EP0572453B1 - Method for manufacturing a mixture of alkoxylated alcohols and its use as antifoam tenside additive in cleaning products for mechanical washing processes - Google Patents

Method for manufacturing a mixture of alkoxylated alcohols and its use as antifoam tenside additive in cleaning products for mechanical washing processes Download PDF

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Publication number
EP0572453B1
EP0572453B1 EP92904485A EP92904485A EP0572453B1 EP 0572453 B1 EP0572453 B1 EP 0572453B1 EP 92904485 A EP92904485 A EP 92904485A EP 92904485 A EP92904485 A EP 92904485A EP 0572453 B1 EP0572453 B1 EP 0572453B1
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Prior art keywords
alcohols
mixture
foam
alkoxylated
alkoxylated alcohols
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EP92904485A
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German (de)
French (fr)
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EP0572453A1 (en
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Dieter Stoeckigt
Richard Baur
Horst Trapp
Johannes Perner
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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
    • C11D3/0005—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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains

Definitions

  • the invention also relates to the use of this mixture as a foam-suppressing surfactant additive in cleaning agents for machine-operated cleaning processes.
  • the invention further relates to such mixtures of cleaning agents containing alkoxylated alcohols I.
  • wetting agents such as ethylene and / or propylene oxide adducts with alcohols, phenols or amines may be mentioned, for example.
  • EP-A 034 275 (1) relates to the use of nonionic surfactants which are obtained by reacting at least one 4- to 14-fold ethoxylated C8-C20-alkanol with 1,2-butylene oxide in a molar ratio of 1: 1.6 to 1: 2.4 have been obtained in biodegradable and low-foaming cleaning and washing-up liquids.
  • EP-A 161 537 (2) relates to the use of non-ionic surfactants end-capped with methyl, ethyl or allyl radicals, which can be obtained by stepwise alkoxylation of C8-C22-alkanols with at least two different alkylene oxides, as low-foam, foam-suppressing and biological degradable surfactants in industrial cleaning processes.
  • EP-B 019 173 (3) relates to the use of C9-C18 alkanols first reacted with propylene oxide and then with ethylene oxide as low-foaming and biodegradable surfactant additives in dishwashing detergents for dishwashers.
  • EP-A 254 208 (4) discloses a low-foam surfactant mixture which contains 10 to 40% by weight of an ethoxylated and then propoxylated alkyl polyalkylene glycol mixed ether.
  • An example is given on page 6 of a mixed ether which essentially contains a mixture of C12 and C14 alcohols ("LS coconut alcohol”), which has the following carbon chain length distribution: C10 o to 2% C12 70 to 75% C14 24 to 30% C16 0 to 2% From the abstract Chemical Abstracts 95, 82812 q (1981) (5) is an 80:20 mixture of a polyether of the formula C12 / C13-alkyl-O (C2H4O) 6 (C3H6O) 2H and a polyether of the formula C12 / C13-alkyl-O (C2H4O) 7 (C3H6O) 20H known as a component of detergents and cleaning agents.
  • EP-A 343 503 (6) relates to a surfactant mixture for use in detergents and cleaning agents, in particular in rinse aids for machine dishwashing, with reduced foaming, which contains longer-chain ethoxylated and then propoxylated or butoxylated alcohols as components.
  • EP-A 018 482 (7) describes biodegradable and low-foaming surfactants which have been prepared by reacting a longer-chain alcohol with an alkylene oxide having at least 3 C atoms and subsequent ethoxylation.
  • the individual components are first alkoxylated and only then mixed with other alkoxylated components or other constituents of the formulations.
  • surfactants of the type mentioned and mixtures thereof also prove to be in need of improvement when used in cleaning agents for machine-based cleaning processes.
  • the foam damping behavior and the dispersibility in water are not yet optimal.
  • the present invention was therefore based on the object of remedying the deficiencies described in the prior art.
  • the process defined at the outset for producing a mixture of alkoxylated alcohols I which is characterized in that at least two mixtures of alcohols of the general formula RAW wherein an alcohol mixture contains straight-chain or branched C8-C18 alkyl groups as the radical R and another alcohol mixture contains straight-chain or branched C10-C20 alkyl groups as the radical R, but the two radicals R in the average number of carbon atoms by at least 0.5 must distinguish and where both alcohol mixtures are in a weight ratio of 10:90 to 90:10, mixes with each other and react this mixture first with the appropriate amount of ethylene oxide and then with the appropriate amount of propylene oxide, and the use of such a mixture as a foam-suppressing surfactant additive found in detergents for automated cleaning processes.
  • RAW mixtures of alcohols of the general formula RAW wherein an alcohol mixture contains straight-chain or branched C8-C18 alkyl groups as the radical R and another alcohol mixture contains straight-chain or branched C10-C20 al
  • Examples of straight-chain or branched C8-C18 or C10-C20 alkyl radicals for R are: n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, n-undecyl, n -Dodecyl, n-tridecyl, iso-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicosyl.
  • the radicals R are preferably straight-chain or only branched to a small extent, i.e. they contain a maximum of 3 methyl or ethyl side chains.
  • R is a residue of naturally occurring fatty alcohols or preferably of synthetically produced oxo or Ziegler alcohols.
  • Examples of readily usable alcohols prepared by oxosynthesis are C9 / C11-, C12 / C14-, C13 / C15- and C16 / C18-alkanol mixtures.
  • Examples of readily usable alcohols produced by the Ziegler synthesis are C8 / C10-, C10 / C12-, C12 / C14-, C12 / C16 and C16 / C20-alkanol mixtures.
  • alkanols used in the synthesis of the compounds I generally represent statistical homologues and also isomer mixtures, it is expedient to speak of an average number of carbon atoms. This average value usually represents the maximum frequency.
  • alkoxylated alcohols I are conveniently by Ethoxylation and subsequent propoxylation of the alkanols mentioned are prepared in a manner known per se. These methods are known to the person skilled in the art and require no further explanation.
  • the degree of ethoxylation x is 1 to 12, preferably 2 to 5, in particular 3 to 4; the degree of propoxylation is 1 to 15, preferably 2 to 6, in particular 4 to 6.
  • the degrees of alkoxylation x and y generally also represent average values.
  • a mixture of at least two, preferably two or three, in particular two, mixtures of alcohols of the formula ROH is used, where two radicals R must differ by at least 0.5 in the average number of carbon atoms, and the corresponding two alcohol mixtures in Ratio from 10:90 to 90:10, preferably 25:75 to 75:25.
  • Mechanical cleaning processes are mainly found in the metal industry, in the food industry, e.g. the beverage, canning, sugar industry or milk, meat and fat processing industry, in the catering trade and also in the household.
  • metal objects often have to be removed after their manufacture or processing soiling and residues, which originate from drawing and rolling greases or organic corrosion protection agents. All surfaces of containers and tools that come into contact with food during production, processing and transportation must be cleaned from food residues and other soiling at certain intervals.
  • a typical example of an industrial machine cleaning process from the beverage industry is the washing of used bottles which, for example, contained beer, milk, soft drinks or mineral water.
  • a rinse aid commonly used here contains nonionic surfactants, hydrotropes (solubilizers) such as isopropanol, ethanol and / or cumene sulfonate, water and, if appropriate, organic or inorganic acids and auxiliaries such as dyes and preservatives.
  • nonionic surfactants such as isopropanol, ethanol and / or cumene sulfonate
  • water such as isopropanol, ethanol and / or cumene sulfonate
  • organic or inorganic acids and auxiliaries such as dyes and preservatives.
  • the present invention also relates to a process for the preparation of cleaning agents for machine-running cleaning processes, in particular rinse aids for machine dishwashing, which is characterized in that a mixture of alkoxylated alcohols I is added to these agents as a foam-suppressing surfactant additive.
  • the present invention furthermore relates to cleaning agents for machine-operated cleaning processes which contain a mixture of alkoxylated alcohols I as a foam-suppressing surfactant additive in an amount of 0.1 to 40% by weight, preferably 0.5 to 20% by weight, based on the Total amount of formulation included.
  • the present invention furthermore relates to rinse aids for machine dishwashing, which comprise a mixture of alkoxylated alcohols I as a foam-suppressing surfactant additive in an amount of 0.5 to 30% by weight, preferably 1 to 15% by weight, based on the total amount of Wording.
  • the mixture of alkoxylated alcohols I prepared according to the invention achieves an optimum of the desired properties when cleaning the hard surfaces mentioned, for example of metal or dishes, namely good wetting action, streak-free drainage from the wash ware, foam-suppressing action or low-foaming action and good dispersibility in water . It is also advantageous that the mixture of compounds I described is readily biodegradable.
  • rinse aid formulations for machine dishwashing in the household were produced.
  • the following table shows the compositions of these formulations.
  • the cloud point was determined in accordance with DIN 53 917. Practical studies have shown that falling cloud points, which means an increase in hydrophobicity, result in improvements in the foaming behavior, but on the other hand reduce the dispersibility, which leads to an uneven distribution of the rinse aid in the washing liquor and thus to a deterioration in the drainage behavior (stains, Streaking and streaking). At cloud points ⁇ 40 ° C, instability, ie phase separation, of the rinse aid formulation is also observed.
  • the foam damping behavior is checked in the dishwasher by the so-called "egg test".
  • the number of revolutions of a spray arm is determined by magnetic induction measurement in a commercial household dishwasher with the help of a counter. Foam formation, which occurs particularly in the presence of proteins (protein), reduces the number of revolutions of the spray arm. Because of the reduced recoil force, the number of revolutions therefore represents a measure of the suitability of surfactants in cleaning devices with high mechanical properties.
  • the test time is 12 minutes, the average number of revolutions per minute being calculated from the total number of revolutions.
  • the washing process is started at room temperature, after about 10 minutes the temperature of the rinsing water is 60 ° C.
  • Example 5 shows that when using the surfactant additives to be used according to the invention (Examples 5 and 6), rinse aid formulations are obtained which combine excellent foam-damping behavior with excellent dispersibility, despite a sometimes very low cloud point (Example 5). Lowering the cloud point by adding a hydrophobic surfactant often leads to an improvement in foam damping, but at the same time to a loss of dispersing properties. The cloud point is usually raised again by the addition of solubilizers and thus the dispersibility is improved.
  • Example 5 shows that by adding the specified mixtures of compounds I to solubilizers to raise the cloud point completely or at least partially.
  • Comparative Examples 2, 3, 4 and 7 show how although the foam damping is somewhat improved by adding or mixing known means of the prior art, the dispersibility is impaired by lowering the cloud point.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

PCT No. PCT/EP92/00289 Sec. 371 Date Aug. 23, 1993 Sec. 102(e) Date Aug. 23, 1993 PCT Filed Feb. 11, 1992 PCT Pub. No. WO92/14808 PCT Pub. Date Sep. 3, 1992.A mixture suitable for use as a foam-suppressing surfactant additament in cleaning compositions for mechanized cleaning processes comprises at least two mixtures of alkoxylated alcohols I R-O-(C2H4O)x-(C3H6O)y-H (I) where x is an average degree of ethoxylation between 1 and 12, y is an average degree of propoxylation between 1 and 15, one alkoxylated alcohol mixture carries straight-chain or branched C8-C18-alkyl groups as the radical R and one other alkoxylated alcohol mixture carries straight-chain or branched C10-C20-alkyl groups as the radical R, subject to the proviso that the two radicals R differ by at least 0.5 in the average number of carbon atoms, and the two alkoxylated alcohol mixtures present in a ratio of from 10:90 to 90:10.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung einer Mischung aus alkoxylierten Alkoholen der allgemeinen Formel I



        R-O-(C₂H₄O)x-(C₃H₆O)y-H   (I)



in der

x
einen mittleren Ethoxylierungsgrad von 1 bis 12 bezeichnet und
y
einen mittleren Propoxylierungsgrad von 1 bis 15 bedeutet.
The present invention relates to a process for the preparation of a mixture of alkoxylated alcohols of the general formula I.



RO- (C₂H₄O) x - (C₃H₆O) y -H (I)



in the
x
denotes an average degree of ethoxylation from 1 to 12 and
y
means an average degree of propoxylation of 1 to 15.

Gegenstand der Erfindung ist auch die Verwendung dieser Mischung als schaumdämpfender Tensidzusatz in Reinigungsmitteln für maschinell ablaufende Reinigungsprozesse. Weiterhin betrifft die Erfindung derartige Mischungen aus alkoxylierten Alkoholen I enthaltende Reinigungsmittel.The invention also relates to the use of this mixture as a foam-suppressing surfactant additive in cleaning agents for machine-operated cleaning processes. The invention further relates to such mixtures of cleaning agents containing alkoxylated alcohols I.

Nach den Erfahrungen der Praxis müssen bei maschinell ablaufenden Reinigungsprozessen, beispielsweise bei der maschinellen Geschirreinigung, im allgemeinen zwei aufeinanderfolgende, meist durch einen Zwischenspülgang mit Wasser getrennte Spülgänge mit verschiedenartigen Reinigungsmitteln angewendet werden. In der eigentlichen Reinigungsflotte kommen alkalisch reagierende Mittel zur Ablösung und Emulgierung von beispielsweise Speiseresten zum Einsatz. In der Nach- oder Klarspülflotte werden dagegen spezielle Klarspülmittel zur Erzielung einer klaren, fleck- und schleierfreien Oberfläche, z.B. auf Geschirr, verwendet. Diese Mittel müssen eine gute Netzwirkung haben, damit das Spülwasser filmartig von der Oberfläche abläuft und keine sichtbaren Rückstände hinterläßt, und gut in Wasser dispergierbar sein. Wegen der starken Flottenbewegung in den hierbei verwendeten Reinigungs- und Spülmaschinen müssen Klarspülmittel zusätzlich ausreichend schaumarm sein.According to experience in practice, in machine cleaning processes, for example in machine dishwashing, two successive rinse cycles with different cleaning agents, usually separated by an intermediate rinse cycle with water, have to be used. In the actual cleaning liquor, alkaline agents are used to detach and emulsify food residues, for example. In the final rinse or rinse liquor, on the other hand, special rinse aids are used to achieve a clear, stain-free and fog-free surface, for example on dishes. These agents must have a good wetting effect so that the rinsing water runs off the surface like a film and no visible residues leaves, and be well dispersible in water. Because of the strong movement of the liquor in the cleaning and dishwashing machines used here, rinse aid must also be low in foam.

Solche Mittel sind in großer Zahl bekannt; es seien beispielsweise Netzmittel wie Ethylen- und/oder Propylenoxidaddukte an Alkohole, Phenole oder Amine erwähnt.Such means are known in large numbers; wetting agents such as ethylene and / or propylene oxide adducts with alcohols, phenols or amines may be mentioned, for example.

So betrifft die EP-A 034 275 (1) die Verwendung von nichtionischen Tensiden, die durch Umsetzung mindestens eines 4- bis 14-fach ethoxylierten C₈-C₂₀-Alkanols mit 1,2-Butylenoxid im Molverhältnis 1 : 1,6 bis 1 : 2,4 erhalten worden sind, in biologisch abbaubaren und schwach schäumenden Reinigungs- und Spülmitteln.For example, EP-A 034 275 (1) relates to the use of nonionic surfactants which are obtained by reacting at least one 4- to 14-fold ethoxylated C₈-C₂₀-alkanol with 1,2-butylene oxide in a molar ratio of 1: 1.6 to 1: 2.4 have been obtained in biodegradable and low-foaming cleaning and washing-up liquids.

Die EP-A 161 537 (2) betrifft die Verwendung von mit Methyl-, Ethyl- oder Allylresten endgruppenverschlossenen nichtionischen Tensiden, die durch stufenweise Alkoxylierung von C₈-C₂₂-Alkanolen mit mindestens zwei verschiedenen Alkylenoxiden erhalten werden können, als schaumarme, schaumdämpfende und biologisch abbaubare Tenside in industriellen Reinigungsprozessen.EP-A 161 537 (2) relates to the use of non-ionic surfactants end-capped with methyl, ethyl or allyl radicals, which can be obtained by stepwise alkoxylation of C₈-C₂₂-alkanols with at least two different alkylene oxides, as low-foam, foam-suppressing and biological degradable surfactants in industrial cleaning processes.

Die EP-B 019 173 (3) betrifft die Verwendung von zuerst mit Propylenoxid und dann mit Ethylenoxid umgesetzten C₉-C₁₈-Alkanolen als schaumarme und biologisch abbaubare Tensidzusätze in Geschirrspülmitteln für Geschirrspülmaschinen.EP-B 019 173 (3) relates to the use of C₉-C₁₈ alkanols first reacted with propylene oxide and then with ethylene oxide as low-foaming and biodegradable surfactant additives in dishwashing detergents for dishwashers.

In der EP-A 254 208 (4) wird ein schaumarmes Tensidgemisch offenbart, welches 10 bis 40 Gew. -% eines ethoxylierten und danach propoxylierten Alkylpolyalkylenglykol-Mischethers enthält. Als Beispiel wird auf S. 6 ein Mischether genannt, der im wesentlichen ein Gemisch aus C₁₂- und C₁₄-Alkoholen beinhaltet ("LS-Kokosalkohol"), welches folgende Kohlenstoffkettenlängenverteilung aufweist:
C₁₀ o bis 2 %
C₁₂ 70 bis 75 %
C₁₄ 24 bis 30 %
C₁₆ 0 bis 2 %
Aus der Zusammenfassung Chemical Abstracts 95, 82812 q (1981) (5) ist ein 80:20-Gemisch aus einem Polyether der Formel C₁₂/C₁₃-Alkyl-O(C₂H₄O)₆(C₃H₆O)₂H und einem Polyether der Formel C₁₂/C₁₃-Alkyl-O(C₂H₄O)₇(C₃H₆O)₂₀H als Bestandteil von Wasch- und Reinigungsmitteln bekannt.EP-A 254 208 (4) discloses a low-foam surfactant mixture which contains 10 to 40% by weight of an ethoxylated and then propoxylated alkyl polyalkylene glycol mixed ether. An example is given on page 6 of a mixed ether which essentially contains a mixture of C₁₂ and C₁₄ alcohols ("LS coconut alcohol"), which has the following carbon chain length distribution:
C₁₀ o to 2%
C₁₂ 70 to 75%
C₁₄ 24 to 30%
C₁₆ 0 to 2%
From the abstract Chemical Abstracts 95, 82812 q (1981) (5) is an 80:20 mixture of a polyether of the formula C₁₂ / C₁₃-alkyl-O (C₂H₄O) ₆ (C₃H₆O) ₂H and a polyether of the formula C₁₂ / C₁₃-alkyl-O (C₂H₄O) ₇ (C₃H₆O) ₂₀H known as a component of detergents and cleaning agents.

Die EP-A 343 503 (6) betrifft ein Tensidgemisch für den Einsatz in Spül- und Reinigungsmitteln, inbesondere in Klarspülmitteln für die maschinelle Geschirreinigung, mit verringerter Schaumbildung, welches als Komponenten längerkettige ethoxylierte und danach propoxylierte oder butoxylierte Alkohole enthält.EP-A 343 503 (6) relates to a surfactant mixture for use in detergents and cleaning agents, in particular in rinse aids for machine dishwashing, with reduced foaming, which contains longer-chain ethoxylated and then propoxylated or butoxylated alcohols as components.

In der EP-A 018 482 (7) werden biologisch abbaubare und schwach schäumende Tenside beschrieben, die durch Umsetzung eines längerkettigen Alkohols mit einem Alkylenoxid mit mindestens 3 C-Atomen und anschließende Ethoxylierung hergestellt worden sind.EP-A 018 482 (7) describes biodegradable and low-foaming surfactants which have been prepared by reacting a longer-chain alcohol with an alkylene oxide having at least 3 C atoms and subsequent ethoxylation.

In allen Dokumenten werden zuerst die Einzelkomponenten alkoxyliert und danach erst Mischungen mit anderen alkoxylierten Komponenten oder anderen Bestandteilen der Formulierungen vorgenommen.In all documents, the individual components are first alkoxylated and only then mixed with other alkoxylated components or other constituents of the formulations.

Tenside der genannten Art und auch Mischungen hieraus erweisen sich bei Verwendung in Reinigungsmitteln für maschinell ablaufende Reinigungsprozesse allerdings noch als verbesserungsbedürftig. Insbesondere das Schaumdämpfungsverhalten und die Dispergierbarkeit in Wasser sind noch nicht optimal.However, surfactants of the type mentioned and mixtures thereof also prove to be in need of improvement when used in cleaning agents for machine-based cleaning processes. In particular, the foam damping behavior and the dispersibility in water are not yet optimal.

Somit lag der vorliegenden Erfindung die Aufgabe zugrunde, den geschilderten Mängeln des Standes der Technik abzuhelfen.The present invention was therefore based on the object of remedying the deficiencies described in the prior art.

Demgemäß wurde das eingangs definierte Verfahren zur Herstellung einer Mischung aus alkoxylierten Alkoholen I, welches dadurch gekennzeichnet ist, daß man mindestens zwei Gemische von Alkoholen der allgemeinen Formel



        R-O-H



wobei ein Alkoholgemisch geradkettige oder verzweigte C₈-C₁₈-Alkylgruppen als Rest R und ein anderes Alkoholgemisch geradkettige oder verzweigte C₁₀-C₂₀-Alkylgruppen als Rest R trägt, die beiden Reste R sich aber in der durchschnittlichen Anzahl der C-Atome um mindestens 0,5 unterscheiden müssen und wobei beide Alkoholgemische im Gew.-Verhältnis von 10:90 bis 90:10 vorliegen, miteinander mischt und diese Mischung zuerst mit der entsprechenden Menge Ethylenoxid und danach mit der entsprechenden Menge Propylenoxid umsetzt, und die Verwendung einer solchen Mischung als schaumdämpfender Tensidzusatz in Reinigungsmitteln für maschinell ablaufende Reinigungsprozesse gefunden.Accordingly, the process defined at the outset for producing a mixture of alkoxylated alcohols I, which is characterized in that at least two mixtures of alcohols of the general formula



RAW



wherein an alcohol mixture contains straight-chain or branched C₈-C₁₈ alkyl groups as the radical R and another alcohol mixture contains straight-chain or branched C₁₀-C₂₀ alkyl groups as the radical R, but the two radicals R in the average number of carbon atoms by at least 0.5 must distinguish and where both alcohol mixtures are in a weight ratio of 10:90 to 90:10, mixes with each other and react this mixture first with the appropriate amount of ethylene oxide and then with the appropriate amount of propylene oxide, and the use of such a mixture as a foam-suppressing surfactant additive found in detergents for automated cleaning processes.

Als geradkettige oder verzweigte C₈-C₁₈- bzw. C₁₀-C₂₀-Alkylreste für R seien beispielsweise genannt: n-Octyl, 2-Ethylhexyl, n-Nonyl, iso-Nonyl, n-Decyl, iso-Decyl, n-Undecyl, n-Dodecyl, n-Tridecyl, iso-Tridecyl, n-Tetradecyl, n-Pentadecyl, n-Hexadecyl, n-Heptadecyl, n-Octadecyl und n-Eicosyl. Die Reste R sind vorzugsweise geradkettig oder nur in geringem Umfang verzweigt, d.h. sie enthalten maximal 3 Methyl- oder Ethylseitenketten.Examples of straight-chain or branched C₈-C₁₈ or C₁₀-C₂₀ alkyl radicals for R are: n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, n-undecyl, n -Dodecyl, n-tridecyl, iso-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-eicosyl. The radicals R are preferably straight-chain or only branched to a small extent, i.e. they contain a maximum of 3 methyl or ethyl side chains.

Je nach der Herkunft des bei der Synthese der Verbindungen I eingesetzten Alkanols handelt es sich bei R um Reste von natürlich vorkommenden Fettalkoholen oder vorzugsweise von synthetisch hergestellten Oxo- oder Ziegler-Alkoholen. Beispiele für gut einsetzbare nach der Oxosynthese hergestellte Alkohole sind C₉/C₁₁-, C₁₂/C₁₄-, C₁₃/C₁₅- und C₁₆/C₁₈-Alkanolgemische. Beispiele für gut einsetzbare nach der Ziegler-Synthese hergestellte Alkohole sind C₈/C₁₀-, C₁₀/C₁₂-, C₁₂/C₁₄-, C₁₂/C₁₆-und C₁₆/C₂₀-Alkanolgemische.Depending on the origin of the alkanol used in the synthesis of the compounds I, R is a residue of naturally occurring fatty alcohols or preferably of synthetically produced oxo or Ziegler alcohols. Examples of readily usable alcohols prepared by oxosynthesis are C₉ / C₁₁-, C₁₂ / C₁₄-, C₁₃ / C₁₅- and C₁₆ / C₁₈-alkanol mixtures. Examples of readily usable alcohols produced by the Ziegler synthesis are C₈ / C₁₀-, C₁₀ / C₁₂-, C₁₂ / C₁₄-, C₁₂ / C₁₆ and C₁₆ / C₂₀-alkanol mixtures.

Da die bei der Synthese der Verbindungen I eingesetzten Alkanole in der Regel statistische Homologen- und auch Isomerengemische darstellen, ist es zweckmäßig, von einer durchschnittlichen Anzahl der C-Atome zu sprechen. Dieser Durchschnittswert stellt üblicherweise das Häufigkeitsmaximum dar.Since the alkanols used in the synthesis of the compounds I generally represent statistical homologues and also isomer mixtures, it is expedient to speak of an average number of carbon atoms. This average value usually represents the maximum frequency.

Die alkoxylierten Alkohole I werden zweckmäßigerweise durch Ethoxylierung und anschließende Propoxylierung der genannten Alkanole in an sich bekannter Weise hergestellt. Diese Verfahren sind dem Fachmann bekannt und bedürfen keiner weiteren Erläuterung.The alkoxylated alcohols I are conveniently by Ethoxylation and subsequent propoxylation of the alkanols mentioned are prepared in a manner known per se. These methods are known to the person skilled in the art and require no further explanation.

Der Ethoxylierungsgrad x liegt bei 1 bis 12, vorzugsweise 2 bis 5, insbesondere 3 bis 4; der Propoxylierungsgrad beträgt 1 bis 15, vorzugsweise 2 bis 6, insbesondere 4 bis 6. Die Alkoxylierungsgrade x und y stellen in der Regel ebenfalls Durchschnittswerte dar.The degree of ethoxylation x is 1 to 12, preferably 2 to 5, in particular 3 to 4; the degree of propoxylation is 1 to 15, preferably 2 to 6, in particular 4 to 6. The degrees of alkoxylation x and y generally also represent average values.

Man verwendet eine Mischung aus mindestens zwei, vorzugsweise zwei oder drei, insbesondere zwei Gemischen von Alkoholen der Formel R-O-H, wobei zwei Reste R sich in der durchschnittlichen Anzahl der C-Atome um mindestens 0,5 unterscheiden müssen, und wobei die entsprechenden zwei Alkoholgemische im Verhältnis von 10:90 bis 90:10, vorzugsweise 25:75 bis 75:25, vorliegen. Besonders günstig ist ein Unterschied in der durchschnittlichen Anzahl der C-Atome der beiden Reste R von mindestens 1, insbesondere ein Unterschied von 1 bis 2.A mixture of at least two, preferably two or three, in particular two, mixtures of alcohols of the formula ROH is used, where two radicals R must differ by at least 0.5 in the average number of carbon atoms, and the corresponding two alcohol mixtures in Ratio from 10:90 to 90:10, preferably 25:75 to 75:25. A difference in the average number of C atoms of the two radicals R of at least 1, in particular a difference of 1 to 2, is particularly favorable.

Maschinell ablaufende Reinigungsprozesse finden sich hauptsächlich in der Metallindustrie, in der Lebensmittelindustrie, z.B. der Getränke-, Konserven-, Zuckerindustrie oder milch-, fleisch- und fettverarbeitenden Industrie, im Gaststättengewerbe und auch im Haushalt. So müssen häufig von Metallgegenständen nach ihrer Herstellung oder Verarbeitung Verunreinigungen und Rückstände, die von beispielsweise Zieh- und Walzfetten oder organischen Korrosionsschutzmitteln herrühren, entfernt werden. Alle Oberflächen von Behältnissen und Arbeitsgeräten, die bei der Herstellung und Weiterverarbeitung sowie beim Transport mit einem Lebensmittel in Berührung kommen, müssen in bestimmten Zeitabständen von Lebensmittelrückständen und sonstigen Verschmutzungen gereinigt werden. Ein typisches Beispiel für einen industriell durchgeführten maschinellen Reinigungsprozeß aus der Getränkeindustrie ist die Wäsche von gebrauchten Flaschen, die beispielsweise Bier, Milch, Erfrischungsgetränke oder Mineralwasser enthielten.Mechanical cleaning processes are mainly found in the metal industry, in the food industry, e.g. the beverage, canning, sugar industry or milk, meat and fat processing industry, in the catering trade and also in the household. For example, metal objects often have to be removed after their manufacture or processing soiling and residues, which originate from drawing and rolling greases or organic corrosion protection agents. All surfaces of containers and tools that come into contact with food during production, processing and transportation must be cleaned from food residues and other soiling at certain intervals. A typical example of an industrial machine cleaning process from the beverage industry is the washing of used bottles which, for example, contained beer, milk, soft drinks or mineral water.

Von besonderer Bedeutung ist die erfindungsgemäße Verwendung der bezeichneten Mischung aus alkoxylierten Alkoholen I bei der maschinellen Geschirreinigung im Haushalt, in Gaststättenbetrieben und in der Industrie. Hierbei werden die genannten Mischungen mit hervorragender Wirkung insbesondere als schaumdämpfende Tensidzusätze in Klarspülmitteln für die maschinelle Geschirreinigung eingesetzt.Of particular importance is the use according to the invention of the designated mixture of alkoxylated alcohols I in machine dishwashing in the home, in restaurants and in industry. Here, the mixtures mentioned are used with excellent action, in particular as foam-suppressing surfactant additives in rinse aids for machine dishwashing.

Nähere Angaben zur Technologie der maschinellen Geschirreinigung und zur Zusammensetzung von hierbei verwendeten Reinigungs- und Klarspülmitteln finden sich beispielsweise in Tenside Detergents Bd. 19 (1982), S. 123-126, (8) , oder in Ullmanns Encyklopädie der technischen Chemie, 4. Auflage, Bd. 20 (1981), S. 149-150, (9).Further information on the technology of machine dishwashing and the composition of detergents and rinse agents used here can be found, for example, in Tenside Detergents Vol. 19 (1982), pp. 123-126, (8), or in Ullmanns Encyklopadie der Technische Chemie, 4. Edition, Vol. 20 (1981), pp. 149-150, (9).

Demnach enthält ein hierbei gebräuchliches Klarspülmittel nichtionische Tenside, Hydrotrope (Solubilisatoren) wie Isopropanol, Ethanol und/oder Cumolsulfonat, Wasser und gegebenenfalls organische oder anorganische Säuren und Hilfsstoffe wie Farbstoffe und Konservierungsmittel.Accordingly, a rinse aid commonly used here contains nonionic surfactants, hydrotropes (solubilizers) such as isopropanol, ethanol and / or cumene sulfonate, water and, if appropriate, organic or inorganic acids and auxiliaries such as dyes and preservatives.

Gegenstand der vorliegenden Erfindung ist auch ein Verfahren zur Herstellung von Reinigungsmitteln für maschinell ablaufende Reinigungsprozesse, insbesondere von Klarspülmitteln für die maschinelle Geschirreinigung, welches dadurch gekennzeichnet ist, daß man diesen Mitteln als schaumdämpfenden Tensidzusatz eine Mischung aus alkoxylierten Alkoholen I zugibt.The present invention also relates to a process for the preparation of cleaning agents for machine-running cleaning processes, in particular rinse aids for machine dishwashing, which is characterized in that a mixture of alkoxylated alcohols I is added to these agents as a foam-suppressing surfactant additive.

Gegenstand der vorliegenden Erfindung sind weiterhin Reinigungsmittel für maschinell ablaufende Reinigungsprozesse, die eine Mischung aus alkoxylierten Alkoholen I als schaumdämpfenden Tensidzusatz in einer Menge von 0,1 bis 40 Gew.-%, vorzugsweise 0,5 bis 20 Gew.-%, bezogen auf die Gesamtmenge der Formulierung, enthalten.The present invention furthermore relates to cleaning agents for machine-operated cleaning processes which contain a mixture of alkoxylated alcohols I as a foam-suppressing surfactant additive in an amount of 0.1 to 40% by weight, preferably 0.5 to 20% by weight, based on the Total amount of formulation included.

Weiterhin sind Gegenstand der vorliegenden Erfindung Klarspülmittel für die maschinelle Geschirreinigung, die eine Mischung aus alkoxylierten Alkoholen I als schaumdämpfenden Tensidzusatz in einer Menge von 0,5 bis 30 Gew.-%, vorzugsweise 1 bis 15 Gew.-%, bezogen auf die Gesamtmenge der Formulierung, enthalten.The present invention furthermore relates to rinse aids for machine dishwashing, which comprise a mixture of alkoxylated alcohols I as a foam-suppressing surfactant additive in an amount of 0.5 to 30% by weight, preferably 1 to 15% by weight, based on the total amount of Wording.

Mit der erfindungsgemäß hergestellte Mischung aus alkoxylierten Alkoholen I erreicht man ein Optimum der gewünschten Eigenschaften bei der Reinigung der genannten harten Oberflächen, also beispielsweise von Metall oder Geschirr, nämlich gute Netzwirkung, streifenfreien Ablauf vom Spülgut, schaumdämpfende Wirkung bzw. Schaumarmut und gute Dispergierbarkeit in Wasser. Weiterhin ist von Vorteil, daß die bezeichnete Mischung der Verbindungen I biologisch gut abbaubar sind.The mixture of alkoxylated alcohols I prepared according to the invention achieves an optimum of the desired properties when cleaning the hard surfaces mentioned, for example of metal or dishes, namely good wetting action, streak-free drainage from the wash ware, foam-suppressing action or low-foaming action and good dispersibility in water . It is also advantageous that the mixture of compounds I described is readily biodegradable.

BeispieleExamples Beispiel 1example 1 Herstellung einer Mischung aus alkoxylierten OxoalkohlenProduction of a mixture of alkoxylated oxo alcohols

In einem Autoklaven wurden 100 g eines C₁₂/C₁₄-Oxoalkohols mit einer durchschnittlichen Anzahl der C-Atome von 13 (entsprechend 0,5 mol) und 107 g eines C₁₃/C₁₅-Oxoalkohols mit einer durchschnittlichen Anzahl der C-Atome von 14 (entsprechend 0,5 mol) zusammen mit 0,2 g Kalilumhydroxid als Alkoxylierungskatalysator vorgelegt. Bei 110 bis 120°C wurden kontinuierlich 154 g Ethylenoxid (entsprechend 3,5 mol) eingegast. Zur Vervollständigung der Umsetzung wurde 1 Stunde bei derselben Temperatur nachgerührt. Dann wurden bei 130 bis 140°C kontinuierlich 319 g Propylenoxid (entsprechend 5,5 mol) zugegeben. Anschließend ließ man 2 Stunden bei dieser Temperatur nachreagieren.In an autoclave, 100 g of a C₁₂ / C₁₄ oxo alcohol with an average number of C atoms of 13 (corresponding to 0.5 mol) and 107 g of a C₁₃ / C₁₅ oxo alcohol with an average number of C atoms of 14 (corresponding 0.5 mol) together with 0.2 g of potassium hydroxide as alkoxylation catalyst. At 110 to 120 ° C, 154 g of ethylene oxide (corresponding to 3.5 mol) were gassed continuously. To complete the reaction, the mixture was stirred at the same temperature for 1 hour. Then 319 g of propylene oxide (corresponding to 5.5 mol) were added continuously at 130 to 140 ° C. The mixture was then left to react for 2 hours at this temperature.

Es resultierten 680 g einer Mischung der alkoxylierten Oxoalkohole mit einer OH-Zahl von 83 und einem Trübungspunkt von 32°C, gemessen in Butyldiglykol gemäß DIN 53 917.The result was 680 g of a mixture of the alkoxylated oxo alcohols with an OH number of 83 and a cloud point of 32 ° C., measured in butyl diglycol in accordance with DIN 53 917.

Anwendungstechnische EigenschaftenApplication properties

Zur Messung der anwendungstechnischen Eigenschaften wurden Klarspülmittelformulierungen für die maschinelle Geschirreinigung im Haushalt hergestellt. Die nachfolgende Tabelle zeigt die Zusammensetzungen dieser Formulierungen.To measure the application properties, rinse aid formulations for machine dishwashing in the household were produced. The following table shows the compositions of these formulations.

Zur Charakterisierung der Formulierungen wurden der Trübungspunkt der Formulierungen, das Schaumdämpfungsverhalten in der Geschirrspülmaschine und die Dispergierbarkeit in heißem Wasser bestimmt.To characterize the formulations, the cloud point of the formulations, the foam-damping behavior in the dishwasher and the dispersibility in hot water were determined.

Der Trübungspunkt wurde gemäß DIN 53 917 bestimmt. Aus Praxisuntersuchungen weiß man, daß fallende Trübungspunkte, gleichbedeutend mit einer Zunahme der Hydrophobie, Verbesserungen im Schaumverhalten zur Folge haben, andererseits aber die Dispergierfähigkeit absenken, was zu einer ungleichmäßigen Verteilung des Klarspülers in der Spülflotte und damit zu einer Verschlechterung des Ablaufverhaltens (Flecken-, Streifen- und Schlierenbildung) führt. Bei Trübungspunkten < 40°C wird außerdem Instabilität, d.h. Phasentrennung, der Klarspülerformulierung beobachtet.The cloud point was determined in accordance with DIN 53 917. Practical studies have shown that falling cloud points, which means an increase in hydrophobicity, result in improvements in the foaming behavior, but on the other hand reduce the dispersibility, which leads to an uneven distribution of the rinse aid in the washing liquor and thus to a deterioration in the drainage behavior (stains, Streaking and streaking). At cloud points <40 ° C, instability, ie phase separation, of the rinse aid formulation is also observed.

Das Schaumdämpfungsverhalten wird in der Geschirrspülmaschine durch den sogenannten "Ei-Test" geprüft. Hierbei wird durch magnetische Induktionsmessung in einem handelsüblichen Haushalts-Geschirrspülautomaten mit Hilfe eines Zählwerks die Zahl der Umdrehungen eines Sprüharms bestimmt. Durch Schaumbildung, die besonders bei Anwesenheit von Proteinen (Eiweiß) auftritt, wird die Umdrehungszahl des Sprüharms vermindert. Die Umdrehungszahl stellt somit wegen der verringerten Rückstoßkraft ein Maß für die Tauglichkeit von Tensiden in Reinigungsgeräten mit hoher Mechanik dar. Die Testzeit beträgt 12 Minuten, wobei die durchschnittliche Umdrehungszahl pro Minute aus der Gesamtumdrehungszahl berechnet wird. Der Waschvorgang wird bei Raumtemperatur begonnen, nach etwa 10 Minuten beträgt die Temperatur des Spülwassers 60°C.The foam damping behavior is checked in the dishwasher by the so-called "egg test". Here, the number of revolutions of a spray arm is determined by magnetic induction measurement in a commercial household dishwasher with the help of a counter. Foam formation, which occurs particularly in the presence of proteins (protein), reduces the number of revolutions of the spray arm. Because of the reduced recoil force, the number of revolutions therefore represents a measure of the suitability of surfactants in cleaning devices with high mechanical properties. The test time is 12 minutes, the average number of revolutions per minute being calculated from the total number of revolutions. The washing process is started at room temperature, after about 10 minutes the temperature of the rinsing water is 60 ° C.

Zur Beurteilung der Dispergierbarkeit wird die Klarspülformulierung mittels einer Membranpumpe in ein Glasrohr, durch das 90°C heißes Leitungswasser strömt, eingedüst. Am Ende des Glasrohres wird die so erzeugte Dispersion durch eine zweite Düse in ein Becherglas gesprüht. Bei einer Laufzeit von ca. 3,5 Min. werden ca. 30 ml Klarspülformulierung in einen Wasserstrom von 2 Liter Wasser von 90°C eindosiert. Die Dispersion wird im Glasrohr und im Becherglas visuell beurteilt und benotet, wobei folgendes Benotungsschema zugrunde liegt:

  • Note 1: keine Dispersion, Produkt schwimmt auf (große Tropfen > 5 mm)
  • Note 2: beginnende Dispergierung im Glasrohr, im Becherglas kleinere Tropfen (2 bis 3 mm)
  • Note 3: mäßige Dispergierung im Glasrohr, im Becherglas mäßig dispergiert (feine Tröpfchen von ca. 1 mm)
  • Note 4: gute Dispergierung im Rohr, im Becherglas feine Dispersion (Tröpfchen < 0,5 mm)
  • Note 5: sehr feinteilige Dispersion im Glasrohr und im Becherglas.
To assess the dispersibility, the rinse aid formulation is injected into a glass tube through which tap water at 90 ° C flows through a membrane pump. At the end of the glass tube, the dispersion produced in this way is sprayed through a second nozzle into a beaker. With a running time of about 3.5 minutes, about 30 ml of rinse aid formulation are metered into a water stream of 2 liters of water at 90 ° C. The dispersion is visually assessed and graded in the glass tube and beaker, based on the following grading scheme:
  • Grade 1: no dispersion, product floats (large drops> 5 mm)
  • Grade 2: beginning dispersion in the glass tube, smaller drops in the beaker (2 to 3 mm)
  • Grade 3: moderate dispersion in the glass tube, moderately dispersed in the beaker (fine droplets of approx. 1 mm)
  • Grade 4: good dispersion in the tube, fine dispersion in a beaker (droplets <0.5 mm)
  • Note 5: very fine dispersion in the glass tube and in the beaker.

Die Ergebnisse der Messungen sind in der nachfolgenden Tabelle wiedergegeben.

Figure imgb0001
The results of the measurements are shown in the table below.
Figure imgb0001

Den obigen Beispielen ist zu entnehmen, daß bei Einsatz der erfindungsgemäß zu verwendenden Tensidzusätze (Beispiele 5 und 6) Klarspülformulierungen erhalten werden, die ein ausgezeichnetes Schaumdämpfungsverhalten mit einer ausgezeichneten Dispergierbarkeit verbinden, trotz eines manchmal sehr tiefen Trübungspunktes (Beispiel 5). Häufig führt die Absenkung des Trübungspunktes durch Zusatz eines hydrophoben Tensids zwar zu einer Verbesserung der Schaumdämpfung, gleichzeitig aber zum Verlust der dispergierenden Eigenschaften. Durch Zusatz von Solubilisatoren wird üblicherweise der Trübungspunkt wieder angehoben und damit die Dispergierfähigkeit verbessert. Beispiel 5 zeigt, daß durch Zusatz der bezeichneten Mischungen aus Verbindungen I auf Solubilisatoren zur Anhebung des Trübungspunktes ganz oder zumindest teilweise verzichtet werden kann.The examples above show that when using the surfactant additives to be used according to the invention (Examples 5 and 6), rinse aid formulations are obtained which combine excellent foam-damping behavior with excellent dispersibility, despite a sometimes very low cloud point (Example 5). Lowering the cloud point by adding a hydrophobic surfactant often leads to an improvement in foam damping, but at the same time to a loss of dispersing properties. The cloud point is usually raised again by the addition of solubilizers and thus the dispersibility is improved. Example 5 shows that by adding the specified mixtures of compounds I to solubilizers to raise the cloud point completely or at least partially.

Die Vergleichsbeispiele 2, 3, 4 und 7 zeigen, wie durch Zusatz bzw. Mischung bekannter Mittel des Standes der Technik die Schaumdämpfung zwar etwas verbessert, die Dispergierfähigkeit aber durch Absenkung des Trübungspunktes verschlechtert wird.Comparative Examples 2, 3, 4 and 7 show how although the foam damping is somewhat improved by adding or mixing known means of the prior art, the dispersibility is impaired by lowering the cloud point.

Claims (10)

  1. A process for preparing a mixture of alkoxylated alcohols of the general formula I



            R-O-(C₂H₄O)x-(C₃H₆O)y-H   (I)



    where
    x   is an average degree of ethoxylation of from 1 to 12 and
    y   is an average degree of propoxylation of from 1 to 15,
    which comprises mixing at least two mixtures of alcohols of the general formula



            R-O-H



    where one alcohol mixture carries straight-chain or branched C₈-C₁₈-alkyl groups as the radical R and one other alcohol mixture carries straight-chain or branched C₁₀-C₂₀-alkyl groups as the radical R, subject to the proviso that the two radicals R differ by at least 0.5 in the average number of carbon atoms, and the two alcohol mixtures are present in a weight ratio of from 10:90 to 90:10, with one another and reacting this mixture first with the corresponding amount of ethylene oxide and then with the corresponding amount of propylene oxide.
  2. A process for preparing a mixture of alkoxylated alcohols I as claimed in claim 1, wherein the amounts of ethylene oxide and propylene oxide are chosen in such a way that the products I have an average degree of ethoxylation x of from 2 to 5 and an average degree of propoxylation y of from 2 to 6.
  3. A process for preparing a mixture of alkoxylated alcohols I as claimed in claim 1 or 2, wherein the mixtures used of alcohols of the general formula



            R-O-H



    are mixtures from the group of the C₉/C₁₁ oxo alcohols, C₁₂/C₁₄ oxo alcohols, C₁₃/C₁₅ oxo alcohols, C₁₆/C₁₈ oxo alcohols, C₈/C₁₀ Ziegler alcohols, C₁₀/C₁₂ Ziegler alcohols, C₁₂/C₁₄ Ziegler alcohols, C₁₂/C₁₆ Ziegler alcohols and C₁₆/C₂₀ Ziegler alcohols.
  4. A process for preparing a mixture of alkoxylated alcohols I as claimed in any of claims 1 to 3, wherein the mixture used of alcohols of the general formula



            R-O-H



    is a mixture of a C₁₂/C₁₄ oxo alcohol and a C₁₃/C₁₅ oxo alcohol.
  5. The use of a mixture of alkoxylated alcohols I as prepared in any of claims 1 to 4 as a foam-suppressing surfactant additament in cleaning compositions for mechanized cleaning processes.
  6. The use of a mixture of alkoxylated alcohols I as prepared in any of claims 1 to 4 as a foam-suppressing surfactant additament for final rinse compositions for mechanized dishwashing.
  7. A process for preparing cleaning compositions for mechanized cleaning processes, which comprises incorporating in these compositions a foam-suppressing surfactant additament comprising a mixture of alkoxylated alcohols I as set forth in any of claims 1 to 4.
  8. A process for preparing final rinse compositions for mechanized dishwashing, which comprises incorporating in these compositions a foam-suppressing surfactant additament comprising a mixture of alkoxylated alcohols I as set forth in any of claims 1 to 4.
  9. A cleaning composition for mechanized cleaning processes comprising a mixture of alkoxylated alcohols I as set forth in any of claims 1 to 4 as a foam-suppressing surfactant additament in an amount of from 0.1 to 40% by weight, based on the total amount of the formulation.
  10. A final rinse composition for mechanized dishwashing comprising a mixture of alkoxylated alcohols I as set forth in any of claims 1 to 4 as a foam-suppressing surfactant additament in an amount of from 0.5 to 30% by weight, based on the total amount of the formulation.
EP92904485A 1991-02-22 1992-02-11 Method for manufacturing a mixture of alkoxylated alcohols and its use as antifoam tenside additive in cleaning products for mechanical washing processes Expired - Lifetime EP0572453B1 (en)

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DK0572453T3 (en) 1995-09-18
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US5536884A (en) 1996-07-16
WO1992014808A1 (en) 1992-09-03
JPH06505044A (en) 1994-06-09
ATE127150T1 (en) 1995-09-15
EP0572453A1 (en) 1993-12-08
CA2104468A1 (en) 1992-08-23

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