EP3194552B1 - Cleaning composition - Google Patents

Description

The present invention relates to a cleaning agent, in particular dishwashing detergent, preferably pre-portioned automatic dishwashing detergent.

Hard surface cleaners, such as dishwashing detergents, are available to the consumer in a variety of forms. In addition to the traditional solid agents are gaining increasingly increasingly flowable and especially liquid to gel detergent in importance. The consumer particularly appreciates the rapid solubility and the associated rapid availability of the ingredients in the cleaning liquor, especially in short-dishwashing programs and at low temperatures.

Consumers have become accustomed to conveniently dosing pre-portioned automatic dishwashing detergents and have been using these products primarily in the form of tablets. In order to put a dishwashing detergent offering the above-mentioned advantages over solid compositions in a pre-portioned form, the use of cold water-soluble films in the form of sachets is common.

In the production of disposable portions for cleaning agents, in particular detergents for machine dishwashing, which comprise detergent-filled bags of water-soluble polyvinyl alcohol-containing film, leakages or leaks of the disposable portion often occur, in particular in the case of liquid detergents. This is often due to a dissolution of the film by the water contained in the liquid detergent.

In order to avoid such leaks, it is proposed in the prior art to equip, spray or otherwise coat the polyvinyl alcohol-containing films with impregnating agents in order to avoid leakage before actual use in the dishwasher. The EP 1 846 482 discloses, for example, the coating of the polyvinyl alcohol-containing film with a salt layer containing carboxymethyl cellulose as a binder.

Alternatively, it is also discussed to reduce the moisture or the freely available water in the detergent, ie within the water-soluble bag. The US 7,259,134 discloses a multi-chamber bag (Mehrkammerpouch), in which a chamber is a liquid A composition comprising a moisture control system comprising a mixture of C ₂ -C ₆ monoalkylpolyol and C ₂ -C ₃ monoalkylpolyol. In this case, systems containing 40% by weight of dipropylene glycol and 4 to 15% by weight of glycerol, which contain 10% by weight of H ₂ O, are disclosed as the liquid detergent component. To improve the sustainability, in particular the sensible use of resources, a waiver of larger amounts of organic solvents would be desirable.

Furthermore, in aqueous cleaning formulations containing enzymes, in particular protease (s) and / or amylase (s), the storage stability of the enzymes by a high water content is not possible without stabilizers.

Boric acid or borates, which are known to stabilize the enzyme, can even lead to compatibility problems in polyvinyl alcohol-containing films even at lower concentrations.

Frequently, divalent cations, in particular from the group of alkaline earth metals, preferably calcium and / or magnesium salts, are also proposed for enzyme stabilization. However, the presence of such divalent salts in dishwashing detergents has the disadvantage that the effectiveness of the added builders is reduced depending on the amount of added salts. Furthermore, if the content of dissolved ions is too high, crosslinking of the polyvinyl alcohol used for the film may occur, thereby worsening the dissolution behavior of the disposable portion in the dishwasher.

The object of the present invention was therefore to provide a cleaning agent which has improved stability, in particular with regard to the stability of the enzyme activities during storage and, if the detergents are present as pre-portioned cleaners, good stability of the pre-portioned detergent units, especially with regard to leakage of the package (especially in packages comprising polyvinyl-containing films).

1. a) 15 bis 30 Gew.-% mindestens einer Aminocarbonsäure ausgewählt aus GLDA und/oder MGDA und/oder deren Salzen,
2. b) 40 bis 65 Gew.-% Wasser,
3. c) weniger als 10 Gew.-% Polyol und
4. d) 0,2 bis 2,5 Gew.-% Xanthan,

dadurch gekennzeichnet, dass es weniger als 0,02 Gew.-% Calciumionen und bezogen auf ihr Gesamtgewicht, 0, 1 bis 12 Gew.-%, vorzugsweise 0,2 bis 10 Gew.-% und insbesondere 0,5 bis 8 Gew.-% Enzym-Zubereitungen enthält.This problem is solved by a cleaning agent, in particular dishwashing detergent, preferably pre-portioned automatic dishwashing detergent containing

1. a) 15 to 30% by weight of at least one aminocarboxylic acid selected from GLDA and / or MGDA and / or their salts,
2. b) 40 to 65% by weight of water,
3. c) less than 10 wt .-% of polyol and
4. d) 0.2 to 2.5% by weight of xanthan,

characterized in that it contains less than 0.02% by weight of calcium ions and, based on its total weight, from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.5 to 8% by weight. - contains% enzyme preparations.

Surprisingly, it has now been found that detergents, in particular liquid detergents, can also be formulated storage-stable with relatively large amounts of water, preferably 40% by weight and more, in combination with at least one aminocarboxylic acid as nonphosphate builders, in particular GLDA or MGDA.

In particular, it is thus possible to produce pre-portioned cleaners according to the invention, in particular automatic dishwashing detergents (especially in disposable portions). These disposable portions show no leaks even during prolonged storage, especially in packaging comprising polyvinyl alcohol-containing films. In addition, the cleaning formulations without the addition of larger amounts of divalent cations, a good and stable performance of the enzymes contained.

Unless otherwise stated below, the term wt .-% refers to the amount of active substance based on the total amount of the cleaning agent.

The cleaning agents according to the invention, in particular the pre-portioned automatic dishwashing agents, contain between 40 and 60% by weight of water.

In this case, the proportion of water is mathematically calculated on the one hand from the explicitly added amount of water and on the other hand from the amount of water, which are introduced by aqueous raw materials, etc. in the formulation.

Particularly preferably, the cleaning agents according to the invention contain between 50 and 60% by weight of water. Most preferably, the water content is between 51 and 55 wt .-% water, each based on the total weight of the detergent formulation.

"Liquid" as used herein with respect to the cleaning agent of the present invention includes all flowable compositions and, in particular, also encompasses gels and pasty compositions. In particular, the term also includes non-Newtonian fluids having a yield point. Because of the relatively high water content, the cleaning agents according to the invention, in particular pre-portioned automatic dishwashing agents, are liquid or, depending on the amount of thickening substances used, also gelatinous to pasty, non-solid cleaning formulations.

The detergents according to the invention, in particular dishwashing detergents, preferably pre-portioned automatic dishwashing detergents, contain at least one aminocarboxylic acid selected from GLDA and / or MGDA and / or their salts.

"At least one" as used herein means 1 or more, for example, 1 or 2 or more. If a plurality of aminocarboxylic acids and / or their salts are used, the amounts stated below are based on the total amount of all aminocarboxylic acids. According to the invention, 15 to 30% by weight of at least one aminocarboxylic acid is selected from methylglycinediacetic acid (MGDA) or its salts and also glutamine-N, N- diacetic acid (GLDA) or its salts. It is preferred to use 15 to 30 wt .-% of MGDA and / or their salts, GLDA and / or their salts or 15 to 30 wt .-% of a mixture of MGDA and / or their salts and GLDA and / or their salts ,

It is particularly preferred to use either 15 to 30% by weight of MGDA (and / or their salts) or 15 to 30% by weight of GLDA (and / or their salts). It is very particularly preferred to use 15 to 30% by weight of GLDA and / or their salts.

The cleaning agents according to the invention contain the selected aminocarboxylic acid (s) in amounts, based in each case on the total weight of the cleaning agent, of from 15 to 25% by weight, preferably from 15 to 20% by weight, of at least one aminocarboxylic acid selected from MGDA and / or salts thereof, and It is particularly preferred to use either 15 to 25% by weight of MGDA and / or its salts or 15 to 25% by weight of GLDA and / or their salts. It is very particularly preferred to use 15 to 20% by weight of MGDA and / or its salts or 15 to 20% by weight of GLDA and / or its salts. 15 to 20 wt .-% GLDA and / or their salts, in particular to use the partially or fully neutralized sodium or potassium salts of GLDA, is particularly preferred.

The present invention contains 0.20 to 2.5% by weight of xanthan, preferably 0.25 to 2.0% by weight, in particular 0.25 to 1.5% by weight, for example 1% by weight of xanthan. Xanthan gum is a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular mass of 2 to 15 million daltons. Xanthan is formed from a chain of β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.

Surprisingly, it has been found that the use of xanthan gum as a thickener leads to stable cleaning agents even on prolonged storage, especially when packaged in water-soluble films, in particular polyvinyl alcohol-containing films, in particular water-soluble ones Disposable portions, not the surrounding packaging, in particular attack the polyvinyl alcohol-containing film and thus do not lead to leaks.

The cleaning agents according to the invention contain less than 10% by weight of polyol (one or more polyhydric alcohols). The term polyol is understood to mean liquid polyols at room temperature (20 ° C. and normal pressure), in particular glycerol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol and mixtures thereof.

The cleaning agents, in particular the pre-portioned automatic dishwashing agents, particularly preferably contain less than 7% by weight, preferably less than 6% by weight, of polyol.

If small quantities of polyol are to be used, a polyol used particularly preferably according to the invention is glycerol. Glycerol is used in inventive compositions preferably in an amount of 0 to 5 wt .-%. The total amount of polyol (including the preferably used in the detergents according to the invention glycerol) is, as described above, a total of less than 10 wt .-%, in particular less than 7 wt .-%, in particular less than 6 wt .-% polyol.

According to a further preferred embodiment, the ratio of water to polyol is at least 4: 1, particularly preferably at least 5: 1, for example 6: 1.

The cleaning agents according to the invention contain less than 0.02% by weight (in each case based on the total weight of the cleaning formulation) of calcium ions.

Reference cleaning agents contain the following combinations of components a) to d) according to Table 1 or Table 2 (in% by weight of active substance): In addition, further active and auxiliary substances (in particular those as described below) may be present Combinations mentioned herein are particularly suitable for detergent in disposable portions, in particular disposable portions in bags of polyvinyl alcohol-containing film. Table 1: 1 2 3 4 5 a) GLDA or GLDA salt 15-30 15-25 15-20 15-20 15-20 b) water 50-60 50-60 51-55 51-55 51-55 c) polyol <7 <7 <6 <6 <6 d) xanthan 0.2-2 0.2-2 0.2-2 0.2-1.5 0.2-1.5 calcium ions <0.1 <0.05 <0.05 <0.05 <0.02 1 2 3 4 5 a) MGDA or MGDA salt 15-30 15-25 15-20 15-20 15-20 b) water 50-60 50-60 51-55 51-55 51-55 c) polyol <7 <7 <6 <6 <6 d) xanthan 0.2-2 0.2-2 0.2-2 0.2-1.5 0.2-1.5 calcium ions <0.05 <0.05 <0.05 <0.05 <0.02

The cleaning agents according to the invention contain, in a preferred embodiment, at least one rinse aid surfactant. In various embodiments, the rinse aid surfactant is a nonionic surfactant. Although all nonionic surfactants known to the person skilled in the art can be used, weakly foaming nonionic surfactants, in particular alkoxylated, in particular ethoxylated, low-foaming nonionic surfactants, are preferably used. In preferred embodiments, the automatic dishwashing agents contain nonionic surfactants from the group of alkoxylated alcohols.

In various embodiments, nonionic surfactants can be used which have a melting point above room temperature. In such embodiments, nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and most preferably between 26.6 and 43.3 ° C, are especially prefers.

Preferably used surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.Particularly preferred nonionic surfactants used are low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently stand for integers from 1 to 6.

Thus, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• R² für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A, A', A" und A'" unabhängig voneinander für einen Rest aus der Gruppe -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, - CH₂-CH(CH₂-CH₃) stehen,
• w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.

Preferred nonionic surfactants here are those of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , in the

• R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, - CH ₂ -CH (CH ₂ -CH ₃ ),
• w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.

By the addition of the aforementioned nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , hereinafter also referred to as "hydroxy mixed ethers", the cleaning performance of the preparations according to the invention can be significantly improved both in comparison to surfactant-free system as well as in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

Preference is given in particular to those end-capped, poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, where x is Values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60 stands.

Particularly preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.
The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ - (EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2 -hydroxydecylether.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO),
(PO) (PO) (EO) and (PO) (PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1 such that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH ) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder-Alkenylrest steht;
• R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A für einen Rest aus der Gruppe CH₂CH₂, CH₂CH₂CH₂, CH₂CH(CH₃), vorzugsweise für CH₂CH₂ steht, und
• w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht

Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise die C_4-22 Fettalkohol-(EO)_10-80-2-hydroxyalkylether, insbesondere auch die C_8-12 Fettalkohol-(EO)₂₂-2-hydroxydecylether und die C_4-22 Fettalkohol-(EO)_40-80-2-hydroxyalkylether.Finally, the nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ^{2 have} proved to be particularly effective, in which

• R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A is a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH (CH ₃ ), preferably CH ₂ CH ₂ , and
• w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40

The group of these nonionic surfactants include, for example, the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ethers and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether.

In various embodiments of the invention, instead of the above-defined end-capped hydroxy mixed ethers, it is also possible to use the corresponding non-end-capped hydroxy mixed ethers. These may satisfy the above formulas, but R ² is hydrogen and R ¹ , R ³ , A, A ', A ", A'", w, x, y and z are as defined above.

The liquid detergents of the invention preferably contain a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant in the total weight of the cleaning agent preferably 0.1 to 3.5, preferably 0.5 to 2.5, more preferably 1.0 to 2.0 wt .-% is.

• R¹ für einen verzweigten oder unverzweigten Alkylrest mit 10 bis 15 Kohlenstoffatomen steht,
• R³ und R⁴ unabhängig voneinander für Wasserstoff oder einen verzweigten oder unverzweigten Alkylrest mit 2 oder 3 Kohlenstoffatomen stehen,
• R² für einen unverzweigten Alkylrest mit 8 bis 16 Kohlenstoffatomen steht,
• x und z unabhängig voneinander für einen Wert von 1 bis 5 stehen und
• y für einen Wert von 20 bis 30.

In einer möglichen Ausführungsform kann das Tensid beispielsweise Plurafac® LF 7319 (ex BASF) umfassen.In a preferred embodiment of the invention, the dishwashing detergent contains as a nonionic surfactant (also in combination with one or more of the other nonionic surfactants mentioned herein) a surfactant of the general formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ CHO] _y [CH ₂ CH (R ⁴ ) O] _z C (O) R ² , where

• R ^{1 is} a branched or unbranched alkyl radical having 10 to 15 carbon atoms,
• R ³ and R ⁴ independently of one another represent hydrogen or a branched or unbranched alkyl radical having 2 or 3 carbon atoms,
• R ^{2 is} an unbranched alkyl radical having 8 to 16 carbon atoms,
• x and z independently represent a value of 1 to 5 and
• y for a value of 20 to 30.

In one possible embodiment, the surfactant may comprise, for example, Plurafac® LF 7319 (ex BASF).

• R¹ und R² unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten Alkylrest mit 4 bis 22 Kohlenstoffatomen;
• Alk für eine verzweigten oder unverzweigten Alkylrest mit 2 bis 4 Kohlenstoffatomen;
• x und y unabhängig voneinander für Werte zwischen 1 und 70; und
• M für einen Alkylrest aus der Gruppe CH₂, CHR³, CR³R⁴, CH²CHR³ und CHR³CHR⁴,

wobei R³ und R⁴ unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten Alkylrest mit 1 bis 18 Kohlenstoffatomen
In einer ersten bevorzugten Ausführungsform enthalten erfindungsgemäße maschinelle Geschirrspülmittel als nichtionisches Tensid ein Tensid der allgemeinen Formel R¹-CH(OH)CH₂-O(CH₂CH₂O)_xCH₂CHR(OCH₂CH₂)_yO-CH₂CH(OH)-R² eingesetzt wird, in der

• R, R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen;
• x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen

Bevorzugt werden insbesondere Verbindungen der allgemeinen Formel R¹-CH(OH)CH₂-O(CH₂CH₂O)_xCH₂CHR(OCH₂CH₂)_yO-CH₂CH(OH)-R², in denen R für einen linearen, gesättigten Alkylrest mit 8 bis 16 Kohlenstoffatomen, vorzugsweise 10 bis 14 Kohlenstoffatomen steht und n und m unabhängig voneinander Werte von 20 bis 30 aufweisen. Entsprechende Verbindungen können beispielsweise durch Umsetzung von Alkyldiolen HO-CHR-CH₂-OH mit Ethylenoxid erhalten werden, wobei im Anschluss eine Umsetzung mit einem Alkylepoxid zum Verschluss der freien OH-Funktionen unter Ausbildung eines Dihydroxyethers erfolgt.In a further preferred embodiment, the cleaning agents according to the invention contain a nonionic surfactant of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ² , in which

• R ¹ and R ² independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;
• Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms;
• x and y independently represent values between 1 and 70; and
• M is an alkyl radical from the group CH ₂ , CHR ³ , CR ³ R ⁴ , CH ² CHR ³ and CHR ³ CHR ⁴ ,

wherein R ³ and R ⁴ independently represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms
In a first preferred embodiment, automatic dishwashing agents according to the invention contain as nonionic surfactant a surfactant of the general formula R ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ^{2 is} used in the

• R, R ¹ and R ² independently represent an alkyl group or alkenyl group having 6 to 22 carbon atoms;
• x and y independently represent values between 1 and 40

Particular preference is given to compounds of the general formula R ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ² , in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values of 20 to 30. Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH ₂ -OH with ethylene oxide, followed by reaction with an alkyle epoxide to close the free OH functions to form a dihydroxy ether.

• R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen;
• R³ und R4 unabhängig voneinander für H oder für einen Alkylrest oder Alkenylrest mit 1 bis 18 Kohlenstoffatomen und
• x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen;

Bevorzugt werden insbesondere Verbindungen der allgemeinen Formel R¹-O(CH₂CH₂O)_xCR³R⁴(OCH₂CH₂)_yO-R², in der R³ und R⁴ für H stehen und die Indices x und y unabhängig voneinander Werte von 1 bis 40, vorzugsweise von 1 bis 15 annehmen.In a further preferred embodiment of machine dishwashing detergents according to the invention contained as the nonionic surfactant, a surfactant of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ² is used in the

• R ¹ and R ² independently represent an alkyl or alkenyl radical having 4 to 22 carbon atoms;
• R ³ and R 4 independently of one another are H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and
• x and y independently represent values between 1 and 40;

In particular compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, are in which R ³ and R ⁴ is H, and the subscripts x and y are preferably independently from each other assume values from 1 to 40, preferably from 1 to 15.

Especially preferred are compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, in which the radicals R ¹ and R ² are independently saturated alkyl groups having 4 to 14 Represent carbon atoms and the indices x and y independently of one another assume values of 1 to 15 and in particular of 1 to 12. Also preferred are those compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which one of the radicals R ¹ and R ^{2 is} branched.
Very particularly preferred compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, in which the indices x and y are independently values 8-12 accept.

In various embodiments of the invention, the at least one rinse aid surfactant is a surfactant selected from the group consisting of polyalkoxylated fatty alcohols, especially hydroxy mixed ethers, preferably end-capped hydroxy mixed ethers, and the at least one hydrophobically modified acrylate polymer or copolymer is an alkyl-modified polyacrylate or alkyl-modified one Acrylate / vinyl ester copolymer, in particular a partially C ₁₀ -C ₃₀ alkyl-modified crosslinked polyacrylate or a partially C ₁₀ -C ₃₀ alkyl modified acrylate / vinyl ester copolymer. In such compositions, in various embodiments, the weight proportion of the polyalkoxylated fatty alcohol, especially the hydroxy mixed ethers, preferably the end-capped hydroxy mixed ethers, may be 0.1 to 3.5, preferably 0.5 to 2.5, more preferably 1.0 to 2.0, weight. % and the weight fraction of the alkyl-modified polyacrylate or alkyl-modified acrylate / vinyl ester copolymer, in particular a partially C ₁₀ -C ₃₀ -alkyl-modified crosslinked polyacrylate or a partially C ₁₀ -C ₃₀ -alkyl-modified acrylate / vinyl ester copolymer, 0, 02 to 0.9, preferably 0.05 to 0.5, more preferably 0.07 to 0.2, most preferably 0.1 wt .-%, each based on the total weight of the cleaning agent, amount.

The cleaning agents according to the invention are preferably a dishwasher detergent, in particular a machine dishwashing detergent.

The cleaning agents according to the invention may contain, in addition to 15 to 30% by weight, preferably 15 to 25% by weight, in particular 15-20% by weight of MGDA and / or its salt, and / or GLDA and / or its salt, also other builders , Be used in particular with the phosphate-free builders. Besides citric acid, ethylenediamine disuccinic acid or its salts (EDDS), iminodisuccinic acid (IDS), iminodiacetic acid (IDA), 2-hydroxyethylimino-diacetic acid (HEIDA), it is also possible to use zeolites, silicates, carbonates, especially the alkali metal carbonates, for example sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, and organic Cobuilder be used.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.

In addition to MGDA and / or GLDA and / or their respective salts, in particular GLDA and / or salts thereof, further useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Particularly preferred is 15 to 25 wt .-%, in particular 15-20 wt .-% of MGDA and / or its salt, and / or 15 to 25 wt .-%, in particular 15-20 wt .-% of GLDA and / or their salt, with 0.1 to 10 wt .-%, in particular 1 to 7 wt .-%, for example, between 3 and 6 wt .-% citrate, to use in the detergents according to the invention. Depending on the desired pH value, the citrate ions can be used as citric acid or its salts, in particular sodium or potassium salts, and the quantities of these substances to be employed are based on the amount of citrate according to the invention to calculate. Particularly preferred is the combination of 15 to 20 wt .-% GLDA and / or their salts with 3 to 6 wt .-% citrate ions.

Reference cleaning agents contain the following combinations of components a) to d) and citrate ion and calcium ion according to Table 3 or Table 4 (in% by weight of active substance): In addition, further active ingredients and auxiliaries (in particular those as described below) may be used. The combinations mentioned herein are particularly suitable for detergents in disposable portions, in particular disposable portions in bags made of polyvinyl alcohol-containing film. Table 3: 1 2 3 4 5 a) GLDA or GLDA salt 15-30 15-25 15-20 15-20 15-20 b) water 50-60 50-60 51-55 51-55 51-55 c) polyol <7 <7 <6 <6 <6 d) xanthan 0.2-2 0.2-2 0.2-2 0.2-1.5 0.2-1.5 citrate 0.1-10 0.1-10 0.1-10 1-7 3-6 calcium ions <0.05 <0.05 <0.05 <0.05 <0.02 1 2 3 4 5 a) MGDA or MGDA salt 15-30 15-25 15-20 15-20 15-20 b) water 50-60 50-60 51-55 51-55 51-55 c) polyol <7 <7 <6 <6 <6 d) xanthan 0.2-2 0.2-2 0.2-2 0.2-1.5 0.2-1.5 citrate 0.1-10 0.1-10 0.1-10 1-7 3-6 calcium ions <0.05 <0.05 <0.05 <0.05 <0.02

It may be preferred for the cleaning agents to contain as further constituent preferably one or more builders (builders / cobuilders) in addition to the at least one aminocarboxylic acid selected according to the invention (and optionally in combinations with the abovementioned citrations).

The proportion by weight of these additional builder components in the total weight of the compositions according to the invention is (with the exception of the amounts of the citrates already mentioned above), preferably 0.1 to 15 wt .-% and in particular 2 to 10 wt .-%. Such builders other than the selected aminocarboxylic acids include those described above, preferably carbonates, phosphonates, iminodisuccinic acid, iminodiacetic acid, EDDS (ethylenediamine-N, N'-disuccinic acid), HEIDA (2-hydroxyethylimino-diacetic acid) or the salts of said acids, others organic cobuilders and silicates.

The cleaning agents may additionally or alternatively, preferably as further builder, more preferably also contain phosphonates. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are preferably present in the compositions in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.3 to 8% by weight, very particularly preferably from 0.5 to 3% by weight, based in each case on the total weight of the cleaning agent.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 1000 to 10 000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

The polyacrylates and acrylate copolymers likewise to be used according to the invention are characterized in that they are at least partially C ₁₀ -C ₃₀ -alkyl-modified crosslinked polyacrylates or at least partially hydrophobic, in particular C ₁₀ -C ₃₀ -alkyl, modified acrylate / vinyl ester copolymers is. "Partially modified" in this context means that at least one part, preferably at least 20, more preferably at least 40, particularly preferably at least 50% of the monomer units each having at least one C ₁₀ -C ₃₀ -alkyl radical is substituted. The polymers are therefore such as acrylate / C ₁₀ -C ₃₀ alkyl acrylate copolymers or acrylate / C ₁₀ -C ₃₀ alkyl acrylate / C ₁₀ -C ₃₀ alkyl Vinylester copolymers.

Such polymers are commercially available as thickeners and emulsifiers. For example, polygels DR (3V Sigma, Italy) and Pemulen® TR1 (Lubrizol, USA) are suitable, without which the invention is restricted to these polymers.

In various embodiments of the invention, the amount of the at least one hydrophobically modified acrylate polymer or copolymer in the detergent is from 0.02 to 0.8, preferably from 0.03 to 0.5, more preferably from 0.05 to 0.15 most preferably 0.1 wt .-% based on the cleaning agent.

The silicates used are in particular crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values x is 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, into account. It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.

In preferred cleaning agents, the content of silicates, based on the total weight of the cleaning agent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight. Particularly preferred cleaning agents are silicate-free. The cleaning agents of the invention may further contain a sulfopolymer. The proportion by weight of the sulfopolymer in the total weight of the cleaning agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 15 wt .-%, particularly preferably 1.0 to 10 wt .-%, in particular from 3 to 9 wt .-%, especially from 4 to 8 wt .-%. The sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70 wt .-%, in particular 30 to 50 wt .-%, preferably about 35 to 40 wt .-% sulfopolymer (s).

The sulfopolymer used is preferably a copolymeric polysulfonate. The copolymers may have two, three, four or more different monomer units.

Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.

As unsaturated carboxylic acid (s) is / are used with particular preference unsaturated carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH, in which R ¹ to R ^{3 are} independently -H, - CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.

In the sulfonic acid-containing monomers are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

in which R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - , -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H,

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, - C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

In a further preferred embodiment, in addition to the carboxyl group-containing monomer and the monomer containing the sulfonic acid group, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.

Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.

The nonionic monomers used are preferably monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X represents an optionally present spacer group selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 represents} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or represents an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, α Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N - (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate octyl acrylate, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, methacrylic acid stearyl ester, N- (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and N- (behenyl) acrylamide or mixtures thereof.

The monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing monomer 60 to 80 wt .-%, the monomers are in this case preferably selected from the aforementioned.

According to a preferred embodiment, the pH of the cleaning agent diluted to 10% by weight in distilled water at 22 ° C., 6.5 to 8.5. The pH of the cleaning agent (10% by weight in distilled water) at 22 ° C. is particularly preferably between 6.8 and 8.3, in particular between 7.0 and 8.2, for example 8.0.

In general, the pH of the cleaning agent can be adjusted by means of customary pH regulators, the pH value being selected depending on the desired application. The pH-adjusting agents are acids and / or alkalis. Suitable acids are, in particular, organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or else sulfamic acid. In addition, however, it is also possible to use the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof. If citric acid is used as a pH adjuster, this is taken into account in the total amount of citrate ions as indicated above.

Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred. In such formulations, which have only the smallest amounts of calcium or magnesium ions, if hydroxides should be used, in particular alkali metal hydroxides, in particular potassium hydroxide and sodium hydroxide are preferred.

However, particularly preferred is volatile alkali, for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule. The alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof. The alkanolamine is preferably contained in agents according to the invention in an amount of 0.1 to 10% by weight, in particular in an amount of 0.5 to 5% by weight. According to a particularly preferred embodiment, the cleaning agent according to the invention contains 0.5 to 5 wt .-% monoethanolamine.

In addition to the aforementioned builders, the detergents may contain alkali metal hydroxides. These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent used. Alternative cleaning agents according to the invention are free of alkali metal hydroxides.

To adjust and / or stabilize the pH, the composition according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of from 0.001 to 5% by weight. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents). Particularly preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate.2H ₂ O and tripotassium citrate H ₂ O or else the corresponding anhydrates.

The compositions according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, bleaching agents, bleach activators, bleach catalysts, phase mediators (for example cumene sulfonate), enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors , Foam inhibitors, dyes, fragrances, bittering agents, and antimicrobial agents and other auxiliaries.

Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates. Also usable in the context of the present invention are fatty acid cyanamides, sulfosuccinates (sulfosuccinic esters), in particular sulfosuccinic mono- and di-C ₈ -C ₁₈ -alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and α-sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

The anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form of their corresponding acid, eg Dodecylbenzenesulfonic.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R ^v ) N ⁺ CH ₂ COO ^- , in which R ^{iii is} an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R ^iv and R ^{v are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -Alkyldimethylcarboxymethylbetain and C ₁₁ -C ₁₇ -Alkylamidopropyl-dimethylcarboxymethylbetain.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^vi ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^- , in which R ^vi to R ^{ix are} four identical or different, in particular two long and two short-chain, alkyl radicals and X ^{- are} an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Further suitable cationic surfactants are the quaternary surface-active compounds, in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. Through the use of quaternary surface-active compounds with antimicrobial action, the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.

To increase the rinsing performance, the agents according to the invention may contain from 0.01 to 10% by weight of at least one polymer having a molecular weight of 2000 gmol ^-1 or more, which has at least one positive charge.

The above positive charge polymers may in principle be cationic or amphoteric polymers. Preferred cleaners according to the invention, in particular automatic dishwasher detergents, are characterized in that the polymer which has cationic monomer units is a cationic polymer and / or an amphoteric polymer.

"Cationic polymers" in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

For the purposes of the present invention, "amphoteric polymers" further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

Detergents according to the invention, in particular automatic dishwasher detergents, characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ , in which each radical R ¹ , R ² , R ³ , R ^{4 is} independently is selected from among hydrogen, derivatized hydroxy group, C1 to C30 linear or branched alkyl groups, aryl, aryl substituted C _1-30 linear or branched alkyl groups, polyalkoyxylierte alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized N- Atom or at least one amino group having a positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without being charged Nitrogen, at least one quaternized nitrogen atom or at least one amino group having a positive charge, are particularly preferred in the context of the present application.

bei der R¹ und R⁴ unabhängig voneinander für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen steht; R² und R³ unabhängig voneinander für eine Alkyl-, Hydroxyalkyl-, oder Aminoalkylgruppe stehen, in denen der Alkylrest linear oder verzweigt ist und zwischen 1 und 6 Kohlenstoffatomen aufweist, wobei es sich vorzugsweise um eine Methylgruppe handelt; x und y unabhängig voneinander für ganze Zahlen zwischen 1 und 3 stehen. X^- repräsentiert ein Gegenion, vorzugsweise ein Gegenion aus der Gruppe Chlorid, Bromid, lodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen.Cationic or amphoteric polymers which are particularly preferred for the purposes of the present invention comprise as monomer unit a compound of the general formula (I)

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X ^- represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumenesulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula (VII) are selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH ) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H.

For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the general formula (I) in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer units of the formula

H ₂ C = CH- (CH ₂ ) -N ⁺ (CH ₃ ) ₂ - (CH ₂ ) -CH = CH ₂ X ^-

in the case of X ^- = chloride, they are also referred to as DADMAC (diallyldimethylammonium chloride).

Further cationic or amphoteric polymers which are particularly preferred for the purposes of the present application comprise a monomer unit of the general formula (II)

R ¹ HC = CR ² -C (O) -NH- (CH ₂ ) _x -N ⁺ R ³ R ⁴ R ⁵ X ^- (II)

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another are a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H and x is an integer between 1 and 6.

In the context of the present application, very particular preference is given to polymers which have a cationic monomer unit of the general formula (II) in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

H ₂ C = C (CH ₃ ) -C (O) -NH- (CH ₂ ) _x -N ⁺ (CH ₃ ) ₃ X ^-

In the case of X ^- = chloride also referred to as MAPTAC (Methyacrylamidopropyl trimethylammonium chloride).

Automated dishwashing agents which are preferred according to the invention are characterized in that the polymer a) contains, as monomer units, diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups. Such anionic Monomereinheinheiten originate for example from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth) acrylic acids, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.

Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth ) -acrylic acid copolymers, the Alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.

Also preferred are amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers Methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) -ammonium chloride.

Particularly preferred amphoteric polymers are selected from the group consisting of the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl - (meth) acrylic acid copolymers and their alkali metal and ammonium salts.

Particular preference is given to amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

• die Verkapselung der Polymere mittels wasserlöslicher oder wasserdispergierbarer Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• -die Verkapselung der Polymere mittel wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30°C;
• die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder (Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the polymers contained in the agents according to the invention having a molecular weight of 2000 gmol ^-1 or more are in prefabricated form. For the preparation of the polymers is suitable inter alia

• the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• the encapsulation of the polymers by means of water-insoluble, meltable coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C .;
• the co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing- or cleaning-active substances, more preferably from the group of builders or cobuilders.

All of these products contain, as a first essential ingredient, one or more polymer (s) having a molecular weight of 2000 gmol ^-1 or above, which has at least one positive charge. The compositions of the invention have a weight fraction of these polymers between 0.01 and 10 wt .-%, each based on the total weight of the cleaning agent. In the context of the present application, however, preference is given to detergents in which the weight fraction of the polymer a) is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight .-%, more preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the cleaning agent is.

The enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly. Detergents ^according to the invention preferably contain enzymes in total amounts of from 1 × 10 ^-6 to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). For example, commercially available alpha-amylases such as Duramyl®, Termamyl® Stainzyme®, Stainzyme Plus® from Novozymes are suitable.

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from, or further developed, Humicola lanuginosa (Thermomyces lanuginosus), in particular those having one or more of the following amino acid exchanges starting from said lipase in positions D96L, T213R and / or N233R, most preferably all of the exchanges D96L, T213R and N233R.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations. Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.

If the enzyme preparations used contain stabilizers (for example reversible inhibitors) in their concentrated form, no further stabilizers are additionally added to the cleaning agent. In the detergent by the stabilizers contained in the enzyme preparations such as calcium or magnesium salts or organic solvents, in particular at room temperature and normal pressure liquid polyols, introduced amounts are already included in the above limits for the respective active ingredients.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.

The novel cleaning compositions contain, based on their total weight, 0.1 to 12 wt .-%, preferably 0.2 to 10 wt .-% and in particular 0.5 to 8 wt .-% enzyme preparations. Zinc and / or bismuth salts, or polyethyleneimines, for example those obtainable under the name Lupasol® from BASF, in particular zinc acetate, are preferably used as glass corrosion inhibitors. Glass corrosion inhibitors are preferably present in compositions according to the invention in an amount of from 0 to 5% by weight, in particular in an amount of from 0 to 2% by weight.

According to another particularly preferred embodiment, less than 0.1% by weight, in particular 0.05% by weight, particularly preferably less than 0.01% by weight, of zinc salt (s) is added. In particular, no zinc salt is used (beyond the usual amount of zinc salt introduced by contamination of raw materials), since, surprisingly, the cleaning formulation is very gentle on the items to be washed, in particular the glasses, and so additional glass corrosion protection can be dispensed with.

Particularly preferred embodiments of the cleaning agent according to the invention comprise the following combinations of components a) to d) and of calcium ions and zinc salts according to Table 5 or Table 6 (details in% by weight of active compound.) The formulations 1-6 in Table 5 and the formulations 1- 7 in Table 6 are reference formulations Furthermore, further active ingredients and auxiliaries (in particular those as described below) may be present The combinations mentioned herein are particularly suitable for detergents in single-use portions, in particular disposable portions in bags made from polyvinyl alcohol-containing film. Table 5: 1 2 3 4 5 6 7 8th a) GLDA or GLDA salt 15-30 15-25 15-20 15-20 15-20 15-20 15-20 15-20 b) water 50-60 50-60 51-55 51-55 51-55 51-55 51-55 51-55 c) polyol <7 <7 <6 <6 <6 <6 <6 <6 d) xanthan 0.2-2 0.2-2 0.2-2 0.2-2 0.2-1.5 0.2-1.5 0.2-1.5 0.2-1.5 calcium ions <0.1 <0.05 <0.05 <0.05 <0.05 <0.05 <0.02 <0.02 Zinc salt (s) <0.1 <0.05 <0.1 <0.05 <0.1 <0.05 <0.05 <0.01 1 2 3 4 5 6 7 8th a) MGDA or MGDA salt 15-30 15-25 15-20 15-20 15-20 15-20 15-20 15-20 b) water 50-60 50-60 51-55 51-55 51-55 51-55 51-55 51-55 c) polyol <7 <7 <6 <6 <6 <6 <6 <6 d) xanthan 0.2-2 0.2-2 0.2-2 0.2-2 0.2-1.5 0.2-1.5 0.2-1.5 0.2-1.5 calcium ions <0.1 <0.05 <0.05 <0.05 <0.05 <0.05 <0.02 <0.02 Zinc salt (s) <0.1 <0.05 <0.1 <0.05 <0.1 <0.05 <0.05 <0.01

Particularly in those embodiments which contain only small amounts of zinc salts (in particular <0.05% by weight of zinc salt (s), very particularly preferably <0.01% by weight of zinc salt (s)), alternative glass corrosion inhibitors, in particular at least one Amine polymer, wherein the amine polymer has an amino group in at least 50% of the constitutional repeat units of the polymer, and wherein one or more nonionic surfactants are contained in an amount of at least 1 wt.% Based on the total weight of the dishwashing detergent. These have the advantage that they counteract the glass corrosion and at the same time adversely affect neither the viscosity nor the stability of the detergents or their components, especially in disposable portions, in particular disposable portions in bags of polyvinyl alcohol-containing film.

Preferably, the at least one aminopolymer, more preferably polyethyleneimine and / or polyvinylamine, is present in an amount in the range of 0.001 to 10 weight percent, more preferably in the range of 0.005 to 1 weight percent, most preferably in the range of 0 , 01 to 0.2 wt.% Based on the total weight of the composition.

Preferably, the amino-polymer is a polyethylenimine which also has primary amino groups. Most preferably, the amino-polymer is a polyethylenimine or polyvinylamine which is not an alkoxylate.

Preferably, the amino polymer has a molecular weight Mw in a range of 3,000 to 10,000 g / mol.

In various embodiments, the detergent has a viscosity above 700 mPas directly after preparation (Brookfield Viscometer DV-II + Pro, Spindle 25, set to achieve 40-60% torque, ie, 30 rpm, 20 ° in the low range C), in particular between 1000 and 10000 mPas (Brookfield Viscometer DV-II + Pro, spindle 31, rotation adjusted so that 40-60% torque is achieved, usually 30 rpm, 20 ° C). After storage, the viscosity may be higher, for example, greater than 1500 mPas, such as in the range 1500-50000 mPas, (Brookfield Viscometer DV-II + Pro, Spindle 31, rotation adjusted to achieve 40-60% torque, 20 ° C). It is preferred that the agent is flowable at room temperature.

In a further aspect, the invention relates to such cleaning agents which may be present in a water-insoluble, water-soluble or water-dispersible packaging, for example a film containing a disposable portion.

The cleaning agent can be in a water-insoluble, water-soluble or water-dispersible packaging. The invention therefore also relates to kits containing the cleaning agent together with such a package. The cleaning agent can be made up so that disposable portions are each packed separately.

The cleaning agent according to the invention is preferably contained in a water-soluble packaging. The water-soluble packaging allows a portioning of the cleaning agent. The amount of detergent in the sachet is preferably 5 to 50 g, more preferably 10 to 30 g, especially 13.5 to 25 g.

The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.

It is preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.

Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol ^-1 , preferably 20,000 to 500,000 gmol ^-1 , more preferably 30,000 to 100,000 gmol ^-1 and especially from 40,000 to 80,000 gmol ^-1 .

The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

In addition, a polymer selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath (Meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added. A preferred additional polymer is polylactic acids.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.

It may be preferred that the film material contains further additives. The film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.

Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

The cleaning agents according to the invention can be used as dishwashing agents, in particular automatic dishwasher detergents. The corresponding use is also the subject of the invention. The invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a cleaning agent according to the invention is used.

The cleaning agents according to the invention are characterized by the fact that they are stable in storage and even after a prolonged period no leaks occur. In addition, they continue to have a good enzyme activity even after prolonged storage.

Particularly preferred are detergents prepared according to the following frame formulation (Tables 7-10): The combinations mentioned herein are especially for Detergent in disposable portions, in particular disposable portions in bags made of polyvinyl alcohol-containing film suitable. Table 7: glycerin 0-5.0 0-5.0 0-5.0 0-5.0 xanthan 0.2-2.5 0.50 0.50 0.40 polyacrylate 0.1-5.0 2.0-4.0 0.0 3.0 sulfopolymer 4-10.00 5.00 to 9.00 7.00-8.00 4.00 to 8.00 GLDA 15 to 30.00 16.00 to 25.00 16.00 to 25.00 16.00 to 25.00 citric acid 0.0 to 10.00 0.1 to 7.00 5.00 5.00 phosphonate 0.0-10.0 0.5-8 0.4-0.8 0.4-0.8 Nonionic surfactant 1.00 to 5.00 2.00 to 4.00 3.00 3.00 Monoethanolamine 0.0 to 7.00 3.00 to 7.00 3.00-5.00 3.00-5.00 Cationic rinse aid polymer 0.01 to 1.00 0.05-0.50 0.1-0.3 0.1-0.3 Amylase (wt% active protein) 0.001 to 1.00 0.005 to 0.50 0.01 to 0.3 0.01 to 0.3 Protease (wt% active protein) 0.001 to 2.00 0.01 to 1.0 0.1 to 0.5 0.1 to 0.5 Dye, bitrex, perfume, preservatives 0.01 to 2.00 0.01-1.0 0.01-1.0 0.01-1.0 Resulting water content of the formulation 40.00 to 65.00 50.00 to 57.00 55,00 55,00 glycerin 0-5.0 0-5.0 0-5.0 0-5.0 xanthan 0.2-2.5 0.50 0.50 0.40 polyacrylate 0.1-5.0 2.0-4.0 0.0 3.0 sulfopolymer 4-10.00 5.00 to 9.00 7.00-8.00 4.00 to 8.00 GLDA 15 to 30.00 16.00 to 25.00 16.00 to 25.00 16.00 to 25.00 Sodium citrate dihydrate 0.0 to 10.00 0.1 to 9.00 7.00 7.00 Monoethanolamine 0.0 to 5.00 0.10 to 4.00 0.10 to 3.00 1.00-3.00 phosphonate 0.0-1.0 0.2-0.8 0.4-0.6 0.4-0.6 Nonionic surfactant 1.00 to 5.00 2.00 to 4.00 3.00 3.00 Cationic rinse aid polymer 0.01 to 1.00 0.05-0.50 0.1-0.3 0.1-0.3 Amylase (wt% active protein) 0.001 to 1.00 0.005 to 0.50 0.01 to 0.3 0.01 to 0.3 Protease (wt% active protein) 0.001 to 2.00 0.01 to 1.0 0.1 to 0.5 0.1 to 0.5 Dye, bitrex, perfume, preservatives 0.01 to 2.00 0.01-1.0 0.01-1.0 0.01-1.0 Resulting water content of the formulation 40.00 to 65.00 50.00 to 57.00 55,00 55,00 glycerin 0-5.0 0-5.0 0-5.0 0-5.0 xanthan 0.2-2.5 0.50 0.50 0.40 polyacrylate 0.1 -5.0 2.0-4.0 0.0 3.0 sulfopolymer 4-10.00 5.00 to 9.00 7.00-8.00 4.00 to 8.00 MGDA 15 to 30.00 16.00 to 25.00 16.00 to 25.00 16.00 to 25.00 citric acid 0.0 to 10.00 0.1 to 7.00 5.00 5.00 phosphonate 0.0-10.0 0.5-8 0.4-0.8 0.4-0.8 Nonionic surfactant 1.00 to 5.00 2.00 to 4.00 3.00 3.00 Monoethanolamine 0.0 to 7.00 3.00 to 7.00 3.00-5.00 3.00-5.00 Cationic rinse aid polymer 0.01 to 1.00 0.05-0.50 0.1-0.3 0.1-0.3 Amylase (wt% active protein) 0.001 to 1.00 0.005 to 0.50 0.01 to 0.3 0.01 to 0.3 Protease (wt% active protein) 0.001 to 2.00 0.01 to 1.0 0.1 to 0.5 0.1 to 0.5 Dye, bitrex, perfume, preservatives 0.01 to 2.00 0.01-1.0 0.01-1.0 0.01-1.0 Resulting water content of the formulation 40.00 to 65.00 50.00 to 57.00 55,00 55,00 glycerin 0-5.0 0-5.0 0-5.0 0-5.0 xanthan 0.2-2.5 0.50 0.50 0.40 polyacrylate 0.1-5.0 2.0-4.0 0.0 3.0 sulfopolymer 4-10.00 5.00 to 9.00 7.00-8.00 4.00 to 8.00 MGDA 15 to 30.00 16.00 to 25.00 16.00 to 25.00 16.00 to 25.00 Sodium citrate dihydrate 0.0 to 10.00 0.1 to 9.00 7.00 7.00 Monoethanolamine 0.0 to 5.00 0.10 to 4.00 0.10 to 3.00 1.00-3.00 phosphonate 0.0-1.0 0.2-0.8 0.4-0.6 0.4-0.6 Nonionic surfactant 1.00 to 5.00 2.00 to 4.00 3.00 3.00 Cationic rinse aid polymer 0.01 to 1.00 0.05-0.50 0.1-0.3 0.1-0.3 Amylase (wt% active protein) 0.001 to 1.00 0.005 to 0.50 0.01 to 0.3 0.01 to 0.3 Protease (wt% active protein) 0.001 to 2.00 0.01 to 1.0 0.1 to 0.5 0.1 to 0.5 Dye, bitrex, perfume, preservatives 0.01 to 2.00 0.01-1.0 0.01-1.0 0.01-1.0 Resulting water content of the formulation 40.00 to 65.00 50.00 to 57.00 55,00 55,00

A further subject of the present application is a machine dishwashing process in which a cleaning agent according to the invention is used. In the method for cleaning dishes in a dishwasher using the dishwashing detergent, the dishwashing detergent is preferably metered into the interior of a dishwasher during the passage of a dishwashing program, before the main wash cycle or during the main wash cycle. The dispensing or the entry of the dishwashing detergent into the interior of the dishwasher can be done manually, but preferably the dishwashing detergent is metered into the interior of the dishwasher by means of the metering chamber of the dishwasher. In the course of the cleaning process preferably no additional water softener and no additional rinse aid is metered into the interior of the dishwasher.
For economic and ecological reasons, the dishwashing process is preferably carried out at a liquor temperature below 60 ° C., preferably not above 50 ° C., preferably at 35 to 45 ° C. In a preferred embodiment, the dishwashing process takes 5 to 90 minutes, in particular 10 to 75 minutes, particularly preferably 20 to 60 minutes. In alternatively preferred embodiments, the dishwashing process takes a maximum of 50, 40 or 30 minutes.

Another object of the present invention is the use of a detergent according to the invention in a dishwasher machine, in particular for the cleaning of dishes, cooking utensils and cutlery. Incidentally, the inside of the dishwasher is also cleaned during use.

All facts, objects and embodiments which are described for cleaning agents according to the invention are also applicable to the cleaning methods according to the invention as well as the uses according to the invention and vice versa. Therefore, reference is made at this point expressly to the disclosure in the appropriate place with the note that the disclosure in the context of the cleaning agent according to the invention also applies to the above inventive use and all methods described.

Example:

A liquid detergent according to the invention is prepared according to the recipe given in Table 11. The detergent according to the invention according to Table 11 has (at a dilution of 10 wt .-% detergent in distilled water, measured at 22 ° C) to a pH of 8.0. Table 11 (data: amount of active substance in% by weight, based on the total cleaning agent): glycerin 2.50 xanthan 0.50 sulfopolymer 7.5 GLDA, tetrasodium salt 18,00 citric acid 5.00 phosphonate 0.6 Nonionic surfactant 3.00 Monoethanolamine 4.00 Cationic rinse aid polymer 0.2 Amylase (wt% active enzyme) 0.0125 Protease (wt% active enzyme) 0.2 Dye, bitrex, perfume, preservatives 0.5 Resulting water content of the formulation 55,00

20 g of this cleaning agent were packed in a single-chamber bag made of deep-drawn polyvinyl alcohol-containing film (M8630, thickness: 76 μm from MONOSOL).

Shelf life:

The single-chamber bags thus prepared were stored at temperatures of 0, room temperature (20 ° -25 ° C), 30, 40 and 50 ° C for 4 weeks. The single-chamber bags were packed in a sealed bag consisting of PE, coated with PET.

The disposable portions showed no leaks after storage (without air exchange) of 4 weeks at all temperatures. The liquid detergents also showed no phase separation.

Enzyme Stability:

The stability of the enzymes was determined by the cleaning performance of the predosed detergent in a dishwasher (type Miele GSL) at 45 ° C (8 min hold time) fresh and after storage times of 4, 8 and 12 weeks at 0 ° C (Table 12), room temperature ( Table 13) and 30 ° C and 80% relative humidity (Table 14). The determination was carried out gravimetrically according to IKW. Changes of 1.0 units are considered significant.

Surprisingly, despite the lack of additional stabilization of the enzymes (for example due to calcium or magnesium salts, reversible protease inhibitors) during storage only small changes in the cleaning performance on protease or amylase-relevant contaminants (yolk and starch) were found. Table 12: Storage at 0 ° C product Egg yolk, 1g Strength Fresh 3.0 8.4 Storage time 4 weeks, 0 ° C 3.0 8.2 Storage time 8 weeks, 0 ° C 2.5 8.2 Storage time 12 weeks, 0 ° C 2.7 8.2 product Egg yolk, 1g Strength Fresh 3.0 8.4 Storage time 4 weeks, room temperature 2.4 8.5 Storage time 8 weeks, room temperature 2.9 7.8 Storage time 12 weeks, room temperature 2.6 7.9 product Egg yolk, 1g Strength Fresh 3.0 8.4 4 weeks, 30 ° C / 80% relative humidity 2.4 8.2 8 weeks, 30 ° C / 80% relative humidity 2.5 6.8 12 weeks, 30 ° C / 80% relative humidity 2.2 6.9

Claims (10)

1. A cleaning agent, in particular a dishwashing detergent, preferably proportioned automatic dishwashing detergent, containing

   a. 15 to 30 wt.% of at least one aminocarboxylic acid selected from glutamic-N,N-diacetic acid (GLDA) and/or methyl glycine diacetic acid (MGDA) and/or the salts thereof,

   b. 40 to 65 wt.% water,

   c. less than 10 wt.% polyol and

   d. 0.2 to 2.5 wt.% xanthan gum,

   characterized in that it contains less than 0.02 wt.% calcium ions and, based on the total weight thereof, 0.1 to 12 wt.%, preferably 0.2 to 10 wt.%, and in particular 0.5 to 8 wt.%, enzyme preparations.
2. The cleaning agent according to the preceding claim, characterized in that it contains 50 to 60 wt.%, preferably 51 to 55 wt.%, water.
3. The cleaning agent according to one of the preceding claims, characterized in that it contains 0.25 to 2.5 wt.% xanthan gum, preferably 0.25 to 1 wt.% xanthan gum.
4. The cleaning agent according to one of the preceding claims, characterized in that it contains less than 7 wt.%, preferably less than 6 wt.%, polyol.
5. The cleaning agent according to one of the preceding claims, characterized in that it contains between 0 and 5 wt.% glycerol.
6. The cleaning agent according to one of the preceding claims, characterized in that it contains 15 to 25 wt.%, 15 to 20 wt.% MGDA and/or GLDA, particularly preferably GLDA.
7. The cleaning agent according to one of the preceding claims, characterized in that it is in a water-soluble, water-insoluble or water-dispersible packaging, in particular in a water-soluble wrapping containing polyvinyl alcohol or polyvinyl alcohol copolymers.
8. The cleaning agent according to one of the preceding claims, characterized in that it contains 0.1 to 10 wt.%, in particular 1 to 7 wt.%, preferably between 3 and 6 wt.%, citrate ions.
9. The use of a cleaning agent according to one of claims 1 to 8 in an automatic dishwashing method.
10. An automatic dishwashing method, characterized in that a cleaning agent according to one of claims 1 to 8 is used.