EP2367919A1

EP2367919A1 - Rinse aid, comprising fatty acid alkanolamide polyalkylene glycol ethers

Info

Publication number: EP2367919A1
Application number: EP09798877A
Authority: EP
Inventors: Frederic Bauer; Sabine Both; Teresa Alexandre; Melanie Nagel; Ansgar Behler; Frank Clasen
Original assignee: Cognis IP Management GmbH
Current assignee: Cognis IP Management GmbH
Priority date: 2008-12-20
Filing date: 2009-12-11
Publication date: 2011-09-28
Also published as: US20110247657A1; WO2010069517A1; EP2204439A1

Abstract

Rinse aids, comprising a) a surfactant according to the general formula (1), where R1 is a saturated or unsaturated, branched or linear alkyl or alkylene radical having 6 to 22 carbon atoms, R2 is hydrogen or an alkyl group having 1 to 6 carbon atoms or a group R3, and R3 is a group A-(O-CH2-CHR4-)m-OR5 and R4 and R5 independently from each other are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and A is a (CH2)n- group or a hydroxyl alkyl group having 2 to 6 carbon atoms and n is an integer from 1 to 6 and m is an integer or fractional number from 1 to 10 and furthermore b) a hydrotrope, c) an organic hydroxycarboxylic acid and d) water, exhibit improved drying properties during automatic dish washing and thus allow cleaning methods at lower temperatures than customer reference agents.

Description

Rinse aid containing fatty acid alkanolamide polyalkylene glycol ether

The present application relates to rinse aids for automatic dishwashing, which must contain certain fatty acid alkanolamidpolyalkylenglykolether, and the use of these amides to improve the drying performance of dishwashing detergents.

Machine-washed dishes today have higher requirements than manually-washed dishes. So even a completely cleaned of leftovers dishes is then rated as not flawless if it has after dishwasher washing whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets. To obtain glossy and spotless dishes, you therefore use rinse aid. The addition of liquid or solid rinse aid ensures that the water runs as completely as possible from the items to be washed, so that the different surfaces at the end of the washing program are residue-free and shiny. Commercially available rinse aids are mixtures of nonionic surfactants, solubilizers, organic acids and solvents, water and optionally preservatives and fragrances. The object of the surfactants in these compositions is to influence the interfacial tension of the water so that it is as thin as possible , coherent film can run off the dishes, so that during the subsequent drying process no drops of water, streaks or films remain (so-called net effect). A distinction is usually made between two types of deposits: On the one hand, the so-called "spotting" is examined, which is caused by drying water droplets, on the other evaluated the "filming", which are layers that result from the drying of thin water films. 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 enhance the drainage of water from the surfaces of the dishes. But there are rinse aid, which does not dry on all substrates, such as plastic as well. To circumvent this effect, elaborate rinse aid are formulated, which have, for example, silicone compounds or fluorinated compounds, as described in US 5,880,089 or US 2005/0143280 Al be described. However, these compounds are biologically difficult or even not degradable and sometimes even dangerous to the environment.

More recently, combination products are increasingly being used in which the various functions, such as cleaning, rinsing, water softening and, if appropriate, metal protection, in particular silver protection or a glass protection function, are combined in one, 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 tablet ("tabs"), are found in the market, however, as a result of the increased use of such multifunctional agents, the drying performance is higher than that of a Drying performance is to be understood as meaning the extent to which the washed ware still has water, preferably water droplets, on the surface after passing through the dishwashing process The water remaining on the surface then has to be removed either mechanically (eg by dry wiping). or you have to let the dishes dry in the air, so the user has to wait for the water to evaporate, but remains on the surface residues (eg lime and / or surfactant residues or other residues that were dissolved or dispersed in the water) to unaesthetic spots or streaks, this applies in particular, with a glossy or transparent surface, e.g. Glass or metal. For improved drying, in a dishwashing machine, in principle, an extension or intensification of the drying phase would also be conceivable, e.g. by increasing the temperature in the drying step. However, not every dishwashing product can tolerate higher temperatures, whereby in particular plastic articles may be sensitive in this case. An extension of the drying phase is usually perceived by the users as disadvantageous.

In addition, such measures lead to increased energy consumption of the machine. However, one wants to avoid the latter because energy consumption is becoming an increasingly important purchasing criterion for dishwashing detergents. Consumers have been paying more and more attention to the energy consumption of household appliances for some time now. There are also standards already in force, including energy consumption and drying performance, such as the ÖVN / ÖNORM EN 50242 + A1 + A2 + A3 standard, edition 2003-11-01, which apply to Austria, or the similar content of the German-English standard. DIN EN 50242. In particular, edition 2005-06 "Domestic dishwashing detergents - Performance measures (IEC 60436: 2004, modified); German version EN 50242: 2004).

There is therefore an increased need for technical solutions to make dishwashing processes more energy-efficient. Such solutions may also be the use of dishwashing detergents, or additives in such compositions, which shorten the energy-consuming drying step, or make it possible to dry at a lower temperature.

It is therefore sought ways to improve the drying performance of cleaning agents for hard surfaces, especially dishwashing detergents for automatic dishwashing, in which case, in particular, those solutions are sought in which the temperature in the rinse cycle can be reduced.

It has been found that the abovementioned problem can be solved by the concomitant use of certain fatty acid alkanolamidepolyalkylene glycol ethers in rinse aids or dishwashing detergents.

In a first embodiment, the application relates to rinse aid comprising at least a) a surfactant according to the general formula (I)

OR ² R ¹ --C - N - R ³ (I)

in which R ^{1 is} a saturated or unsaturated, branched or linear alkyl or alkenyl radical having 6 to 22 C atoms, R ^{2 is} hydrogen or an alkyl radical having 1 to 6 C atoms or a radical R ³ , and R ^{3 is} a radical A- (O-CH ₂ -CHR ⁴ -) _m -OR ⁵ and R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl radical having 1 to 4 C atoms and A is a group ( CH ₂ ) _n - or a hydroxyalkyl group having 2 to 6 C atoms, and n is an integer from 1 to 6 and m is integers or fractions of 1 to 10, b) is a hydrotop, c) is an organic hydroxycarboxylic acid and d) is water. The compounds a) of the formula (I) are known per se and can be described as fatty acid alkanolamidepolyalkylene glycol ethers. DE 102 59 405 A1 describes the preparation of such light-colored amides by alkoxylation of fatty acid alkanolamides. This document describes a process for the preparation of light-colored fatty acid alkanolamidepolyalkylene glycol ethers according to the above general formula (I), wherein an addition of alkylene oxides to fatty acid alkanolamides takes place in the presence of alkaline catalysts, which is characterized by carrying out the alkoxylation in the presence of reducing agents and then subjecting the reaction products obtained in this way to a steam treatment under alkaline conditions.

From WO 00/08125 Al rinse aids are known, must contain surfactants, hydrotopes and a polymer. As possible surfactants, specifically, pure ethoxylated carboxylic acid amides are disclosed with a maximum of 3 parts of ethylene oxide, without which this document discloses the benefits of selecting this class of surfactants for energy efficiency of rinse.

The selection of the fatty acid alkanolamides used, which are condensation products of technical fatty acids with mono- or dialkanolamines, is not critical per se. Typical starting materials used are those fatty acid alkanoamides which follow the formula R'CO-NR "R '" in which R'CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R 'is a hydroxyalkyl group having 2 to 4 carbon atoms and R "and R'" is hydrogen or R '. Typical examples are the condensation products of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, petroselinic acid, elaeostearic acid, 12-hydroxystearic acid, ricinoleic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid and their technical properties Mixtures, in particular coconut fatty acid, palm kernel fatty acid, palm fatty acid and tallow fatty acid with monoethanolamine, diethanolamine, monopropanolamine and dipropanolamine and mixtures thereof. Preferably, condensation products of coconut or Taigfettsäuren be used with monoethanolamine. These condensation products are then reacted with alkoxides, for example according to the teaching of DE 102 59 405 A1. Suitable alkoxides are ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO) or mixtures thereof. The compounds of formula (I) may either be reacted with only one alkoxide or different alkoxides may be present side by side in the molecules. In such mixed alkoxylates, especially those having ethylene oxide and propylene oxide side by side are preferred.

In the case of mixed alkoxylates, the different alkoxylates may be distributed in blocks or in random distribution The preparation is carried out by alkoxilating condensation products of alkanolamides with fatty acids in a manner known per se, using products which have been prepared according to the process of the above German Offenlegungsschrift No. 1,692,015 discloses carboxylic acid amides having 8-20 carbon atoms, and addition products thereof to less than 5 parts of ethylene oxide, in which case an adduct of a C 12/14 carboxylic acid amide with 3, 5 parts of ethylene oxide is described concretely, the latter being excluded from the protection of the present application.

Structurally, preferred amides a) are characterized in that, in the formula (I), R ^{1 is} a linear, saturated alkyl radical having 8 to 18 C atoms and R ^{4 is} hydrogen, n is 2 and m is a whole or broken number between 1 and 6 means. In addition, such amides a) are preferably those in which in the formula (I) the radical R ^{3 has} the meaning (CH ₂ ) _n - (OC ₂ H ₄ ) _x (OC ₃ H ₆ ) _y -OH, where n is the abovementioned Represents numbers and preferably x represents numbers from 1 to 6, preferably to 4, and y represents integers or fractions from 1 to 6, preferably to 4 or has the value zero, with the proviso that the sum of x and y is a maximum 10 and preferably a maximum of 8, in particular a maximum of 5. As a preferred lower limit of the sum of x and y (or only x if y = zero) may be a straight or broken numbers of 3 to 8, preferably 4 to 7 selected. The distribution of the alkoxylates may be random or random.The representation of the groups (OC ₂ H ₄ ) _X and (OC ₃ H ₆ ) _y in the above formulas therefore also encompasses all other conceivable sequences of the alkoxylates.

Particularly preferred are those compounds in which the index y has a value of 1 to 6, but is not zero, ie compounds which are ethoxylated and propoxylated means. Preferably, such ethoxylated and pro- polyoxylated compounds of the general formula (I) which contain 1 to 4 parts of propylene oxide and 2 to 3 parts of ethylene oxide. Preferred compounds contain, for example, 3 parts of ethylene oxide and 1, 2 or 4 parts of propylene oxide, or 2 parts of ethylene oxide and 1 part of propylene oxide. Further preferred compounds of the general formula (I) are the products of Examples 1 and 2, paragraphs [0012] to [0014] of the document disclosed in DE 102 59 405 A1.

Typical examples of compounds according to the formula (I) are alkoxylates of the condensation products of caproic, caprylic, capric, lauric, myristic, palmitic, stearic, isostearic, oleic, linoleic, linolenic, petroselic, elaeostearic, 12-hydroxystearic, ricinoleic, gadoleic, arachidonic acid , Behenic acid, erucic acid and their technical mixtures, in particular coconut oil fatty acid, palm kernel fatty acid, palm oil fatty acid and tallow fatty acid with monoethanolamine, diethanolamine, monopropanolamine and dipropanolamine and mixtures thereof. Condensation products of coconut or tallow fatty acids with monoethanolamine in alkoxylated form are preferably used.

The compounds according to a) can be mono- or dialkylated amides. In the case of monoalkylamides R ² in the formula (I) is a hydrogen atom, in the case of dialkylamides that R ² and R ^{3 are} each independently of one another radicals of

Structure - (CH ₂ ) _n - (O-CH ₂ -CHR ⁴ -) _m -OR ⁵ meaning the exact structure, ie

O ¹ X, for example, the number and distribution of the alkoxide groups in the radicals R and R may be different.

Preferred amides are those which have ethylene oxide and propylene oxide groups next to one another in the molecule, the proportion of the ethylene oxide groups preferably being higher than the proportion of the propylene oxide groups. Particularly preferred compounds of the formula (I) contain 3 to 4 parts of ethylene oxide and 2 to 3 parts of propylene oxide. Preference is furthermore generally given to those compounds of the formula (I) in which the radical R ^{5 is} a hydrogen atom.

Compounds that do not contain propylene oxide units may be less advantageous. Thus, a preferred embodiment of the invention relates to such rinse aid. in which the compounds of the formula (I) necessarily contain ethylene oxide and propylene oxide groups. It may furthermore be preferred to use those compounds of the general formula (I) in which the index x has a higher value than the index, or the y has a value greater than x, or the x and y are equal.

DE OS 1692015 describes agents which do not contain hydrotopes but adducts of carboxylic acid amides having 8 to 20 carbon atoms with less than 5 mol of ethylene oxide. The agents of the present invention may preferably be free of these adducts.

As a further component, the rinse aid contains a hydrotrope, preferably selected from the group of cumene sulfonates, xylene sulfonates, propylene glycols and preferably 1, 2-monopropylene glycol, alkyl (oligo) glycosides, ethoxylated alkyl (oligo) glycosides, alkylated alkyl (oligo) glycosides Alkyl phosphates and / or fatty alcohol alkoxylates are preferred with cumene and xylene sulfonates or the alkyl (oligo) glucosides. Hydrotropes are agents that act as solubilizers for a second, less soluble substance.

Cumene and xylene sulfonates are to be regarded as particularly preferred component b), here in particular the sodium salts of cumene or xylene sulfonate. Particularly preferred is the cumene sulfonate, sodium salt.

Alkyl and alkenyl (available from the applicant under the brand name APG ^®) are known nonionic surfactants of the formula R ⁶ O- [G] _p in which R ¹ is an alkyl and / or alkenyl group containing 4 to 22 Carbon atoms, G is a sugar residue with 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula indicates the degree of oligomerization (DP), ie the distribution of mono- and OH-goglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound, and especially the Values p = 1 to 6 For example, for a given alkyloligoglycoside, the value p is an analytically determined arithmetic size, which is usually a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having a mean degree of oligomerization p of from 1.1 to 3.0. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, as well as their technical meanings, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Preference is given to alkyl (oligo) glucosides based on the chain length C ₈ -C ₁₀ (DP ⁼ 1 to 3), which are obtained as a feedstock in the distillative separation of technical C 9 -C ₁₈ coconut fatty alcohol and with a fraction of less than 6% by weight. -% Ci ₂ alcohol may be contaminated and alkyl (oligo) glucoside based on technical Cg _/ π-oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ⁶ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, e-laidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and technical mixtures thereof which can be obtained as described above. Alkyl are preferred (oligo) glucoside based on hydrogenated Ci _{2 /} i ₄ coconut alcohol with a DP of 1 to 3. A particularly preferred alkyl (oligo) glycoside is a product of Fa. Cognis, which under the designation Glucopon ^® 215 UP is offered. It is an alkyl (oligo) glucoside, where R is linear alkyl radicals having 6 to 8 carbon atoms, the DP degree is between 1.1 and 1.2.

In addition to the above-described ^APG® which preferably have linear alkyl radicals, it is also possible to use those alkyl (oligo) glycosides which contain branched alkyl radicals. Such compounds are disclosed, for example, in US Pat. No. 71, or in WO 94/21655 A1. Advantageous are alkyl (oligo) glycosides based on branched alcohols, preferably of the Guerbet alcohols type, where kyl (oligo) glycosides based on 2-ethylhexanol and 2-propylheptanol can be particularly preferred.

Also suitable are alkoxylated alkyl (oligo) glycosides which follow the formula (II)

OR ⁸

R ⁷ OCH ₂ CHCH ₂ O- [G] _P (II)

in which R ^{7 is} an optionally hydroxyl-functionalized alkyl, alkenyl or acyl radical having 6 to 22 carbon atoms, R is hydrogen or R, G is a sugar radical having 5 to 12 carbon atoms and p is a number from 1 to 10. The preparation of such alkoxylates is described in DE 197 28 900 A1.

Further suitable hydrotropes b) are methylated alkyl (oligo) glycosides, as described e.g. in the earlier, non-prepublished European Patent Application No. 08007291.1. These are alkyl and / or alkenyl ether mixtures of alkyl and / or alkenyl polyglycosides of the formula (III)

(G _m -R ⁹ ) R ¹⁰ _n (III)

in which G is a sugar radical having 5 to 6 C atoms, R ^{9 is} a C6 to C22 alkyl and / or alkenyl radical in the acetal bond, R ^{10 is} a Cl to C4 alkyl and / or alkenyl group in ether bond, m is an average of from 1.2 to 1.8, and n is a number from 1.4 to 2.6, preferably wherein at least 50% by weight of the alkyl and / or alkenyl ethers is a radical R ⁹ greater than or equal to a C chain 12 included. The compounds of the formula (III) are prepared by reacting alkyl (oliog) glycosides with alkylating reagents such as alkenyl halides and / or alkyl or alkenyl tosylates and / or dialkyl or dialkenyl sulphates.

Further suitable hydrotropes b) are also the alkyl esters of phosphoric acid, preferably the mono- or dialkyl esters, the alkyl radicals preferably having 6 to 12 and in particular 8 to 12 C atoms. Another suitable group of hydrotropes b) are the alkoxylated fatty alcohols. Fatty alcohol ethoxylates are referred to as fatty alcohol or oxo alcohol alkoxylates and preferably follow the formula (IV),

R ⁿ O (CH 2 CHR ¹² O) _q H (IV)

in which R ¹ 'is a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, R ^{12 is} hydrogen or an alkyl radical having 1 to 3 C atoms and q is a number from 1 to 50. The fatty alcohol alkoxylates of the formula (IV) may preferably contain ethylene oxide, propylene oxide or both alkoxides, these being blockwise (first one block ethylene oxide, then one block propylene oxide, or vice versa; or the molecule contains several blocks of different alkoxylates in a row, wherein at least two equal alkoxide groups are to be understood as meaning a block) or irregularly distributed (so-called "random distribution") The preparation takes place in the manner known to the person skilled in the art by reacting fatty alcohols with the alkoxides in the presence of acidic or basic catalysts For the purposes of the present technical teaching, fatty alcohol alkoxides which are ethoxylated and propoxylated are preferred.

As third component c), the rinse aids according to the invention comprise an acid and here usually organic hydroxycarboxylic acids, which are preferably selected from the group consisting of mandelic acid, lactic acid, malic acid and tartaric acid, the citric acid being particularly preferred.

In addition, the rinse aid according to the invention still contain water, preferably in amounts, based on the total weight of the compositions, of from 10 to 90% by weight, preferably from 40 to 75% by weight and in particular from 50 to 65% by weight. Preference is given to the use of deionized water. The amide component a) is preferably present in amounts of 1 to 80 wt .-%, preferably 10 to 50 wt .-% and in particular from 20 to 45 wt .-%, based on the weight of the total composition. The hydrotropes b) are preferably present in amounts of 1 to 30 wt .-%, preferably 1 to 20 wt .-% and in particular from 1 to 10 wt .-% based on the weight of the total composition. The acid component c) is preferably contained in amounts of 1 to 10 wt .-%, preferably from 1 to 5 wt .-% based on the weight of the total rinse aid.

Particularly preferred rinse aids contain the compounds of the formula (I) together with citric acid and either cumene sulfonates or alkyl (oligo) glucosides.

The agents of the present invention may also contain polymers, it being more preferred that the agents be free of polymers, especially free of polymers containing poly (meth) acrylic acid monomers.

The preparation of the agent is carried out by mixing the different components, optionally with entry of energy by stirring and / or heating of the mixtures. Preferably, after submission of the water, the remaining components are added in any order with stirring and then stirred further until the mixture is clear.

In addition to the essential components a) to c) and water, further conventional ingredients may be present in the rinse aids according to the invention. These are preferably selected from the group of alcohols and here preferably the short-chain alcohols ethanol, propanol, isopropanol, butanol, isobutanol. In addition, the agents may also contain other surfactants, e.g. Fatty alcohol alkoxylates or alkylpyrrolidones, polymers, e.g. Polycarboxylates or preservatives, e.g. Isothiazolinone included. The concomitant use of phosphates, in particular of alkyl phosphates is possible.

However, the compositions may also contain perfumes, dyes, UV protection, eg benzophenones, pH regulants and other customary additives, for example those for the prevention of glass or metal corrosion or for tarnish protection of metals. The pH of the agents may range from pH 3 to 10, preferably from pH 3.5 to 8 and more preferably from 4 to 7 or 4 to 6. It generally applies that acidic agent (pH <7) may be preferred. However, preference is given to those aqueous compositions which contain only components a) to c). Furthermore, it may be advantageous to dispense with the presence of hydrocarbons and in particular terpenes. In a preferred embodiment of the invention, the agents are therefore free of terpenes and / or hydrocarbons.

Another object of the present application relates to the use of compounds of general formula (I) according to claim 1 for the preparation of aqueous rinse aids, or for the production of dishwashing detergents. It is also particularly preferred to use compounds of general formula (I) as described above for improving the drying performance of dishwashing rinse aids or dishwashing detergents.

The fatty acid alkanolamide polyalkylene glycol ethers according to the formula (I) can be incorporated alone or in combination with the components a) to c) into common rinse aids and, in particular, dishwashing detergents. The dishwashing agents may be solid or in compressed form, e.g. be present as a tablet, or be liquid or gel. The compounds of the formula (I) are present in ready-form dishwashing agents, preferably in amounts of from 1 to 45% by weight, in particular in amounts of from 4 to 30% by weight and more preferably in amounts of from 15 to 30% by weight.

Such ready-formulated so-called dishwashing detergents contain e.g. Builder materials, surfactants, bleaches, bleach activators, enzymes, enzyme stabilizers, corrosion inhibitors, scale inhibitors, complexing agents, inorganic salts, grayness inhibitors, foam inhibitors, silicone oils, soil release compounds, dye transfer inhibitors, salts of polyphosphonic acids, optical brighteners, fluorescers, disinfectants, fragrances, Dyes, antistatic agents, ironing auxiliaries, repellents and impregnating agents, swelling and anti-slip agents, UV absorbers, pH regulators, or mixtures thereof.

Typical formulations of such automatic dishwashing compositions contain pentasodium triphosphate (see Sodium Phosphates) in amounts of 0 or 1 to 50% by weight.

%. Sodium citrate in amounts of 30 to 45 wt .-%, sodium polycarboxylates in Amounts of from 5 to 8% by weight, sodium metasilicate in amounts of from 10 to 60% by weight, sodium hydrogencarbonate in amounts of from 10 to 25% by weight, sodium disilicate in amounts of from 10 to 30% by weight, sodium perborate in quantities from 5 to 10 wt .-%, bleach activators in amounts of 2 to 4 wt .-%, enzymes, preferably protease and amylase in amounts of 1 to 6 wt .-%, low-foam nonionic surfactants in amounts of 1 to 20 wt. %, Silver / glass protection and fragrances in amounts up to 5 wt .-%. Suitable surfactants are anionic, nonionic, cationic and / or amphoteric surfactants, nonionic surfactants and here low-foam nonionic surfactants may be particularly preferred. The latter are preferably selected from the class of the fatty alcohol alkoxylate, preferably the fatty alcohol ethoxylates, although end-capped derivatives may also be suitable.

Fatty alcohol ethoxylates are known as fatty alcohol or oxo alcohol ethoxylates and preferably follow the formula RO (CH ₂ CH ₂ O) _n H in the R for a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and n is Numbers from 1 to 50 stands. Typical examples are the adducts of an average of 1 to 50, preferably 5 to 40, and especially 10 to 25, moles of 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, arabyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical mixtures thereof, for example in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxo synthesis and as monomer fraction incurred in the dimerization of unsaturated fatty alcohols. Preferred are adducts of 10 to 40 moles of ethylene oxide with technical fatty alcohols having 12 to 18 carbon atoms, such as coconut, palm, palm kernel or Taigfettalkohol.

The fatty acid alkanolamidepolyalkylene glycol ethers of the formula (I) show improved drying behavior on porcelain, glass, metal and plastic, alone or preferably in combination with hydrotropes b) in rinse aids or dishwashing agents in automatic dishwashing (for example in Tupperware, SAN (= Styrene-acrylonitrile), melamine, polypropylene, polyethylene). Particularly pronounced is the improved drying performance on glass and metal substrates. The improved drying behavior is also more pronounced in use low-temperature programs or economy or ecoprograms with a reduced maximum temperature in the rinse cycle or in the dry step. In a preferred embodiment, therefore, the compounds of the formula (I) rinse aids or dishwashing agents are used as additives which serve to improve the drying and / or cleaning performance. The amides of general formula (I) can be used both in aqueous agents, preferably in aqueous rinse aids, but also in solid agents. In general, the amides of the formula (I) are suitable for the production of rinse aids or dishwashing detergents.

A further subject of the present application therefore relates to a method for automatic dishwashing, wherein the ware undergoes at least one cleaning cycle using a cleaning agent and water, at least one rinse using a rinse aid and water and a final drying cycle, the temperature in the Drying cycle does not exceed 50 ° C, wherein in step i) and / or ii) an agent containing a compound of formula (I) as described above, use. By using the amides according to formula (I), the drying temperatures can be reduced from those otherwise usual in such processes from 70 to 60 ° C to 55 ° C or even below, e.g. be reduced to 45 or 50 ° C.

Thus, the use of the amides of formula (I) in dishwashing detergents and / or in rinse aids allows for significant energy savings compared to today's dishwashing processes and techniques since, due to the improved drying behavior, a shorter drying time or, preferably, a lower drying temperature, preferably less 60 ° C and especially from 40 to 59 ° C, most preferably from 45 to 55 ° C can be used. Typical values for energy savings, which can be achieved in each case one run of the entire purification process, are preferably 0.05 to 0.2 kWh, compared to the same method, but that a reference rinse aid without the essential amide invention a). As reference rinse aid the rinse aid is selected according to the description in ÖVE / ÖNORM EN 50242 (Issue: 2003-11-01) Annex B.2 Rinse Aid [formula III]. The cleaning method according to the above description is suitable. net to meet the requirements of drying performance and energy consumption according to the German standard DIN EN 50242.

Examples

To test the performance properties of the fatty acid alkanolamide polyalkylene glycol ethers according to the invention, the following formulations 1 to 8 (all percentages are based on wt .-% based on the active substance content) were prepared by the ingredients were added successively with stirring in water. EO stands for ethylene oxide, PO for propylene oxide units.

Formulation 1:

40% amide of the formula (I) with 3 EO / 2PO based on coconut fatty acids, 4% alkylpolyglucosides C8-10, (Glucopon ^® 215 UP, Fa. Cognis) 5% citric acid 51% Deionized water

(. Tresolit ^® AP-36, Cognis): Formulation 2 40% amide of the formula (I) with 3 EO / 2PO based on coconut fatty alkyl phosphate C8-10 4% 5% citric acid 51% Deionized water Formulation 3:

40% amide according to formula (I) with 3EO / 2PO based on coconut fatty acids

4% sodium cumene sulphonate

5% citric acid

51% deionized water

Formulation 4:

40% amide according to formula (I) with 3EO / 4PO based on coconut fatty acids

4% APG-methyl ether (Eumulgin ^® GTS, Fa. Cognis)

5% Citric Acid 51% Deionized Water

Formulation 5:

40% amide according to formula (I) with 3EO / 4PO based on coconut fatty acids 4% alkyl polyglucosides C8-10. (Glucopon ^® 215 UP, Fa. Cognis) 5% citric acid

51% deionized water

Formulation 6:

33% amide of the formula (I) with 2EO / 1PO based on coconut fatty acids 11% C8 alkyl polyglucosides 10, (Glucopon ^® 215 UP, Fa. Cognis) 5% citric acid 51% Deionized water Formulation 7:

28% amide of the formula (I) with 2E0 / 1P0 based on coconut fatty acids 16% Alkylpolyglucoside C8-10 ^(β Glucopon 215 UP, Fa. Cognis) 5% citric acid

51% deionized water

Formulation 8:

26.7% amide of the formula (I) with 3 EO / 2PO based on coconut fatty acids 13.3% C12-14 fatty alcohol containing 5 EO / 4PO (Dehypon LS 54 ^®, Fa. Cognis) 4% sodium cumene sulfonate 5% citric acid 51% Deionized Water reference rinse aid:

EN 50242 B.2 Rinse aid [formula III]

With the formulations 1 to 8 were then in each case under the same conditions dishes of glass, porcelain, metal (= cutlery) Tupperware and styrene acrylonitrile plastic in modified AEG Electrolux (model Favorit 60870) dishwashers in the program 50 ° C rinsed without a fan and the Rinse well then visually inspected for residues / water drops (drying performance according to Cognis).

Using formulation 1, dishware made of glass, porcelain, metal (= cutlery) Tupperware and styrene acrylonitrile plastic were likewise rinsed in two commercially available dishwasher types Miele G 696-2 SC Plus in the programs Spar and Universal 55 under the same conditions and the rinse then visually inspected for residues / drops of water (drying performance according to Cognis).

Furthermore, with the formulation 1 under the same conditions tableware parts made of glass, porcelain, metal (= cutlery) and styrene acrylonitrile plastic in 3 different commercially available dishwashers examined: a) AEG Favorit 60870, 50 ° C, hot rinse without fan; b) Miele G 696-2 SC Plus, "Spar" program and c) Bosch SMS65T25EU "Active Water", in the eco 50 ° C program. The machine of type c) works with zeolite-dried hot air in the drying step, so as to achieve a better machine-side drying result. The cleaned dishes were then visually inspected for residues / water drops. When evaluating the drying performance, each part of the load was evaluated individually and graded as follows:

Dry (part is completely free of moisture) 0

1 drop / lane 1

2 drops / lane 2

3 drops / lane 3

4 drops / track 4

5 drops / track 5

6 drops / lane and more 6

Cups / bowls / glasses:

Water in glass; Cup or bowl cavity 6

Only "wet" 3

Dry 0

The results for the three machines can be found in the following tables Ia to Ic. The values determined for 3 ml of an agent according to the invention, the values of the reference agent, and a relative evaluation were reproduced where: values better than standard: +, equal to the standard: 0, worse than standard:

Table Ia (AEG Favorit 60870):

Mean value mean

Porcelain plastic glass cutlery all of all substrate groups substrates

3mL Formulie¬

4.9 4.4 3.7 1.7 3.7 3.4 compared to 3mL EN 50242

5.8 5.5 5.6 3.0 5.0 4.6 B.2 rinse aid [formula III] compared to 3mL EN 50242 + ++ ++ ++ ++ ++ B.2 rinse aid [formula III ] Table Ib (rent G 696-2 SC Plus)

Mean value mean

Porcelain plastic glass cutlery of all

Substrate groups Substrates

3mL formulation

0.2 0.2 0.0 0.1 0.1 0.1

1 compared to

3mL EN 50242

0.4 0.4 0.6 0.3 0.4 0.4 B.2 Rinse Aid

[Formula III]

Relative to 3mL EN + + ++ + + +

50242 B.2 Rinse aid [formula III]

Table Ic (Bosch SMS65T25EU "Active Water")

Medium-

Average

Kunstaller

Porcelain glass cutlery all fabric sub-substrate green strate ppen

3mL formulation

0.0 0.1 0.0 0.0 0.0 0.0 1

compared to

3mL EN 50242

0.2 0.4 0.0 0.0 0.1 0.1 B.2 rinse aid

[Formula HI]

Relative to 3mL EN + + + +

50242 B.2 Clarifier [Formula III]

Furthermore, with the formulation 1, under the same conditions, special substrate plates of glass, ceramic, metal, PP = polypropylene, SAN = styrene acrylonitrile plastic were rinsed in two commercially available dishwashers of the Miele G 681 SC Plus type in the Spar program and the substrates were digitally processed Image analysis, as described in EP 1 635 167 A1 of the Applicant, tested for residues (rinse performance: spotting on PP = polypropylene, stainless steel, glass, Ceramic, SAN = styrene-acrylonitrile as well as filming on glass and SAN = styrene-acrylonitrile). The results are shown in Tables 2a and 2b:

Table 2a (filming ^")

Filming on glass Filming on SAN weak medium strong weak medium strong

3mL Formulation 1 98.27 99.85 99.92 65.10 91.82 98.93

compared to 3mL EN 50242

99,23 99,91 99,93 53,00 84,30 97,10 B.2 Rinse aid [formula III]

Relative in comparison to 3mL EN

0 0 0 ++ ++ + 50242 B.2 Rinse aid [formula III]

Table 2b f Spotting)

Spotting glass ceramic metal PP SAN

3mL Formulation 1 98.49 99.05 99.03 99.37 92.14

compared to 3mL EN 50242 B.2 clear winder [formula III]

Relative to 3mL EN 50242 B.2

0 0 Rinse aid [formula III]

The investigations show that good drying performances are achieved on all relevant substrates even when the cleaning or drying temperature in the automatic dishwasher is low, as a result of the use of the novel amides. you can. This also applies to the use of modern dishwashers, which already provide a high drying performance on the machine side, as the experiment with the machine c) shows.

Using formulation 1 and the reference rinse aid, dishes made of glass, porcelain, metal (^ cutlery) Tupperware and styrene-acrylonitrile plastic were likewise rinsed in a modified AEG Electrolux (model Favorit 60870) dishwashing machine under the same conditions and the drying was assessed and compared in accordance with EN 50242 , The individual multi-cycle test runs were tested in variable programs at 50 ° C as well as at 60 ° C in a rinse cycle and without a blower.

In Figure 1, the results are plotted by plotting the drying index T _D against the drying temperature. It can be seen that formulation 1 enables savings of 0.15 KWh per run compared to the reference rinse aid with the same drying performance.

Claims

claims

1. rinse aid containing at least

a) a surfactant according to the general formula (I)

OR ²

R ¹ --C - N - R ³ (I)

in which R ^{1 is} a saturated or unsaturated, branched or linear alkyl or alkenyl radical having 6 to 22 C atoms, R ^{2 is} hydrogen or an alkyl radical having 1 to 6 C atoms or a radical R ³ , and R is ^{3 is} a radical A- (O-CH ₂ -CHR ⁴ -) _m -OR ⁵ and R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl radical having 1 to 4 C atoms and A is a group (CH ₂ ) _n - or a hydroxyalkyl group having 2 to 6 carbon atoms and n is an integer from 1 to 6 and m is whole or fractional numbers from 1 to 10, b) a hydrotrope, c) an organic hydroxycarboxylic acid d) water ,

2. Rinse aid according to claim 1, characterized in that in the formula (I) R ^{1 is} a linear saturated alkyl radical having 8 to 18 carbon atoms and R ^{4 is} hydrogen, n is 2 and m is an integer or fractional

Number between 1 and 6 means.

3. Rinse aid according to at least one of claims 1 to 2, characterized in that the radical R ^{3 has} the following meaning (CH ₂ ) _n - (OC ₂ H ₄ ) χ (OC ₃ H ₆ ) _y -OH, in the n represents the above numbers and x for

Numbers from 1 to 4, and y stands for integers or fractions from 1 to 4 or has the value zero, with the proviso that the sum of x and y is a maximum of 10.

4. rinse aid according to claim 3, characterized in that the index x in the general formula (I) has a higher value than the index y in the general formula (I), or the y has a value greater than x, or the x and y are the same.

5. rinse aid according to at least one of claims 1 to 4, that the radical R ^{3 has} the following meaning (CH ₂ ) _n - (OC ₂ H ₄ ) χ (OC ₃ H ₆ ) _y -OH, in which n the above Represents numbers and x represents numbers from 1 to 4, and y represents integers or fractions from 1 to 4, with the proviso that the sum of x and y is a maximum of 10.

6. Rinse aid according to at least one of claims 1 to 5, characterized in that the hydrotrope b) is selected from the group of the cumene sulfonates, xylene sulfonates, alkyl (oligo) glycosides, ethoxylated alkyl (oligo) glycosides, alkylated alkyl ( oligo) glycosides, alkyl phosphates and / or fatty alcohol alkoxylates, preference being given to cumene, xylene sulfonates or alkyl oligogoglucosides.

7. Rinse aid according to at least one of claims 1 to 6, character- ized in that the organic carboxylic acid is selected from the group

Mandelic acid, lactic acid, malic acid, citric acid and tartaric acid, wherein the citric acid is particularly preferred.

8. Rinse aid according to at least one of claims 1 to 7, character- ized in that the surfactant a) in amounts of 1 to 80 wt .-%, preferably 10 to 50 wt .-% and in particular from 15 to 40 wt. %, based on the weight of the total agent.

9. rinse aid according to at least one of claims 1 to 8, character- ized in that the hydrotrope b) in amounts of 1 to 30 wt .-%, preferably 1 to 20 wt .-% and in particular from 1 to 10 wt. % based on the weight of the total agent.

10. Rinse aid according to at least one of claims 1 to 9, characterized in that the organic hydroxycarboxylic acid c) are contained in amounts of 1 to 10 wt .-%, preferably from 1 to 5 wt .-% based on the weight of the total composition ,

11. Rinse aid according to at least one of claims 1 to 10, characterized in that it comprises water in amounts of 10 to 90 wt .-%, preferably from 40 to 75 wt .-% and in particular from 50 to 65 wt .-% based on contains the weight of the entire agent.

12. Rinse aid according to at least one of claims 1 to 11, characterized in that they are free of addition products of less than 5 and in particular less than 4 moles of ethylene oxide to carboxylic acid amides having 8 to 20 carbon atoms.

13. Rinse aid according to at least one of claims 1 to 12, characterized in that the compounds of formula (I) necessarily contain ethylene oxide and propylene oxide groups.

14. Use of compounds of general formula (I) according to claim 1 for the preparation of rinse aids, or for the production of dishwashing detergents.

15. Use of compounds of general formula (I) according to claim 1 for improving the drying performance and / or rinsing performance of rinse aids for dishwashing, or dishwashing detergents.

16. A method of automatic dishwashing wherein the ware undergoes at least i) a cleaning cycle using a detergent and water, at least ii) a rinse cycle using a rinse aid and water, and iii) a final drying cycle, wherein the temperature in the drying cycle does not exceed 55 ° C, characterized in that in step i) and / or ii) an agent containing a compound of formula (I) according to claim 1 is used.

17. The method according to claim 18, characterized in that the dishwashing method meets the requirements of the standard DIN EN 50242 in terms of drying performance and energy consumption.