EP0489768B1 - Anti-foaming agents for machine-washing of crockery and bottles - Google Patents
Anti-foaming agents for machine-washing of crockery and bottles Download PDFInfo
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- EP0489768B1 EP0489768B1 EP90912439A EP90912439A EP0489768B1 EP 0489768 B1 EP0489768 B1 EP 0489768B1 EP 90912439 A EP90912439 A EP 90912439A EP 90912439 A EP90912439 A EP 90912439A EP 0489768 B1 EP0489768 B1 EP 0489768B1
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- European Patent Office
- Prior art keywords
- general formula
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- decanol
- hexyl
- mole
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D1/72—Ethers of polyoxyalkylene glycols
- C11D1/721—End blocked ethers
-
- 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 novel, selected active substance mixtures of alkali-resistant polyalkylene glycol ether compounds which, in the case of their own surfactant action, are distinguished in particular by pronounced foam-suppressing properties when formulated with other known components of foam-like cleaning agents, and their use for machine dishwashing and bottle cleaning in the home and business.
- nonionic surfactants based on polyoxyalkylated alkylphenols and / or fatty alcohols for cleaning hard surfaces is known.
- the high foaming power of these compounds has an unfavorable effect.
- DE-OS 25 56 544 describes cleaning agents, in particular machine dishwashing detergents, which also use end-capped non-ionogenic polyalkylene glycol ether compounds, the class of compounds highlighted there being derived from polyoxyalkylated alcohols having 6 to 22 carbon atoms in the straight-chain or branched alkyl or alkylene radical and are characterized in that they are end-capped with a tert-butyl ether group.
- Compounds of this type are said to be able to be used as foam dampers for nonionic and cationic compounds.
- EP 254 208 A2 describes a special low-foam or foam-suppressing surfactant mixture composed of 20-80% by weight of polyethylene glycol ethers of the general formula R1-O- (CH2CH2O) n -R2, in which R1 is a straight-chain or branched alkyl radical or alkenyl radical with 8 - 18 carbon atoms, R2 is an alkyl radical with 4 to 8 carbon atoms and n is a number from 3 to 7, 10 to 40 wt .-% alkyl polyalkylene glycol mixed ether of the general formula R3-O- (CH2CH2O) x - (CH2-CH (CH3) O) y -H, in which R3 is a straight-chain or branched alkyl radical having 8 to 18 carbon atoms, x is a number from 1 to 3 and y is a number of 3 to 6, and 0 to 40% by weight of alkyl (poly) propylene glycol ether of the
- EP 124 815 A3 the use of polyglycol ethers of the formula R1-O- (CH2CH2O) n -R2, in which R1 is a straight-chain or branched alkyl or alkenyl radical with 8 to 18 carbon atoms, R2 is an alkyl radical with 4 to 8 carbon atoms and n is a number from 7 to 12, recommended as foam-suppressing additives for low-foam cleaning agents.
- Such compounds can optionally also be part of the active ingredient combination according to the invention.
- EP 326 795 A2 the use of polyethylene glycol ether of the general formula (I) R1O- (CH2CH2O) n -R2, in which R1 is a straight-chain or branched alkyl or alkenyl radical having 20 to 28 C atoms, R2 is an alkyl radical having 4 up to 8 carbon atoms and n are a number from 6 to 20, described as foam-suppressing additives for low-foam cleaning agents. These compounds are very effective, but sometimes insoluble.
- the teaching of the present invention is based on the object of enabling further improvements of such cleaning and / or rinsing agents for hard surfaces, in particular for the mechanical cleaning of glass, dishes, bottles and the like.
- the invention intends to provide mixtures of substances which, on the one hand, are themselves surfactant-like, but in particular are suitable for use as strongly foam-suppressing additives in low-foam alkali-resistant detergent mixtures of the type concerned here.
- the active substance combinations according to the invention should be able to be used in particular in combination with other customary nonionic, cationic or anionic surface-active substances, builders and other additives or auxiliaries in the dishwashing and cleaning agent formulations of the subject area concerned.
- An essential component for the active ingredient mixtures of the invention are the mixed ethers of the general formula (III) which, as a rule, can even make up the main part of the active ingredient mixture described according to the invention and used for the stated purpose.
- These components known per se are substantially improved by the addition of the active ingredient components to (1) and (2) provided according to the invention. This improvement affects both the ability to inhibit or limit foam and that Formulation of the active ingredient mixture into clearly soluble aqueous concentrates.
- the invention provides for the mixture components of the general formula (I) to (1) on the one hand and the mixture components of the general formula (II) to (2) on the other hand in combination with one another together with the compounds of the general formula (III) - mixture component to ( 3) - and the mixture components (4) additionally used if desired.
- these mixture components to (1) and (2) can produce effective effects in the sense of the desired improvements.
- up to about 20% by weight based on the total mixture of the active compounds according to the invention, of the components to (1) and (2) or even with amounts of up to about 10% by weight of these additives according to the invention, a significant reduction foam formation on the one hand and improvement of the aqueous formulability of the active ingredients on the other hand can be achieved.
- alcohols of this type are formed by the condensation of fatty alcohols with a lower carbon number in the presence of alkali, e.g. As potassium hydroxide or potassium alcoholate. The reaction takes place, for example, at temperatures from 200 to 300 ° C. and leads to branched Guerbet alcohols which have branching in the 2-position to the hydroxyl group.
- alkali e.g. As potassium hydroxide or potassium alcoholate.
- the reaction takes place, for example, at temperatures from 200 to 300 ° C. and leads to branched Guerbet alcohols which have branching in the 2-position to the hydroxyl group.
- the invention predominantly or preferably exclusively uses straight-chain fatty alcohols for the preparation of the 2-branched Guerbet alcohols and ultimately for the synthesis of the compounds of the general formula (I).
- Fatty alcohols of natural origin are known to have at least largely predominantly even chain lengths, so that their 2-branched Guerbet alcohol with 18 C atoms cannot be obtained as a uniform condensation product of only one selected fatty alcohol via their dimerization.
- the necessary dimerization of a mixture of the two fatty alcohols with 8 and 10 C atoms leads to the isomer mixture of the 18 C Guerbet alcohol from 2-hexyldodecanol-1 and 2-octyldecanol-1.
- the condensation products of the two alcohols used arise with themselves, i. that is, the 2-hexyldecanol-1 from the octanol used and the 2-octyldodecanol-1 from the decanol used.
- Analogous considerations apply to Guerbet alcohol with 14 carbon atoms.
- the end group-capped fatty alcohol polyglycol ethers of the formula (I) are prepared in accordance with the specifications of DE-OS 33 15 951.
- the fatty alcohols of higher carbon number described above are advantageously reacted with ethylene oxide in a molar ratio of 1: 5 to 1: 9 and then etherified the hydroxyl groups present in the reaction product obtained.
- the reaction with ethylene oxide takes place under the known acoxylation conditions, preferably in the presence of suitable alkaline catalysts.
- the etherification of the free hydroxyl groups is preferably carried out under the known conditions of Williamson's ether synthesis using straight-chain or branched C4- to C8-alkyl halides.
- n-butyl radical for the radical R2 from the general formula (I) is of particular importance in the course of the inventive action.
- examples of such a final etherification are accordingly n-butyl halides such as n-butyl chloride.
- the invention is not limited to this. Further examples are amyl halides, hexyl halides and the higher alkyl halides in the range mentioned. It may be expedient to use alkyl halide and alkali in a stoichiometric excess, for example from 10 to 50%, over the hydroxyl groups to be etherified.
- the compounds of the general formula (II) which are not end-capped are prepared in a manner known per se by reacting the selected Guerbet alcohols with ethylene oxide in a molar ratio of 1: 2 to 1: 5.
- the compounds of the general formula (III) - mixture components to (3) - are obtained in a manner known per se - by reacting the selected linear or branched alkanols ROH with ethylene oxide and propylene oxide - in particular 1,2-propylene oxide - in the stated molar ratios.
- the preparation of the if necessary the mixture components of the general formula (IV) used are analogous to the information on the preparation of the end group-sealed mixture components of the general formula (I).
- the active compound mixtures according to the invention are suitable both as a foam-suppressing additive to typical cleaning agent mixtures, in particular low-foam mixtures of the type mentioned, in order to further reduce their tendency to foam, and also for the formulation of rinse aids.
- low-foam surfactants can be used in a manner known per se, the foam formation of which is further suppressed by the active ingredient systems according to the invention.
- the content of the active ingredient mixtures of (1) to (4) in the detergents and cleaning agents can vary within wide limits. It is essential that the polyglycol ether mixtures give effective effects even in low concentrations. In a preferred embodiment, they are added to the cleaning agents in such amounts that their concentration in the ready-to-use solutions is approximately in the range from 50 to 500 ppm. However, the invention is not restricted to this; in particular, far higher amounts of the active compound mixtures according to the invention can be used.
- a whisked whole egg yolk and egg white
- this liquid is heated to 60 o C in a double-walled 2000 ml measuring cylinder.
- this solution is sucked from the bottom of the measuring cylinder with a glass tube.
- the liquid is returned to the measuring cylinder via a second tube, the lower end of which ends at the height of the upper edge of the measuring cylinder.
- the liquid is at a circulation rate of 4 l / min. pumped over and falls back into the measuring cylinder. By pumping around this liquid can be foamed up to 2000 ml.
- the examined products are the following:
- Product B has a better anti-foaming effect than products A, C and D.
Abstract
Description
Die Erfindung betrifft neuartige ausgewählte Wirkstoffgemische von Alkali-resistenten Polyalkylenglykolether-Verbindungen, die bei eigener Tensidwirkung sich insbesondere durch ausgeprägte schaumdrückende Eigenschaften bei der Formulierung mit weiteren bekannten Komponenten schaumartiger Reinigungsmittel auszeichnen sowie ihre Verwendung für die maschinelle Geschirr- und Flaschenreinigung in Haushalt und Gewerbe.The invention relates to novel, selected active substance mixtures of alkali-resistant polyalkylene glycol ether compounds which, in the case of their own surfactant action, are distinguished in particular by pronounced foam-suppressing properties when formulated with other known components of foam-like cleaning agents, and their use for machine dishwashing and bottle cleaning in the home and business.
Die Verwendung nichtionogener Tenside auf Basis polyoxyalkylierter Alkylphenole und/oder Fettalkohole für die Reinigung harter Oberflächen ist bekannt. Bei vielen Anwendungsgebieten, beispielsweise bei ihrer Verwendung als Bestandteil in Geschirrspülmaschinen wirkt sich jedoch das starke Schaumvermögen dieser Verbindungen ungünstig aus.The use of nonionic surfactants based on polyoxyalkylated alkylphenols and / or fatty alcohols for cleaning hard surfaces is known. In many areas of application, for example when used as a component in dishwashers, however, the high foaming power of these compounds has an unfavorable effect.
Es besteht eine ganze Reihe von Vorschlägen, die unerwünschte starke Schaumneigung solcher Reinigungsmittel durch Mitverwendung geeigneter Mischungskomponenten zu dämpfen. Bekannt ist beispielsweise die Verwendung bzw. Mitverwendung von Blockpolymerisaten aus Polypropylenglykol und Ethylenoxid und anderen Schaumdämpfungssystemen. Eine besondere Schwierigkeit für das Gebiet der maschinellen Oberflächenreinigung mit solchen Systemen liegt in der häufig gegebenen Alkali-Instabilität der eingesetzten Hilfsstoffe. Es ist bekannt, daß beispielsweise maschinelle Geschirrreinigungsmittel hoch alkalische Systeme mit beträchtlichen Gehalten von Alkalihydroxiden, Alkalisilikaten und/oder Alkaliphosphaten sind.There are a number of proposals to dampen the undesirable high foaming tendency of such cleaning agents by using suitable mixture components. For example, the use or concomitant use of block polymers of polypropylene glycol and ethylene oxide and other foam damping systems is known. A particular difficulty in the field of mechanical surface cleaning with such systems is the frequently present alkali instability of the auxiliaries used. It is known that, for example, machine dishwashing detergents are highly alkaline systems with considerable contents of alkali hydroxides, alkali silicates and / or alkali phosphates.
In der DE-OS 25 56 544 sind Reinigungsmittel, insbesondere Maschinengeschirrspülmittel beschrieben, die Endgruppen-verschlossene nichtionogene Polyalkylenglykolether-Verbindungen mitverwenden, wobei die dort herausgestellte Verbindungsklasse sich von polyoxyalkylierten Alkoholen mit 6 bis 22 C-Atomen im geradkettigen oder verzweigten Alkyl- oder Alkylenrest ableiten und dadurch gekennzeichnet sind, daß sie mit einer tert.-Butylethergruppierung Endgruppen-verschlossen sind. Verbindungen dieser Art sollen als Schaumdämpfer für nichtionogene und kationaktive Verbindungen eingesetzt werden können.DE-OS 25 56 544 describes cleaning agents, in particular machine dishwashing detergents, which also use end-capped non-ionogenic polyalkylene glycol ether compounds, the class of compounds highlighted there being derived from polyoxyalkylated alcohols having 6 to 22 carbon atoms in the straight-chain or branched alkyl or alkylene radical and are characterized in that they are end-capped with a tert-butyl ether group. Compounds of this type are said to be able to be used as foam dampers for nonionic and cationic compounds.
In der EP 254 208 A2 wird ein spezielles schaumarmes bzw. schaumdämpfendes Tensidgemisch aus 20 - 80 Gew.-% an Polyethylenglykolethern der allgemeinen Formel R₁-O-(CH₂CH₂O)n-R₂, in der R₁ einen geradkettigen oder verzweigten Alkylrest oder Alkenylrest mit 8 - 18 C-Atomen, R₂ einen Alkylrest mit 4 bis 8 C-Atomen und n eine Zahl von 3 bis 7 bedeuten, 10 bis 40 Gew.-% Alkylpolyalkylenglykol-Mischether der allgemeinen Formel
R₃-O-(CH₂CH₂O)x-(CH₂-CH(CH₃)O)y-H, in der R₃ einen geradkettigen oder verzweigten Alkylrest mit 8 bis 18 C-Atomen, x eine Zahl von 1 bis 3 und y eine Zahl von 3 bis 6 bedeuten, sowie 0 bis 40 Gew.-% Alkyl-(poly)-propylenglykolether der allgemeinen Formel R₄-O-(CH₂CH(CH₃)O)z-H, in der R₄ einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest mit 16 bis 22 C-Atomen und z eine Zahl von 1 bis 3 bedeuten, beschrieben.EP 254 208 A2 describes a special low-foam or foam-suppressing surfactant mixture composed of 20-80% by weight of polyethylene glycol ethers of the general formula R₁-O- (CH₂CH₂O) n -R₂, in which R₁ is a straight-chain or branched alkyl radical or alkenyl radical with 8 - 18 carbon atoms, R₂ is an alkyl radical with 4 to 8 carbon atoms and n is a number from 3 to 7, 10 to 40 wt .-% alkyl polyalkylene glycol mixed ether of the general formula
R₃-O- (CH₂CH₂O) x - (CH₂-CH (CH₃) O) y -H, in which R₃ is a straight-chain or branched alkyl radical having 8 to 18 carbon atoms, x is a number from 1 to 3 and y is a number of 3 to 6, and 0 to 40% by weight of alkyl (poly) propylene glycol ether of the general formula R₄-O- (CH₂CH (CH₃) O) z -H, in which R₄ is a straight-chain or branched alkyl or alkenyl radical 16 to 22 carbon atoms and z represent a number from 1 to 3.
In der EP 124 815 A3 wird die Verwendung von Polyglykolethern der Formel R¹-O-(CH₂CH₂O)n-R², in der R¹ einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest mit 8 bis 18 Kohlenstoffatomen, R² einen Alkylrest mit 4 bis 8 Kohlenstoffatomen und n eine Zahl von 7 bis 12 bedeutet, als schaumdrückende Zusätze für schaumarme Reinigungsmittel empfohlen. Derartige Verbindungen können gegebenenfalls auch Bestandteil der erfindungsgemäßen Wirkstoffkombination sein.In EP 124 815 A3 the use of polyglycol ethers of the formula R¹-O- (CH₂CH₂O) n -R², in which R¹ is a straight-chain or branched alkyl or alkenyl radical with 8 to 18 carbon atoms, R² is an alkyl radical with 4 to 8 carbon atoms and n is a number from 7 to 12, recommended as foam-suppressing additives for low-foam cleaning agents. Such compounds can optionally also be part of the active ingredient combination according to the invention.
In der EP 326 795 A2 wird die Verwendung von Polyethylenglykolether der allgemeinen Formel (I) R₁O-(CH₂CH₂O)n-R₂, in der R₁ einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest mit 20 bis 28 C-Atomen, R₂ einen Alkylrest mit 4 bis 8 C-Atomen und n eine Zahl von 6 bis 20 bedeuten, als schaumdrückende Zusätze für schaumarme Reinigungsmittel beschrieben. Diese Verbindungen sind sehr wirksam, aber teilweise unlöslich.In EP 326 795 A2 the use of polyethylene glycol ether of the general formula (I) R₁O- (CH₂CH₂O) n -R₂, in which R₁ is a straight-chain or branched alkyl or alkenyl radical having 20 to 28 C atoms, R₂ is an alkyl radical having 4 up to 8 carbon atoms and n are a number from 6 to 20, described as foam-suppressing additives for low-foam cleaning agents. These compounds are very effective, but sometimes insoluble.
Die Verwendung von ethoxylierten Guerbetalkoholen ist im Stand der Technik nicht erwähnt.The use of ethoxylated Guerbet alcohols is not mentioned in the prior art.
Die Lehre der vorliegenden Erfindung geht von der Aufgabe aus, weitere Verbesserungen solcher Reinigungs- und/oder Spülmittel für harte Oberflächen, insbesondere zur maschinellen Reinigung von Glas, Geschirr, Flaschen und dergleichen zu ermöglichen. Die Erfindung will dabei insbesondere Stoffmischungen zur Verfügung stellen, die sowohl einerseits selber Tensidcharakter besitzen, insbesondere aber geeignet sind, als stark schaumdämpfende Zusatzstoffe in schaumarmen Alkali-resistenten Reinigungsmittelmischungen der hier betroffenen Art Verwendung zu finden. Angesprochen ist dabei sowohl der Bereich der festen und/oder flüssigen Reinigungsmittel der hier genannten Art wie auch der Bereich der sogenannten Klarspüler, die bekanntlich in einem abschließenden Verfahrensschritt vor der Trocknung des gereinigten Gutes zum Einsatz kommen. Die erfindungsgemäßen Wirkstoffkombinationen sollen insbesondere in Kombination mit anderen üblichen nichtionischen, kationischen oder anionischen oberflächenaktiven Substanzen, Gerüstsubstanzen und anderen Zusatz- oder Hilfsstoffen in den Spül- und Reinigungsmittelformulierungen des hier betroffenen Sachgebietes verwendet werden können.The teaching of the present invention is based on the object of enabling further improvements of such cleaning and / or rinsing agents for hard surfaces, in particular for the mechanical cleaning of glass, dishes, bottles and the like. In particular, the invention intends to provide mixtures of substances which, on the one hand, are themselves surfactant-like, but in particular are suitable for use as strongly foam-suppressing additives in low-foam alkali-resistant detergent mixtures of the type concerned here. This addresses both the area of solid and / or liquid cleaning agents of the type mentioned here and the area of so-called rinse aids, which are known to be used in a final process step before the cleaned items are dried. The active substance combinations according to the invention should be able to be used in particular in combination with other customary nonionic, cationic or anionic surface-active substances, builders and other additives or auxiliaries in the dishwashing and cleaning agent formulations of the subject area concerned.
Die Lehre der Erfindung geht von der Feststellung aus, daß die im nachfolgenden angegebenen bestimmt ausgewählten Wirkstoffgemische das komplexe Anforderungsprofil erfüllen. Wirkstoffgemische der erfindungsgemäßen Art zeichnen sich dazu noch durch eine verbesserte Formulierbarkeit in Flüssigsystemen aus, so daß hier für die gewerbliche Verwertung zusätzliche Erleichterungen geschaffen werden.The teaching of the invention is based on the finding that those specified below are definitely selected Mixtures of active ingredients meet the complex requirement profile. Mixtures of active substances of the type according to the invention are also notable for improved formulability in liquid systems, so that additional relief is provided here for commercial use.
Gegenstand der Erfindung ist dementsprechend die Verwendung ausgewählter Mischungen von Alkali-resistenten Polyalkylenglykolether-Verbindungen mit Tensidcharakter und schaumdrückender Wirkung für die maschinelle Geschirr- und Flaschenreinigung in Haushalt und Gewerbe, wobei das Kennzeichen der Erfindung darin liegt, daß Wirkstoffkombinationen der folgenden Komponenten eingesetzt werden - Gew.-% jeweils bezogen auf Wirkstoffkombination:
- 1. bis zu 40 Gew.-% Endgruppen-verschlossener Polyethylenglykolether der allgemeinen Formel (I)
R₁O-(CH₂CH₂O)n-R₂ (I)
in der sich der Rest R₁O- von Guerbetalkoholen mit 16 bis 20 C-Atomen ableitet, der Rest R₂ einen Alkylrest mit 4 bis 8 C-Atomen und n eine Zahl von 5 bis 9 bedeuten
- 2. bis zu 40 Gew.-% nicht Endgruppen-verschlossener Polyethylenglykolether-Verbindungen der allgemeinen Formel (II)
R₅O-(CH₂CH₂O)z-H (II)
in der sich der Rest R₅O- von Guerbetalkoholen mit 12 bis 20 C-Atomen ableitet und z eine Zahl von 2 bis 5 ist
- 3. 20 bis 98 Gew.-% an Mischethern der allgemeinen Formel (III)
R₆O-(EO)u-(PO)v-H (III)
in der R₆O- den Rest eines linearen oder verzweigten Alkanols mit 8 bis 18 C-Atomen, EO den Rest des Ethylenglykols, PO den Rest des Propylenglykols, u eine Zahl von 2 bis 6 und v eine Zahl von 3 bis 7 bedeuten
- 4. Endgruppen-verschlossener Polyethylenglykolether der allgemeinen Formel (IV)
R₃O-(CH₂CH₂O)m-R₄ (IV)
in der R₃ einen linearen Alkylrest mit 8 bis 18 C-Atomen oder einen verzweigten Alkylrest mit 8 bis 14 C-Atomen, R₄ einen Alkylrest mit 4 bis 10 C-Atomen und m eine Zahl von 5 bis 15 bedeuten.
- 1. up to 40% by weight end-capped polyethylene glycol ether of the general formula (I)
R₁O- (CH₂CH₂O) n -R₂ (I)
in which the radical R₁O is derived from Guerbet alcohols with 16 to 20 C atoms, the radical R₂ is an alkyl radical with 4 to 8 C atoms and n is a number from 5 to 9
- 2. up to 40% by weight of non-end-capped polyethylene glycol ether compounds of the general formula (II)
R₅O- (CH₂CH₂O) z -H (II)
in which the rest R₅O- is derived from Guerbet alcohols with 12 to 20 carbon atoms and z is a number from 2 to 5
- 3. 20 to 98% by weight of mixed ethers of the general formula (III)
R₆O- (EO) u - (PO) v -H (III)
in the R₆O- the residue of a linear or branched alkanol with 8 to 18 carbon atoms, EO the rest of the ethylene glycol, PO the rest of the propylene glycol, u is a number from 2 to 6 and v is a number from 3 to 7
- 4. End group-capped polyethylene glycol ether of the general formula (IV)
R₃O- (CH₂CH₂O) m -R₄ (IV)
in which R₃ is a linear alkyl radical having 8 to 18 carbon atoms or a branched alkyl radical having 8 to 14 carbon atoms, R₄ is an alkyl radical having 4 to 10 carbon atoms and m is a number from 5 to 15.
Es kann erfindungsgemäß bevorzugt sein, die Wirkstoffkomponenten zu (1) bis (4) in den folgenden Mischungsverhältnissen einzusetzen:
- 1) bis zu 30 Gew.-% an Verbindungen der allgemeinen Formel (I)
- 2) bis zu 40 Gew.-% an Verbindungen der allgemeinen Formel (II)
- 3) 40 bis 95 Gew.-% an Verbindungen der allgemeinen Formel (III)
- 4) 0 bis 50 Gew.-% an Verbindungen der allgemeinen Formel (IV).
- 1) up to 30% by weight of compounds of the general formula (I)
- 2) up to 40% by weight of compounds of the general formula (II)
- 3) 40 to 95% by weight of compounds of the general formula (III)
- 4) 0 to 50% by weight of compounds of the general formula (IV).
Eine wesentliche Komponente für die Wirkstoffgemische der Erfindung sind die Mischether der allgemeinen Formel (III), die in der Regel sogar den Hauptanteil des erfindungsgemäß beschriebenen und zum angegebenen Zweck eingesetzten Wirkstoffgemisches ausmachen können. Diese an sich vorbekannten Komponenten werden durch den erfindungsgemäß vorgesehenen Zusatz der Wirkstoffkomponenten zu (1) und (2) substantiell verbessert. Diese Verbesserung betrifft dabei sowohl die Fähigkeit der Schauminhibierung bzw. -begrenzung als auch die Formulierbarkeit des Wirkstoffgemisches zu klar löslichen wäßrigen Konzentraten.An essential component for the active ingredient mixtures of the invention are the mixed ethers of the general formula (III) which, as a rule, can even make up the main part of the active ingredient mixture described according to the invention and used for the stated purpose. These components known per se are substantially improved by the addition of the active ingredient components to (1) and (2) provided according to the invention. This improvement affects both the ability to inhibit or limit foam and that Formulation of the active ingredient mixture into clearly soluble aqueous concentrates.
Die Erfindung sieht dabei vor, die Mischungskomponenten der allgemeinen Formel (I) zu (1) einerseits sowie die Mischungskomponenten der allgemeinen Formel (II) zu (2) andererseits in Kombination miteinander zusammen mit den Verbindungen der allgemeinen Formel (III) - Mischungskomponente zu (3) - und den gewünschtenfalls zusätzlich eingesetzten Mischungskomponenten (4) einzusetzen. Zusätzlich gilt, daß schon vergleichsweise geringe Mengen dieser Mischungskomponenten zu (1) und (2) wirkungsvolle Effekte im Sinne der angestrebten Verbesserungen bewirken können. So kann mit dem Zusatz bis zu etwa 20 Gew.-% - bezogen auf Gesamtgemisch der erfindungsgemäßen Wirkstoffe - der Komponenten zu (1) und (2) oder gar schon mit Mengen bis zu etwa 10 Gew.-% dieser erfindungsgemäßen Zusatzstoffe eine deutliche Verringerung der Schaumbildung einerseits sowie Verbesserung der wäßrigen Formulierbarkeit der Wirkstoffe andererseits erzielt werden.The invention provides for the mixture components of the general formula (I) to (1) on the one hand and the mixture components of the general formula (II) to (2) on the other hand in combination with one another together with the compounds of the general formula (III) - mixture component to ( 3) - and the mixture components (4) additionally used if desired. In addition, even comparatively small amounts of these mixture components to (1) and (2) can produce effective effects in the sense of the desired improvements. Thus, with the addition of up to about 20% by weight, based on the total mixture of the active compounds according to the invention, of the components to (1) and (2) or even with amounts of up to about 10% by weight of these additives according to the invention, a significant reduction foam formation on the one hand and improvement of the aqueous formulability of the active ingredients on the other hand can be achieved.
Im einzelnen gilt zu den erfindungsgemäß vorgesehenen Mischungskomponenten zu (1) und (2) das folgende:The following applies in detail to the mixture components for (1) and (2) provided according to the invention:
undand
Als besonders wirkungsvoll haben sich solche Vertreter dieser beiden Klassen erwiesen, die sich von verzweigten Alkanolen von der Art der Guerbet-Alkohole ableiten. Alkohole dieser Art entstehen bekanntlich durch Kondensation von Fettalkoholen niedrigerer Kohlenstoffzahl in Gegenwart von Alkali, z. B. Kaliumhydroxid oder Kaliumalkoholat. Die Reaktion läuft beispielsweise bei Temperaturen von 200 bis 300 °C ab und führt zu verzweigten Guerbet-Alkoholen, die die Verzweigung in 2-Stellung zur Hydroxylgruppe aufweisen. In einer besonderen Ausführungsform will dabei die Erfindung überwiegend oder bevorzugt ausschließlich geradkettige Fettalkohole zur Herstellung der 2-verzweigten Guerbet-Alkohole und letztlich dann zur Synthese der Verbindungen der allgemeinen Formel (I) einsetzen. Fettalkohole natürlichen Ursprungs haben bekanntlich wenigstens weitaus überwiegend geradzahlige Kettenlängen, so daß über ihre Dimerisierung der 2-verweigte Guerbet-Alkohol mit 18 C-Atomen nicht als einheitliches Kondensationsprodukt nur eines ausgewählten Fettalkohols erhalten werden kann. Die hier notwendige Dimerisierung eines Gemisches der beiden Fettalkohole mit 8 und 10 C-Atomen führt zu dem Isomerengemisch des 18 C-Guerbet-Alkohols aus 2-Hexyldodecanol-1 und 2-Octyldecanol-1. Daneben entstehen die Kondensationsprodukte der beiden eingesetzten Alkohole mit sich selbst, d. h., das 2-Hexyldecanol-1 aus dem eingesetzten Octanol und das 2-Octyldodecanol-1 aus dem eingesetzten Decanol. Sinngemäß gleiche Überlegungen gelten zum Guerbet-Alkohol mit 14 C-Atomen.Representatives of these two classes, which are derived from branched alkanols of the type of Guerbet alcohols, have proven to be particularly effective. As is known, alcohols of this type are formed by the condensation of fatty alcohols with a lower carbon number in the presence of alkali, e.g. As potassium hydroxide or potassium alcoholate. The reaction takes place, for example, at temperatures from 200 to 300 ° C. and leads to branched Guerbet alcohols which have branching in the 2-position to the hydroxyl group. In a particular embodiment, the invention predominantly or preferably exclusively uses straight-chain fatty alcohols for the preparation of the 2-branched Guerbet alcohols and ultimately for the synthesis of the compounds of the general formula (I). Fatty alcohols of natural origin are known to have at least largely predominantly even chain lengths, so that their 2-branched Guerbet alcohol with 18 C atoms cannot be obtained as a uniform condensation product of only one selected fatty alcohol via their dimerization. The necessary dimerization of a mixture of the two fatty alcohols with 8 and 10 C atoms leads to the isomer mixture of the 18 C Guerbet alcohol from 2-hexyldodecanol-1 and 2-octyldecanol-1. In addition, the condensation products of the two alcohols used arise with themselves, i. that is, the 2-hexyldecanol-1 from the octanol used and the 2-octyldodecanol-1 from the decanol used. Analogous considerations apply to Guerbet alcohol with 14 carbon atoms.
Stoffgemische dieser Art, die zur Lösung der erfindungsgemäßen Aufgabe geeignet sind, sind im Anspruch 4 beschrieben. Auch die erfindungsgemäß vorgesehene Alternative (1b), die frei ist von Guerbet-Alkoholen mit 18 C-Atomen, jedoch geeignete Mischungsverhältnisse der Guerbet-Alkohole mit einerseits 16 und andererseits 20 C-Atomen führt zum Ziel.Mixtures of this type which are suitable for achieving the object according to the invention are described in claim 4. The alternative (1b) provided according to the invention, which is free of Guerbet alcohols with 18 C atoms, but suitable mixing ratios of the Guerbet alcohols with 16 and 20 C atoms on the one hand, leads to the goal.
Die Herstellung der Endgruppen-verschlossenen Fettalkoholpolyglykolether der Formel (I) erfolgt entsprechend den Angaben der DE-OS 33 15 951. So setzt man zweckmäßigerweise die vorstehend beschriebenen Fettalkohole höherer Kohlenstoffzahl mit Ethylenoxid im Molverhältnis von 1 : 5 bis 1 : 9 um und verethert anschließend die im erhaltenen Reaktionsprodukt vorhandenen Hydroxylgruppen. Die Umsetzung mit Ethylenoxid erfolgt dabei unter den bekannten Akoxylierungsbedingungen, vorzugsweise in Gegenwart von geeigneten alkalischen Katalysatoren. Die Veretherung der freien Hydroxylgruppen wird bevorzugt unter den bekannten Bedingungen der Williamsonschen Ethersynthese mit geradkettigen oder verzweigten C₄- bis C₈-Alkylhalogeniden durchgeführt. Besondere Bedeutung kommt im Rahmen des erfindungsgemäßen Handelns dem n-Butylrest für den Rest R₂ aus der allgemeinen Formel (I) zu. Beispiele für eine solche abschließende Veretherung sind dementsprechend n-Butylhalogenide wie n-Butylchlorid. Die Erfindung ist allerdings hierauf nicht beschränkt. Weitere Beispiele sind Amylhalogenide, Hexylhalogenide und die höheren Alkylhalogenide des genannten Bereichs. Dabei kann es zweckmäßig sein, Alkylhalogenid und Alkali im stöchiometrischen Überschuß, beispielsweise von 10 bis 50 %, über die zu verethernden Hydroxylgruppen einzusetzen.The end group-capped fatty alcohol polyglycol ethers of the formula (I) are prepared in accordance with the specifications of DE-OS 33 15 951. The fatty alcohols of higher carbon number described above are advantageously reacted with ethylene oxide in a molar ratio of 1: 5 to 1: 9 and then etherified the hydroxyl groups present in the reaction product obtained. The reaction with ethylene oxide takes place under the known acoxylation conditions, preferably in the presence of suitable alkaline catalysts. The etherification of the free hydroxyl groups is preferably carried out under the known conditions of Williamson's ether synthesis using straight-chain or branched C₄- to C₈-alkyl halides. The n-butyl radical for the radical R₂ from the general formula (I) is of particular importance in the course of the inventive action. Examples of such a final etherification are accordingly n-butyl halides such as n-butyl chloride. However, the invention is not limited to this. Further examples are amyl halides, hexyl halides and the higher alkyl halides in the range mentioned. It may be expedient to use alkyl halide and alkali in a stoichiometric excess, for example from 10 to 50%, over the hydroxyl groups to be etherified.
Die Herstellung der nicht Endgruppen-verschlossenen Verbindungen der allgemeinen Formel (II) erfolgt in an sich bekannter Weise durch Umsetzung der ausgewählten Guerbet-Alkohole mit Ethylenoxid im Mol-Verhältnis 1 : 2 bis 1 : 5.The compounds of the general formula (II) which are not end-capped are prepared in a manner known per se by reacting the selected Guerbet alcohols with ethylene oxide in a molar ratio of 1: 2 to 1: 5.
Entsprechend werden in an sich bekannter Weise die Verbindungen der allgemeinen Formel (III) - Mischungskomponenten zu (3) - durch Umsetzung der ausgewählten linearen oder verzweigten Alkanole R₆OH mit Ethylenoxid und Propylenoxid - insbesondere 1,2-Propylenoxid - in den angegebenen Molverhältnissen erhalten. Die Herstellung der gegebenenfalls mitverwendeten Mischungskomponenten der allgemeinen Formel (IV) erfolgt sinngemäß zu den Angaben der Herstellung der Endgruppen-verschlossenen Mischungskomponenten der allgemeinen Formel (I).Correspondingly, the compounds of the general formula (III) - mixture components to (3) - are obtained in a manner known per se - by reacting the selected linear or branched alkanols ROH with ethylene oxide and propylene oxide - in particular 1,2-propylene oxide - in the stated molar ratios. The preparation of the if necessary the mixture components of the general formula (IV) used are analogous to the information on the preparation of the end group-sealed mixture components of the general formula (I).
Wie bereits angegeben eignen sich die erfindungsgemäßen Wirkstoffgemische sowohl als schaumdämpfender Zusatz zu typischen Reinigungsmittelgemischen, insbesondere schaumarmen Mischungen der angegeben Art, um deren Schaumneigung noch weiter herabzusetzen als auch zur Formulierung von Klarspülern. Auch im zuletzt genannten Fall können in an sich bekannter Weise schaumarme Tenside mitverwendet werden, deren Schaumbildung durch die erfindungsgemäßen Wirkstoffsysteme nach weiter gedrückt wird. Insbesondere im zuletzt genannten Einsatzgebiet kann aber auch sinnvoll Gebrauch gemacht werden von den tensidischen Eigenschaften der erfindungsgemäß zur Anwendung kommenden Wirkstoffmischungen.As already stated, the active compound mixtures according to the invention are suitable both as a foam-suppressing additive to typical cleaning agent mixtures, in particular low-foam mixtures of the type mentioned, in order to further reduce their tendency to foam, and also for the formulation of rinse aids. In the last-mentioned case too, low-foam surfactants can be used in a manner known per se, the foam formation of which is further suppressed by the active ingredient systems according to the invention. In the last-mentioned field of use in particular, however, it is also sensible to make use of the surfactant properties of the active compound mixtures used according to the invention.
Der Gehalt der erfindungsgemäßen Wirkstoffmischungen zu (1) bis (4) in den Wasch- und Reinigungsmitteln kann in weiten Grenzen variieren. Wesentlich ist, daß die Polyglykolethergemische bereits in geringen Konzentrationen wirkungsvolle Effekte ergeben. In einer bevorzugten Ausführungsform werden sie den Reinigungsmitten in solchen Mengen zugesezt, daß ihre Konzentration in den gebrauchsfertigen Lösungen etwa im Bereich von 50 bis 500 ppm liegt. Die Erfindung ist hierauf allerdings nicht eingeschränkt, es können insbesondere auch weitaus höhere Mengen der erfindungsgemäßen Wirkstoffgemische zum Einsatz kommen.The content of the active ingredient mixtures of (1) to (4) in the detergents and cleaning agents can vary within wide limits. It is essential that the polyglycol ether mixtures give effective effects even in low concentrations. In a preferred embodiment, they are added to the cleaning agents in such amounts that their concentration in the ready-to-use solutions is approximately in the range from 50 to 500 ppm. However, the invention is not restricted to this; in particular, far higher amounts of the active compound mixtures according to the invention can be used.
In den nachfolgenden Beispielen wird die Schaumdämpfung der erfindungsgemäß ausgewählten Zusatzstoffe - und im Vergleich dazu einer strukturähnlichen jedoch nicht in den Rahmen der Erfindung fallenden Zusatz-Mischung - nach einer Prüfmethode ermittelt, die wie folgt beschrieben wird:In the following examples, the foam damping of the additives selected according to the invention - and, in comparison, a structurally similar additive mixture which does not fall within the scope of the invention - is determined using a test method which is described as follows:
In 450 ml Wasser mit einer Wasserhärte von 16 odH werden 50 g eines verquirlten Volles (Eigelb und Eiweiß) homogen verteilt und diese Flüssigkeit in eine doppelwandigen 2000-ml-Meßzylinder auf 60 oC temperiert. Mit Hilfe einer Laborschlauchpumpe wird diese Lösung mit einem Glasrohr vom Boden des Meßzylinders angesaugt. Die Rückführung der Flüssigkeit in den Meßzylinder erfolgt über ein zweites Rohr, dessen unteres Ende in der Höhe der Oberkante des Meßzylinders endet. Die Flüssigkeit wird dabei mit einer Umwälzgeschwindigkeit von 4 l/min. umgepumpt und fällt in den Meßzylinder zurück. Durch das Umpumpen kann man diese Flüssigkeit bis auf 2000 ml aufschäumen. Wenn dies erreicht ist, dosiert man 0,1 ml des zu prüfenden schaumarmen bzw. schaumdrückenden Wirkstoffgemisches - hier die Produkte A, B, C und D - in die Flüssigkeit, wobei der gebildete Schaum in Abhängigkeit von der Wirksamkeit des Produktes mehr oder weniger schnell zusammenbricht. Bei weiterem Umpumpen wird dann stets ein Wiederanstieg des Schaums beobachtet. Nach 0,5, 1, 2, 3, 5, 10, 15, 20 und 30 Minuten Umpumpdauer nach Dosierung des schaumarmen Wirkstoffgemisches werden dann jeweils die in der Tabelle angegebenen Volumina abgelesen, welche sich aus Schaum und Flüssigkeit nach diesen Zeiten gebildet haben.50 g of a whisked whole (egg yolk and egg white) are homogeneously distributed in 450 ml of water with a water hardness of 16 o dH and this liquid is heated to 60 o C in a double-walled 2000 ml measuring cylinder. With the help of a laboratory hose pump, this solution is sucked from the bottom of the measuring cylinder with a glass tube. The liquid is returned to the measuring cylinder via a second tube, the lower end of which ends at the height of the upper edge of the measuring cylinder. The liquid is at a circulation rate of 4 l / min. pumped over and falls back into the measuring cylinder. By pumping around this liquid can be foamed up to 2000 ml. When this is achieved, 0.1 ml of the low-foam or foam-suppressing active substance mixture to be tested - here products A, B, C and D - are metered into the liquid, the foam formed depending on the effectiveness of the product more or less quickly collapses. If the pump is pumped further, a rise in the foam is always observed. After 0.5, 1, 2, 3, 5, 10, 15, 20 and 30 minutes of pumping over after metering in the low-foam active ingredient mixture, the volumes given in the table are then read, which have formed from foam and liquid after these times.
Die untersuchten Produkte sind dabei die folgenden:The examined products are the following:
95 % Kokosalkohol-(EO)₅-(PO)₄
5 % 2-Hexyldecanol-1, umgesetzt mit 2 Mol Ethylenoxid95% coconut alcohol (EO) ₅- (PO) ₄
5% 2-hexyldecanol-1, reacted with 2 moles of ethylene oxide
90 % Kokosalkohol-(EO)₅-(PO)₄
5 % 2-Hexyldecanol-1, umgesetzt mit 2 Mol Ethylenoxid
5 % R₁O-(CH₂CH₂O)₇-n-Butylether, wobei gilt
- R₁OH =
- 28 % 2-Octyldodecanol-1
25 % 2-Hexyldodecanol-1
25 % 2-Octyldecanol-1
22 % 2-Hexyldecanol-1
5% 2-hexyldecanol-1, reacted with 2 moles of ethylene oxide
5% R₁O- (CH₂CH₂O) ₇-n-butyl ether, where applies
- R₁OH =
- 28% 2-octyldodecanol-1
25% 2-hexyldodecanol-1
25% 2-octyldecanol-1
22% 2-hexyldecanol-1
47,5 % Kokosalkohol-(EO)₁₀-n-butylether
47,5 % Kokosalkohol-(EO)₅-(PO)₄
5 % R₁O-(CH₂CH₂O)₇-n-Butylether gemäß Produkt B47.5% coconut alcohol (EO) ₁₀-n-butyl ether
47.5% coconut alcohol (EO) ₅- (PO) ₄
5% R₁O- (CH₂CH₂O) ₇-n-butyl ether according to product B.
50 % Kokosalkohol-(EO)₅-(PO)₄
50 % Kokosalkohol-(EO)₄-(PO)₅
Die jeweils bestimmten Werte sind in der nachfolgenden Tabelle zusammengefaßt:
50% coconut alcohol (EO) ₄- (PO) ₅
The values determined in each case are summarized in the table below:
Zur Formulierbarkeit der jeweiligen Produktgemische werden die folgenden Untersuchungen durchgeführt:The following tests are carried out to determine the formulability of the respective product mixtures:
20 % Produkt A
5 % Cumolsulfonat (40%ig)
75 % Wasser
Diese Formulierung ist bis 46 oC klar-flüssig.20% product A
5% cumene sulfonate (40%)
75% water
This formulation is clear-liquid up to 46 o C.
20 % Produkt B
5 % Cumolsulfonat (40%ig)
75 % Wasser
Diese Formulierung ist bis 46 oC klar-flüssig.20% product B
5% cumene sulfonate (40%)
75% water
This formulation is clear-liquid up to 46 o C.
20 % Produkt C
5 % Cumolsulfonat (40%ig)
75 % Wasser
Diese Formulierung ist bis 46 oC klar-flüssig.20% product C
5% cumene sulfonate (40%)
75% water
This formulation is clear-liquid up to 46 o C.
20 % Produkt D
5 % Cumolsulfonat (40%ig)
75 % Wasser
Diese Formulierung ist nur bis 40 oC klar-flüssig.20% product D
5% cumene sulfonate (40%)
75% water
This formulation is only clear and liquid up to 40 o C.
Das Produkt B hat eine bessere Antischaumwirkung als die Produkte A, C und D.Product B has a better anti-foaming effect than products A, C and D.
Claims (6)
- The use of selected mixtures of alkali-resistant, surface-active and foam-suppressing polyalkylene glycol ether compounds in domestic and institutional dishwashing and bottle-washing machines, characterized in that combinations of the following active components (% by weight, based on 100% by weight of the combination) are used:1. up to 40% by weight of end-capped polyethylene glycol ethers corresponding to general formula (I):and
R₁O-(CH₂CH₂O)n-R₂ (I)
in which R₁O is derived from C₁₆₋₂₀ Guerbet alcohols, R₂ is a C₄₋₈ alkyl radical and n is a number of 5 to 9,2. up to 40% by weight of non-end-capped polyethylene glycol ether compounds corresponding to general formula (II):together with
R₅O-(CH₂CH₂O)z-H (II)
in which R₅O is derived from C₁₂₋₂₀ Guerbet alcohols and z is a number of 2 to 5,3. 20 to 98% by weight of mixed ethers corresponding to general formula (III):and, if desired,
R₆O-(EO)u-(PO)v-H (III)
in which R₆O- is the residue of a linear or branched C₈₋₁₈ alkanol, EO is an ethylene glycol residue, PO is a propylene glycol residue, u is a number of 2 to 6 and v is a number of 3 to 7,4. end-capped polyethylene glycol ethers corresponding to general formula (IV):
R₃O-(CH₂CH₂O)m-R₄ (IV)
in which R₃ is a linear C₈₋₁₈ alkyl radical or a branched C₈₋₁₄ radical, R₄ is a C₄₋₁₀ alkyl radical and m is a number of 5 to 15. - The use claimed in claim 1, characterized in that active components (1) to (4) are used in the following quantities in 100% by weight of the combination:1) up to 30% by weight of compounds corresponding to general formula (I),2) up to 40% by weight of compounds corresponding to general formula (II),3) 40 to 95% by weight of compounds corresponding to general formula (III),4) 0 to 50% by weight of compounds corresponding to general formula (IV).
- The use claimed in claims 1 and 2, characterized in that polyethylene glycol ether compounds corresponding to general formula (II), in which R₅O- is derived from at least one of the following alkanols: 2-butyl-1-octanol, 2-butyl-1-decanol, 2-hexyl-1-octanol, 2-hexyl-1-decanol, 2-hexyl-1-dodecanol, 2-octyl-1-decanol and/or 2-octyl-1-dodecanol, are used.
- The use claimed in claims 1 to 3, characterized in that polyethylene glycol ether compounds corresponding to general formula (I), in which R₁O- is derived from the following alcohol mixtures (a) or (b):a) 10 to 100 mole-% of an equimolar isomer mixture of 2-hexyl-1-dodecanol and 2-octyl-1-decanol,or
0 to 90 mole-% of 2-hexyl-1-decanol,
0 to 50 mole-% of 2-octyl-1-dodecanol,b) 40 to 70 mole-% of 2-hexyl-1-decanol, 60 to 30 mole-% of 2-octyl-1-dodecanol,are used. - The use claimed in claims 1 to 4, characterized in that polyethylene glycol ether mixtures corresponding to general formula (I), in which R₁O- is derived from alcohol mixtures of the following composition:
at least 45 mole-% of the isomer mixture of 2-hexyl-1-dodecanol and 2-octyl-1-decanol,
0 to 55 mole-% of 2-hexyl-1-decanol,
no more than 30 mole-% of 2-octyl-1-dodecanol,
are used. - The use claimed in claims 1 to 5, characterized in that the substituents R₂ (general formula (I)) and/or R₄ (general formula (IV)) are also linear alkyl radicals containing the number of carbon atoms mentioned.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3928600 | 1989-08-30 | ||
| DE3928600A DE3928600A1 (en) | 1989-08-30 | 1989-08-30 | FOAM-ABSORBING MULTI-MATERIAL MIXTURES WITH TENSIDE CHARACTER FOR MACHINE CLEANING AND BOTTLE CLEANING |
| PCT/EP1990/001384 WO1991003540A1 (en) | 1989-08-30 | 1990-08-21 | Anti-foaming agents for machine-washing of crockery and bottles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0489768A1 EP0489768A1 (en) | 1992-06-17 |
| EP0489768B1 true EP0489768B1 (en) | 1995-06-14 |
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ID=6388136
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90912439A Expired - Lifetime EP0489768B1 (en) | 1989-08-30 | 1990-08-21 | Anti-foaming agents for machine-washing of crockery and bottles |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0489768B1 (en) |
| AT (1) | ATE123800T1 (en) |
| DE (2) | DE3928600A1 (en) |
| DK (1) | DK0489768T3 (en) |
| ES (1) | ES2073032T3 (en) |
| PT (1) | PT95121B (en) |
| WO (1) | WO1991003540A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0598973A1 (en) * | 1992-11-26 | 1994-06-01 | The Procter & Gamble Company | Multi-purpose liquid cleaning composition |
| ATE172234T1 (en) * | 1992-11-26 | 1998-10-15 | Procter & Gamble | CLEANING AGENT COMPOSITIONS WITH A COMBINATION OF HIGHLY HYDROPHILIC AND HIGHLY HYDROPHOBIC NON-IONIC SURFACTANTS |
| DE4323252C2 (en) * | 1993-07-12 | 1995-09-14 | Henkel Kgaa | Rinse aid for machine cleaning hard surfaces |
| DE4327327A1 (en) * | 1993-08-13 | 1995-02-16 | Henkel Kgaa | Detergent mixtures |
| DE4342214C1 (en) * | 1993-12-10 | 1995-05-18 | Henkel Kgaa | Nonionic detergent mixtures |
| DE4431158C2 (en) * | 1994-09-01 | 1999-10-21 | Henkel Kgaa | Methyl end-capped alkyl and / or alkenyl polyglycol ethers |
| DE4439086C2 (en) * | 1994-11-02 | 1997-11-27 | Henkel Kgaa | Process for the preparation of end-capped nonionic surfactants |
| DE19500842C2 (en) * | 1995-01-13 | 1996-12-19 | Henkel Kgaa | Process for the preparation of end-capped nonionic surfactants |
| DE19738866A1 (en) | 1997-09-05 | 1999-03-11 | Henkel Kgaa | Low-foaming surfactant mixtures with hydroxy mixed ethers |
| DE19851453A1 (en) | 1998-11-09 | 2000-05-11 | Cognis Deutschland Gmbh | Rinse aid for automatic dishwashing |
| DE19856727A1 (en) | 1998-12-09 | 2000-06-15 | Cognis Deutschland Gmbh | All-purpose cleaner |
| DE19920559A1 (en) * | 1999-05-05 | 2000-11-16 | Cognis Deutschland Gmbh | Process for the preparation of alkyl-terminated alkyl and / or alkenyl ethers |
| WO2011071492A1 (en) | 2009-12-09 | 2011-06-16 | Dow Global Technologies Llc | Polyether derivatives of secondary hydroxy fatty acids and derivatives thereof |
| CN103642033A (en) * | 2013-11-18 | 2014-03-19 | 南京理工大学 | Guerbet alcohol nonionic surfactant |
| US10947480B2 (en) | 2016-05-17 | 2021-03-16 | Conopeo, Inc. | Liquid laundry detergent compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0124815A2 (en) * | 1983-05-02 | 1984-11-14 | Henkel Kommanditgesellschaft auf Aktien | Use of polyglycol ethers as foam-depressing additives in cleaning agents producing little foam |
| EP0326795A2 (en) * | 1988-01-11 | 1989-08-09 | Henkel Kommanditgesellschaft auf Aktien | Use of polyglycol ethers as anti-foaming agents in detergents |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2026494T3 (en) | 1986-07-24 | 1992-05-01 | Henkel Kommanditgesellschaft Auf Aktien | MIXTURES OF POOR FOAM SURFACES AND / OR FOAM REDUCERS AND THEIR USE. |
| CH676994A5 (en) * | 1987-05-06 | 1991-03-28 | Sandoz Ag |
-
1989
- 1989-08-30 DE DE3928600A patent/DE3928600A1/en not_active Withdrawn
-
1990
- 1990-08-21 ES ES90912439T patent/ES2073032T3/en not_active Expired - Lifetime
- 1990-08-21 EP EP90912439A patent/EP0489768B1/en not_active Expired - Lifetime
- 1990-08-21 AT AT90912439T patent/ATE123800T1/en not_active IP Right Cessation
- 1990-08-21 WO PCT/EP1990/001384 patent/WO1991003540A1/en active IP Right Grant
- 1990-08-21 DK DK90912439.8T patent/DK0489768T3/en active
- 1990-08-21 DE DE59009251T patent/DE59009251D1/en not_active Expired - Lifetime
- 1990-08-28 PT PT95121A patent/PT95121B/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0124815A2 (en) * | 1983-05-02 | 1984-11-14 | Henkel Kommanditgesellschaft auf Aktien | Use of polyglycol ethers as foam-depressing additives in cleaning agents producing little foam |
| EP0326795A2 (en) * | 1988-01-11 | 1989-08-09 | Henkel Kommanditgesellschaft auf Aktien | Use of polyglycol ethers as anti-foaming agents in detergents |
Also Published As
| Publication number | Publication date |
|---|---|
| DK0489768T3 (en) | 1995-10-30 |
| EP0489768A1 (en) | 1992-06-17 |
| DE59009251D1 (en) | 1995-07-20 |
| WO1991003540A1 (en) | 1991-03-21 |
| ES2073032T3 (en) | 1995-08-01 |
| ATE123800T1 (en) | 1995-06-15 |
| PT95121A (en) | 1991-05-22 |
| PT95121B (en) | 1997-05-28 |
| DE3928600A1 (en) | 1991-03-07 |
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