EP1764408B1 - Mixture of surface-active compounds for use in cleaning compositions - Google Patents

Mixture of surface-active compounds for use in cleaning compositions Download PDF

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Publication number
EP1764408B1
EP1764408B1 EP06018517A EP06018517A EP1764408B1 EP 1764408 B1 EP1764408 B1 EP 1764408B1 EP 06018517 A EP06018517 A EP 06018517A EP 06018517 A EP06018517 A EP 06018517A EP 1764408 B1 EP1764408 B1 EP 1764408B1
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EP
European Patent Office
Prior art keywords
carbon atoms
alkyl
alkenyl radical
compounds
mixtures
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Not-in-force
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EP06018517A
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German (de)
French (fr)
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EP1764408A1 (en
Inventor
Sabine Both
Corinna Böhme
Rainer Eskuchen
Melanie Maik
Hans-Christian Raths
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/40—Monoamines or polyamines; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • 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
    • C11D1/74—Carboxylates or sulfonates esters 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the present invention relates to mixtures of surface-active substances 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. This applies in particular to automatic dishwashing.
  • the three components of the machine system are cleaner, rinse aid and regenerating salt.
  • 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.
  • Conventional multifunctional automatic dishwashing detergents (so-called "ADD" automatic dish detergents) have a much poorer drying performance compared to the conventional rinse aid system (detergent, salt and rinse aid as separate products). Drying performance is to be understood in how far a dishwashing item which has been cleaned with a dishwashing detergent still has water, preferably water droplets, on the surface after passing through the dishwashing process.
  • 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.
  • 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.
  • 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 are usually 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)
  • solubilizers eg cumene sulfonate
  • organic acids eg citric acid
  • solvents eg ethanol
  • hydroxymix ethers with a high degree of ethoxylation are known, which are used as defoamers in detergents, dishwashing detergents and cleaners. Specific mixtures of these hydroxy mixed ethers are not disclosed in the document.
  • the DE 100 03 809 A1 discloses rinse aids containing hydroxy mixed ethers and alkyl and / or alkenyl (oligo) glycosides side by side in aqueous solution. Mixtures of structurally different hydroxy mixed ethers are not disclosed concretely in the document.
  • the EP 1 167 499 A1 describes a liquid detergent containing hydroxymix ether. Blends of various hydroxy mixed ethers are not disclosed concretely in the document.
  • the EP 1 254 948 A1 relates dishwashing detergent with Hydroxymischethern, which must have at least 2 hydroxyl groups in the molecule.
  • the EP 1 321 511 A2 Mixtures of hydroxy mixed ethers and fatty alcohol alkoxylates known for rinse aid, wherein the hydroxy mixed ether must have at least 2 hydroxyl groups side by side in the molecule.
  • the present invention therefore relates, in a first embodiment, to mixtures consisting of two different surface-active substances a) and b), wherein the surface-active compound a) is selected from compounds of the general formula (I) R 1 O [CH 2 CH 2 O] x CH 2 CH (OM) R 2 (I) 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, and the surfactant b) is selected from the group of b) Compounds of the formula (II) R 3 O [CH 2 CH 2 O] y [CH 2 CHCH 3 O] z CH 2 CH (OH) R 4 (II
  • the mixtures according to the invention necessarily contain compounds of the type a). These are so-called hydroxy mixed ethers or their derivatives. Hydroxy mixed ethers (HMEs) follow the general formula RO [AO] x CH 2 CH (OM) R 'in which R is a linear or branched alkyl and / or alkenyl group containing 4 to 22 carbon atoms, R "is branched a linear or Alkyl and / or alkenyl radical having 2 to 22 carbon atoms x is 10 to 80 and AO represents an ethylene oxide, propylene oxide or butylene oxide radical and M can stand for a hydrogen atom or an alkyl or alkenyl radical.
  • HMEs 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'-OH 1,2-epoxyalkanes
  • R '-OH having 4 to 18 carbon atoms
  • 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 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.
  • other hydroxy mixed ethers are known, namely those which have more than one free hydroxyl group in the molecule.
  • Such compounds can be prepared, for example, by reacting diols, preferably alkylene glycols and their derivatives, preferably polyethylene glycols, each with two moles of an alkyl epoxide (R-CHOCH 2 ) per mole of the diol.
  • the present invention now makes use of the finding that the presence of selected HME, or of their derivatives, namely compounds of general formula (I) in combination with structurally different surface-active compounds of type b), have advantageous drying and / or drying properties. or the rinse aid performance of detergent formulations for hard surfaces, and particularly dishwashing detergents.
  • 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 which are derived from ethoxylates of monohydric alcohols of the formula R 1 -OH having 6 to 18 carbon atoms, preferably 6 to 16 and especially 8 to 10 carbon atoms, where R 1 is a linear alkyl radical and x for 40 to 60.
  • R 1 is a linear alkyl radical and x for 40 to 60.
  • those compounds of the general formula (I) are preferred in which the index x is a number from 40 to 70, preferably 40 to 60 and in particular from 40 to 50.
  • M is then a hydrogen atom.
  • hydroxy mixed ethers of the formula (I) 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 1 is an alkyl or alkenyl radical having 8 to 10 carbon atoms
  • R 2 is a radical having 8 to 12 carbon atoms
  • M is a saturated alkyl radical with 1 to 6, preferably 1 to 4 carbon atoms.
  • the latter compound contains no free hydroxyl groups - rather, the hydroxyl functions have been alkylated with suitable reagents, for example alkyl halides.
  • the present invention requires that at least one compound of type a) is used in combination with one of the compounds of type b) described below.
  • Particularly preferred compounds of type b) are, for example, those in which, in the formula (II), the index y is a number from 20 to 30, preferably from 20 to 25.
  • R 3 in the formula (II) represents an alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms
  • R 4 represents an alkyl radical having 10 to 12, preferably 10 carbon atoms
  • y a number from 15 to 35, preferably 20 to 30
  • z is a number from 1 to 3, preferably 1 means.
  • mixtures which contain as surface-active compound of type b) a compound of the general formula (II) in which R 3 is an alkyl and / or alkenyl radical having 11 to 18 carbon atoms and R 4 is an alkyl radical 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 b) a compound of the general formula (II) 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 b) are also hydroxy mixed ether derivatives which can be prepared by reacting propoxylated and / or ethoxylated fatty alcohols with Alkylepoxiden by ring opening in an alkaline medium.
  • mixed alkoxylates which means both a propylene oxide residue CH 2 CHCH 3 O (PO) and an ethylene oxide residue 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, wherein the sequence first PO, then EO is possible.
  • 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 compounds b can each be combined alone with at least one compound of the type a). Particularly preferred are binary mixtures of a) and a compound of type b). However, it is also possible to combine mixtures of different substances of the type class b) with the HME of the type a). It may be advantageous for mixtures containing a plurality of different compounds of type b) to use these compounds in a weight ratio of 1: 1.
  • fatty alcohols are to be understood as meaning primary aliphatic alcohols of the formula ROH 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 which are obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis 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
  • the compounds of type a) and b) are 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 side by side available.
  • the compounds of the type b 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 for improving the drying performance and / or the rinsing performance of cleaning agents and in particular for dishwashing detergents, preferably for dishwashing detergents for automatic dishwashing.
  • 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 0.1 to 8 wt .-% wherein advantageously from 1 to 6.0 wt .-% and in particular amounts of 2.0 to 5 wt .-% are included. Particularly preferred is the range of 2.0 to 4.0 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. It can also be several phases next to each other, for example, a compressed Tablet containing 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.
  • the machine is loaded with a practice-relevant machine load consisting of 24 porcelain plates, 3 porcelain bowls, 10 porcelain cups, 12 drinking glasses, 4 melamine plates, 6 styrene acrylonitrile (SAN) plates, 2 polypropylene (PP) bowls, 40 pieces of standard stainless steel cutlery.
  • SAN styrene acrylonitrile
  • PP polypropylene
  • Test soil is: 50 g of dirt with the following composition: Based on 1000 g: 25 g each of ketchup, mustard and gravy, 300 g margarine, 150 g drinking milk, 15 g potato starch, 9 g egg yolk, 3 g benzoic acid, balance: water. Each surfactant tested was rinsed three times and tested for drying performance after the drying cycle. The same lighting conditions as well as room humidity and room temperature are always set.
  • the grade 1 stands for the best, the grade 5 for the worst result.
  • Table 1 indicates what the drying performance rating can be over the mean of all substrates. At the same time, the results from Table 1 demonstrate the state of the art, as well as a water value, ie no cleaners or other additives have been added to the dishwasher. ⁇ u> Table 1 ⁇ / u> formulation number of drops ADD cleaner with classic rinse aid 0.8 3-in-1 brand product 3.6 water 4.1
  • Amount of surface-active substance (s) in each case 25 g of the standard formulation Glass plastic total Rinse power on glass Spotting / filming 1 2% by weight of A 0.8 2.3 2 1.5 1.5 2 * 2% by weight of A 2% by weight of C 0.2 0.5 0.8 1 1 3 * 2% by weight of A 2% by weight D 0.2 0.7 0.8 1 1 4 4% by weight of E 0.4 0.9 1.1 2 2 5 2% by weight of A 2% by weight of E 0.6 1.0 1.2 1 1 6 2% by weight of A 1% by weight B 0.3 0.9 1.3 1 1 7 4% by weight B 0.4 0.9 1.2 3 3 8th 4% by weight of G 0.3 0.5 0.7 4 4 9 2% by weight of A 2% by weight of G 0.3 0.6 1.1 1 1 10 4% by weight H 0.5 1.8 1.3 2.5 2 11 2% by weight of A 2% by weight H 0.3 1.1 1.2 1 1 12 4% by weight F 0.3 0.7 0.9 4 4 13 2% by weight of A

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  • Engineering & Computer Science (AREA)
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Description

Die vorliegende Erfindung betrifft Mischungen oberflächenaktiver Substanzen zum Einsatz in Reinigungsmitteln und insbesondere in Geschirrspülmitteln für das automatische Geschirrspülen.The present invention relates to mixtures of surface-active substances 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. Hierbei sind die zentralen Aufgaben des Hauptbestandteils Reiniger die Schmutzablösung, die Schmutzdispergierung, die Bindung von Restwasserhärte sowie die Korrosionsinhibierung.
Herkömmliche multifunktionale Reinigungsmittel für das automatische Geschirrspülen (sog. "automatic dish detergents" kurz ADD) haben im Vergleich zum klassischen Klarspülsystem (Reiniger, Salz und Klarspüler als separate Produkte) eine sehr viel schlechtere Trocknungsleistung. Unter Trocknungsleistung ist dabei zu verstehen, in wie weit ein mit einem Geschirrspülmittel gereinigtes 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, also muss der Anwender 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.
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.
Durch den vermehrten Einsatz von multifunktionalen Mitteln (also der Kombination von z.B. Reinigern, Klarspülern und ggf. Wassserenthärtung in einer Angebotsform) ist die Trocknungsleistung im Vergleich zum klassischen Klarspüler schlechter geworden. 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.
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.
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 Fettalkohol-polyethylen/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.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 regenerating salt. 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.
Conventional multifunctional automatic dishwashing detergents (so-called "ADD" automatic dish detergents) have a much poorer drying performance compared to the conventional rinse aid system (detergent, salt and rinse aid as separate products). Drying performance is to be understood in how far a dishwashing item which has been cleaned with a dishwashing detergent still has water, preferably water droplets, on the surface after passing through the dishwashing process. 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, so the user must wait for the water to evaporate. 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.
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 circumvent this effect, elaborate conventional rinse aid are formulated, which have, for example, 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.
Due to the increased use of multifunctional agents (ie the combination of eg cleaners, rinse aids and possibly water softening in a supply form) is the Drying performance has become worse compared to the classic rinse aid. 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.
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.
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 are usually 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) Means is to influence the interfacial tension of the water so that it can run off in a very thin, coherent film from the items to be washed, so that remain in the subsequent drying process, no drops of water, streaks 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.

Aus der WO 02/061025 A1 sind so genannte Hydroxymischether mit hohem Ethoxylierungsgrad bekannt, die als Entschäumer in Wasch-, Spül- und Reinigungsmitteln eingesetzt werden. Spezifische Mischungen dieser Hydroxymischether werden in der Schrift nicht offenbart. Die DE 100 03 809 A1 offenbart Klarspülmittel, die Hydroxymischether und Alkyl- und/oder Akenyl(oligo)glycoside nebeneinander in wässriger Lösung enthalten. Mischungen strukturell unterschiedlicher Hydroxymischether werden in der Schrift nicht konkret offenbart. Die EP 1 167 499 A1 beschreibt ein Flüssigwaschmittel, das Hydroxymischether enthält. Abmischungen verschiedener Hydroxymischether werden in der Schrift nicht konkret offenbart. Die EP 1 254 948 A1 betrifft Geschirrspülmittel mit Hydroxymischethern, wobei diese mind. 2 Hydroxylgruppen im Molekül aufweisen müssen. Schließlich sind aus der EP 1 321 511 A2 Mischungen aus Hydroxymischethern und Fettalkoholalkoxylaten für Klarspülmittel bekannt, wobei die Hydroxymischether mind. 2 Hydroxylgruppen nebeneinander im Molekül aufweisen müssen.From the WO 02/061025 A1 So-called hydroxymix ethers with a high degree of ethoxylation are known, which are used as defoamers in detergents, dishwashing detergents and cleaners. Specific mixtures of these hydroxy mixed ethers are not disclosed in the document. The DE 100 03 809 A1 discloses rinse aids containing hydroxy mixed ethers and alkyl and / or alkenyl (oligo) glycosides side by side in aqueous solution. Mixtures of structurally different hydroxy mixed ethers are not disclosed concretely in the document. The EP 1 167 499 A1 describes a liquid detergent containing hydroxymix ether. Blends of various hydroxy mixed ethers are not disclosed concretely in the document. The EP 1 254 948 A1 relates dishwashing detergent with Hydroxymischethern, which must have at least 2 hydroxyl groups in the molecule. Finally, from the EP 1 321 511 A2 Mixtures of hydroxy mixed ethers and fatty alcohol alkoxylates known for rinse aid, wherein the hydroxy mixed ether must have at least 2 hydroxyl groups side by side in the molecule.

Es wurde nun gefunden, dass die Kombination bestimmter oberflächenaktiver Substanzen geeignet ist, die Trocknungsleistung und die Klarspülleistung von Reinigungsmitteln für harte Oberflächen, insbesondere von Mitteln zum Geschirrspülen, zu verbessern und gleichzeitig ökologisch unbedenklich zu sein.It has now been found that the combination of certain surface-active substances is suitable, the drying performance and the rinsing performance of cleaning agents for hard Surfaces, especially dishwashing agents, to improve and at the same time to be ecologically safe.

Gegenstand der vorliegenden Erfindung sind daher in einer ersten Ausführungsform Mischungen, bestehend aus zwei verschiedene oberflächenaktive Substanzen a) und b),
wobei die oberflächenaktive Verbindung a) ausgewählt ist aus Verbindungen der allgemeinen Formel (I)

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

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,
und die oberflächenaktive Substanz b) ausgewählt ist aus der Gruppe der
b) Verbindungen der Formel (II)

        R3O[CH2CH2O]y[CH2CHCH3O]zCH2CH(OH)R4     (II)

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, das das Gewichtsverhältnis zwischen den oberflächenaktiven Substanzen a) und b) im Bereich von 10 : 1 bis 1 : 10 liegt.The present invention therefore relates, in a first embodiment, to mixtures consisting of two different surface-active substances a) and b),
wherein the surface-active compound a) is selected from compounds of the general formula (I)

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

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,
and the surfactant b) is selected from the group of
b) Compounds of the formula (II)

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

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 the weight ratio between the surface-active substances a) and b) is in the range from 10: 1 to 1:10.

Die erfindungsgemäßen Mischungen enthalten zwingend Verbindungen des Typs a). Dabei handelt es sich um so genannte Hydroxymischether bzw. deren Derivate. Hydroxymischether (HME) 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- oder Butylenoxid-Rest symbolisiert und M für ein Wasserstoffatom oder einen Alkyl- bzw. Alkenylrest stehen kann.
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. 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.
Daneben sind auch andere Hydroxymischether bekannt, nämlich solche die mehr als eine freie Hydroxylgruppe im Molekül aufweisen. Solche Verbindungen können beispielsweise hergestellt werden, indem man Diole, vorzugsweise Alkylenglykole und deren Derivate, vorzugsweise Polyethylenglykole, jeweils mit zwei Mol eines Alkylepoxids (R-CHOCH2) pro Mol des Diols zur Reaktion bringt.The mixtures according to the invention necessarily contain compounds of the type a). These are so-called hydroxy mixed ethers or their derivatives. Hydroxy mixed ethers (HMEs) follow the general formula RO [AO] x CH 2 CH (OM) R 'in which R is a linear or branched alkyl and / or alkenyl group containing 4 to 22 carbon atoms, R "is branched a linear or Alkyl and / or alkenyl radical having 2 to 22 carbon atoms x is 10 to 80 and AO represents an ethylene oxide, propylene oxide or butylene oxide radical and M can stand for a hydrogen atom or an alkyl or alkenyl radical.
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. 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.
In addition, other hydroxy mixed ethers are known, namely those which have more than one free hydroxyl group in the molecule. Such compounds can be prepared, for example, by reacting diols, preferably alkylene glycols and their derivatives, preferably polyethylene glycols, each with two moles of an alkyl epoxide (R-CHOCH 2 ) per mole of the diol.

Die vorliegende Erfindung macht nun von der Erkenntnis gebrauch, dass die Anwesenheit von ausgewählten HME, oder von deren Derivaten, nämlich Verbindungen der allgemeinen Formel (I) in Kombination mit strukturverschiedenen oberflächenaktiven Verbindungen des Typs b) 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, or of their derivatives, namely compounds of general formula (I) in combination with structurally different surface-active compounds of type b), have advantageous drying and / or drying properties. or the rinse aid performance of detergent formulations for hard surfaces, and particularly dishwashing detergents.

Oberflächenaktive Verbindungen vom Typ a)Surface-active compounds of the type a)

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

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

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 a) der allgemeinen Formel (I) verwendet, die mindestens eine freie Hydroxylgruppe (= -OH) enthalten.These are commercially available surfactants of the general formula (I)

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

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 a) of the general formula (I) are used which contain at least one free hydroxyl group (= -OH).

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 (I) 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 (I), 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 (I) 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.
Geeignet sind aber such solche Verbindungen des Typs a) der Formel (I) bei denen R1 für einen Alkyl- oder Alkenylrest mit 8 bis 10 Kohlenstoffatomen steht, R2 für einen Rest mit 8 bis 12 Kohlenstoffatomen steht und M einen gesättigten Alkylrest mit 1 bis 6, vorzugsweise 1 bis 4 Kohlenstoffatomen bedeutet. Letztere Verbindung enthält keine freien Hydroxylgruppen - vielmehr wurden die Hydroxyl-Funktionen mit geeigneten Reagenzien, z.B. Alkylhalogeniden alkyliert.Preferred for the purposes of the invention are those hydroxy mixed ethers which are derived from ethoxylates of monohydric alcohols of the formula R 1 -OH having 6 to 18 carbon atoms, preferably 6 to 16 and especially 8 to 10 carbon atoms, where R 1 is a linear alkyl radical and x for 40 to 60. Furthermore, in the mixtures according to the invention those compounds of the general formula (I) are preferred in which the index x is a number from 40 to 70, preferably 40 to 60 and in particular from 40 to 50. M is then a hydrogen atom.
Very particular preference is given to hydroxy mixed ethers of the formula (I) 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 (I) 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 with 8 to 10 carbon atoms and x is a number from 40 to 50, wherein also here M stands for a hydrogen atom.
However, such compounds of the type a) of the formula (I) are suitable in which R 1 is an alkyl or alkenyl radical having 8 to 10 carbon atoms, R 2 is a radical having 8 to 12 carbon atoms and M is a saturated alkyl radical with 1 to 6, preferably 1 to 4 carbon atoms. The latter compound contains no free hydroxyl groups - rather, the hydroxyl functions have been alkylated with suitable reagents, for example alkyl halides.

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

Die vorliegende Erfindung setzt voraus, dass mindestens eine Verbindung des Typs a) mit einer der im Folgenden beschriebenen Verbindungen des Typs b) in Kombination Verwendung findet.The present invention requires that at least one compound of type a) is used in combination with one of the compounds of type b) described below.

Bei diesen Verbindungen handelt es sich ebenfalls um HME, allerdings haben diese eine andere Struktur als die HME der allgemeinen Formel (I). Die Verbindungen des Typs b) folgen der Formel (II)

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

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 b1) ausgewählt werden in denen der Index z mindestens 1 ist. Sofern Mischungen der oberflächenaktiven Verbindungen vom Typ a) mit denen des Typs b1) 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.
Besonders bevorzugte Verbindungen vom Typ b) sind beispielsweise solche bei denen in der Formel (II) der Index y für einen Zahl von 20 bis 30, vorzugsweise von 20 bis 25 steht. Weiterhin bevorzugt sind solche Verbindungen des Typs b1) bei denen in der Formel (II) 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.These compounds are also HME, but they have a different structure than the HME of the general formula (I). The compounds of the type b) follow the formula (II)

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

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 b1) are selected in which the index z is at least 1. If mixtures of the surface-active compounds of type a) with those of type b1) are used, only those mixtures within the meaning of the present technical teaching in which the molecules structurally differ from one another are used. So there must always be different structure connections side by side.
Particularly preferred compounds of type b) are, for example, those in which, in the formula (II), 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 b1) in which R 3 in the formula (II) represents an alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms, R 4 represents 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 b) eine Verbindung nach der allgemeinen Formel (II) enthalten, in der R3 für eine Alkyl- und/oder Alkenylrest mit 11 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 which contain as surface-active compound of type b) a compound of the general formula (II) in which R 3 is an alkyl and / or alkenyl radical having 11 to 18 carbon atoms and R 4 is an alkyl radical 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 b) eine Verbindung nach der allgemeinen Formel (II) 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 b) stellen ebenfalls Hydroxymischetherderivate dar, die durch Umsetzung von propoxylierten und/oder ethoxylierten Fettalkoholen mit Alkylepoxiden durch Ringöffnung im alkalischen Milieu hergestellt werden können.
Dabei ist es bei Derivaten des Typs b) 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.Also preferred are mixtures containing as surface-active compound of type b) a compound of the general formula (II) 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 b) are also hydroxy mixed ether derivatives which can be prepared by reacting propoxylated and / or ethoxylated fatty alcohols with Alkylepoxiden by ring opening in an alkaline medium.
It is with derivatives of the type b) as well as with all other in this description listed mixed alkoxylates, which means both a propylene oxide residue CH 2 CHCH 3 O (PO) and an ethylene oxide residue 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, wherein the sequence first PO, then EO is possible. 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.

Die Verbindungen b können jeweils alleine mit mindestens einer Verbindung des Typs a) kombiniert werden. Besonders bevorzugt sind dabei binäre Mischungen aus a) und einer Verbindung vom Typ b). Es ist aber auch möglich, Mischungen aus verschiedenen Substanzen der Typklasse b) mit den HME des Typs a) zu kombinieren. Dabei kann es vorteilhaft sein bei Mischungen die mehrere unterschiedliche Verbindungen des Typs b) enthalten, diese Verbindungen im Gewichtsverhältnis von jeweils 1 : 1 einzusetzen.The compounds b can each be combined alone with at least one compound of the type a). Particularly preferred are binary mixtures of a) and a compound of type b). However, it is also possible to combine mixtures of different substances of the type class b) with the HME of the type a). It may be advantageous for mixtures containing a plurality of different compounds of type b) to use these compounds in a weight ratio of 1: 1.

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.
Unter Fettalkoholen sind primäre aliphatische Alkohole der Formel ROH 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.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.
Fatty alcohols are to be understood as meaning primary aliphatic alcohols of the formula ROH 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 which are obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis 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 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 b 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 type a) and b) are 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 side by side available. The compounds of the type b 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 und / oder der Klarspülleistung von Reinigungsmitteln und insbesondere für Geschirrspülmittel, bevorzugt für Geschirrspülmittel für das maschinelle Geschirrspülen.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 for improving the drying performance and / or the rinsing performance of cleaning agents and in particular for dishwashing detergents, preferably for dishwashing detergents for automatic dishwashing.

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 8 Gew.-% wobei vorteilhafter weise 1 bis 6,0 Gew.-% und insbesondere Mengen von 2,0 bis 5 Gew.-% enthalten sind. Besonders bevorzugt ist der Bereich von 2,0 bis 4,0 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 0.1 to 8 wt .-% wherein advantageously from 1 to 6.0 wt .-% and in particular amounts of 2.0 to 5 wt .-% are included. Particularly preferred is the range of 2.0 to 4.0 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 verpressten 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.Preferably, machine dishwashing detergents are in solid form, for example as powders or granules or as shaped articles, preferably in tablet form. It can also be several phases next to each other, for example, a compressed Tablet containing 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.

BeispieleExamples a) Trocknungsleistunga) drying performance

Zur Prüfung der Trocknungsleistung wurde die folgende Methode eingesetzt. Es wurde die Trocknung von Geschirr nach dem Trocknungsgang einer Miele Geschirrspüler Typ G 696 SC, Spülprogramm: 55°C - Universal Plus, Wasser Härte: 16 °dH überprüft. Die Maschine wird mit einer praxisrelevanten Maschinenbeladung bestehend aus 24 Porzellan Teller, 3 Porzellan Schüsseln, 10 Porzellan Tassen, 12 Trinkgläser, 4 Melamin Teller, 6 Styrolacrylonitril (SAN) Teller, 2 Polypropylen (PP) Schüsseln, 40 Stück gängiges Edelstahlbesteck beladen.
Testanschmutzung ist: 50 g Schmutz mit folgender Zusammensetzung: Bezogen auf 1000 g: Mischung aus je 25 g Ketchup, Senf und Bratensauce, 300g Margarine, 150 g Trinkmilch, 15 g Kartoffelstärke, 9 g Eigelb, 3g Benzoesäure, Rest: Wasser. Jedes untersuchte Tensid wurde dreimal einem Spülzyklus unterworfen und nach dem Trocknungsgang auf die Trocknungsleistung getestet. Dabei werden immer die gleichen Lichtbedingungen sowie Raumfeuchte und Raumtemperatur eingestellt.To test the drying performance, the following method was used. It was the drying of dishes after the drying cycle of a Miele dishwasher type G 696 SC, washing program: 55 ° C - Universal Plus, water hardness: 16 ° dH checked. The machine is loaded with a practice-relevant machine load consisting of 24 porcelain plates, 3 porcelain bowls, 10 porcelain cups, 12 drinking glasses, 4 melamine plates, 6 styrene acrylonitrile (SAN) plates, 2 polypropylene (PP) bowls, 40 pieces of standard stainless steel cutlery.
Test soil is: 50 g of dirt with the following composition: Based on 1000 g: 25 g each of ketchup, mustard and gravy, 300 g margarine, 150 g drinking milk, 15 g potato starch, 9 g egg yolk, 3 g benzoic acid, balance: water. Each surfactant tested was rinsed three times and tested for drying performance after the drying cycle. The same lighting conditions as well as room humidity and room temperature are always set.

Die Trocknungsleistung wurde folgendermaßen bewertet:

  • 0 = 0 Wassertropfen auf einem Substrat= bestes Ergebnis, trocken
  • 1 = 1 Wassertropfen auf einem Substrat
  • 2 = 2 Wassertropfen auf einem Substrat
  • 3 = 3 Wassertropfen auf einem Substrat
  • 4 = 4 Wassertropfen auf einem Substrat
  • 5 = 5 Wassertropfen auf einem Substrat
  • 6 = mehr als 5 Wassertropfen auf einem Substrat, schlechtestes Ergebnis
The drying performance was evaluated as follows:
  • 0 = 0 drops of water on a substrate = best result, dry
  • 1 = 1 drops of water on a substrate
  • 2 = 2 drops of water on a substrate
  • 3 = 3 drops of water on a substrate
  • 4 = 4 drops of water on a substrate
  • 5 = 5 drops of water on a substrate
  • 6 = more than 5 drops of water on a substrate, worst result

b) Klarspülleistungb) rinse power

Zur Bewertung der Klarspülleistung wurde das im Folgenden beschrieben Verfahren angewandt: Die Substrate aus dem Trocknungstest a) wurden nochmals visuell bewertet, wobei aber nur die Glassubstrate geprüft wurden.The following procedure was used to evaluate the rinse performance: The substrates from the drying test a) were evaluated again visually, but only the glass substrates were tested.

Dabei wurde sowohl das "spotting" als auch das "filming" bewertet, und zwar nach der folgenden Skala: Note Spotting Filming 1 Keine spots Kein filming 2 Sehr wenig spots Sehr schwaches filming 3 Wenig spots Schwaches filming 4 Viele spots Starkes filming 5 Sehr viele spots Sehr starke, flächiges filming Both "spotting" and "filming" were rated, according to the following scale: grade spotting Filming 1 No spots No filming 2 Very little spots Very weak filming 3 Little spots Weak filming 4 Many spots Strong filming 5 Very many spots Very strong, areal filming

Die Note 1 steht dabei für das beste, die Note 5 für das schlechteste Ergebnis.The grade 1 stands for the best, the grade 5 for the worst result.

In den Beispielen für die Testung der Trocknungseigenschaften wurden die Mittelwerte über alle Substrate sowie Glas und Plastik als separates Ergebnis angegeben. Es wurde für die Untersuchungen verschiedene oberflächenaktiven Verbindungen alleine und in Kombination untersucht.
Dabei wurde jeweils die folgende Standardformulierung zugrunden gelegt: Substanz Gew.-% Oberflächenaktive Verbindung 4 Natriumsilikat (SKS-6) 7 Natrium-tripolyphosphat 51 TAED (Tetra acetyl ethylene diamine) 2,5 Natriumcarbonat 27,5 Natriumpercarbonat 8 In the drying properties testing examples, the mean values across all substrates as well as glass and plastic were reported as a separate result. Different surface-active compounds alone and in combination were investigated for the investigations.
The following standard formulation was used in each case: substance Wt .-% Surface-active compound 4 Sodium silicate (SKS-6) 7 Sodium tripolyphosphate 51 TAED (Tetra acetyl ethylene diamine) 2.5 sodium 27.5 sodium 8th

Untersuchte oberflächenaktive Verbindungen:

A
HME gemäß Formel (I) mit R1 = C8-C10; R2 = C10, x = 40
B
HME gemäß Formel (I) mit R1 = C8-C10; R2= C10, x = 40; M = Butyl
C
HME gemäß Formel (II) mit R3= C11; R4 = C8, y = 22, z = 0
D
HME gemäß Formel (II) mit R3= C8-C10, R4 = C8, y = 22, z = 0
E
Poleytheylenglykolderivat gemäß Formel b3) mit R6 = C11 und R7 = COR6
F
Talgalkohol mit 2 Teilen Ethylenoxid pro Mol Alkohol
G
Talgalkohol mit 5 Teilen Ethylenoxid pro Mol Alkohol
H
Betain auf Basis von Kokosfettsäuren (Dehyton® AB 30, Fa. Cognis)
K
Alkyl(oligo)glucosid (Glucopon® 600 CS UP, Fa. Cognis)
Investigated surface-active compounds:
A
HME according to formula (I) with R 1 = C8-C10; R 2 = C10, x = 40
B
HME according to formula (I) with R 1 = C8-C10; R 2 = C10, x = 40; M = butyl
C
HME according to formula (II) with R 3 = C11; R 4 = C8, y = 22, z = 0
D
HME according to formula (II) with R 3 = C 8 -C 10, R 4 = C 8, y = 22, z = 0
e
Poleytheylenglykolderivat according to formula b3) with R 6 = C11 and R 7 = COR 6
F
Tallow alcohol with 2 parts of ethylene oxide per mole of alcohol
G
Tallow alcohol with 5 parts of ethylene oxide per mole of alcohol
H
Betaine based on coconut fatty acids (Dehyton® AB 30, Cognis)
K
Alkyl (oligo) glucoside (Glucopon® 600 CS UP, Cognis)

Tabelle 1 gibt an, wie die Bewertung der Trocknungsleistung über die Mittelwerte aller Substrate aussehen kann. Gleichzeitig demonstrieren die Ergebnisse aus der Tabelle 1 den Stand der Technik, sowie einen Wasserwert, d.h. hier sind keine Reiniger oder sonstige Zusätze in die Spülmaschine gegeben worden. Tabelle 1 Formulierung Tropfenanzahl ADD Reiniger mit klassischem Klarspüler 0,8 3-in-1 Markenprodukt 3,6 Wasser 4,1 Table 1 indicates what the drying performance rating can be over the mean of all substrates. At the same time, the results from Table 1 demonstrate the state of the art, as well as a water value, ie no cleaners or other additives have been added to the dishwasher. <u> Table 1 </ u> formulation number of drops ADD cleaner with classic rinse aid 0.8 3-in-1 brand product 3.6 water 4.1

In der folgenden Tabelle 2 werden Ergebnisse für den oben unter a) beschriebenen Trocknungstest für verschiedene Formulierungen an unterschiedlichen Substraten (Glas, Plastik und Gesamt) aufgeführt. Basis waren jeweils 25 g einer Basisformulierung gemäß obiger Beschreibung. Angegeben werden jeweils die Anzahl der Tropfen auf der jeweiligen Oberfläche. In den rechten beiden Spalten der Tabelle 2 sind die Ergebnisse des Klarspültests b) jeweils an der Oberfläche Glas wiedergegeben.In the following Table 2 results for the drying test described above under a) for different formulations on different substrates (glass, plastic and total) are listed. The basis was in each case 25 g of a base formulation as described above. The number of drops on each surface is given. In the right two columns of Table 2, the results of the rinse test b) are each reproduced on the surface glass.

Man erkennt, dass erwartungsgemäß Wasser alleine (Versuch Nr. 18) das schlechteste Ergebnis bezüglich der Trocknung und der Klarspülleistung liefert. Aber auch die Reinigerformulierung alleine (versuch Nr. 17) zeigt in Summe eine schlechte Trocknungs- und Klarspülleistung. Der Zusatz einzelner Tenside (Versuche Nr. 1, 4, 7, 8, 10, 12 uns 15) führt zwar teilweise entweder zu einer Verbesserung der Trocknung oder einer Verbesserung der Klarspülleistung. Nur die erfindungsgemäße Kombination der Tenside der Typen a) und b) verbessert gleichzeitig das Trocknungs- und das Klarspülverhalten der Testformulierung. Tabelle 2 Versuch Nr. Menge an oberflächenaktive Substanz(en) in jeweils 25 g der Standardrezeptur Glas Plastik Gesamt Klarspülleistung an Glas Spotting / Filming 1 2 Gew.-% A 0,8 2,3 2 1,5 1,5 2* 2 Gew.-% A
2 Gew.-% C 0,2 0,5 0,8 1 1 3* 2 Gew.-% A
2 Gew.-% D 0,2 0,7 0,8 1 1 4 4 Gew.-% E 0,4 0,9 1,1 2 2 5 2 Gew.-% A
2 Gew.-% E 0,6 1,0 1,2 1 1 6 2 Gew.-% A
1 Gew.-% B 0,3 0,9 1,3 1 1 7 4 Gew.-% B 0,4 0,9 1,2 3 3 8 4 Gew.-% G 0,3 0,5 0,7 4 4 9 2 Gew.-% A
2 Gew.-% G 0,3 0,6 1,1 1 1 10 4 Gew.-% H 0,5 1,8 1,3 2,5 2 11 2 Gew.-% A
2 Gew.-% H 0,3 1,1 1,2 1 1 12 4 Gew.-% F 0,3 0,7 0,9 4 4 13 2 Gew.-% A
2 Gew.-% F 0,4 0,8 1,1 1 1,5 14 2 Gew.-% A
1 Gew.-% F 0,3 0,8 1,1 1 1 15 2 Gew.-% K 0,4 1,8 1,5 3 2 16 2 Gew.-% A
2 Gew.-% K 0,2 0,6 0,9 1 1 17 0% 1,3 4,1 3,1 4 5 18 Reines Wasser 5,8 4,9 4,1 5 5 * erfindungsgemäße Beispiele It can be seen that, as expected, water alone (Run No. 18) gives the worst result in terms of drying and rinse performance. But also the detergent formulation alone (experiment No. 17) shows in total a poor drying and rinsing performance. The addition of individual surfactants (Experiments Nos. 1, 4, 7, 8, 10, 12 and 15) leads, in part, either to an improvement in the drying or an improvement in the final rinse performance. Only the combination according to the invention of the surfactants of types a) and b) simultaneously improves the drying and rinsing properties of the test formulation. <u> Table 2 </ u> Experiment No. Amount of surface-active substance (s) in each case 25 g of the standard formulation Glass plastic total Rinse power on glass Spotting / filming 1 2% by weight of A 0.8 2.3 2 1.5 1.5 2 * 2% by weight of A
2% by weight of C 0.2 0.5 0.8 1 1 3 * 2% by weight of A
2% by weight D 0.2 0.7 0.8 1 1 4 4% by weight of E 0.4 0.9 1.1 2 2 5 2% by weight of A
2% by weight of E 0.6 1.0 1.2 1 1 6 2% by weight of A
1% by weight B 0.3 0.9 1.3 1 1 7 4% by weight B 0.4 0.9 1.2 3 3 8th 4% by weight of G 0.3 0.5 0.7 4 4 9 2% by weight of A
2% by weight of G 0.3 0.6 1.1 1 1 10 4% by weight H 0.5 1.8 1.3 2.5 2 11 2% by weight of A
2% by weight H 0.3 1.1 1.2 1 1 12 4% by weight F 0.3 0.7 0.9 4 4 13 2% by weight of A
2% by weight F 0.4 0.8 1.1 1 1.5 14 2% by weight of A
1% by weight F 0.3 0.8 1.1 1 1 15 2% by weight K 0.4 1.8 1.5 3 2 16 2% by weight of A
2% by weight K 0.2 0.6 0.9 1 1 17 0% 1.3 4.1 3.1 4 5 18 Pure water 5.8 4.9 4.1 5 5 * Examples of the invention

Claims (10)

  1. Mixtures consisting of two different surface-active substances a) and b),
    wherein the surface-active compound a) is selected from compounds of general formulae (I):

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

    in which R1 is a linear or branched alkyl and/or alkenyl radical having 4 to 22 carbon atoms, or is an R2-CH(OH)CH2 radical where R2 is a linear or branched alkyl and/or alkenyl radical having 8 to 16 carbon atoms, x is a number from 40 to 80, and M is a hydrogen atom or a saturated alkyl radical having 1 to 18 carbon atoms,
    and the surface-active substance b) is selected from the group of
    b) compounds corresponding to formula (II):

            R3O[CH2CH2O]y[CH2CHCH3O]zCH2CH(OH)R4     (II)

    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 0 or a number from 1 to 5,
    with the proviso that the weight ratio between the surface-active substances a) and b) is in the range from 10:1 to 1:10.
  2. Mixture according to Claim 1, characterized in that in formula (I) the index x is a number from 40 to 70, preferably 40 to 60 and particularly from 40 to 50.
  3. Mixture according to Claims 1 to 2, characterized in that in formula (II) the index y is a number from 20 to 30, preferably from 20 to 25.
  4. Mixture according to Claims 1 to 3, characterized in that the surface-active compounds of type a) and b) are present alongside each other in a weight ratio of 5:1 to 1:5, particularly of 3:1 to 1:3 and more preferably of 1:1.
  5. Mixture according to Claims 1 to 4, characterized in that the surface-active compound of type a) comprises a compound according to general formula (I) in which R1 is an alkyl and/or alkenyl radical having 8 to 10 carbon atoms, R2 is an alkyl or alkenyl radical having 8 to 10 carbon atoms and x is a number from 40 to 50.
  6. Mixture according to Claims 1 to 5, characterized in that the surface-active compound of type b) comprises a compound according to general formula (II) in which R3 is an alkyl and/or alkenyl radical having 11 to 18 carbon atoms, R4 is an alkyl or alkenyl radical having 8 to 10 carbon atoms and y is a number from 20 to 35.
  7. Mixture according to Claims 1 to 6, characterized in that the surface-active compound of type b) comprises a compound according to general formula (II) in which R3 is an alkyl and/or alkenyl radical having 8 to 12 carbon atoms, R4 is an alkyl or alkenyl radical having 8 to 10 carbon atoms, y is a number from 20 to 35 and z is a number from 1 to 3.
  8. Use of mixtures according to Claims 1 to 7 in cleaning compositions for hard surfaces and particularly in cleaning compositions for automatic dishwashing.
  9. Use according to Claim 8, characterized in that the mixtures are used in the cleaning compositions in amounts of 0.1% to 8% by weight, preferably of 2% to 5% by weight.
  10. Use of mixtures according to Claims 1 to 7 for improving the drying and clear-rinse performance of cleaning compositions, preferably of dishwashing compositions.
EP06018517A 2005-09-14 2006-09-05 Mixture of surface-active compounds for use in cleaning compositions Not-in-force EP1764408B1 (en)

Applications Claiming Priority (1)

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DE102005044028A DE102005044028A1 (en) 2005-09-14 2005-09-14 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

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EP1764408A1 EP1764408A1 (en) 2007-03-21
EP1764408B1 true EP1764408B1 (en) 2010-04-07

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EP1764408A1 (en) 2007-03-21
ES2343074T3 (en) 2010-07-22
US20070082836A1 (en) 2007-04-12
DE502006006627D1 (en) 2010-05-20
DE102005044028A1 (en) 2007-03-15

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