EP2240562B1 - Use of surface-active substances in cleaning agents - Google Patents

Use of surface-active substances in cleaning agents Download PDF

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Publication number
EP2240562B1
EP2240562B1 EP09711301A EP09711301A EP2240562B1 EP 2240562 B1 EP2240562 B1 EP 2240562B1 EP 09711301 A EP09711301 A EP 09711301A EP 09711301 A EP09711301 A EP 09711301A EP 2240562 B1 EP2240562 B1 EP 2240562B1
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carbon atoms
alkyl
radical
independently
alkenyl
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EP09711301A
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German (de)
French (fr)
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EP2240562A2 (en
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Teresa Alexandre
Hans-Christian Raths
Manfred Weuthen
Sabine Both
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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Priority to PL09711301T priority Critical patent/PL2240562T3/en
Priority to EP10187277A priority patent/EP2267110B1/en
Publication of EP2240562A2 publication Critical patent/EP2240562A2/en
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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
    • 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

Definitions

  • the present invention relates to the use of selected surface-active substances, alone or in combination, for use in cleaning agents and in particular in dishwashing detergents for automatic dishwashing.
  • the cleaning of hard surfaces and especially the washing of dishes makes special demands on the cleaner used.
  • the three components of the machine system are cleaner, rinse aid and regeneration salt for water softening.
  • the central tasks of the main component cleaners are the soil release, the dirt dispersion, the binding of residual water hardness and the corrosion inhibition.
  • An essential parameter for dishwashing is the rinse aid performance. It is determined how large the proportion of deposits on the dishes, after they were rinsed.
  • the deposits are essentially mineral compounds, in particular Ca and / or Mg salts, but also surfactant residues. However, lime mainly leads to undesirable deposits for the user.
  • common dishwashing agents in particular those for automatic dishwashing, generally contain so-called rinse aid.
  • rinse aids usually comprise mixtures of low foaming nonionic surfactants, typically fatty alcohol polyethylene / polypropylene glycol ethers, solubilizers (eg cumene sulfonate), organic acids (eg citric acid) and solvents (eg ethanol) It is to influence the interfacial tension of the water so that it can run in a very thin, coherent film of items to be washed, so that remain in the subsequent drying process no water droplets, stripes or films. There are differences between two types of deposits. On the one hand, the so-called “spotting”, which is caused by drying drops of water, is examined. On the other hand, the "filming”, which are layers that result from the drying of thin water films, is evaluated.
  • solubilizers eg cumene sulfonate
  • organic acids eg citric acid
  • solvents eg ethanol
  • combination products are increasingly being used, in which the various functions, such as cleaning, rinsing, water softening and, if appropriate, metal, in particular silver protection or a glass protection function, are combined in a preferably solid form.
  • agents are referred to as multifunctional agents.
  • so-called 3-in-1 products which combine cleaners, rinse aids and water softening in the form of a solid compact ("tabs"), are found in the market. Due to the increased use of such multifunctional agents but the drying performance has become worse compared to the use of a classic rinse aid. Drying performance is to be understood in how far the cleaned items to be washed, after passing through the dishwashing process, still have water, preferably water drops, on the surface.
  • the remaining water on the surface must then either be removed mechanically (eg by dry wiping) or the ware must be allowed to air-dry. The user must wait until the water evaporates. However, residues (eg lime and / or surfactant residues or other residues dissolved or dispersed in the water) remain on the surface which lead to unaesthetic spots or streaks. This applies in particular to shiny or transparent surfaces, such as glass or metal. It is therefore sought ways to improve the drying performance of cleaning agents for hard surfaces, especially dishwashing detergents.
  • the EP 1 306 423 A2 discloses aqueous detergents which contain alkyl ether sulfates and amphoteric glycine compounds and are suitable for improving the drying behavior of dishwashing detergents.
  • the DE 100 45 289 A1 describes hand dishwashing detergents which contain certain quaternary ammonium compounds and alkyl ether sulfates side by side and also show a particularly good drying behavior.
  • additives for cleaning agents must not adversely affect the rinsing and in particular the rinse performance of the cleaner. Ideally, an additive should even improve the overall performance of the cleaner.
  • the present invention therefore relates, in a first embodiment, to mixtures comprising at least two different surface-active substances from groups a) and b), the surface-active compound a) being selected from compounds which have the general formula (Ia): wherein M is a radical CH 2 -CH 2 or CHR-CH 2 , R, R 'and R "independently represent saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 6 to 22 carbon atoms, and the indices n and m independently of one another can assume values between 1 and 40, and / or compounds of the general formula (Ib) follow wherein R "'and R""independently of one another represent saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 4 to 22 C atoms, and the indices n and m independently of one another can assume values between 1 and 40, X' and X "independently of one another are H or are saturated, unsaturated, linear or branched alky
  • R 1 O [CH 2 CH 2 O] x CH 2 CH (OM) R 2 (II) in which R 1 is a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, or a radical R 2 is -CH (OH) CH 2 , where R 2 is a linear or branched alkyl and / or Alkenyl radical having 8 to 16 carbon atoms, x is a number from 20 to 80, preferably 40 to 80, and M is a hydrogen atom or a saturated alkyl radical having 1 to 18 carbon atoms, and / or compounds of group b2) according to the general formula III R 3 O [CH 2 CH 2 O] y [CH 2 CHCH 3 O] 2 CH 2 CH (OH) R 4 (III) in which R 3 is a linear or branched alkyl and / or alkenyl radical having 8 to 22 carbon atoms, R 4 is a linear or branched alkyl and / or alkenyl radical having 8 to
  • the mixtures according to the invention necessarily contain compounds of the type a). These are compounds of the above formulas (Ia) and / or (Ib) wherein certain structures are preferred.
  • compounds according to the general formula (Ia) are preferred when M is a CH 2 -CRH group, R is a linear, saturated alkyl radical having 8 to 16, preferably 8 to 12 and in particular 8 to 10 carbon atoms, and R 'and R "each independently represent a linear, saturated alkyl radical having from 10 to 16, preferably 10 to 14, carbon atoms, and n and m independently of one another may have values of from 20 to 30.
  • Such compounds may For example, by reacting alkyldiols, HO-CHR-CH 2 -OH are obtained with ethylene oxide followed by a reaction with an Alkylepoxid to close the free OH functions, so that a dihydroxy ether is formed in the sequence.
  • the second component of the mixtures are compounds of the formulas (II) and (III), which can be referred to as hydroxy mixed ethers.
  • HME Hydroxy mixed ethers
  • hydroxy mixed ethers are known from the literature and are described, for example, in the German application DE 19738866 described. They are prepared, for example, by reaction of 1,2-epoxyalkanes (R "CHOCH 2 ), where R" is an alkyl and / or alkenyl radical having 2 to 22, in particular 6 to 16, carbon atoms, with alkoxylated alcohols.
  • R "CHOCH 2 ) 1,2-epoxyalkanes
  • Preferred for the purposes of the invention are those hydroxy mixed ethers which are derived from alkoxylates of monohydric alcohols of the formula R'-OH having 4 to 18 carbon atoms, where R 'is an aliphatic, saturated, straight-chain or branched alkyl radical, in particular having 6 to 16 carbon atoms, stands.
  • Suitable straight-chain alcohols are butanol-1, caproic, eananthic, caprylic, pelargonic, capric alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, palmityl alcohol, heptadecanol-1, stearyl alcohol, nonadecanol- 1, arachidyl alcohol, heneicosanol-1, behenyl alcohol and their technical mixtures, as obtained in the high pressure hydrogenation of technical methyl esters based on fats and oils.
  • branched alcohols examples include so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are prepared by the oxo process and so-called Guerbet alcohols which are branched in the 2-position with an alkyl group.
  • Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol.
  • the alcohols are used in the form of their alkoxylates, which are prepared by reaction of the alcohols with ethylene oxide in a known manner.
  • R 1 is a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, or a radical R 2 is -CH (OH) CH 2 , where R 2 is a linear or branched alkyl and / or Alkenyl radical having 8 to 16 carbon atoms, x represents a number from 40 to 80, and M represents a hydrogen atom or a saturated alkyl radical having 1 to 18 carbon atoms.
  • Preferred for the purposes of the invention are those hydroxy mixed ethers derived from ethoxylates of monohydric alcohols of the formula R 1 -OH having 6 to 18 carbon atoms, preferably 6 to 16 and in particular 8 to 10 carbon atoms, wherein R 1 is a linear alkyl radical and x is 40 to 60.
  • those compounds of general formula (II) are preferred in which the index x for a Number from 40 to 70, preferably 40 to 60 and in particular from 40 to 50 stands. M is then a hydrogen atom.
  • hydroxy mixed ethers of the formula (II) where R 1 is an alkyl radical having 8 to 10 carbon atoms, in particular based on a native fatty alcohol, R 2 is an alkyl radical having 10 carbon atoms, in particular a linear alkyl radical and x is 40 to 60 stands.
  • R ' is a saturated alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms and R "is an alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms
  • the index x can have values of from 20 to 80, preferably from 30 to 60 and in particular from 40 to 50, wherein in general those compounds are preferred in which the index x is greater than 40 are preferred.
  • Particularly preferred compounds of type b2) are, for example, those in which, in the formula (III), the index y is a number from 20 to 30, preferably from 20 to 25. Preference is furthermore given to those compounds of the type b2) in which R 3 in the formula (III) represents an alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms, R 4 is an alkyl radical having 10 to 12, preferably 10 carbon atoms, y a number from 15 to 35, preferably 20 to 30 and z is a number from 1 to 3, preferably 1 means.
  • mixtures containing as surface-active compound of type b2) a compound of the general formula (III) in which R 3 is an alkyl and / or alkenyl radical having 9 to 18 carbon atoms and R 4 is an alkyl or Alkenyl radical having 8 to 10 carbon atoms and y is a number from 20 to 35.
  • mixtures containing as surface-active compound of type b2) a compound of the general formula (III) in which R 3 is an alkyl and / or alkenyl radical having 8 to 12 carbon atoms and R 4 is an alkyl or Alkenyl radical having 8 to 10 carbon atoms and y is a number from 20 to 35 and z is a number from 1 to 3.
  • the compounds of type b2) are also hydroxy mixed ether derivatives which can be prepared by reacting propoxylated and / or ethoxylated fatty alcohols with alkyl epoxides by ring opening in an alkaline medium.
  • both a propylene oxide radical CH 2 CHCH 3 O (PO) and an ethylene oxide radical CH 2 CH 2 O (EO) contain, possible that from the direction of the C atom with the free hydroxyl group first the EO residues and then the PO residues are arranged in blocks, whereby the sequence first PO, then EO possible is.
  • the alkoxide groups can also be randomly distributed (randomized) in the molecule. It is also possible to use both block and random alkoxylates side by side.
  • the values are average values since, due to their production, different alkoxylated derivatives are present side by side.
  • the number of alkoxide groups can therefore also be odd.
  • HME of the general formula (III) is described by the following Markush formula: where R 'and R "independently of one another represent a saturated alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms.
  • the present invention now makes use of the finding that the presence of selected HME (type b)), or their derivatives, in combination with structure-different surface-active compounds of type a) advantageous drying and / or rinsing performance of cleaner formulations for hard surfaces, and particularly dishwashing detergents.
  • Particularly preferred mixtures within the meaning of the present technical teaching relate to combinations of the compounds of the formulas (Ia) and / or (Ib) with compounds of the formula (III).
  • Fatty alcohols are primary aliphatic alcohols of the formula R-OH in which R is an aliphatic, linear or branched hydrocarbon radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds.
  • R is an aliphatic, linear or branched hydrocarbon radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds.
  • Typical examples are caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidy
  • the compounds of the type a) and b) are preferably present in a weight ratio of 10: 1 to 1:10 side by side in the mixtures according to the invention. However, preference may be given to those mixtures in which the surface-active compounds of the type a) and b) in a weight ratio of 5: 1 to 1: 5, in particular from 3: 1 to 1: 3 and particularly preferably from 2: 1 to 1: 2 and most preferably 1: 1 are present side by side.
  • the compounds of type b1) and / or b2) can - as stated above - also be present side by side in any mixtures. Preferably, however, the mixtures consist only of a compound of type a) and a compound of type b).
  • the mixtures described above are preferably suitable for use in cleaners, in particular in dishwashing detergents and in particular in automatic dishwashing detergents.
  • the mixtures can be used to improve the drying performance of cleaning agents and in particular for dishwashing detergents, preferably dishwasher detergents for automatic dishwashing.
  • Another preferred use relates to the use of the mixtures in multifunctional solid Dishwashing detergents for automatic dishwashing. The improvement of the drying concerns in particular surfaces of plastic.
  • agents which contain from 0.1 to 15% by weight of the mixtures according to the invention and also other ingredients customary in detergents and, preferably, dishwashing detergents.
  • the detergents contain the mixtures according to the invention in amounts of from 0.1 to 12% by weight, advantageously from 1 to 10% by weight and in particular from 1.0 to 8% by weight. Particularly preferred is the range of 2.0 to 8.0 wt .-%.
  • compositions according to the invention in the sense of the above description can be, for example, further nonionic, anionic and / or cationic surfactants, builders, enzymes, bleaching agents, such as e.g. Be percarbonates.
  • agents may contain silicates, phosphorus compounds, carbonates, but also special rinse aids and other known and customary auxiliaries and additives, e.g. pH regulators or enzymes.
  • solvents such as water or lower aliphatic alcohols, preferably ethanol or propanol, solubilizers, polymers or organic acids, preferably citric acid and derivatives thereof.
  • the cleaning agents can be both liquid and solid, for example as granules, powders or tablets.
  • Liquid detergents may still contain viscosity builders, e.g. to obtain gel-like agents.
  • machine dishwashing detergents are in solid form, for example as powders or granules or as shaped articles, preferably in tablet form. There may also be several phases next to one another, for example a compressed tablet which contains in a bulge a non-compressed part, eg a waxy rinse aid phase.
  • Such multifunctional agents are marketed as 2-in-1 or 3-in-1 products.
  • the preparation is carried out in any manner known to the person skilled in the art, wherein in a preferred embodiment the mixtures according to the invention are present as a compound and are preferably mixed with the other ingredients in any order. But it is also possible to mix the surfactants of the type a) and b) individually with the other ingredients and, for example, then to press or granulate this mixture to the finished agent.
  • inventive 1 1 mixtures A to C were incorporated (at 8% by weight, based on the dishwashing detergent) in a commercial formulation for a solid automatic dishwashing agent.
  • the assessment of the drying performance is done by counting the still adhering to the items to be washed after the rinsing process drops. Glasses, cutlery, plastic and porcelain plates are rinsed under defined conditions (water at 21 ° dH, 50 g standard soiling) in a household dishwashing machine. After completion of the wash program, the items to be washed are assessed under defined light conditions according to the number of drops.
  • the results were made by comparing the drops of water remaining on a plastic surface after passing through the rinsing process.
  • the standard formulation is composed of 2% by weight of a C8 / C10-alkyl-1EO-22EO-hydroxy-C10-alkyl ether, 1% by weight. a polymer, 7% by weight of sodium silicate, 52% by weight of sodium triphosphate, 2.5% by weight of TAED, 27.5% by weight of sodium carbonate and 8% by weight of sodium percarbonate.
  • compositions containing mixtures A to C showed a reduction in the number of drops of plastic by 1 to 3.

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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

Mixture (I) comprises at least two different surface active substances of group (a) and (b), where: (a) is an ether compound (Ia) and/or an acetal compound (Ib); and (b) is an ether compound (II) and/or (III). Mixture (I) comprises at least two different surface active substances (a) and (b), where: (a) is an ether compound of formula (R1a-CH(OH)-CH 2-(O-CH 2-CH 2) n-O-M-O-(CH 2-CH 2-O) m-CH 2-CH(OH)-R2a) (Ia), and/or acetal compound of formula (R3a-(O-CH 2-CH 2) n-O-X1aCX2a-O-(CH 2-CH 2-O) m-R4a) (Ib); and (b) is an ether compound of formula (R 1>-O-[CH 2-CH 2-O] xCH 2CH(OM)R 2>) (II) and/or (R 3>-O-[CH 2-CHCH 3-O] z[CH 2CH 2O] yCH 2CH(OH)R 4>) (III). M : CH 2-CH 2or CHR-CH 2; R, R1a, R2a : optionally saturated 6-22C alkyl and/or 6-22C alkenyl; m, n : 1-40; R3a, R4a : optionally saturated 4-22C alkyl and/or 4-22C alkenyl; X1a, X2a : H or optionally saturated 1-18C alkyl and/or 1-18C alkenyl; R 3>8-22C alkyl or 8-22C alkenyl; R 4>8-16C alkyl or 8-16C alkenyl; x : 20-80, preferably 40-50; y : 10-35, preferably 20-35; and z : 0-5, preferably 1-3. An independent claim is included for a cleaning agent comprising: 0.1-15 wt.% of (I); other non-ionic, anionic and/or cationic surfactant; optionally forming agent, enzyme, rinsing agent and/or further auxiliary agents; and additives.

Description

Die vorliegende Erfindung betrifft den Einsatz von ausgewählten oberflächenaktiver Substanzen, allein oder in Kombination, zum Einsatz in Reinigungsmitteln und insbesondere in Geschirrspülmitteln für das automatische Geschirrspülen.The present invention relates to the use of selected surface-active substances, alone or in combination, for use in cleaning agents and in particular in dishwashing detergents for automatic dishwashing.

Das Reinigen harter Oberflächen und insbesondere des Spülen von Geschirr stellt besondere Anforderungen an die verwendeten Reiniger. Dies gilt im Besonderen für das maschinelle Geschirrspülen. Die drei Komponenten des maschinellen Systems sind Reiniger, Klarspüler und Regenerier-Salz zur Wasserenthärtung. Hierbei sind die zentralen Aufgaben des Hauptbestandteils Reiniger die Schmutzablösung, die Schmutzdispergierung, die Bindung von Restwasserhärte sowie die Korrosionsinhibierung. Ein wesentlicher Parameter für das Geschirrspülen ist die Klarspülleistung. Dabei wird ermittelt, wie groß der Anteil an Ablagerungen auf den Geschirrteilen ist, nachdem diese gespült wurden. Bei den Ablagerungen handelt es sich im Wesentlichen um mineralische Verbindungen, insbesondere Ca- und/oder Mg-Salze, aber auch um Tensidrückstände. Hauptsächlich führt aber Kalk zu den für den Anwender unerwünschten Ablagerungen. Um den Anteil dieser Ablagerungen zu verringern enthalten gängige Geschirrspülmittel, insbesondere solche für das automatische Geschirrspülen, in der Regel so genannte Klarspülmittel. Marktübliche Klarspülmittel stellen üblicherweise Gemische aus schwach schäumenden nichtionischen Tensiden, typischerweise Fettalkoholpolyethylen/polypropylenglykolethern, Lösungsvermittlern (z. B. Cumolsulfonat), organischen Säuren (z. B. Zitronensäure) und Lösungsmitteln (z. B. Ethanol) dar. Die Aufgabe dieser Mittel besteht darin, die Grenzflächenspannung des Wassers so zu beeinflussen, dass es in einem möglichst dünnen, zusammenhängenden Film vom Spülgut ablaufen kann, so dass beim anschließenden Trocknungsvorgang keine Wassertropfen, Streifen oder Filme zurückbleiben. Unterschieden wird zwischen zwei Arten von Ablagerungen. Zum einen wird das so genannte "Spotting" untersucht, welches durch abtrocknende Wassertropfen entsteht, zum anderen bewertet man das "Filming", das sind Schichten, die durch das Abtrocknen dünner Wasserfilme entstehen. Zur Bewertung werden derzeit Probanden eingesetzt, die visuell bei gereinigten Objekten, z.B. Teller, Gläser, Messer etc. die Parameter "Spotting" und "Filming" bewerten. Moderne Reinigungsmittel für das Geschirrspülen enthalten daher Klarspüler, um das Ablaufen von Wasser von den Oberflächen des Spülgutes zu verbessern. Es gibt Klarspüler, die trocknen nicht auf allen Substraten, wie z.B. Plastik gleich gut. Um diesen Effekt zu umgehen, werden aufwendige klassische Klarspüler formuliert, die z.B. Silikonverbindungen bzw. fluorierte Verbindungen aufweisen, wie sie in der US 5,880,089 oder der US 2005/0143280 A1 beschrieben werden. Diese Verbindungen sind aber biologisch schwer bzw. gar nicht abbaubar und teilweise sogar umweltgefährlich.The cleaning of hard surfaces and especially the washing of dishes makes special demands on the cleaner used. This applies in particular to automatic dishwashing. The three components of the machine system are cleaner, rinse aid and regeneration salt for water softening. Here, the central tasks of the main component cleaners are the soil release, the dirt dispersion, the binding of residual water hardness and the corrosion inhibition. An essential parameter for dishwashing is the rinse aid performance. It is determined how large the proportion of deposits on the dishes, after they were rinsed. The deposits are essentially mineral compounds, in particular Ca and / or Mg salts, but also surfactant residues. However, lime mainly leads to undesirable deposits for the user. In order to reduce the proportion of these deposits, common dishwashing agents, in particular those for automatic dishwashing, generally contain so-called rinse aid. Commercially available rinse aids usually comprise mixtures of low foaming nonionic surfactants, typically fatty alcohol polyethylene / polypropylene glycol ethers, solubilizers (eg cumene sulfonate), organic acids (eg citric acid) and solvents (eg ethanol) It is to influence the interfacial tension of the water so that it can run in a very thin, coherent film of items to be washed, so that remain in the subsequent drying process no water droplets, stripes or films. There are differences between two types of deposits. On the one hand, the so-called "spotting", which is caused by drying drops of water, is examined. On the other hand, the "filming", which are layers that result from the drying of thin water films, is evaluated. For the evaluation, test persons are currently used who visually evaluate the parameters "spotting" and "filming" for cleaned objects, eg plates, glasses, knives, etc. Modern dishwashing detergents, therefore, contain rinse aid to improve the drainage of water from the surfaces of the dishes. There are rinse aids that do not dry on all substrates, such as plastic as well. To get around this effect, consuming formulated conventional rinse aid, for example, have silicone compounds or fluorinated compounds, as described in the US 5,880,089 or the US 2005/0143280 A1 to be discribed. However, these compounds are biologically difficult or even not degradable and sometimes even dangerous to the environment.

In jüngerer Zeit finden zunehmend Kombinationsprodukte Verwendung, bei denen die verschiedenen Funktionen, wie Reinigen, Klarspülen, Wasserenthärtung und ggf. Metallinsbesondere Silberschutz oder eine Glasschutzfunktionen in einer, vorzugsweise festen Angebotsform kombiniert werden. Solche Mittel werden als multifunktionale Mittel bezeichnet. So finden sich im Mark beispielsweise so genannte 3-in-1-Produkte, die Reiniger, Klarspüler und Wasserenthärtung in Form eines festen Presslings ("Tabs") vereinen. Durch den vermehrten Einsatz solcher multifunktionalen Mittel ist aber die Trocknungsleistung im Vergleich zum Einsatz eines klassischen Klarspüler schlechter geworden. Unter Trocknungsleistung ist dabei zu verstehen, in wie weit das gereinigte Spülgut nach Durchlaufen des Geschirrspülverfahrens noch Wasser, vorzugsweise Wassertropfen, auf der Oberfläche aufweist. Das auf der Oberfläche verbleibende Wasser muss dann entweder mechanisch entfernt werden (z.B. durch Trockenwischen) oder man muss das Spülgut an der Luft trocknen lassen. Der Anwender muss also warten bis das Wasser verdunstet ist. Dabei verbleiben aber auf der Oberfläche Rückstände (z.B. Kalk und/oder Tensidreste oder andere Rückstände, die im Wasser gelöst oder dispergiert waren) die zu unästhetischen Flecken oder Streifen führen. Dies gilt in besonderem Maßen bei glänzenden oder transparenten Oberfläche, wie z.B. Glas oder Metall. Es wird daher nach Wegen gesucht, die Trocknungsleistung von Reinigungsmitteln für harte Oberflächen, insbesondere von Geschirrspülmitteln zu verbessern. Die EP 1 306 423 A2 offenbart wässerige Reinigungsmittel, die Alkylethersulfate und amphothere Glycinverbindungen enthalten und geeignet sind, das Trocknungsverhalten von Geschirrspülmitteln zu verbessern. Die DE 100 45 289 A1 beschreibt Handgeschirrspülmittel, die bestimmte quaternäre Ammoniumverbindungen und Alkylethersulfate nebeneinander enthalten und ebenfalls ein besonders gutes Trocknungsverhalten zeigen.More recently, combination products are increasingly being used, in which the various functions, such as cleaning, rinsing, water softening and, if appropriate, metal, in particular silver protection or a glass protection function, are combined in a preferably solid form. Such agents are referred to as multifunctional agents. For example, so-called 3-in-1 products, which combine cleaners, rinse aids and water softening in the form of a solid compact ("tabs"), are found in the market. Due to the increased use of such multifunctional agents but the drying performance has become worse compared to the use of a classic rinse aid. Drying performance is to be understood in how far the cleaned items to be washed, after passing through the dishwashing process, still have water, preferably water drops, on the surface. The remaining water on the surface must then either be removed mechanically (eg by dry wiping) or the ware must be allowed to air-dry. The user must wait until the water evaporates. However, residues (eg lime and / or surfactant residues or other residues dissolved or dispersed in the water) remain on the surface which lead to unaesthetic spots or streaks. This applies in particular to shiny or transparent surfaces, such as glass or metal. It is therefore sought ways to improve the drying performance of cleaning agents for hard surfaces, especially dishwashing detergents. The EP 1 306 423 A2 discloses aqueous detergents which contain alkyl ether sulfates and amphoteric glycine compounds and are suitable for improving the drying behavior of dishwashing detergents. The DE 100 45 289 A1 describes hand dishwashing detergents which contain certain quaternary ammonium compounds and alkyl ether sulfates side by side and also show a particularly good drying behavior.

Weiterhin dürfen Zusätze für Reinigungsmittel die Spül- und insbesondere die Klarspülleistung der Reiniger nicht nachteilig beeinflussen. Im Idealfall sollte ein Zusatz sogar die Leistung des Reinigers insgesamt verbessern.Furthermore, additives for cleaning agents must not adversely affect the rinsing and in particular the rinse performance of the cleaner. Ideally, an additive should even improve the overall performance of the cleaner.

Es wurde nun gefunden, das die Kombination bestimmter oberflächenaktiver Substanzen geeignet ist, die Trocknungsleistung von Reinigungsmitteln für harte Oberflächen, insbesondere von Mitteln zum Geschirrspülen, und hier ganz besonders in multifunktionellen Mittel, zu verbessern und gleichzeitig ökologisch unbedenklich zu sein.It has now been found that the combination of certain surface-active substances is suitable for improving the drying performance of hard-surface cleaners, in particular dishwashing compositions, and more particularly in multifunctional compositions, while being ecologically harmless.

Gegenstand der vorliegenden Erfindung sind daher in einer ersten Ausführungsform Mischungen, enthaltend mindestens zwei verschiedene oberflächenaktive Substanzen aus den Gruppen a) und b), wobei die oberflächenaktive Verbindung a) ausgewählt ist aus Verbindungen, die der allgemeinen Formel (Ia) folgen:

Figure imgb0001
worin M für einen Rest CH2-CH2 oder CHR-CH2 steht, R, R' bzw. R" unabhängig voneinander für gesättigte, ungesättigte, lineare oder verzweigte Alkyl- bzw. Alkenylreste mit 6 bis 22 C-Atomen stehen, und die Indices n und m unabhängig voneinander Werte zwischen 1 und 40 annehmen können, und/oder Verbindungen der allgemeinen Formel (Ib) folgen
Figure imgb0002
 worin R"' und R"" unabhängig voneinander für gesättigte, ungesättigte, lineare oder verzweigte Alkyl- bzw. Alkenylreste mit 4 bis 22 C-Atomen stehen, und die Indices n und m unabhängig voneinander Werte zwischen 1 und 40 annehmen können, X' und X" stehen unabhängig voneinander für H oder für gesättigte, ungesättigte, lineare oder verzweigte Alkyl- bzw. Alkenylreste mit 1 bis 18 C-Atomen stehen die Komponente b) ausgewählt ist ausThe present invention therefore relates, in a first embodiment, to mixtures comprising at least two different surface-active substances from groups a) and b), the surface-active compound a) being selected from compounds which have the general formula (Ia):
Figure imgb0001
 wherein M is a radical CH 2 -CH 2 or CHR-CH 2 , R, R 'and R "independently represent saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 6 to 22 carbon atoms, and the indices n and m independently of one another can assume values between 1 and 40, and / or compounds of the general formula (Ib) follow
Figure imgb0002
 wherein R "'and R""independently of one another represent saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 4 to 22 C atoms, and the indices n and m independently of one another can assume values between 1 and 40, X' and X "independently of one another are H or are saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 1 to 18 C atoms and the component b) is selected from

b1) Verbindungen der allgemeinen Formel (II)b1) compounds of the general formula (II)



        R1O[CH2CH2O]xCH2CH(OM)R2     (II)

in der R1 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen bedeutet, oder für einen Rest R2-CH(OH)CH2 steht, wobei R2 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 8 bis 16 Kohlenstoffatomen, x für eine Zahl von 20 bis 80, vorzugsweise 40 bis 80 steht, und M für ein Wasserstoffatom oder einen gesättigten Alkylrest mit 1 bis 18 Kohlenstoffatomen, und/oder aus Verbindungen der Gruppe b2) gemäß der allgemeinen Formel III

        R3O[CH2CH2O]y[CH2CHCH3O]2CH2CH(OH)R4     (III)

in der R3 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 8 bis 22 Kohlenstoffatomen, R4 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 8 bis 16 Kohlenstoffatomen, y für eine Zahl von 10 und 35 steht, z Null bedeutet oder eine Zahl von 1 bis 5, mit der Maßgabe, dass wenn R3 = R1 und gleichzeitig R4 = R2 ist, dass dann z mindestens 1 sein muss.

R 1 O [CH 2 CH 2 O] x CH 2 CH (OM) R 2 (II)

in which R 1 is a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, or a radical R 2 is -CH (OH) CH 2 , where R 2 is a linear or branched alkyl and / or Alkenyl radical having 8 to 16 carbon atoms, x is a number from 20 to 80, preferably 40 to 80, and M is a hydrogen atom or a saturated alkyl radical having 1 to 18 carbon atoms, and / or compounds of group b2) according to the general formula III

R 3 O [CH 2 CH 2 O] y [CH 2 CHCH 3 O] 2 CH 2 CH (OH) R 4 (III)

in which R 3 is a linear or branched alkyl and / or alkenyl radical having 8 to 22 carbon atoms, R 4 is a linear or branched alkyl and / or alkenyl radical having 8 to 16 carbon atoms, y is a number of 10 and 35, z is zero or a number from 1 to 5, with the proviso that if R 3 = R 1 and at the same time R 4 = R 2 , then z must be at least 1.

Aus der EP 1 645 618 A1 der Anmelderin sind bereits Mischungen von Hydroxymischethern gemäß den Formeln (II) und (III) mit Polyolhydroxyalkylethern und deren Verwendung in Geschirrspülmitteln bekannt. Allerdings betreffen diese Mischungen gegenüber der vorliegenden Anmeldung unterschiedliche Komponenten vom Typ a). Die beschriebenen Mischungen enthalten mindestens eine Komponente ausgewählt aus Verbindungen der Formeln (Ia) oder (Ib), und mindestens eine Verbindungen ausgewählt aus Verbindungen der Formeln (II) oder (III). Die Verbindungen der Formeln (Ia) ( EP1254948 , EP1321511 , EP1288281 ), (Ib) ( WO9513260 , WO9600253 ), (II) ( EP1764408 ) und (III) ( DE19738866 ) sind dem Fachmann bekannte chemische Verbindungen.From the EP 1 645 618 A1 the applicant are already known mixtures of Hydroxymischethern according to the formulas (II) and (III) with Polyolhydroxyalkylethern and their use in dishwashing detergents. However, these mixtures relate to the present application different components of the type a). The mixtures described contain at least one component selected from compounds of the formulas (Ia) or (Ib), and at least one compound selected from compounds of the formulas (II) or (III). The compounds of the formulas (Ia) ( EP1254948 . EP1321511 . EP1288281 (Ib) ( WO9513260 . WO9600253 (II) ( EP1764408 ) and (III) DE19738866 ) are known to the expert chemical compounds.

Verbindungen der Gruppe a)Compounds of group a)

Die erfindungsgemäßen Mischungen enthalten zwingend Verbindungen des Typs a). Dabei handelt es sich um Verbindungen der obigen Formeln (Ia) und/oder (Ib) wobei bestimmte Strukturen bevorzugt sind. Bevorzugt sind insbesondere Verbindungen gemäß der allgemeinen Formel (Ia), wenn M für einen CH2-CRH-Gruppe steht, R einen linearen, gesättigten Alkylrest mit 8 bis 16, vorzugsweise 8 bis 12 und insbesondere 8 bis 10 C-Atomen bedeutet, und R' und R" jeweils unabhängig voneinander für einen linearen, gesättigten Alkylrest mit 10 bis 16, vorzugsweise 10 bis 14 C-Atomen steht, und n und m unabhängig voneinander Werte von 20 bis 30 aufweisen kann. Solche Verbindungen können beispielsweise durch Umsetzung von Alkyldiolen, HO-CHR-CH2-OH mit Ethylenoxid erhalten werden wobei im Anschluss eine Umsetzung mit einem Alkylepoxid zum Verschluss der freien OH-Funktionen erfolgt, so dass in der Folge ein Dihydroxyether entsteht.The mixtures according to the invention necessarily contain compounds of the type a). These are compounds of the above formulas (Ia) and / or (Ib) wherein certain structures are preferred. In particular, compounds according to the general formula (Ia) are preferred when M is a CH 2 -CRH group, R is a linear, saturated alkyl radical having 8 to 16, preferably 8 to 12 and in particular 8 to 10 carbon atoms, and R 'and R "each independently represent a linear, saturated alkyl radical having from 10 to 16, preferably 10 to 14, carbon atoms, and n and m independently of one another may have values of from 20 to 30. Such compounds may For example, by reacting alkyldiols, HO-CHR-CH 2 -OH are obtained with ethylene oxide followed by a reaction with an Alkylepoxid to close the free OH functions, so that a dihydroxy ether is formed in the sequence.

Ebenfalls bevorzugt sind Strukturen, die der allgemeinen Formel (Ib) folgen:

Figure imgb0003
wobei X' und X" = H sind, und in der Formel (Ib) die Indices n und m unabhängig voneinander Werte von 1 bis 40, vorzugsweise aber von 1 bis 15 annehmen können. Besonders bevorzugt sind hierbei Verbindungen der Formel (Ib), in der die Reste R"' bzw. R"" unabhängig voneinander gesättigte Alkylrest mit 4 bis 14 C-Atomen darstellen, und die Indices n und m unabhängig voneinander Werte von 1 bis 15 und insbesondere von 1 bis 12 annehmen. Weiterhin bevorzugt sind solche Verbindungen der Formel (Ib) in der ein Rest R"' oder R"" verzweigt ist. Unabhängig davon sind Verbindungen der Formel (Ib) bevorzugt, bei denen die Indices n und m gleichzahlig sind und Werte im Bereich von 8 bis 12 aufweisen.Also preferred are structures which follow the general formula (Ib):
Figure imgb0003
 where X 'and X "= H, and in the formula (Ib) the indices n and m can independently of one another assume values of 1 to 40, but preferably of 1 to 15. Particular preference is given in this connection to compounds of the formula (Ib) in which the radicals R "'and R""independently of one another represent saturated alkyl radicals having 4 to 14 C atoms, and the indices n and m independently of one another assume values of 1 to 15 and in particular of 1 to 12. Preference is furthermore given to those compounds of the formula (Ib) in which a radical R "'or R""is branched, preference being given to compounds of the formula (Ib) in which the indices n and m are equal and values in the range from 8 to 12 have.

Die zweite Komponente der Mischungen sind Verbindungen der Formeln (II) bzw. (III), die als Hydroxymischether bezeichnet werden können.The second component of the mixtures are compounds of the formulas (II) and (III), which can be referred to as hydroxy mixed ethers.

Hydroxymischetherhydroxy mixed

Hydroxymischether (im Weiteren als HME abgekürzt) folgen der breiten allgemeinen Formel

        R'O[AO]xCH2CH(OM)R"

in der R' für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, R" für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 2 bis 22 Kohlenstoffatomen x für 10 bis 80 steht und AO einen Ethylenoxid-, Propylenoxid- und/oder Butylenoxid-Rest symbolisiert und M für ein Wasserstoffatom oder einen Alkyl- bzw. Alkenylrest stehen kann.Hydroxy mixed ethers (hereinafter abbreviated to HME) follow the broad general formula

R'O [AO] x CH 2 CH (OM) R "

in which R 'is a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, R "is a linear or branched alkyl and / or alkenyl radical having 2 to 22 carbon atoms x is 10 to 80 and AO is an ethylene oxide radical , Propylene oxide and / or butylene oxide radical symbolized and M can stand for a hydrogen atom or an alkyl or alkenyl radical.

Solche Hydroxymischether sind literaturbekannt und werden beispielsweise in der deutschen Anmeldung DE 19738866 beschrieben. Sie werden beispielsweise hergestellt durch Umsetzung von 1,2-Epoxyalkanen (R"CHOCH2), wobei R" für einen Alkyl- und/oder Alkenylrest mit 2 bis 22, insbesondere 6 bis 16 Kohlenstoffatomen steht, mit alkoxylierten Alkoholen.Such hydroxy mixed ethers are known from the literature and are described, for example, in the German application DE 19738866 described. They are prepared, for example, by reaction of 1,2-epoxyalkanes (R "CHOCH 2 ), where R" is an alkyl and / or alkenyl radical having 2 to 22, in particular 6 to 16, carbon atoms, with alkoxylated alcohols.

Bevorzugt im Sinne der Erfindung werden solche Hydroxymischether, die sich von Alkoxylaten von einwertigen Alkoholen der Formel R'-OH mit 4 bis 18 Kohlenstoffatomen ableiten, wobei R' für einen aliphatischen, gesättigten, geradkettigen oder verzweigten Alkylrest, insbesondere mit 6 bis 16 Kohlenstoffatomen, steht. Beispiele für geeignete geradkettige Alkohole sind Butanol-1, Capron-, Önanth-, Capryl-, Pelargon-, Caprinalkohol, Undecanol-1, Laurylalkohol, Tridecanol-1, Myristylalkohol, Pentadecanol-1, Palmitylakohol, Heptadecanol-1, Stearylalkohol, Nonadecanol-1, Arachidylalkohol, Heneicosanol-1, Behenylalkohol sowie deren technische Mischungen, wie sie bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und Ölen anfallen. Beispiele für verzweigte Alkohole sind so genannte Oxoalkohole, die meist 2 bis 4 Methylgruppen als Verzweigungen tragen und nach dem Oxoprozeß hergestellt werden und so genannte Guerbetalkohole, die in 2-Stellung mit einer Alkylgruppe verzweigt sind. Geeignete Guerbetalkohole sind 2-Ethylhexanol, 2-Butyloctanol, 2-Hexyldecanol und/oder 2-Octyldodecanol. Die Alkohole werden in Form ihrer Alkoxylate eingesetzt, die durch Umsetzung der Alkohole mit Ethylenoxid auf bekannte Weise hergestellt werden.Preferred for the purposes of the invention are those hydroxy mixed ethers which are derived from alkoxylates of monohydric alcohols of the formula R'-OH having 4 to 18 carbon atoms, where R 'is an aliphatic, saturated, straight-chain or branched alkyl radical, in particular having 6 to 16 carbon atoms, stands. Examples of suitable straight-chain alcohols are butanol-1, caproic, eananthic, caprylic, pelargonic, capric alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, palmityl alcohol, heptadecanol-1, stearyl alcohol, nonadecanol- 1, arachidyl alcohol, heneicosanol-1, behenyl alcohol and their technical mixtures, as obtained in the high pressure hydrogenation of technical methyl esters based on fats and oils. Examples of branched alcohols are so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are prepared by the oxo process and so-called Guerbet alcohols which are branched in the 2-position with an alkyl group. Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol. The alcohols are used in the form of their alkoxylates, which are prepared by reaction of the alcohols with ethylene oxide in a known manner.

Oberflächenaktive Verbindungen vom Typ b1)Surface-active compounds of type b1)

Es handelt sich hier um handelsübliche Tenside der allgemeinen Formel (II)

        R1O[CH2CH2O]xCH2CH(OM)R2     (II)

in der R1 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen bedeutet, oder für einen Rest R2-CH(OH)CH2 steht, wobei R2 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 8 bis 16 Kohlenstoffatomen, x für eine Zahl von 40 bis 80 steht, und M für ein Wasserstoffatom oder einen gesättigten Alkylrest mit 1 bis 18 Kohlenstoffatomen steht. Vorteilhaft werden solche Verbindungen des Typs b) der allgemeinen Formel (II) verwendet, die mindestens eine freie Hydroxylgruppe (= -OH) enthalten. Bevorzugt im Sinne der Erfindung werden solche Hydroxymischether, die sich von Ethoxylaten von einwertigen Alkoholen der Formel R1-OH mit 6 bis 18 Kohlenstoffatomen, vorzugsweise 6 bis 16 und insbesondere 8 bis 10 Kohlenstoffatomen ableiten, wobei R1 für einen linearen Alkylrest steht und x für 40 bis 60. Weiterhin sind in den erfindungsgemäßen Mischungen solche Verbindungen der allgemeinen Formel (II) bevorzugt, bei denen der Index x für eine Zahl von 40 bis 70, vorzugsweise 40 bis 60 und insbesondere von 40 bis 50 steht. M ist dabei dann ein Wasserstoffatom. Ganz besonders bevorzugt sind Hydroxymischether der Formel (II), wobei R1 für einen Alkylrest mit 8 bis 10 Kohlenstoffatomen, insbesondere auf Basis eines nativen Fettalkohols, R2 für einen Alkylrest mit 10 Kohlenstoffatome, insbesondere für einen linearen Alkylrest und x für 40 bis 60 steht. Bevorzugt sind weiterhin Mischungen, die als oberflächenaktive Verbindung vom Typ a) eine Verbindung nach der allgemeinen Formel (II) enthält, in der R1 für eine Alkyl- und/oder Alkenylrest mit 8 bis 10 Kohlenstoffatomen steht und R2 für einen Alkyl- oder Alkenylrest mit 8 bis 10 Kohlenstoffatomen steht und x eine Zahl von 40 bis 50 bedeutet, wobei auch hier M für ein Wasserstoffatom steht.These are commercially available surfactants of the general formula (II)

R 1 O [CH 2 CH 2 O] x CH 2 CH (OM) R 2 (II)

in which R 1 is a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, or a radical R 2 is -CH (OH) CH 2 , where R 2 is a linear or branched alkyl and / or Alkenyl radical having 8 to 16 carbon atoms, x represents a number from 40 to 80, and M represents a hydrogen atom or a saturated alkyl radical having 1 to 18 carbon atoms. Advantageously, those compounds of the type b) of the general formula (II) are used which contain at least one free hydroxyl group (= -OH). Preferred for the purposes of the invention are those hydroxy mixed ethers derived from ethoxylates of monohydric alcohols of the formula R 1 -OH having 6 to 18 carbon atoms, preferably 6 to 16 and in particular 8 to 10 carbon atoms, wherein R 1 is a linear alkyl radical and x is 40 to 60. Furthermore, in the mixtures according to the invention those compounds of general formula (II) are preferred in which the index x for a Number from 40 to 70, preferably 40 to 60 and in particular from 40 to 50 stands. M is then a hydrogen atom. Very particular preference is given to hydroxy mixed ethers of the formula (II) where R 1 is an alkyl radical having 8 to 10 carbon atoms, in particular based on a native fatty alcohol, R 2 is an alkyl radical having 10 carbon atoms, in particular a linear alkyl radical and x is 40 to 60 stands. Preference is furthermore given to mixtures which contain as surface-active compound of type a) a compound of the general formula (II) in which R 1 is an alkyl and / or alkenyl radical having 8 to 10 carbon atoms and R 2 is an alkyl or Alkenyl radical having 8 to 10 carbon atoms and x is a number from 40 to 50, wherein also here M stands for a hydrogen atom.

Ein besonders bevorzugter HME im Sinne der vorliegenden Lehre folgt der allgemeinen Formel

Figure imgb0004
A particularly preferred HME in the context of the present teaching follows the general formula
Figure imgb0004

Wobei R' für ein gesättigten Alkylrest mit 8 bis 12, vorzugsweise 8 bis 10 C-Atomen steht und R" einen Alkylrest mit 8 bis 12, vorzugsweise 8 bis 10 C-Atomen darstellt. Der Index x kann Werte von 20 bis 80, vorzugsweise von 30 bis 60 und insbesondere von 40 bis 50 aufweisen, wobei generell solche Verbindungen bevorzugt sind, bei denen der Index x größer als 40 ist.Wherein R 'is a saturated alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms and R "is an alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms The index x can have values of from 20 to 80, preferably from 30 to 60 and in particular from 40 to 50, wherein in general those compounds are preferred in which the index x is greater than 40 are preferred.

Oberflächenaktive Verbindungen vom Typ b2)Surface-active compounds of type b2)

Bei diesen Verbindungen handelt es sich ebenfalls um HME, allerdings haben diese eine andere Struktur als die HME der allgemeinen Formel (II).These compounds are also HME, but they have a different structure than the HME of the general formula (II).

Die Verbindungen des Typs b2) folgen der Formel (III)

        R3O [CH2CHCH3O]z[CH2CH2O]yCH2CH(OH)R4     (III)

in der R3 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 8 bis 22 Kohlenstoffatomen, R4 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 8 bis 16 Kohlenstoffatomen, y für eine Zahl von 10 und 35 steht, z Null bedeutet oder eine Zahl von 1 bis 5 sein muss. Es kann vorteilhaft sein dass, wenn R3 = R1 und gleichzeitig R4 = R2 solche Verbindungen der Formel b2) ausgewählt werden in denen der Index z mindestens 1 ist. Sofern Mischungen der oberflächenaktiven Verbindungen vom Typ a) mit denen des Typs b2) Verwendung finden, sind nur solche Mischungen im Sinne der vorliegenden technischen Lehre, bei denen sich die Moleküle strukturell voneinander unterscheiden. Es müssen also immer strukturverschiedene Verbindungen nebeneinander vorliegen.The compounds of the type b2) follow the formula (III)

R 3 O [CH 2 CHCH 3 O] z [CH 2 CH 2 O] y CH 2 CH (OH) R 4 (III)

in which R 3 is a linear or branched alkyl and / or alkenyl radical having 8 to 22 carbon atoms, R 4 is a linear or branched alkyl and / or alkenyl radical having 8 to 16 carbon atoms, y is a number of 10 and 35, z is zero or must be a number from 1 to 5. It may be advantageous if R 3 = R 1 and at the same time R 4 = R 2 those compounds of the formula b 2 ) are selected in which the index z is at least 1. If mixtures of the surface-active compounds of the type a) with those of the type b2) are used, only those mixtures within the meaning of the present technical teaching in which the molecules structurally differ from one another. So there must always be different structure connections side by side.

Besonders bevorzugte Verbindungen vom Typ b2) sind beispielsweise solche bei denen in der Formel (III) der Index y für einen Zahl von 20 bis 30, vorzugsweise von 20 bis 25 steht. Weiterhin bevorzugt sind solche Verbindungen des Typs b2) bei denen in der Formel (III) R3 einen Alkylrest mit 8 bis 12, vorzugsweise 8 bis 10 Kohlenstoffatomen repräsentiert, R4 für einen Alkylrest mit 10 bis 12, vorzugsweise mir 10 Kohlenstoffatomen bedeutet, y eine Zahl von 15 bis 35, vorzugsweise 20 bis 30 bedeutet und z eine Zahl von 1 bis 3, vorzugsweise 1 bedeutet.Particularly preferred compounds of type b2) are, for example, those in which, in the formula (III), the index y is a number from 20 to 30, preferably from 20 to 25. Preference is furthermore given to those compounds of the type b2) in which R 3 in the formula (III) represents an alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms, R 4 is an alkyl radical having 10 to 12, preferably 10 carbon atoms, y a number from 15 to 35, preferably 20 to 30 and z is a number from 1 to 3, preferably 1 means.

Bevorzugt sind auch Mischungen, die als oberflächenaktive Verbindung vom Typ b2) eine Verbindung nach der allgemeinen Formel (III) enthalten, in der R3 für eine Alkyl- und/oder Alkenylrest mit 9 bis 18 Kohlenstoffatomen steht und R4 für einen Alkyl- oder Alkenylrest mit 8 bis 10 Kohlenstoffatomen steht und y eine Zahl von 20 bis 35 bedeutet.Preference is also given to mixtures containing as surface-active compound of type b2) a compound of the general formula (III) in which R 3 is an alkyl and / or alkenyl radical having 9 to 18 carbon atoms and R 4 is an alkyl or Alkenyl radical having 8 to 10 carbon atoms and y is a number from 20 to 35.

Ebenfalls bevorzugt sind Mischungen, die als oberflächenaktive Verbindung vom Typ b2) eine Verbindung nach der allgemeinen Formel (III) enthält, in der R3 für eine Alkyl- und/oder Alkenylrest mit 8 bis 12 Kohlenstoffatomen steht und R4 für einen Alkyl- oder Alkenylrest mit 8 bis 10 Kohlenstoffatomen steht und y eine Zahl von 20 bis 35 und z eine Zahl von 1 bis 3 bedeutet. Die Verbindungen des Typs b2) stellen ebenfalls Hydroxymischetherderivate dar, die durch Umsetzung von propoxylierten und/oder ethoxylierten Fettalkoholen mit Alkylepoxiden durch Ringöffnung im alkalischen Milieu hergestellt werden können.Also preferred are mixtures containing as surface-active compound of type b2) a compound of the general formula (III) in which R 3 is an alkyl and / or alkenyl radical having 8 to 12 carbon atoms and R 4 is an alkyl or Alkenyl radical having 8 to 10 carbon atoms and y is a number from 20 to 35 and z is a number from 1 to 3. The compounds of type b2) are also hydroxy mixed ether derivatives which can be prepared by reacting propoxylated and / or ethoxylated fatty alcohols with alkyl epoxides by ring opening in an alkaline medium.

Dabei ist es bei Derivaten des Typs b2) wie auch bei allen anderen in dieser Beschreibung aufgeführten gemischten Alkoxylaten, die also sowohl einen Propylenoxid-Rest CH2CHCH3O (PO) als auch einen Ethylenoxid-Rest CH2CH2O (EO) enthalten, möglich, dass aus Richtung des C-Atoms mit der freien Hydroxylgruppe zunächst die EO-Reste und dann die PO-Reste blockweise angeordnet sind, wobei auch die Abfolge erst PO, dann EO möglich ist. Weiterhin können die Alkoxid-Gruppen auch statistisch verteilt (randomisiert) im Molekül vorliegen. Es ist auch möglich sowohl Block- als auch Random-Alkoxylate nebeneinander zu verwenden.It is in the case of derivatives of the type b2) as well as in all other mixed alkoxylates listed in this description, that is to say both a propylene oxide radical CH 2 CHCH 3 O (PO) and an ethylene oxide radical CH 2 CH 2 O (EO) contain, possible that from the direction of the C atom with the free hydroxyl group first the EO residues and then the PO residues are arranged in blocks, whereby the sequence first PO, then EO possible is. Furthermore, the alkoxide groups can also be randomly distributed (randomized) in the molecule. It is also possible to use both block and random alkoxylates side by side.

Was die Anzahl der EO bzw. PO-Gruppen in einem Molekül gemäß den Formel der vorliegenden Anmeldung angeht so gilt, dass es sich bei den Werten um Mittelwerte handelt, da herstellungsbedingt unterschiedlich alkoxylierte Derivate nebeneinander vorliegen. Die Anzahl der Alkyoxidgruppen kann daher auch ungeradzahlig sein.As far as the number of EO or PO groups in a molecule according to the formula of the present application is concerned, the values are average values since, due to their production, different alkoxylated derivatives are present side by side. The number of alkoxide groups can therefore also be odd.

Ein besonders bevorzugter Typ von HME der allgemeinen Formel (III) wird durch die folgende Markush-Formel beschrieben:

Figure imgb0005
wobei R' und R" unabhängig voneinander für einen gesättigten Alkylrest mit 8 bis 12, vorzugsweise 8 bis 10 C-Atomen stehen. Der Index x kann Werte von 1 bis 10, vorzugsweise von 1 bis 4 und insbesondere von 1 bis 2 aufweisen, und y hat Werte von 10 bis 30, vorzugsweise von 15 bis 25 und insbesondere von 20 bis 22, wobei generell solche Verbindungen bevorzugt sind, bei denen der Index x = 1 ist.A particularly preferred type of HME of the general formula (III) is described by the following Markush formula:
Figure imgb0005
 where R 'and R "independently of one another represent a saturated alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms. The index x can have values of from 1 to 10, preferably from 1 to 4 and in particular from 1 to 2, and y has values of from 10 to 30, preferably from 15 to 25 and in particular from 20 to 22, preference being generally given to those compounds in which the index x = 1.

Die vorliegende Erfindung macht nun von der Erkenntnis gebrauch, dass die Anwesenheit von ausgewählten HME (Typ b)), oder von deren Derivaten, in Kombination mit strukturverschiedenen oberflächenaktiven Verbindungen des Typs a) vorteilhafte Eigenschaften in Bezug auf die Trocknung- und/oder der Klarspülleistung von Reinigerformulierungen für harte Oberflächen und insbesondere von Geschirrspülmitteln haben kann.The present invention now makes use of the finding that the presence of selected HME (type b)), or their derivatives, in combination with structure-different surface-active compounds of type a) advantageous drying and / or rinsing performance of cleaner formulations for hard surfaces, and particularly dishwashing detergents.

Besonders bevorzugte Mischungen im Sinne der vorliegenden technischen Lehre betreffen Kombinationen der Verbindungen gemäß den Formeln (Ia) und/oder (Ib) mit Verbindungen gemäß der Formel (III).Particularly preferred mixtures within the meaning of the present technical teaching relate to combinations of the compounds of the formulas (Ia) and / or (Ib) with compounds of the formula (III).

Neben den oben beschrieben oberflächenaktiven Verbindungen kann es vorteilhaft sein, weitere oberflächenaktive Verbindungen (also Tenside) mit zu verwenden. Hier kommen insbesondere reine Fettalkohole in Frage.In addition to the surface-active compounds described above, it may be advantageous to use further surface-active compounds (ie surfactants). Pure fatty alcohols in particular come into question here.

Unter Fettalkoholen sind primäre aliphatische Alkohole der Formel R-OH zu verstehen, in der R für einen aliphatischen, linearen oder verzweigten Kohlenwasserstoffrest mit 6 bis 22 Kohlenstoffatomen und 0 und/oder 1, 2 oder 3 Doppelbindungen steht. Typische Beispiele sind Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen, die z.B. bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und Ölen oder Aldehyden aus der Roelen'schen Oxosynthese sowie als Monomerfraktion bei der Dimerisierung von ungesättigten Fettalkoholen anfallen. Bevorzugt sind technische Fettalkohole mit 12 bis 18 Kohlenstoffatomen, wie beispielsweise Kokos-, Palm-, Palmkern- oder Talgfettalkohol.Fatty alcohols are primary aliphatic alcohols of the formula R-OH in which R is an aliphatic, linear or branched hydrocarbon radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds. Typical examples are caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and the like technical mixtures, eg incurred in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Preferred are technical fatty alcohols having 12 to 18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty alcohol.

Die Verbindungen des Typs a) und b) liegen vorzugsweise in einem Gewichtsverhältnis von 10 : 1 bis 1 : 10 nebeneinander in den Mischungen im Sinne der Erfindung vor. Bevorzugt können dabei aber solche Mischungen sein, bei denen die oberflächenaktiven Verbindungen des Typs a) und b) im Gewichtsverhältnis von 5 : 1 bis 1 : 5, insbesondere von 3 : 1 bis 1 : 3 und besonders bevorzugt von 2 : 1 bis 1 : 2 und ganz besonders bevorzugt von 1 : 1 nebeneinander vorliegen. Die Verbindungen des Typs b1) und/oder b2) können - wie oben bereits ausgeführt - auch nebeneinander in beliebigen Mischungen vorliegen. Vorzugsweise bestehen die Mischungen aber nur aus einer Verbindung des Typs a) und einer Verbindung des Typs b).The compounds of the type a) and b) are preferably present in a weight ratio of 10: 1 to 1:10 side by side in the mixtures according to the invention. However, preference may be given to those mixtures in which the surface-active compounds of the type a) and b) in a weight ratio of 5: 1 to 1: 5, in particular from 3: 1 to 1: 3 and particularly preferably from 2: 1 to 1: 2 and most preferably 1: 1 are present side by side. The compounds of type b1) and / or b2) can - as stated above - also be present side by side in any mixtures. Preferably, however, the mixtures consist only of a compound of type a) and a compound of type b).

Die oben beschriebenen Mischungen eignen sich vorzugsweise zur Verwendung in Reinigungsmitteln, insbesondere in Geschirrspülmitteln und insbesondere in Mitteln für das automatische Geschirrspülen. Die Mischungen können Verwendung finden zur Verbesserung der Trocknungsleistung von Reinigungsmitteln und insbesondere für Geschirrspülmittel, bevorzugt für Geschirrspülmittel für das maschinelle Geschirrspülen. Eine weitere, bevorzugte Verwendung betrifft den Einsatz der Mischungen in multifunktionalen festen Geschirrspülmitteln für das automatische Geschirrspülen. Die Verbesserung der Trocknung betrifft insbesondere Oberflächen aus Plastik.The mixtures described above are preferably suitable for use in cleaners, in particular in dishwashing detergents and in particular in automatic dishwashing detergents. The mixtures can be used to improve the drying performance of cleaning agents and in particular for dishwashing detergents, preferably dishwasher detergents for automatic dishwashing. Another preferred use relates to the use of the mixtures in multifunctional solid Dishwashing detergents for automatic dishwashing. The improvement of the drying concerns in particular surfaces of plastic.

In einer weiteren Ausführungsform werden Mittel beansprucht, die 0,1 bis 15 Gew.-% der erfindungsgemäßen Mischungen, sowie weitere, in Reinigungsmittel und vorzugsweise Geschirrspülmitteln übliche Inhaltsstoffe enthalten. Vorzugweise enthalten die Reinigungsmittel die erfindungsgemäßen Mischungen in Mengen von 0,1 bis 12 Gew.-% wobei vorteilhafter weise 1 bis 10 Gew.-% und insbesondere Mengen von 1,0 bis 8 Gew.-% enthalten sind. Besonders bevorzugt ist der Bereich von 2,0 bis 8,0 Gew.-%.In a further embodiment, agents are claimed which contain from 0.1 to 15% by weight of the mixtures according to the invention and also other ingredients customary in detergents and, preferably, dishwashing detergents. Preferably, the detergents contain the mixtures according to the invention in amounts of from 0.1 to 12% by weight, advantageously from 1 to 10% by weight and in particular from 1.0 to 8% by weight. Particularly preferred is the range of 2.0 to 8.0 wt .-%.

Die üblichen Inhaltsstoffe der erfindungsgemäßen Mittel im Sinne der obigen Beschreibung können beispielsweise weitere nichtionische, anionische und/oder kationische Tenside, Builder, Enzyme, Bleichmittel, wie z.B. Percarbonate sein. Weiterhin können solche Mittel Silikate, Phosphor-Verbindungen, Carbonate, aber auch spezielle Klarspüler und sonstige bekannte und übliche Hilfs- und Zusatzstoffe enthalten, z.B. pH-Regulantien oder Enzyme. Außerdem Lösungsmittel, wie Wasser oder niedere aliphatische Alkohole, vorzugsweise Ethanol oder Propanol, Solubilisatoren, Polymere oder organische Säuren, vorzugsweise Zitronensäure und deren Derivate.The usual ingredients of the compositions according to the invention in the sense of the above description can be, for example, further nonionic, anionic and / or cationic surfactants, builders, enzymes, bleaching agents, such as e.g. Be percarbonates. Furthermore, such agents may contain silicates, phosphorus compounds, carbonates, but also special rinse aids and other known and customary auxiliaries and additives, e.g. pH regulators or enzymes. In addition, solvents, such as water or lower aliphatic alcohols, preferably ethanol or propanol, solubilizers, polymers or organic acids, preferably citric acid and derivatives thereof.

Die Reinigungsmittel können sowohl flüssig als auch fest, beispielsweise als Granulate, Pulver oder Tabletten vorliegen. Flüssige Reinigungsmittel können noch Viskositätsbildner enthalten, um z.B. gelförmige Mittel zu erhalten.The cleaning agents can be both liquid and solid, for example as granules, powders or tablets. Liquid detergents may still contain viscosity builders, e.g. to obtain gel-like agents.

Vorzugsweise liegen Reinigungsmittel für das maschinelle Geschirrspülen in fester Form, so z.B. als Pulver oder Granulat oder als Formkörper, vorzugsweise in Tablettenform vor. Es können dabei auch mehrere Phasen nebeneinander vorliegen, beispielsweise eine verpresste Tablette, die in einer Ausbuchtung einen nicht verpresste Teil, z.B. eine wachsartige Klarspülerphase enthält. Solche multifunktionalen Mittel werden als 2-in-1 oder auch 3-in-1 Produkte vermarktet. Die Herstellung erfolgt auf jede, dem Fachmann bekannte Art und Weise, wobei in einer bevorzugten Ausführungsform die erfindungsgemäßen Mischungen als Compound vorliegen und vorzugsweise mit den anderen Inhaltsstoffen in beliebiger Reihenfolge vermischt werden. Es ist aber auch möglich die Tenside des Typs a) und b) einzeln mit den anderen Inhaltsstoffen zu vermischen und beispielsweise dann diese Mischung zum fertigen Mittel zu verpressen oder zu granulieren.Preferably, machine dishwashing detergents are in solid form, for example as powders or granules or as shaped articles, preferably in tablet form. There may also be several phases next to one another, for example a compressed tablet which contains in a bulge a non-compressed part, eg a waxy rinse aid phase. Such multifunctional agents are marketed as 2-in-1 or 3-in-1 products. The preparation is carried out in any manner known to the person skilled in the art, wherein in a preferred embodiment the mixtures according to the invention are present as a compound and are preferably mixed with the other ingredients in any order. But it is also possible to mix the surfactants of the type a) and b) individually with the other ingredients and, for example, then to press or granulate this mixture to the finished agent.

BeispieleExamples Herstellung der oberflächenaktiven VerbindungenPreparation of surface-active compounds

Im Weiteren werden Verfahren zur Herstellung der erfindungsgemäßen oberflächenaktiven Verbindungen gemäß den allgemeinen Formeln (Ia) bzw. (Ib) beschrieben:

  • 1. Herstellung eines Ethers gemäß Formel (Ia):
    Vorstufe Ethoxylat: 1 Mol 1,2-Dodecandiol und 0,06 Mol KOH als 45%ige Lösung werden in einem Rührautoklaven unter Stickstoff vorgelegt. Anschließend wird 30min bei 120°C evakuiert. Das Vakuum wird dann mit Stickstoff aufgehoben und es wird auf 160-180°C erhitzt. Bei 160°C beginnt die Zugabe von 40 Mol Ethylenoxid bei einem maximalen Druck von 5bar. Nach abgeschlossener Reaktion wird auf 120°C gekühlt und für 30min evakuiert. Für eine anschließende Lagerung wird das Produkt nach Erkalten neutralisiert (vorzugsweise mit Milchsäure oder Essigsäure). Für die weitere Umsetzung wird nicht neutralisiert. Die Vorstufe wird unter Stickstoff mit weiteren 0,05 Mol KOH versetzt und auf 160-180°C erhitzt. Dann tropft man 2 Mol 1,2-Epoxyhexadecan innerhalb von 1Stunde zu und rührt 2 Stunden bei 180°C nach. Anschließend kühlt man auch 60°C und neutralisiert (vorzugsweise mit Milchsäure oder Essigsäure).
  • 2. Herstellung eines Acetals gemäß (Ib):
    Vorstufe Fettalkoholethoxylat: 1 Mol Decanol und 0,03 Mol KOH als 45%ige Lösung werden in einem Rührautoklaven unter Stickstoff vorgelegt. Anschließend wird 30min bei 120°C evakuiert. Das Vakuum wird dann mit Stickstoff aufgehoben und es wird auf 160-180°C erhitzt. Bei 160°C beginnt die Zugabe von 9 Mol Ethylenoxid bei einem maximalen Druck von 5bar. Nach abgeschlossener Reaktion wird auf 120°C gekühlt und für 30min evakuiert. Für eine anschließende Lagerung oder Weiterverwendung wird das Produkt nach Erkalten neutralisiert (vorzugsweise mit Milchsäure oder Essigsäure).
  • 3. Herstellung eines unsymmetrischen Acetals gemäß (Ib):
    Das entsprechend unter 1. hergestellte Fettalkoholethoxylat wird mit überschüssigem Di-butylglykolformal in Gegenwart eines sauren Katalysators, bevorzugt Methansulfonsäure, umgesetzt. Hierzu werden Fettalkoholethoxylat und Di-butylglykolformal im Molverhältnis von ca. 1,1 Mol : 1,7 Mol vorgelegt und mit 6g Methansulfonsäure langsam auf 180°C bei einem Druck von ca. 5mbar angehoben. Bei einer Brüdentemperatur von ca. 121-137°C destilliert Butylglykol und überschüssige Formal ab. Das Produkt wird anschließend auf 50-70°C abgekühlt und durch Zugabe von NaOH neutralisiert.
  • 4. Herstellung eines symmetrischen Acetals gemäß (Ib):
    1Mol Fettalkoholethoxylat gem. 3) und 0,5 Mol Di-butylglykolformal werden unter Stickstoff vorgelegt und mit 0,02 Mol Schwefelsäure versetzt. Bei 97-152°C Sumpftemperatur und 5mbar werden Butylglykol und Reste des Formals abdestilliert. Anschließend wird mit NaOH oder einer anderen Base neutralisiert.
In addition, processes for the preparation of the surface-active compounds according to the invention according to the general formulas (Ia) or (Ib) are described:
  • 1. Preparation of an ether according to formula (Ia):
    Precursor ethoxylate: 1 mol of 1,2-dodecanediol and 0.06 mol of KOH as a 45% solution are placed in a stirred autoclave under nitrogen. The mixture is then evacuated at 120 ° C for 30 min. The vacuum is then quenched with nitrogen and heated to 160-180 ° C. At 160 ° C, the addition of 40 moles of ethylene oxide begins at a maximum pressure of 5 bar. After the reaction is cooled to 120 ° C and evacuated for 30 min. For subsequent storage, the product is neutralized after cooling (preferably with lactic acid or acetic acid). For further implementation is not neutralized. The precursor is added under nitrogen with a further 0.05 mol of KOH and heated to 160-180 ° C. Then added dropwise 2 moles of 1,2-epoxyhexadecane within 1 hour and stirred for 2 hours at 180 ° C after. Then it is also cooled to 60 ° C and neutralized (preferably with lactic acid or acetic acid).
  • 2. Preparation of an acetal according to (Ib):
    Precursor fatty alcohol ethoxylate: 1 mol of decanol and 0.03 mol of KOH as a 45% solution are placed in a stirred autoclave under nitrogen. The mixture is then evacuated at 120 ° C for 30 min. The vacuum is then quenched with nitrogen and heated to 160-180 ° C. At 160 ° C, the addition of 9 moles of ethylene oxide begins at a maximum pressure of 5 bar. After the reaction is cooled to 120 ° C and evacuated for 30 min. For subsequent storage or reuse, the product is neutralized after cooling (preferably with lactic acid or acetic acid).
  • 3. Preparation of an unsymmetrical acetal according to (Ib):
    The fatty alcohol ethoxylate prepared in accordance with 1. is reacted with excess di-butylglycol formal in the presence of an acidic catalyst, preferably methanesulfonic acid. For this purpose, fatty alcohol ethoxylate and di-butylglykolformal in a molar ratio of about 1.1 mol: submitted to 1.7 mol and slowly raised with 6g of methanesulfonic acid to 180 ° C at a pressure of about 5 mbar. At a Brüdentemperatur of about 121-137 ° C distilled butyl glycol and excess formal. The product is then cooled to 50-70 ° C and neutralized by addition of NaOH.
  • 4. Preparation of a symmetrical acetal according to (Ib):
    1 mole fatty alcohol ethoxylate acc. 3) and 0.5 mol of di-butylglykolformal are placed under nitrogen and treated with 0.02 mol of sulfuric acid. At 97-152 ° C bottom temperature and 5mbar butyl glycol and residues of the formal are distilled off. It is then neutralized with NaOH or another base.

Anwendunizstechnische UntersuchungApplication technical examination

Es wurden drei Mischungen (1 : 1 w/w) von Verbindungen gemäß der allgemeinen Formeln (Ia) und (Ib) mit einem propoxylierten Hydroxymischether gemäß der allgemeinen Formel (III) hergestellt. Als Tenside der Gruppe a) wurden verwendet: C10-Alkyldiol-40 EO di-2-hydroxyhexadecylether für die Mischung A; Butylglykol-Isotridecylalkohol-9EO-formal für die Mischung B; Di-C8/C10-Alkyl-11 EO-formal für die Mischung C. Als Hydroxymischether vom Typ b2) wurde jeweils ein C8/C10-Alkyl-1EO-22EO-hydroxy-C10-alkylether eingesetzt.Three mixtures (1: 1 w / w) of compounds according to the general formulas (Ia) and (Ib) with a propoxylated hydroxy mixed ether according to the general formula (III) were prepared. As surfactants of group a) were used: C10-alkyldiol-40 EO di-2-hydroxyhexadecyl ether for the mixture A; Butylglycol-isotridecyl alcohol-9EO formal for the mixture B; Di-C8 / C10-alkyl-11 EO-formal for the mixture C. As hydroxymix ether of the type b2) in each case a C8 / C10-alkyl-1EO-22EO-hydroxy-C10-alkyl ether was used.

Diese erfindungsgemäßen 1 : 1 Mischungen A bis C wurden (zu 8 Gew.-%, bezogen auf das Geschirrspülmittel) in eine handelsübliche Formulierung für ein festes Mittel für das automatische Geschirrspülen eingearbeitet. Die Beurteilung der Trocknungsleistung erfolgt durch Zählen der an dem Spülgut nach dem Spülprozess noch haftenden Tropfen. Dabei werden Gläser, Besteck, Kunststoff- sowie Porzellanteller unter definierten Bedingungen (Wasser mit 21 °dH, 50 g Standard-Anschmutzung) in einer Haushaltsgeschirrspülmaschine gespült. Nach Beendigung des Spülprogramms wird das Spülgut unter definierten Lichtverhältnissen nach Tropfenanzahl beurteilt.These inventive 1: 1 mixtures A to C were incorporated (at 8% by weight, based on the dishwashing detergent) in a commercial formulation for a solid automatic dishwashing agent. The assessment of the drying performance is done by counting the still adhering to the items to be washed after the rinsing process drops. Glasses, cutlery, plastic and porcelain plates are rinsed under defined conditions (water at 21 ° dH, 50 g standard soiling) in a household dishwashing machine. After completion of the wash program, the items to be washed are assessed under defined light conditions according to the number of drops.

Die Ergebnisse erfolgten durch Vergleich der auf einer Plastikoberfläche nach Durchlaufen des Spülverfahrens verbleibenden Wassertropfen. Die Standardformulierung setzt sich zusammen aus 2 Gew.-% eines C8/C10-Alkyl-1EO-22EO-hydroxy-C10-alkylethers, 1 Gew.-% eines Polymers, 7 Gew.-% Natriumsilikat, 52 Gew.% Natriumtriphosphat, 2,5 Gew.-% TAED, 27,5 Gew.% Natriumcarbonat und 8 Gew.-% Natriumpercarbonat.The results were made by comparing the drops of water remaining on a plastic surface after passing through the rinsing process. The standard formulation is composed of 2% by weight of a C8 / C10-alkyl-1EO-22EO-hydroxy-C10-alkyl ether, 1% by weight. a polymer, 7% by weight of sodium silicate, 52% by weight of sodium triphosphate, 2.5% by weight of TAED, 27.5% by weight of sodium carbonate and 8% by weight of sodium percarbonate.

Im Vergleich zum Standard zeigten die Mittel, die die Mischungen A bis C enthielten eine Verringerung der Tropfenzahl auf Kunststoff um 1 bis 3.Compared to the standard, the compositions containing mixtures A to C showed a reduction in the number of drops of plastic by 1 to 3.

Claims (14)

  1. Mixtures comprising at least two different surface-active substances from the groups a) and b), where the surface-active compound a) is selected from compounds of the general formula (Ia)
    Figure imgb0008
     in which M is a radical CH2-CH2 or CHR-CH2, R, R' and R", independently of one another, are saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 6 to 22 carbon atoms, and the indices n and m, independently of one another, can assume values between 1 and 40, and/or compounds of the general formula (Ib)
    Figure imgb0009
     in which R"' and R"", independently of one another, are saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 4 to 22 carbon atoms, and the indices n and m, independently of one another, can assume values between 1 and 40, X' and X", independently of one another, are H or saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 1 to 18 carbon atoms
    and the compounds of type b) correspond to the general formula (II)

            R1O[CH2CH2O]xCH2CH(OM)R2     (II)

    in which R1 is a linear or branched alkyl and/or alkenyl radical having 4 to 22 carbon atoms, or is a radical R2-CH(OH)CH2, where R2 is a linear or branched alkyl and/or alkenyl radical having 8 to 16 carbon atoms, x is a number from 20 to 80, preferably from 40 to 80, and M is a hydrogen atom or a saturated alkyl radical having 1 to 18 carbon atoms
    and/or the general formula (III)

            R3O[CH2CHCH3O]z[CH2CH2O]yCH2CH(OH)R9     (III)

    in which R3 is a linear or branched alkyl and/or alkenyl radical having 8 to 22 carbon atoms, R4 is a linear or branched alkyl and/or alkenyl radical having 8 to 16 carbon atoms, y is a number from 10 to 35, z is zero or must be a number from 1 to 5.
  2. Mixtures according to Claim 1, characterized in that it comprise only one surface-active compound a) in combination with only one surface-active compound b).
  3. Mixtures according to Claims 1 to 2, characterized in that, in the formula (Ia), R, R' and R" are in each case a linear, saturated alkyl radical, where R is an alkyl radical having 8 to 16 carbon atoms, R' and R", independently of one another, are an alkyl radical having 10 to 16 carbon atoms and n and m, independently of one another, assume a value from 20 to 30.
  4. Mixtures according to Claims 1 to 3, characterized in that, in the formula (Ib), the radicals R''' and R"", independently of one another, are saturated alkyl radicals having 4 to 14 carbon atoms, and the indices n and m, independently of one another, assume values from 1 to 15 and in particular from 1 to 12.
  5. Mixtures according to Claims 1 to 4, characterized in that, in the formula (II), the index x is a number from 40 to 70, preferably 40 to 60 and in particular from 40 to 50.
  6. Mixtures according to Claims 1 to 5, characterized in that, in the formula (III), the index y is a number from 20 to 30, preferably from 20 to 25.
  7. Mixtures according to Claims 1 to 6, characterized in that the surface-active compounds of type a) and b) are present alongside one another in the weight ratio of from 5 : 1 to 1 : 5, in particular of from 3 : 1 to 1 : 3 and particularly preferably of 1 : 1.
  8. Mixtures according to Claims 1 to 7, characterized in that it comprises, as surface-active compound of type b1), a compound according to the general formula (II) in which R1 is an alkyl and/or alkenyl radical having 8 to 10 carbon atoms and R2 is an alkyl or alkenyl radical having 8 to 10 carbon atoms and x is a number from 40 to 50.
  9. Mixtures according to Claims 1 to 8, characterized in that it comprises, as surface-active compound of type b2), a compound according to the general formula (III) in which R3 is an alkyl and/or alkenyl radical having 11 to 18 carbon atoms and R4 is an alkyl or alkenyl radical having 8 to 10 carbon atoms and y is a number from 20 to 35.
  10. Mixtures according to Claims 1 to 9, characterized in that it comprises, as surface-active compound of type b2), a compound according to the general formula (III) in which R3 is an alkyl and/or alkenyl radical having 8 to 12 carbon atoms and R4 is an alkyl or alkenyl radical having 8 to 10 carbon atoms and y is a number from 20 to 35 and z is a number from 1 to 3.
  11. Use of mixtures according to Claims 1 to 10 in washing and cleaning agents, preferably in cleaning agents for hard surfaces and in particular in cleaning agents for automatic dishwashing.
  12. Use according to Claim 11, characterized in that the mixtures are used in the cleaning agents in amounts of from 0.1 to 15% by weight, preferably from 1 to 10% by weight.
  13. Use of mixtures according to Claims 1 to 10, for improving the drying performance of cleaning agents, preferably of dishwashing agents.
  14. Cleaning agent comprising 0.1 to 15% by weight of mixtures according to Claims 1 to 10, and further nonionic, anionic and/or cationic surfactants, and also optionally builders, enzymes, rinse aids and/or further auxiliaries and additives.
EP09711301A 2008-02-14 2009-02-06 Use of surface-active substances in cleaning agents Active EP2240562B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL09711301T PL2240562T3 (en) 2008-02-14 2009-02-06 Use of surface-active substances in cleaning agents
EP10187277A EP2267110B1 (en) 2008-02-14 2009-02-06 Use of surface-active substances in cleaning agents

Applications Claiming Priority (2)

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DE102008009366A DE102008009366A1 (en) 2008-02-14 2008-02-14 Use of surface-active substances in cleaning agents
PCT/EP2009/000823 WO2009100855A2 (en) 2008-02-14 2009-02-06 Use of surface-active substances in cleaning agents

Related Child Applications (1)

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EP10187277.8 Division-Into 2010-10-12

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EP2240562B1 true EP2240562B1 (en) 2011-09-07

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US (1) US8148313B2 (en)
EP (2) EP2240562B1 (en)
CN (1) CN101945986B (en)
AT (1) ATE523582T1 (en)
AU (1) AU2009214382A1 (en)
CA (1) CA2713335A1 (en)
DE (1) DE102008009366A1 (en)
ES (2) ES2373084T3 (en)
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WO (1) WO2009100855A2 (en)

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GB201104244D0 (en) * 2011-03-14 2011-04-27 Reckitt Benckiser Nv Detergent composition with improved drying performance
DE102011086639A1 (en) 2011-11-18 2013-05-23 Henkel Ag & Co. Kgaa Use of a nonionic surfactant for the treatment of surfaces of metal, glass and porcelain dishes to enable easier detachment of dirt e.g. burned dirt
DE102012223339A1 (en) * 2012-12-17 2014-06-18 Henkel Ag & Co. Kgaa Surfactant combination for improved drying
CN109072132A (en) * 2016-04-18 2018-12-21 巴斯夫欧洲公司 The method of cleaning of hard surfaces and the preparaton that can be used for the method

Family Cites Families (15)

* Cited by examiner, † Cited by third party
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WO1995013260A1 (en) * 1993-11-10 1995-05-18 Basf Aktiengesellschaft Method of producing mixtures of low-foaming non-ionic surfactants with an acetal structure
WO1996000253A1 (en) 1994-06-23 1996-01-04 The Dow Chemical Company A surface active composition containing an acetal or ketal adduct
NZ285317A (en) 1994-09-12 1998-05-27 Ecolab Inc Rinse aid composition for use with plasticware
DE19738866A1 (en) 1997-09-05 1999-03-11 Henkel Kgaa Low-foaming surfactant mixtures with hydroxy mixed ethers
WO2002000580A1 (en) * 2000-06-26 2002-01-03 Basf Aktiengesellschaft Alcohol mixtures having 13 and 15 carbon atoms and the use thereof in the preparation of surface-active substances
DE10045289A1 (en) 2000-09-13 2002-03-28 Henkel Kgaa Fast-drying detergent and cleaning agent, especially hand dishwashing liquid
DE10121724A1 (en) * 2001-05-04 2002-11-07 Cognis Deutschland Gmbh gemini
DE10121723A1 (en) * 2001-05-04 2002-11-07 Cognis Deutschland Gmbh gemini
DE10137925A1 (en) * 2001-08-07 2003-02-20 Cognis Deutschland Gmbh Mixtures for improving hard surface wettability especially in machine dish washing comprise Gemini surfactant and polyethylene glycol
DE10153047A1 (en) 2001-10-26 2003-05-08 Goldschmidt Ag Th Aqueous surfactant-based cleaning agent with improved drying behavior for cleaning hard surfaces, especially dishes
DE10162023A1 (en) * 2001-12-18 2003-07-03 Cognis Deutschland Gmbh Mixtures of gemini surfactants and fatty alcohol alkoxylates in rinse aid
EP1553160B1 (en) 2003-12-29 2007-10-17 The Procter & Gamble Company Rinse aid compositions
DE102004048779A1 (en) 2004-10-07 2006-04-13 Cognis Ip Management Gmbh Cleaning agent containing Polyolhydroxyalkylether
DE102005044028A1 (en) 2005-09-14 2007-03-15 Cognis Ip Management Gmbh Mixture, useful e.g. in detergents and cleaning agent for hard surface and automatic dishwasher, comprises two different surface active substance e.g. alkyl compound, ethoxylated fatty alcohol, alkyl (oligo)glycoside and betaine
EP1897933A1 (en) * 2006-09-05 2008-03-12 Cognis IP Management GmbH Use of long-chained alkoxylated fatty alcohols as detergent additives for hard surface cleaning

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AU2009214382A1 (en) 2009-08-20
CA2713335A1 (en) 2009-08-20
US20100323948A1 (en) 2010-12-23
ATE523582T1 (en) 2011-09-15
EP2267110A3 (en) 2011-04-27
US8148313B2 (en) 2012-04-03
EP2267110A2 (en) 2010-12-29
DE102008009366A1 (en) 2009-08-20
WO2009100855A3 (en) 2009-10-08
ES2373084T3 (en) 2012-01-31
ES2400791T3 (en) 2013-04-12
PL2240562T3 (en) 2012-02-29
CN101945986A (en) 2011-01-12
EP2267110B1 (en) 2012-11-28
EP2240562A2 (en) 2010-10-20
CN101945986B (en) 2012-10-10
WO2009100855A2 (en) 2009-08-20

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