DE102014204144A1 - Pre-portioned detergents comprising at least two separate liquid preparations - Google Patents

Abstract

The invention relates to pre-portioned detergent, preferably machine dishwashing detergent, in a water-soluble packaging having at least two compartments, comprising at least a first and a second liquid preparation, characterized in that the first liquid preparation alkali metal carbonate, preferably sodium carbonate, in an amount of 20 to 60 wt. % (based on the total weight of the first liquid preparation).

Description

The invention relates to pre-portioned detergent, preferably machine dishwashing detergent, in a water-soluble packaging having at least two compartments, comprising at least a first and a second liquid preparation, characterized in that the first liquid preparation alkali metal carbonate, preferably sodium carbonate, in an amount of 20 to 60 wt. % (based on the total weight of the first liquid preparation).

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. In addition, over- or under-dosing of individual components or of the entire cleaning agent is avoided by the pre-portioning compared to multicomponent liquid or gel-like cleaning agents from multi-chamber bottles.

Further, 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 provide a liquid dishwashing detergent which offers the above-mentioned advantages over solid compositions in a pre-portioned form, the use of water-soluble films in the form of sachets lends itself. Disposable portions, especially water-soluble bags enjoy the consumer not only because of increasing popularity, because the consumer with the chemical composition is no longer in contact, but not least because of the attractive appearance of the bag.

However, such liquid detergents often have the problem that the cleaning performance, especially on burnt dirt, is not sufficient. This results from the fact that the liquid pre-portioned detergents often can not contain high amounts of highly alkaline substances, since otherwise the tightness and storability of the pre-portioned detergent in the water-soluble packaging is not guaranteed.

In particular, larger amounts (more than 10% by weight) of alkali metal hydroxides or meta-silicates can not be used, since the water-soluble packaging can be at least partially attacked by such ingredients. This results in unwanted leaks or leaks in the water-soluble packaging. The same applies to larger amounts of aliphatic amines, in particular of diethylenetriamine. Ortho-silicates in larger quantities are also undesirable because they lead to strong deposits on the items to be washed.

The object of the invention was thus to provide liquid pre-portioned machine dishwashing detergents which have an improved cleaning performance and are simultaneously storage-stable.

The object is achieved by providing a pre-portioned detergent, preferably dishwasher detergent, in a water-soluble packaging with at least two compartments comprising at least a first and a second liquid preparation, characterized in that the first liquid preparation alkali metal carbonate, preferably sodium carbonate, in an amount of 20 to 60 wt .-% (based on the total weight of the first liquid preparation).

"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.

Pre-portioned detergents are generally present in a water-soluble packaging, for example a film containing a disposable portion. The pre-portioned detergent is in a water-soluble packaging. The cleaning agent, in particular machine dishwashing detergent, can be made up in such a way that disposable portions are each packed separately. The water-soluble packaging allows a portioning of the cleaning agent. The amount of total detergent in the sachet is preferably 5 to 50 g, more preferably 10 to 30 g, especially 15 to 25 g, in particular 17 to 23 g.

The water-soluble packaging in this case has at least two or more spatially separated compartments (chambers) into which spatially separated at least a first liquid and a second liquid preparation are filled.

Particularly suitable are two-compartment bags which contain a first liquid preparation and a second liquid preparation in separate compartments. A preparation (phase) is understood here to mean a detergent (partial) composition which, in combination with the other preparation (s), results in a cleaning agent, in particular a machine dishwashing detergent.

It may be particularly preferred that the pre-portioned detergent according to the invention contains, in addition to the two preparations mentioned, one or two further preparations in further, separate compartments. For example, two liquid and one solid preparation, two liquid and two solid preparations, three or four liquid preparations may be present in a corresponding number of separate compartments.

A packaging according to the invention with two compartments may preferably be present, the first and the second liquid preparation being present separately from one another in each of the compartments.

Preferred may be pre-portioned detergents in which the water-soluble package contains, in addition to two or more liquid preparations, one, two or more chambers with solid preparations. When two or more solid preparations are provided, it is preferred that they be of different composition and / or have a different solid form

The cleaning agent according to the invention, in particular machine dishwashing detergent, can also be present in a water-soluble packaging, which in particular contains more than two, so for example, three, four, five or six compartments. Preferably, the package contains two, three or more chambers, wherein two, three or more of these chambers are filled with liquid preparations, which are preferably different from each other (for example in the weight proportions of individual components), and in particular have one or more different ingredients from each other.

"At least one" as used herein means 1 or more, for example, 1, 2, 3, 4, 5, or more. "At least two" as used herein means 2 or more, for example, 2, 3, 4, 5, 6 or more.

The first liquid preparation contains from 20 to 60% by weight of alkali metal carbonate, especially sodium carbonate (Na ₂ CO ₃ ). In addition to or instead of sodium carbonate, it is also possible to use potassium carbonate or lithium carbonate. For the purposes of the present invention, alkali metal carbonates are not to be understood as meaning alkali metal bicarbonates, such as, for example, sodium bicarbonate, or alkali metal sesquicarbonates. The alkali metal carbonates may be in solution or as a dispersion, depending on their amount and the water content of the first preparation. Due to a lower tendency to separate into dispersions, it may be preferable to use sodium carbonate, in particular in the case of relatively high amounts of alkali metal carbonate in the first preparation or in the case of small amounts of water in the first preparation. It is particularly advantageous when using sodium carbonate, that the incorporation of the alkali reserve in the form of sodium carbonate (soda) is stable in the liquid preparation.

Mixtures of various alkali metal carbonates, e.g. Sodium carbonate and potassium carbonate, or sodium carbonate and lithium carbonate are used. The amounts stated below then apply to the total amount of alkali metal carbonates used in the first liquid preparation. It is preferred to use a single alkali metal carbonate, especially sodium carbonate.

It is preferred to use from 20 to 60% by weight, preferably from 25 to 50% by weight, in particular from 30 to 45% by weight, of alkali metal carbonate, preferably sodium carbonate (soda), in the first liquid preparation.

It may also be contained in the second liquid preparation (and optionally in further preparations) alkali metal carbonate, but it is preferred that the second liquid preparation (or if given also all other preparations (ie all preparations contained in the pre-portioned detergent except the first preparation ) is substantially free of alkali metal carbonate.

"Substantially free of" alkali metal carbonate means that the second (and possibly the other, separate from the first preparation) preparations, less than 10 wt .-%, in particular less than 5 wt. %, preferably less than 1 wt .-%, in particular less than 0.5 wt .-%, alkali metal carbonate (in each case based on the weight of the individual preparation).

Particular preference is given to using 20 to 60% by weight, preferably 25 to 50% by weight, in particular 30 to 45% by weight, of alkali metal carbonate, preferably sodium carbonate (soda), in the first liquid preparation, with the proviso that the total amount of the alkali metal carbonate, preferably the alkali metal carbonate, in particular the sodium carbonate (soda) ,. per detergent portion 1 to 3 g, in particular 1.5 to 2.5 g. The said total amount of 1 to 3 g of alkali metal carbonate, in particular sodium carbonate (soda), may also be the total amount per job (ie the total amount of cleaning agent used in a complete cleaning program of a dishwashing machine).

According to a preferred embodiment, the ratio of alkali metal carbonate to water in the first liquid preparation, based in each case on the total amount of the first liquid preparation, is preferably between 7: 1 and 1: 1, in particular between 6: 1 and 2: 1, particularly preferably between 5: 1 and 3: 1. This ratio applies in particular to the weight ratio of sodium carbonate (soda) to water.

In a preferred embodiment, the first liquid preparation is preferably low in water. "Low-water" as used herein means that the first liquid preparation contains less than 20% by weight of water, more preferably less than 15% by weight of water, most preferably less than 13% by weight of water (based on the total weight of water) first liquid phase). The water content as defined herein refers to the water content determined by Karl Fischer titration. The low-water first liquid preparation preferably contains from 5 to 12% by weight of water. (based on the total weight of the first liquid phase). Surprisingly, it has been found that in such low-water liquid preparations, in particular those having less than 15 wt .-%, preferably less than 13 wt .-% water, even larger amounts, in particular 25 to 50 wt .-%, in particular 30 to 45 wt % Alkali metal carbonate, in particular sodium carbonate (soda), can be stably incorporated (in particular dispersed) without there being any sedimentation of solids or segregation of the liquid phase during storage.

This has the advantage that with such a selected ratio of alkali metal carbonate to water in the first liquid preparation, migration of water from the second liquid preparation is minimized.

According to a particularly preferred embodiment of the low-water first liquid preparation, the weight ratio of alkali metal carbonate, in particular sodium carbonate (soda) to water, between 7: 1 and 2: 1 is in particular between 6: 1 and 2.5: 1, particularly preferably between 5: 1 and 3: 1.

According to a preferred embodiment, a phyllosilicate, in particular magnesium-containing phyllosilicate, preferably sodium-magnesium-containing phyllosilicates, very particularly a Li-Na-Mg phyllosilicate, are also present in the first liquid preparation. It has now been found that phyllosilicates, in particular magnesium-containing phyllosilicate, preferably sodium-magnesium-containing phyllosilicates, preferably prepared synthetically, are suitable for achieving formation of a stable and storage-stable dispersion of the large amount of alkali metal carbonate without a. During storage of the agent Demixing takes place. These phyllosilicates, in particular the lithium-magnesium-sodium phyllosilicates, have the effect that no separation of different liquid phases or sedimentation of solid constituents takes place in the first liquid preparation.

These include, for example, available under the trade name Laponite ^® magnesium or sodium magnesium phyllosilicates BYK Additives GmbH, in particular the Laponite ^® RD or Laponite ^® RDS, or the Optigel ^® SH.

Particularly preferred sheet silicates are lithium magnesium sodium phyllosilicates, for example, under the trade name Laponite ^® RD, which are particularly suitable for ensuring the stability of the dispersion of the alkali metal in the first liquid preparation for a longer period of time during storage. In addition, the phyllosilicates can also serve to thicken or to adjust the viscosity of the first liquid preparation.

With particular preference the phyllosilicate in the first liquid preparation is from 0.01 to 10% by weight, preferably from 0.1 to 8% by weight, in particular from 0.3 to 5% by weight, very particularly preferably from 0.6 to 3 wt .-% (active substance, in each case based on the total weight of the first liquid preparation). The These concentrations are low enough to avoid increased deposit formation on the surfaces to be cleaned, such as the dishes or glasses.

The detergents prepared according to the invention preferably further comprise at least one nonionic surfactant. In the cleaning agents according to the invention, one or more nonionic surfactants may be present in the first and / or in the second (and further liquid) preparations. Preference is given to using at least one nonionic surfactant which is a rinse aid surfactant which positively influences the rinse aid result (after the end of the dishwashing program). These can be used in the first and / or the second liquid preparation. It may be preferable to use a nonionic surfactant other than the second liquid preparation in the first liquid preparation.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. Most preferably, the automatic dishwashing detergents contain nonionic surfactants from the group of alkoxylated alcohols which constitute an important group of rinse-action nonionic surfactants (i.e., rinse aid surfactants).

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.

In the context of the present invention, particularly preferred nonionic surfactants have been low-foaming nonionic surfactants which have alternating ethylene oxide (EO) and alkylene oxide units (AO). These surfactants show a good effect as rinse aid surfactants. 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 following formula (I) R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ wherein R ^{1 is} selected from straight-chain or branched, saturated C _6-24 alkyl radicals;
R ² and R ⁴ are -H, R ³ and R ⁵ are -CH ₃ ,
R ^{6 is} selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ -CH ₂ -CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ , C _5-20 alkyl (linear or branched),
and the indices w, x, y, z are independently 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 represents} 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''andA''' are independently 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 abovementioned 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 "hydroxymix ether", the performance, in particular the rinse performance of the preparations according to the invention can be significantly improved both in comparison to surfactant-free system and in comparison to systems that only alternative nonionic surfactants, for example from Group of polyalkoxylated fatty alcohols. Such surfactants are therefore also to be understood as rinse aid surfactants in the context of the invention. It may be preferable, in addition to nonionic surfactants from the group of polyakoxylated fatty alcohols, to use the previously mentioned hydroxy mixed ethers.

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 from 1 to 30 carbon atoms and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

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 include, 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

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 represents} 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.

Preferred liquid cleaning agents are characterized in that the cleaning agent contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant in the total weight of the total cleaning agent preferably 0.1 to 10 wt .-%, preferably 0.5 to 8.0 wt .-% and in particular 1.0 to 4.0 wt .-% is. According to a preferred embodiment, such hydroxy mixed ethers are contained in the first and / or the second liquid preparation. If further preparation is present in the cleaning agent, these may also contain nonionic surfactants, in particular alkoxylated fatty alcohols and / or hydroxy mixed ethers. It may be particularly preferred if the o.g. Hydroxymischether contained in the second liquid preparation.

According to a preferred embodiment, the first liquid preparation contains at least one nonionic surfactant, preferably selected from the group of the alkoxylated alcohols, in particular the abovementioned alkoxylated alcohols.

According to a preferred embodiment, the first liquid preparation contains between 1 and 75% by weight, preferably 5 to 60% by weight, more preferably 10 to 50% by weight (based in each case on the total weight of the first liquid preparation) of at least one nonionic surfactant. If several nonionic surfactants are included, the aforementioned amount refers to the sum of all nonionic surfactants in the first liquid preparation.

It is particularly preferred if the first liquid preparation contains 25 to 50% by weight of alkali metal carbonate, preferably sodium carbonate, and 10 to 50% by weight of nonionic surfactant selected from the alkoxylated alcohols, in particular those alkoxylated alcohols of the abovementioned general formula (I) , contains (in each case based on the total weight of the first liquid preparation). The quantitative ratios given here are based on the sum of all nonionic surfactants selected from the alkoxylated alcohols in the first liquid preparation.

According to a particularly preferred embodiment, the first liquid preparation contains as a nonionic surfactant a component according to the following formula (I) R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ wherein R ^{1 is} selected from straight-chain or branched, saturated C _8-16 -alkyl radicals;
R ² and R ⁴ are -H, R ³ and R ⁵ are -CH ₃ ,
R ^{6 is} selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ -CH ₂ -CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ , C _5-20 alkyl (linear or branched),
and are independently selected
w = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
x = 0 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
y = 0 to 6, preferably 1.5 to 4.5, 2 to 3;
z = 0 to 6, preferably 1.5 to 4.5, 2 to 3.

These nonionic surfactants selected above as preferred have the advantage that they are generally liquid to pasty, and in addition to their action as rinse aid surfactant, they can also serve as liquid matrix component (s) in the first liquid preparation.

It is particularly preferred if the first liquid preparation contains 25 to 50% by weight of alkali metal carbonate, preferably sodium carbonate, and 10 to 50% by weight of at least one of the nonionic surfactants described in the preceding paragraph as being particularly preferred according to formula (I). If a plurality of nonionic surfactants contain the surfactants mentioned as preferred in the preceding paragraph, the stated amounts in each case relate to the total amount of those falling under the preferred formula nonionic surfactants. Particular preference is given in particular to those combinations which additionally comprise from 0.3 to 5% by weight, preferably from 0.6 to 3% by weight, of a synthetic Li-Na-Mg phyllosilicate.

The nonionic surfactants mentioned, in particular those mentioned as being preferred, may also be present (also in addition) in the second liquid preparation.

According to a further preferred embodiment, the liquid preparations each contain one or more solvents, preferably organic solvents.

According to a further embodiment, suitable solvents are, for example, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, dipropylene glycol, diethylene glycol, alkanolamines, glycerol, and / or mixtures thereof.

Alkanolamines, in particular monoethanolamine and triethanolamine, are also suitable, although it is preferred to use them only in small amounts, in particular to about 5% by weight, since otherwise impairment of the integrity of the enveloping packaging (especially in the case of PVA-containing films ) can occur.

Particularly preferred solvents are 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, dipropylene glycols (individually or as a mixture), glycerol, and / or a mixture thereof. Very particular preference is given to the use according to the invention of 1,2-propanediol, glycerol or a mixture of 1,2-propanediol and glycerol.

In another embodiment, solvents are suitable which are selected from non-volatile organic solvents. Non-volatile organic solvents for the purposes of the present invention have a volatility (also called volatility or evaporation number) of at least 10, and in particular more than 35, on. The volatility is given as the ratio of the vapor pressure of the substance under consideration to the vapor pressure of the volatile reference substance diethyl ether at 20 ° C and a relative humidity of 65 ± 5%.

Preferred organic solvents having a volatility of at least 10, and especially greater than 35 include polyhydric alcohols such as 2-methyl-1,3-propanediol, 1,3-propanediol, 1,2-propylene glycol and glycerin. In particular, those organic solvents, in particular polyhydric alcohols, which have a volatility of more than 50 are preferred. In particular, organic solvents which have a volatility of less than 10 are completely dispensed with. Particularly preferred non-volatile solvents are 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, dipropylene glycols, glycerol, and / or a mixture thereof. Very particular preference is given to the use according to the invention of 1,2-propanediol, glycerol or a mixture of 1,2-propanediol and glycerol. When using said solvents in the first liquid preparation, preference is additionally given to using from 0.3 to 5% by weight, in particular from 0.6 to 3% by weight, of magnesium-containing phyllosilicate, in particular lithium-magnesium-sodium phyllosilicate.

According to a further embodiment, the ratio of the water content of the first and the second liquid preparations to one another (in each case given in% by weight, based on the amount of water in the total weight of the respective liquid preparation) is between 5: 1 and 1: 5, preferably 3 : 1 and 1: 3, preferably between 2: 1 and 1: 2. This has the advantage that no too large (in particular optically conspicuous) migrations of the water and / or the solvents occur between the individual liquid preparations via the water-soluble packaging. Visually noticeable migrations can cause one of the chambers to continue to inflate / fill with more fluid while the other chamber loses fluid and thereby shrinks. In particular, the shrinkage leads to visually unsightly pre-portioned cleaning agents that are not accepted by the end user.

Advantageously, in addition to the alkali metal carbonates, additional builders can be used. The additional builders that can be used include, in particular, the zeolites, silicates, bicarbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates. Preferably, however, the agents are phosphate-free.

Preference is given to using crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, in which M represents sodium or hydrogen, x denotes a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x are 2, 3 or 4, and y for a number from 0 to 33, preferably from 0 to 20. The crystalline layer-form silicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O are for example sold by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite). Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O, in which x is 2. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ .yH ₂ O and furthermore especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t- Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

Machine dishwashing detergents preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} · yH ₂ O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular of 0.4 to 10 wt .-%, each based on the total weight of these agents.

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. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.

In the context of the present invention, it is preferred that these silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous Alkalidisilikate, in the compositions in amounts of from 3 to 60 wt .-%, preferably from 8 to 50 wt. % and in particular from 20 to 40 wt .-%, each based on the weight of the automatic dishwashing detergent are included.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate) in the detergent industry have the greatest importance.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations on crockery and also contribute to the cleaning performance.

Technically particularly important phosphates are the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate) and corresponding mixed salts (Natriumkaliumtripolyphosphate). Preferably, however, the agents are phosphate-free.

If phosphates are used as washing or cleaning substances in machine dishwashing detergent in the present application, preferred agents comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate ), in amounts of 5 to 80 wt .-%, preferably from 10 to 75 wt .-% and in particular from 12.5 to 70 wt .-%, each based on the weight of the total automatic dishwashing detergent.

Alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances can likewise be used in addition to the alkali metal carbonates according to the invention, preference being given for the purposes of this invention to the use of the alkali hydrogencarbonates and / or -sequicarbonates, preferably sodium bicarbonate or sodium sesquicarbonate.

In another embodiment, a builder system containing a mixture of tripolyphosphate and sodium carbonate is preferred. Because of their low chemical compatibility with the other ingredients of dishwasher detergents in comparison with other builders, the optional alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 % By weight and in particular below 2% by weight, in each case based on the total weight of the automatic dishwashing detergent. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.

As an alternative or in addition to the phosphates, in particular the polyphosphates, it is also possible to use other builders, such as, for example, zeolites, silicates, and in particular also the sodium bicarbonate or sodium sesquicarbonate, and organic cobuilders. The agent is preferably free of water-insoluble builders and particularly preferably contains no zeolites.

The silicates used are, in particular, crystalline layered silicates of the general formula NaMSi _x O _{2x +} 1yH 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 for x is 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, into consideration. 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.

According to a preferred embodiment, one of the liquid preparations, preferably at least the second liquid preparation, for example the first and the second liquid preparation (and possibly further preparations present in the cleaning agent) further contains at least one builder or co-builder, in particular selected from the group formed from citrate, aminocarboxylates (especially MGDA and / or GLDA), polyphosphates (preferably a tripolyphosphate) as well as phosphonates and mixtures thereof.

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.

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 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.

Another important class of builders are aminocarboxylic acids and / or their salts. Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts and glutamic diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or its salts (EDDS). Also suitable are iminodisuccinic acid (IDS) and iminodiacetic acid (IDA). Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.

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 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 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. To be particularly suitable Copolymers of acrylic acid with maleic acid containing 50 to 90 wt .-% of acrylic acid and 50 to 10 wt .-% of maleic acid. 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 detergents may contain, in particular, phosphonates as builder. 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 contained in the compositions preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the cleaning agent.

If the cleaning agents according to the invention contain phosphates, in particular tripolyphosphates, it is preferred that they contain as further constituent preferably one or more builder (s) (builder / cobuilder) in addition to the phosphate-containing builder component. The proportion by weight of these additional builders differing from the phosphate-containing builder component in the total weight of the compositions according to the invention is preferably from 0.1 to 10% by weight and in particular from 2 to 7% by weight. These builders other than the phosphate-containing builder component include in particular those described above as further builders, preferably citrates, phosphonates, MGDA, GLDA, iminodisuccinic acid, iminodiacetic acid, EDDS (ethylenediamine-N, N'-disuccinic acid) or the salts of said acids, other organic Cobuilders and silicates.

Particularly preferred phosphate-containing detergents contain citrate, for example sodium or potassium citrate, as one of their essential builders other than the phosphate-containing builder component. Detergents containing from 1 to 10% by weight, preferably from 2 to 5% by weight, of citrate are preferred according to the invention. Additionally or alternatively, particularly preferred phosphate-containing detergents may contain phosphonates, such as HEDP, as a builder other than the phosphate-containing builder component. Detergents containing from 1 to 10% by weight, preferably from 2 to 5% by weight, of phosphonate, in particular HEDP, are preferred according to the invention.

The cleaning agents of the invention may further contain a sulfopolymer. Preferably, the sulfopolymer is contained in the second liquid phase. 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 18 wt .-%, particularly preferably 1.0 to 15 wt .-%, in particular from 2 to 14 wt .-%, especially from 3 to 12 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). For low-water preparations, the sulfopolymers can also be used as solids, for example as granules.

The sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified 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.

Unsaturated carboxylic acid (s) used are, 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 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, 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. Through the use of these hydrophobically modified polymers, it was possible in particular to improve the performance, in particular the rinsing performance of automatic dishwasher 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.

In addition to the aforementioned builders other than the phosphate-containing builder component, 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.

The agents according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, bleaches, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances , Bitter substances, and antimicrobial agents.

In the first liquid preparation, in particular pH stabilizers (in particular alkali metal bicarbonate (s)), dye (s), fragrances and / or preservatives may be contained.

According to a further preferred embodiment, one of the liquid preparations, preferably the second liquid preparation, preferably contains one or more substances selected from the group consisting of pH regulators, anionic, cationic and amphoteric surfactants, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, Electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, perfumes, bitter substances, and antimicrobial agents.

According to a particularly preferred embodiment, the second liquid preparation contains one or more substances selected from the group consisting of pH regulators, anionic, cationic and amphoteric surfactants, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, Fragrances, bitter substances, and antimicrobial agents.

Dyes are preferably present in at least one, preferably in the first and the second liquid preparation, in particular in all preparations.

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.

Examples of glass corrosion inhibitors used are polyethyleneimines or zinc salts, preferably zinc salts, in particular zinc acetate. Glass corrosion inhibitors are preferably present in compositions according to the invention in an amount of from 0.05 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight.

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 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).

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, particularly 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, xanthan lyases, 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.

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.

Particular preference is given to detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations.

According to a particularly preferred embodiment, the first liquid preparation is substantially free of enzymes. Substantially free of enzymes means that the first liquid preparation containing the alkali metal carbonate, especially the sodium carbonate, less than 1 wt .-%, in particular less than 0.1 wt .-% enzyme preparation (based on the total weight of the first liquid Preparation).

The enzymes, in particular the amylase (s) and / or protease (s), are preferably used in the second liquid preparation.

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. In different Embodiments, the pH is in a range of 5.5 to 10.5, preferably 5.5 to 9.5, more preferably 7 to 9, especially greater than 7, especially in the range 7.5 to 8.5. 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 amidosulfonic acid. In addition, however, it is also possible to use the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof. Suitable bases are selected from the group of alkali metal hydroxides and alkaline earth metal hydroxides and carbonates, in particular the alkali metal bicarbonates, of which potassium bicarbonate and especially sodium bicarbonate is preferred.

It may also be 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 contained in agents according to the invention preferably in an amount of 0.5 to 5 wt .-%, in particular in an amount of 1 to 4 wt .-%. In another embodiment, the cleaning agent according to the invention is free of alkanolamine and ammonia.

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.

Suitable thickeners are all viscosity regulators customarily used in detergents and cleaners, for example organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, Casein), organic modified natural products (carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and the like, gum ethers), organic fully synthetic thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides).

Examples of polyacrylic and polymethacrylic compounds include the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry, and Fragrance Association (US Pat. CTFA): carbomers), also referred to as carboxyvinyl polymers. Such polyacrylic acids are obtainable inter alia from Fa. 3V Sigma under the tradename Polygel ^® such as Polygel ^® DA, and by the company. BFGoodrich under the tradename Carbopol ^®, such as Carbopol ^® 940 (molecular weight about 4,000,000), Carbopol ^® 941 (molecular weight approximately 1,250,000) and Carbopol 934 ^® (molecular weight about 3,000,000). Furthermore, the following acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple ester, preferably formed with C _1-4 -alkanols (INCI acrylates copolymer), such as the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS name according to Chemical Abstracts service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and, for example, by the company Rohm & Haas under the trade names Aculyn ^®. and Acusol ^®, and from Degussa (Goldschmidt) under the trade name Tego ^® polymers are available, for example the anionic non-associative polymers Aculyn ^® 22, Aculyn ^® 28, Aculyn ^® 33 (crosslinked), Acusol ^® 810, Acusol ^® 823 and Acusol ^® 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of C _10-30 alkyl acrylates with one or more monomers selected from the group of acrylic acid, methacrylic acid and their simple, preferably with C _1-4 alkanols formed, esters (INCI acrylates / C10-30 alkyl acrylate crosspolymer) and which are obtainable for example from the company. BFGoodrich under the tradename Carbopol ^®, Carbopol ^® example hydrophobized ETD 2623 and Carbopol ^® 1382 (INCI acrylates / C10 30 alkyl acrylate Crosspolymer) and Carbopol AQUA ^® 30 (formerly Carbopol ^® EX 473). In the international application WO 97/38076 there is listed a series of polymers derived from acrylic acid which are suitable viscosity regulators. Further thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, for example propoxylated guar, and also their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, may alternatively or preferably be used in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropylmethyl or Hydroxyethyl methyl cellulose or cellulose acetate. A particularly preferred polysaccharide thickener is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15 × 10 ^6, and for example, by Fa. Kelco under the trade names Keltrol ^® and Kelzan ^® or from Rhodia is available under the trade name Rhodopol ^®.

In various embodiments, the second liquid preparation has a viscosity above 1000 mPas directly after preparation (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C.), in particular between 2000 and 10000 mPas. After storage, the viscosity may be higher, for example greater than 10,000 mPas, such as in the range 10000-50000 mPas, (Brookfield Viscometer DV-II + Pro, spindle 25, 5 rpm, 20 ° C). It is preferable that the second liquid preparation is flowable at room temperature.

The cleaning agents according to the invention are characterized in that they are stable in storage and even after a prolonged period, no phase separation occurs.

The water-soluble packaging of the cleaning agent (also referred to as a water-soluble coating) is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The package 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.

According to a further preferred embodiment, the water-soluble packaging is a water-soluble packaging made of a polyvinyl alcohol or polyvinyl alcohol copolymer-containing film. It is preferable that the water-soluble packaging contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble packaging containing polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, in particular cold water solubility.

Suitable water-soluble films for preparing the water-soluble packaging 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 packaging 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 consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above can be additionally used as a polyvinyl alcohol-containing film material suitable for producing the water-soluble packaging Be added polymers. 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. Other 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 packaging / water-soluble packaging according to the invention are films marketed by MonoSol LLC, for example under the designation M8630, M8534, C8400 or M8900. Other suitable films include films with the label Solublon ^® PT, Solublon ^® GA, Solublon KC ^® or Solublon ^® KL by Aicello Chemical Europe GmbH, or VF-HP film available from Kuraray.

The cleaning agents according to the invention can be used as dishwashing detergents, in particular automatic dishwashing detergents (machine dishwashing 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 particular embodiments described above also apply to the use or the method.

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

Example recipe:

Stated quantities are active substance (unless stated otherwise). Chamber I Chamber II Soda (calcined, anhydrous) 40 - 1,2-propylene glycol 8th 10 sodium 0.5 - Synthetic Li-Na-Mg phyllosilicate 2 - C10-C12 alcohol with EO / PO (nonionic surfactant) 40 - potassium - 20 hydroxy mixed - 2 Acrylic acid polymer, Na salt - 0.5 sulfopolymer - 8th Sodium citrate (dihydrate) - 4 glycerin - 25 ethanolamine - 3 phosphonate - 2 Enzyme preparations, liquid (containing protease, amylase) - 5 Zinc acetate (anhydrous) - 0.2 Perfume, dye, excipients, preservatives 0.5 0.5 water To 100% To 100%

There was obtained a particularly stable dispersion in the first liquid phase (chamber I), which had no sedimentation of the soda even after a storage time of 4 weeks at 40 ° C.

The pre-portioned detergent according to the invention, which was provided in a Zweikammerpouch (two-chamber bag) of PVA-containing film and 5 g of the first liquid phase (chamber I) and 15 g of the second liquid phase (chamber II) contained, showed when used in a conventional Dishwasher a good cleaning performance on burnt stains compared to a commercially available pre-portioned liquid detergent in a Einkammerpouch.

Comparative Formulation 1:

Stated quantities are active substance (unless stated otherwise). Chamber I Chamber II Soda (calcined, anhydrous) 40 - 1,2-propylene glycol 10 10 sodium 0.5 - Synthetic Li-Na-Mg phyllosilicate - - C10-C12 alcohol with EO / PO (nonionic surfactant) 40 - potassium - 20 hydroxy mixed - 2 Acrylic acid polymer, Na salt - 0.5 sulfopolymer - 8th Sodium citrate (dihydrate) - 4 glycerin - 25 ethanolamine - 3 phosphonate - 2 Enzyme preparations, liquid (containing protease, amylase) - 5 Zinc acetate (anhydrous) - 0.2 Perfume, dye, excipients, preservatives 0.5 0.5 water To 100% To 100%

There was no stable dispersion in the first liquid phase (chamber I); After only a few hours of storage at room temperature, sedimentation of the sodium carbonate (soda) was observed.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 97/38076 [0131]

Claims (14)

Preportioned detergent, preferably machine dishwashing detergent, in a water-soluble packaging with at least two compartments, comprising at least a first and a second liquid preparation, characterized in that the first liquid preparation contains alkali metal carbonate, preferably sodium carbonate, in an amount of from 20 to 60% by weight ( based on the total weight of the first liquid preparation). Cleaning agent according to claim 1, characterized in that in the first liquid preparation, a layered silicate, in particular magnesium-containing phyllosilicate, is also included. Cleaning agent according to claim 2, characterized in that the phyllosilicate in the first liquid preparation to 0.01 to 10 wt .-%, preferably 0.1 to 8 wt .-%, in particular 0.3 to 5 wt .-%, completely particularly preferably 0.6 to 3 wt .-% (in each case based on the total weight of the first liquid preparation) is contained. Cleaning agent according to one of claims 1 to 3, characterized in that further comprises the first liquid preparation at least one nonionic surfactant, preferably selected from the group of alkoxylated alcohols. Detergent according to claim 4, characterized in that the first liquid preparation between 1 and 75 wt .-%, preferably 5 to 60 wt .-%, more preferably 10 to 50 wt .-% (each based on the total weight of the first liquid preparation ) contains nonionic surfactant. Cleaning agent according to one of claims 4 or 5, characterized in that the first liquid preparation as nonionic surfactant, a component according to formula (I) R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) w- (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ wherein R ^{1 is} selected from straight-chain or branched, saturated C _8-16 -alkyl radicals; R ² and R ⁴ are -H, R ³ and R ⁵ are -CH ₃ , R ^{6 is} selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ -CH ₂ -CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ , C _5-20 alkyl (linear or branched), and independently selected w = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3; x = 0 to 6, preferably 1.5 to 4.5, in particular 2 to 3; y = 0 to 6, preferably 1.5 to 4.5, 2 to 3; z = 0 to 6, preferably 1.5 to 4.5, 2 to 3, contains. Cleaning agent according to one of claims 1 to 6, characterized in that the liquid preparations in each case one or more solvents, preferably propanediols (1,2-propanediol and / or 1,3-propanediol), 2-methyl-1,3-propanediol, dipropylene glycol , Glycerin, and / or mixture thereof, in particular 1,2-propanediol and / or glycerol. Detergent according to one of claims 1 to 7, characterized in that the ratio of the water content of the first and the second liquid preparations to each other (in each case based on the total weight of the respective liquid preparation) is between 5: 1 and 1: 5. Detergent according to one of claims 1 to 8, characterized in that one of the liquid preparations, preferably at least the second liquid preparation, further comprises at least one builder or co-builder, in particular selected from the group formed from citrate, aminocarboxylates (especially citrate, MGDA and or GLDA), polyphosphates, preferably a tripolyphosphate), as well as phosphonates and mixtures thereof. Cleaning agent according to one of claims 1 to 9, characterized in that one of the liquid preparations, preferably the second liquid preparation further comprises one or more of the substances selected from the group consisting of pH adjusters, anionic, cationic and amphoteric surfactants, bleach activators, bleach catalysts, Enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, bitter substances, perfumes and antimicrobial agents. Cleaning agent according to one of claims 1 to 10, characterized in that the first liquid preparation is substantially free of enzymes (less than 1 wt .-%, in particular less than 0.1 wt .-% enzyme preparation contains). Cleaning agent according to one of claims 1 to 11, characterized in that it is a water-soluble packaging made of a polyvinyl alcohol or polyvinyl alcohol copolymer-containing film.  Use of the cleaning agent according to one of claims 1 to 12 as a dishwashing detergent, in particular automatic dishwashing detergent. Machine dishwashing process, characterized in that a cleaning agent according to one of claims 1 to 12 is used.