquor, preferably at 0.1 to 2 g per liter.
  • the application concentrations mentioned are non-critical Information, since the amount varies to a certain extent according to Art the surface to be cleaned and the type and extent of the Impurities.
  • the invention Mixtures of surfactants and other additives Production of customary formulations added become. These are, for example, dyes, fragrances, Corrosion inhibitors and disinfectants.
  • the known builders that optionally are complexing agents at the same time.
  • the condensed phosphates such as tripolyphosphates and Pentasodium triphosphate
  • the complexing Aminopolycarboxylic acids and their salts such as the Alkali salts of nitrilotriacetic acid and Ethylenediaminetetraacetic acid
  • the complexing Hydroxycarboxylic acids and polymeric carboxylic acids such as Citric acid, tartaric acid and the like.
  • builders polyphosphonic acid salts, such as the alkali salts of aminophosphonic acid.
  • builders can also such as silicates, for example sodium metasilicate, carbonates, Bicarbonates, borates and citrates can be added.
  • the additives according to the invention can be used with the aid of such additives Surfactant mixtures are optionally converted into powder form and are used in this form.
  • the mixtures according to the invention are characterized by a high foam suppressing effect. You have one extremely low tendency to foam and tendency to foam both at low and at elevated temperatures (for Example in the range from 15 to 80 ° C) and also at a very strong fleet movement and presence foam-promoting soiling such as protein, milk, beer, Lemonade, glue or other adhesives and the like.
  • the Mixtures according to the invention also have a high Cleaning effect and a high dirt absorption capacity. This latter property allows long service life in the system until it is refilled without impairment the cleaning effect. Your good network assets and Drainage behavior enables quick dirt removal and thus a high throughput of items to be cleaned. Likewise the freedom from stains and streaks as well as high gloss of the cleaned good guaranteed.
  • the invention Mixtures are also resistant to alkali and acids and together with these they have a long shelf life.
  • the surfactant mixtures according to the invention are suitable for Foam suppression in general in cleaning liquors.
  • she are particularly suitable for alkaline fleets mechanical cleaning of hard surfaces, for example for fleets in household dishwashers and in commercial cleaning equipment. They are particularly suitable in the case of industrial cleaning systems for hard Surfaces such as crockery and bottle rinsing systems with aqueous alkaline liquors under high mechanical Fleet movements work in continuous operation, the pH values ⁇ 10 or ⁇ 12 (highly alkaline Fleets).
  • cleaning liquors essentially consist of 95 to 99 wt .-% water and 1 to 5 wt .-% sodium and / or Potassium hydroxide.
  • the agent according to the invention is also suitable for aqueous acid cleaning liquors, which are known to essentially from 50 to 80 wt .-% water and 20 to 50% by weight of preferably phosphoric acid or sulfuric acid consist.
  • the components given in the examples and comparative examples were mixed together at room temperature with stirring.
  • the mixtures according to the invention and mixtures of the prior art obtained in this way were tested for foam behavior.
  • 0.3 g of the mixture was dissolved in one liter of deionized water. 200 ml of this solution were added to the 1000 ml measuring cylinder and beaten 30 times with the perforated beating disc.
  • the resulting foam height in the measuring cylinder expressed in milliliters, represents the foam value of the mixture.
  • the mixtures according to the invention have a unexpectedly low foam level.
  • the invention Mixtures are due to their extremely low foam levels and their other advantageous properties excellent Additives, in particular, to cleaning liquors for cleaning of hard surfaces.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Degasification And Air Bubble Elimination (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

A mixt. of alkoxylates contains (A) 10-90 wt.% of a fatty alcohol ethoxylate-propoxylate of formula R<1>-O-(C2H4O)x-(C3H6O)y-H (I) and (B) 90-10% of a fatty amine and/or fatty amine ethoxylate of formula (II). In formulae, R<1>, R<2> = 6-22C alkyl or alkenyl; x, y = 1-10; m + n = 0-10. Pref. compsn. contains 70-90% of (A) and 30-10% of (B). Pref. R<1>, R<2> = 8-18C alk(en)yl; x = 2.5-5; y = 3-6; m + n = 2-8.

Description

Die Erfindung betrifft Mischungen von Alkoxylaten als schaumdämpfendes Mittel und deren Verwendung in Reinigungsflotten.The invention relates to mixtures of alkoxylates as foam suppressant and its use in Cleaning liquors.

Für die Reinigung von harten Oberflächen wie Flaschen aus Kunststoff oder Glas, Geschirr aus Porzellan, Keramik, Glas oder Kunststoff und anderen Gegenständen aus diesen Werkstoffen oder auch Metallen werden vor allem maschinelle Reinigungsverfahren angewandt. Während bei Haushaltsspülmaschinen nur relativ geringe Flottenbewegungen entsprechend dem geringen Durchsatz an zu reinigendem Gut erforderlich sind, arbeiten gewerbliche und insbesondere industrielle Reinigungsanlagen bei großem Durchsatz mit sehr hohen Flottenbewegungen und Sprühintensitäten. Um eine schnelle Ablösung und Emulgierung der anhaftenden Verunreinigungen zu gewährleisten, werden in gewerblichen und insbesondere in industriellen Reinigungsanlagen üblicherweise wäßrige alkalische oder saure Reinigungsflotten eingesetzt. Wegen der hohen mechanischen Flottenbewegungen muß das System möglichst schaumarm oder schaumfrei sein, da übermäßige Schaumbildung zu Störungen im Betriebsverhalten der Anlage führen kann, so zum Beispiel, wenn der in der Schaumschicht sich ansammelnde Schmutz nicht ausreichend ausgetragen werden kann. Zusätzliche Tendenzen zur Schaumbildung werden durch die vom Reinigungsgut in die Flotte eingeschleppten Verunreinigungen, besonders durch proteinhaltige Reste am Reinigungsgut, hervorgerufen. Im Falle der Flaschenreinigung gilt dies besonders auch für die zu entfernenden Etiketten, durch die Leimreste und Reste von Druckfarben einschließlich der in letzteren enthaltenden Tensidhilfsmittel in die Reinigungsflotte eingebracht werden.For cleaning hard surfaces like bottles Plastic or glass, dishes made of porcelain, ceramic, glass or plastic and other objects made of these Materials or metals are primarily mechanical Cleaning procedures applied. While at Household dishwashers only have relatively small movements of the fleet corresponding to the low throughput of goods to be cleaned are required to work commercial and in particular industrial cleaning systems with high throughput with very high liquor movements and spray intensities. To one rapid detachment and emulsification of the adherent To ensure contamination, are used in commercial and especially in industrial cleaning systems usually aqueous alkaline or acidic Cleaning liquors used. Because of the high mechanical Fleet movements must be as low-foaming as possible or be foam-free because excessive foaming leads to disturbances in the Operating behavior of the system, for example, if the dirt accumulating in the foam layer is not can be carried out sufficiently. Additional trends Foam formation is caused by the items to be cleaned in the Fleet introduced contaminants, especially through protein-containing residues on the items to be cleaned. in the In the case of bottle cleaning, this also applies to the labels to be removed, through the glue residues and residues of Inks including those contained in the latter Surfactant aids introduced into the cleaning liquor become.

Es ist schon seit langem bekannt, nichtionische Tenside als schaumdämpfende (schaumunterdrückende) Mittel in wäßrigen Reinigungsflotten einzusetzen. Dies sind insbesondere Anlagerungsprodukte von Ethylenoxid und/oder Propylenoxid an Amine, längerkettige Fettalkohole oder Alkylphenole, Polyglykoletherformale oder -acetale oder Blockcopolymerisate des Ethylen- und Propylenoxids. Derartige Tensidsysteme können durch geeignete Variation der Ethylenoxid- und Propylenoxid-Anteile auf möglichst geringe Schaumneigung und erhöhte Reinigungswirkung eingestellt werden, wobei ein Übergewicht des Propylenoxids die erstere Eigenschaft, ein Übergewicht des Ethylenoxids die letztere Eigenschaft begünstigt. Jedoch stellt eine solche Einstellung dieser Eigenschaften immer einen Kompromiß dar, und es wäre wünschenswert, mehr von der einen Eigenschaft zu erhalten, ohne auf Anteile der anderen verzichten zu müssen. Bei maschinellen Reinigungsprozessen für Flaschen, Geschirr und dergleichen im industriellen Bereich, die unter hoher mechanischer Bewegung ablaufen, ist für einen störungsfreien Betrieb - wie oben erwähnt - vor allem Schaumarmut der Reinigungsflotten (Reinigungsbäder) erforderlich.It has long been known as nonionic surfactants foam suppressing (foam suppressing) agents in aqueous Use cleaning liquors. These are in particular Addition products of ethylene oxide and / or propylene oxide Amines, longer-chain fatty alcohols or alkylphenols, Polyglycol ether formals or acetals or Block copolymers of ethylene and propylene oxide. Such surfactant systems can be modified appropriately Ethylene oxide and propylene oxide proportions to the lowest possible Foam tendency and increased cleaning effect set be, an excess weight of propylene oxide the former Property, an excess weight of ethylene oxide the latter Property favors. However, such represents Setting these properties is always a compromise and it would be desirable to have more of one property received without having to give up shares in the other. In machine cleaning processes for bottles, dishes and the like in the industrial field, which under high mechanical movement, is for a trouble-free Operation - as mentioned above - especially low foam Cleaning liquors (cleaning baths) required.

In den neueren Druckschriften WO 91/09925 und WO 92/14808 werden Mischungen von Alkoxylaten als Schaumunterdrücker bei der maschinellen Reinigung von harten Oberflächen beschrieben. Das in WO 91/09925 beschriebene Mittel besteht im wesentlichen aus mindestens einem Fettalkoholethoxylat mit 2 bis 12 Ethylenoxid-Einheiten und mindestens einem Fettalkoholethoxylatpropoxylat mit 2 bis 10 Ethylenoxid-Einheiten und 2 bis 8 Propylenoxid-Einheiten im Gewichtsverhältnis von 10 : 1 bis 1 : 10 und jenes gemäß WO 92/14808 aus 2 Fettalkoholethoxylatpropoxylaten im Gewichtsverhältnis von 10 : 90 bis 90 : 10, wobei der eine Fettalkylrest 8 bis 18 C-Atome und der andere 10 bis 20 C-Atome hat, mit der Maßgabe, daß sich die beiden Fettalkylreste in der durchschnittlichen Anzahl der C-Atome um mindestens 0,5 unterscheiden. Auch diese auf Fettalkoholalkoxylaten allein basierenden Mischungen lassen insbesondere bezüglich Schaumverhalten noch zu wünschen übrig.In the more recent publications WO 91/09925 and WO 92/14808 are mixtures of alkoxylates as foam suppressants the mechanical cleaning of hard surfaces described. The agent described in WO 91/09925 exists essentially from at least one fatty alcohol ethoxylate with 2 to 12 ethylene oxide units and at least one Fatty alcohol ethoxylate propoxylate with 2 to 10 ethylene oxide units and 2 to 8 propylene oxide units in Weight ratio of 10: 1 to 1:10 and that according to WO 92/14808 from 2 fatty alcohol ethoxylate propoxylates in Weight ratio of 10:90 to 90:10, one being Fatty alkyl radical 8 to 18 carbon atoms and the other 10 to Has 20 C atoms, with the proviso that the two Fatty alkyl residues in the average number of carbon atoms differ by at least 0.5. These too Leave fatty alcohol alkoxylates alone based mixtures still to be desired, especially with regard to foam behavior left.

Es wurde nun gefunden, daß bestimmte Kombinationen von Fettalkoholethoxylatpropoxylaten und Fettaminen oder Fettaminethoxylaten eine unerwartet hohe schaumdämpfende Wirkung aufweisen.It has now been found that certain combinations of Fatty alcohol ethoxylate propoxylates and fatty amines or Fatty amine ethoxylates are an unexpectedly high foam suppressant Have effect.

Die erfindungsgemäßen Mischungen bestehen im wesentlichen aus

  • A) 10 bis 90 Gew.-%, vorzugsweise 70 bis 90 Gew.-%, von mindestens einem Fettalkoholethoxylatpropoxylat der allgemeinen Formel I R1-O-(C2H4O)x-(C3H6O)y-H worin R1 ein Alkylrest oder ein Alkenylrest mit 6 bis 22 C-Atomen ist, vorzugsweise 8 bis 18 C-Atomen, x eine Zahl von 1 bis 10, vorzugsweise von 2,5 bis 5, und y eine Zahl von 1 bis 10 ist, vorzugsweise von 3 bis 6, und
  • B) 10 bis 90 Gew.-%, vorzugsweise 10 bis 30 Gew.-%, von mindestens einem Fettamin oder Fettaminethoxylat oder einer Mischung davon der allgemeinen Formel II
    Figure 00030001
    worin R2 ein Alkylrest oder ein Alkenylrest mit 6 bis 22 C-Atomen ist, vorzugsweise 8 bis 18 C-Atomen, und
    m plus n eine Zahl von 0 bis 10 ist, vorzugsweise von 2 bis 8, Gewichtsprozente bezogen auf die Mischung.
    • The mixtures according to the invention essentially consist of
  • A) 10 to 90% by weight, preferably 70 to 90% by weight, of at least one fatty alcohol ethoxylate propoxylate of the general formula I R 1 -O- (C 2 H 4 O) x - (C 3 H 6 O) y -H wherein R 1 is an alkyl radical or an alkenyl radical having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, x is a number from 1 to 10, preferably from 2.5 to 5, and y is a number from 1 to 10 , preferably from 3 to 6, and
  • B) 10 to 90% by weight, preferably 10 to 30% by weight, of at least one fatty amine or fatty amine ethoxylate or a mixture thereof of the general formula II
    Figure 00030001
    wherein R 2 is an alkyl radical or an alkenyl radical having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and
    m plus n is a number from 0 to 10, preferably from 2 to 8 percent by weight, based on the mixture.

    • Zu den erfindungsgemäß einzusetzenden Komponenten A) und B) sei noch folgendes gesagt: Die Alkylreste und Alkenylreste, R1 und R2, können gerade oder verzweigt sein, wobei gerade bevorzugt sind. Die Alkenylreste weisen vorzugsweise 1 bis 3 Doppelbindungen auf. Die für x, y und m plus n angegebenen Zahlen sind statistische Mittelwerte (Durchschnittswerte), das heißt x, y, m und n können jeweils eine ganze oder gebrochene Zahl sein. Die Komponente A) ist also ein Umsetzungsprodukt von einem Fettalkohol mit zunächst x mol Ethylenoxid und anschließend y mol Propylenoxid, das vom Typ -CH2-CH(CH3)O- oder -CH(CH3)-CH2O- sein kann, wobei letzterer bevorzugt ist. Die Komponente B) ist ein Fettamin (primäres Amin) mit den angegebenen Alkyl- oder Alkenylgruppen oder vorzugsweise ein Umsetzungsprodukt von einem solchen Fettamin mit m plus n mol Ethylenoxid. Als Komponente B) sind also die Fettaminethoxylate gemäß Formel II bevorzugt. Beispiele für Alkyl- und Alkenylreste in Formel I und II sind n-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, iso-Nonyl, n-Decyl, iso-Decyl, n-Dodecyl, Stearyl, n-Eikosyl, Oleyl, Cocosalkyl und Talgalkyl sowie Alkyl- oder Alkenyl-Gemische, zum Beispiel ein Gemisch aus C12-Alkyl bis C14-Alkyl (C12/14). All die Verbindungen gemäß Komponente A) und B) sind bekannt und im Handel erhältlich.The following may be said about components A) and B) to be used according to the invention: The alkyl radicals and alkenyl radicals, R 1 and R 2 , can be straight or branched, with preference being given to straight. The alkenyl radicals preferably have 1 to 3 double bonds. The numbers given for x, y and m plus n are statistical averages (average values), i.e. x, y, m and n can each be an integer or fractional number. Component A) is therefore a reaction product of a fatty alcohol with first x mol ethylene oxide and then y mol propylene oxide, which can be of the type -CH 2 -CH (CH 3 ) O- or -CH (CH 3 ) -CH 2 O- , the latter being preferred. Component B) is a fatty amine (primary amine) with the specified alkyl or alkenyl groups or preferably a reaction product of such a fatty amine with m plus n mol of ethylene oxide. The fatty amine ethoxylates according to formula II are therefore preferred as component B). Examples of alkyl and alkenyl radicals in formulas I and II are n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, iso-nonyl, n-decyl, iso-decyl, n-dodecyl, stearyl, n-eikosyl, Oleyl, cocoalkyl and tallow alkyl as well as alkyl or alkenyl mixtures, for example a mixture of C 12 alkyl to C 14 alkyl (C 12/14 ). All of the compounds according to component A) and B) are known and commercially available.

    Die Herstellung der erfindungsgemäßen schaumdämpfenden Mittel erfolgt einfach durch Zusammenmischen der Komponenten A) und B) und gegebenenfalls weiterer zweckmäßiger Komponenten und Additive bei einer Temperatur von 15 bis 50 °C, vorzugsweise 20 bis 30 °C, und vorteilhafterweise unter Rühren.The production of the foam-suppressant according to the invention Means are made simply by mixing the Components A) and B) and optionally further expedient components and additives at one temperature from 15 to 50 ° C, preferably 20 to 30 ° C, and advantageously with stirring.

    Die erfindungsgemäßen Mischungen können in unverdünnter Form, das heißt als solche oder zum Beispiel zwecks besserer Dosierbarkeit in Form wäßriger Konzentrate eingesetzt werden, gegebenenfalls unter Zusatz eines organischen Lösungsmittels. Selbstverständlich können die Komponenten A) und B) auch getrennt der wäßrigen Reinigungsflotte zugesetzt werden. Die Anwendungskonzentration in den wäßrigen Flotten (alkalisch oder sauer) liegt zweckmäßigerweise bei 0,05 bis 10 g des erfindungsgemäßen Gemisches pro Liter Reinigungsflotte, vorzugsweise bei 0,1 bis 2 g pro Liter. Die genannten Anwendungskonzentrationen sind nicht-kritische Angaben, da sich die Menge in gewissem Ausmaß nach der Art der zu reinigenden Oberfläche und nach Art und Umfang der Verunreinigungen richtet.The mixtures according to the invention can be used in undiluted form Form, that is as such or, for example, for the purpose of better Dosage in the form of aqueous concentrates used are, optionally with the addition of an organic Solvent. Of course, components A) and B) also added separately to the aqueous cleaning liquor become. The application concentration in the aqueous liquors (alkaline or acidic) is advantageously 0.05 to 10 g of the mixture according to the invention per liter Cleaning liquor, preferably at 0.1 to 2 g per liter. The application concentrations mentioned are non-critical Information, since the amount varies to a certain extent according to Art the surface to be cleaned and the type and extent of the Impurities.

    Wie oben erwähnt, können den erfindungsgemäßen Tensidgemischen weitere Zusatz- und Hilfsstoffe zur Herstellung handelsüblicher Formulierungen beigegeben werden. Dies sind beispielsweise Farbstoffe, Duftstoffe, Korrosionsinhibitoren und Desinfektionsmittel. Hier sind ferner zu nennen die bekannten Gerüststoffe, die gegebenenfalls gleichzeitig Komplexbildner sind. Dazu gehören die kondensierten Phosphate wie Tripolyphosphate und Pentanatriumtriphosphat, die komplexbildend wirkenden Aminopolycarbonsäuren und deren Salze, so zum Beispiel die Alkalisalze der Nitrilotriessigsäure und der Ethylendiamintetraessigsäure, und die komplexbildenden Hydroxycarbonsäuren und polymeren Carbonsäuren wie Zitronensäure, Weinsäure und dergleichen. Eine weitere Klasse von komplexbildenden Gerüststoffen sind polyphosphonsaure Salze, wie beispielsweise die Alkalisalze von Aminophosphonsäure. Schließlich können auch Gerüststoffe wie Silicate, beispielsweise Natriummetasilicat, Carbonate, Bicarbonate, Borate und Citrate hinzugefügt werden. Mit Hilfe solcher Zusatzstoffe können die erfindungsgemäßen Tensidgemische gegebenenfalls in Pulverform überführt werden und in dieser Form zum Einsatz gelangen. As mentioned above, the invention Mixtures of surfactants and other additives Production of customary formulations added become. These are, for example, dyes, fragrances, Corrosion inhibitors and disinfectants. Here are also to name the known builders that optionally are complexing agents at the same time. To include the condensed phosphates such as tripolyphosphates and Pentasodium triphosphate, the complexing Aminopolycarboxylic acids and their salts, such as the Alkali salts of nitrilotriacetic acid and Ethylenediaminetetraacetic acid, and the complexing Hydroxycarboxylic acids and polymeric carboxylic acids such as Citric acid, tartaric acid and the like. Another Are class of complexing builders polyphosphonic acid salts, such as the alkali salts of aminophosphonic acid. Finally, builders can also such as silicates, for example sodium metasilicate, carbonates, Bicarbonates, borates and citrates can be added. With The additives according to the invention can be used with the aid of such additives Surfactant mixtures are optionally converted into powder form and are used in this form.

    Die erfindungsgemäßen Mischungen zeichnen sich durch eine hohe schaumunterdrückende Wirkung aus. Sie besitzen eine extrem niedrige Schaumneigung und Schaumbildungstendenz sowohl bei niedrigen als auch bei erhöhten Temperaturen (zum Beispiel im Bereich von 15 bis 80 °C) und ebenso auch bei einer sehr starken Flottenbewegung und Anwesenheit schaumfördernder Verschmutzungen wie Eiweiß, Milch, Bier, Limonade, Leim oder anderen Klebstoffen und dergleichen. Die erfindungsgemäßen Mischungen weisen daneben eine hohe Reinigungswirkung und ein hohes Schmutzaufnahmevermögen auf. Diese letztere Eigenschaft gestattet lange Standzeiten in der Anlage bis zu deren Neubefüllung ohne Beeinträchtigung der Reinigungswirkung. Ihr gutes Netzvermögen und Ablaufverhalten ermöglichen eine schnelle Schmutzablösung und somit einen hohen Durchsatz an Reinigungsgut. Ebenso ist die Freiheit von Flecken und Schlieren sowie hoher Glanz des gereinigten Gutes gewährleistet. Die erfindungsgemäßen Gemische sind auch beständig gegen Alkali und Säuren und zusammen mit diesen über lange Zeiträume lagerstabil.The mixtures according to the invention are characterized by a high foam suppressing effect. You have one extremely low tendency to foam and tendency to foam both at low and at elevated temperatures (for Example in the range from 15 to 80 ° C) and also at a very strong fleet movement and presence foam-promoting soiling such as protein, milk, beer, Lemonade, glue or other adhesives and the like. The Mixtures according to the invention also have a high Cleaning effect and a high dirt absorption capacity. This latter property allows long service life in the system until it is refilled without impairment the cleaning effect. Your good network assets and Drainage behavior enables quick dirt removal and thus a high throughput of items to be cleaned. Likewise the freedom from stains and streaks as well as high gloss of the cleaned good guaranteed. The invention Mixtures are also resistant to alkali and acids and together with these they have a long shelf life.

    Die erfindungsgemäßen Tensidgemische eignen sich zur Schaumunterdrückung in Reinigungsflotten ganz allgemein. Sie eignen sich insbesondere für alkalische Flotten zur maschinellen Reinigung harter Oberflächen, so zum Beispiel für Flotten in Haushaltsgeschirrspülmaschinen und in gewerblichen Reinigungsanlagen. Sie sind vor allem geeignet im Falle von industriellen Reinigungsanlagen für harte Oberflächen wie Geschirr- und Flaschenspülanlagen, die mit wäßrigen alkalischen Flotten unter hohen mechanischen Flottenbewegungen im Dauerbetrieb arbeiten, wobei die pH-Werte ≧ 10 oder ≧ 12 sein können (hochalkalische Flotten). Als weiteres Beispiel sei die Reinigung von Flaschen aus Glas oder Kunststoff (vorzugsweise Polyester wie Polyethylenterephthalat) in Brauereien genannt, wobei aufgrund der weitgehenden Schaumfreiheit ein problemloses Austragen der abgelösten Etiketten möglich ist und außerdem gewährleistet ist, daß bei Befüllung der gereinigten Flaschen mit dem schäumenden Bier keine Beeinträchtigung durch Schaumzusammenbruch eintritt. Alkalische Reinigungsflotten bestehen bekanntlich im wesentlichen aus 95 bis 99 Gew.-% Wasser und 1 bis 5 Gew.-% Natrium- und/oder Kaliumhydroxid. Das erfindungsgemäße Mittel eignet sich auch für wäßrige saure Reinigungsflotten, die bekanntlich im wesentlichen aus 50 bis 80 Gew.-% Wasser und 20 bis 50 Gew.-% von vorzugsweise Phosphorsäure oder Schwefelsäure bestehen.The surfactant mixtures according to the invention are suitable for Foam suppression in general in cleaning liquors. she are particularly suitable for alkaline fleets mechanical cleaning of hard surfaces, for example for fleets in household dishwashers and in commercial cleaning equipment. They are particularly suitable in the case of industrial cleaning systems for hard Surfaces such as crockery and bottle rinsing systems with aqueous alkaline liquors under high mechanical Fleet movements work in continuous operation, the pH values ≧ 10 or ≧ 12 (highly alkaline Fleets). Another example is the cleaning of Glass or plastic bottles (preferably polyester such as polyethylene terephthalate) in breweries, where a problem-free due to the largely lack of foam Removal of the detached labels is possible and also it is guaranteed that when the cleaned Bottles with the foaming beer have no impact due to foam breakdown. Alkaline As is well known, cleaning liquors essentially consist of 95 to 99 wt .-% water and 1 to 5 wt .-% sodium and / or Potassium hydroxide. The agent according to the invention is also suitable for aqueous acid cleaning liquors, which are known to essentially from 50 to 80 wt .-% water and 20 to 50% by weight of preferably phosphoric acid or sulfuric acid consist.

    Die Erfindung wird durch die folgenden Beispiele und Vergleichsbeispiele noch näher erläutert (EO = Ethylenoxid und PO = Propylenoxid).The invention is illustrated by the following examples and Comparative examples explained in more detail (EO = ethylene oxide and PO = propylene oxide).

    Beispiel 1example 1

    70 Gew.-%70% by weight
    von einem Alkoxylat der Formel
    R1-O-(C2H4O)2-(C3H6O)4-H, worin R1 C12/14-Alkyl ist (das ist kurz ausgedrückt: C12/14-Alkohol + 2 EO + 4 PO), und    of an alkoxylate of the formula
    R 1 -O- (C 2 H 4 O) 2 - (C 3 H 6 O) 4 -H, where R 1 is C 12/14 alkyl (in short: C 12/14 alcohol + 2 EO + 4 PO), and
    30 Gew.-%30% by weight
    von einem Cocosaminethoxylat mit 8 mol Ethylenoxid (das ist kurz ausgedrückt: Cocosamin + 8 EO).of a cocosamine ethoxylate with 8 mol ethylene oxide (in short: cocosamine + 8 EO).
    Beispiel 2Example 2

  • 80 Gew.-% C12/15-Alkohol + 5 EO + 5 PO80% by weight C 12/15 alcohol + 5 EO + 5 PO
  • 20 Gew.-% Oleylamin + 2 EO20% by weight oleylamine + 2 EO

    • Beispiel 3Example 3

  • 80 Gew.-% C12/14-Alkohol + 3 EO + 4,5 PO80% by weight C 12/14 alcohol + 3 EO + 4.5 PO
  • 20 Gew.-% Stearylamin + 8 EO20% by weight stearylamine + 8 EO

    • Beispiel 4Example 4

  • 70 Gew.-% C10/12-Alkohol + 4 EO + 4 PO70% by weight of C 10/12 alcohol + 4 EO + 4 PO
  • 30 Gew.-% Cocosamin + 2 EO30% by weight cocosamine + 2 EO

    • Vergleichsbeispiel 1 (gemäß WO 91/09925)Comparative Example 1 (according to WO 91/09925)

  • 50 Gew.-% C12/14-Alkohol + 4 EO50% by weight C 12/14 alcohol + 4 EO
  • 50 Gew.-% C12/14-Alkohol + 3,6 EO + 5 PO50% by weight C 12/14 alcohol + 3.6 EO + 5 PO

    • Vergleichsbeispiel 2 (gemäß WO 91/09925)Comparative Example 2 (according to WO 91/09925)

  • 50 Gew.-% C12/16-Alkohol + 7 EO50% by weight C 12/16 alcohol + 7 EO
  • 50 Gew.-% C12/14-Alkohol + 2 EO + 4 PO50% by weight C 12/14 alcohol + 2 EO + 4 PO

    • Vergleichsbeispiel 3 (gemäß WO 91/09925)Comparative Example 3 (according to WO 91/09925)

  • 66,5 Gew.-% C12/14-Alkohol + 5,6 EO + 4 PO66.5% by weight C 12/14 alcohol + 5.6 EO + 4 PO
  • 33,5 Gew.-% C11-Alkohol + 5 EO33.5% by weight of C 11 alcohol + 5 EO

    • Vergleichsbeispiel 4 (gemäß WO 92/14808)Comparative Example 4 (according to WO 92/14808)

  • 50 Gew.-% C12/14-Alkohol + 4 EO + 4 PO50% by weight C 12/14 alcohol + 4 EO + 4 PO
  • 50 Gew.-% C12/15-Alkohol + 5 EO + 5 PO50% by weight C 12/15 alcohol + 5 EO + 5 PO

    • Vergleichsbeispiel 5 (gemäß WO 92/14808)Comparative Example 5 (according to WO 92/14808)

  • 50 Gew.-% C12/14-Alkohol + 5,6 EO + 4 PO50% by weight C 12/14 alcohol + 5.6 EO + 4 PO
  • 50 Gew.-% C12/15-Alkohol + 5 EO + 5 PO50% by weight C 12/15 alcohol + 5 EO + 5 PO

    • Die in den Beispielen und Vergleichsbeispielen angegebenen Komponenten wurden bei Raumtemperatur unter Rühren zusammengemischt. Die so erhaltenen erfindungsgemäßen Mischungen und Mischungen des Standes der Technik wurden bezüglich Schaumverhalten geprüft. Die Prüfung erfolgte nach DIN 53 902 (DIN = Deutsche Industrienorm) bei 15 und 65 °C. Dazu wurden 0,3 g von der Mischung in einem Liter vollentsalztem Wasser gelöst. Von dieser Lösung wurden 200 ml in den 1000-ml-Meßzylinder gegeben und mit der gelochten Schlagscheibe 30mal geschlagen. Die entstandene Schaumhöhe im Meßzylinder, ausgedrückt in Milliliter, stellt den Schaumwert der Mischung dar. Die Ergebnisse sind in der nachstehenden Tabelle zusammengefaßt: Mischungen der Schaumverhalten 15 °C 65 °C Beispiele 1 60 ml 0 ml 2 60 ml 0 ml 3 60 ml 0 ml 4 70 ml 0 ml Vergleichsbeispiele 1 80 ml 20 ml 2 80 ml 20 ml 3 110 ml 10 ml 4 110 ml 0 ml 5 100 ml 10 ml The components given in the examples and comparative examples were mixed together at room temperature with stirring. The mixtures according to the invention and mixtures of the prior art obtained in this way were tested for foam behavior. The test was carried out according to DIN 53 902 (DIN = German industrial standard) at 15 and 65 ° C. For this purpose, 0.3 g of the mixture was dissolved in one liter of deionized water. 200 ml of this solution were added to the 1000 ml measuring cylinder and beaten 30 times with the perforated beating disc. The resulting foam height in the measuring cylinder, expressed in milliliters, represents the foam value of the mixture. The results are summarized in the table below: Mixtures of Foaming behavior 15 ° C 65 ° C Examples 1 60 ml 0 ml 2nd 60 ml 0 ml 3rd 60 ml 0 ml 4th 70 ml 0 ml Comparative examples 1 80 ml 20 ml 2nd 80 ml 20 ml 3rd 110 ml 10 ml 4th 110 ml 0 ml 5 100 ml 10 ml

    Wie die Ergebnisse der Beispiele und Vergleichsbeispiele zeigen, weisen die erfindungsgemäßen Mischungen einen unerwartet niedrigen Schaumwert auf. Die erfindungsgemäßen Mischungen sind aufgrund ihrer extrem niedrigen Schaumwerte und ihrer übrigen vorteilhaften Eigenschaften ausgezeichnete Zusätze insbesondere zu Reinigungsflotten für die Reinigung von harten Oberflächen.Like the results of the examples and comparative examples show, the mixtures according to the invention have a unexpectedly low foam level. The invention Mixtures are due to their extremely low foam levels and their other advantageous properties excellent Additives, in particular, to cleaning liquors for cleaning of hard surfaces.

    Claims (5)

    1. A mixture of alkoxylates as foam-suppressing composition, essentially comprising
      A) 10 to 90% by weight of at least one fatty alcohol ethoxylate-propoxylate of the formula I R1-O-(C2H4O)x-(C3H6O)y-H in which R1 is an alkyl radical or an alkenyl radical having 6 to 22 carbon atoms, x is a number from 1 to 10 and y is a number from 1 to 10, and
      B) 10 to 90% by weight of at least one fatty amine or fatty amine ethoxylate, or of a mixture thereof, of the formula II
      Figure 00120001
      in which R2 is an alkyl radical or an alkenyl radical having 6 to 22 carbon atoms and m plus n is a number from 0 to 10, the percentages by weight being based on the mixture.
    2. A mixture as claimed in claim 1, wherein component A) is present in an amount of 70 to 90% by weight and component B) is present in an amount of 10 to 30% by weight.
    3. A mixture as claimed in claim 1 or 2, wherein, in formula I, R1 is an alkyl radical or an alkenyl radical having 8 to 18 carbon atoms, x is a number from 2.5 to 5 and y is a number from 3 to 6, and, in formula II, R2 is an alkyl radical or an alkenyl radical having 8 to 18 carbon atoms and m plus n is a number from 2 to 8.
    4. The use of a mixture as claimed in one or more of claims 1 to 3 in aqueous cleaning liquors for mechanical cleaning of hard surfaces.
    5. The use of a mixture as claimed in one or more of claims 1 to 3 in aqueous cleaning liquors for mechanical cleaning of bottles of glass or polyester
    EP95111558A 1994-07-29 1995-07-22 Mixtures of alkoxylates as foam depressing agent and use thereof Expired - Lifetime EP0694606B1 (en)

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    DE4426889A DE4426889A1 (en) 1994-07-29 1994-07-29 Mixtures of alkoxylates as foam suppressants and their use

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    JP2983884B2 (en) * 1995-05-19 1999-11-29 日本ペイント株式会社 Alkaline degreasing cleaning method
    DE19652680A1 (en) * 1996-12-18 1998-06-25 Clariant Gmbh Mixtures of alkoxylates with foam-suppressing and disinfecting effects and their use in cleaning agents
    DE19738108A1 (en) * 1997-09-01 1999-03-04 Henkel Kgaa Cold stable fatty alcohol alkoxylates
    DE10313461A1 (en) * 2003-03-26 2004-10-07 Henkel Kgaa Cleaning solution and cleaning method for paint lines and / or paint application devices
    DE102005018501A1 (en) * 2005-04-21 2006-10-26 Clariant Produkte (Deutschland) Gmbh Detergents and cleaning agents containing alcohol ethoxylate propoxylates
    DE102005037971A1 (en) * 2005-08-11 2007-02-15 Clariant Produkte (Deutschland) Gmbh Compositions containing fatty alcohol alkoxylates
    US7906474B2 (en) * 2007-01-11 2011-03-15 Dow Global Technologies Llc Alkoxylate blend surfactants
    EP2192107A4 (en) * 2007-09-27 2013-08-28 Sanyo Chemical Ind Ltd Aliphatic amine alkylene oxide adduct
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    EP0694606A3 (en) 1997-05-21
    ATE187761T1 (en) 2000-01-15
    DE59507417D1 (en) 2000-01-20
    HU214093B (en) 1997-12-29
    HU9502249D0 (en) 1995-09-28
    EP0694606A2 (en) 1996-01-31

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