EP3114198A1

EP3114198A1 - Pre-portioned cleaning agent comprising at least two separate liquid preparations

Info

Publication number: EP3114198A1
Application number: EP15708188.6A
Authority: EP
Inventors: Ulrich Pegelow; Noelle Wrubbel; Volker Blank; Matthias Sunder; Martina Hutmacher; Klaus Dorra; Britta Strauss; Oliver Kurth; von den Karl-Josef DRIESCH; Friedhelm Siepmann; Mario Sturm
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2014-03-06
Filing date: 2015-03-04
Publication date: 2017-01-11
Anticipated expiration: 2035-03-04
Also published as: PL3114198T3; WO2015132279A1; DE102014204144A1; EP3114198B1

Abstract

The invention relates to a pre-portioned cleaning agent, preferably dishwasher detergent, in a water-soluble package having at least two compartments, comprising at least one first and one 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 (relative to the total weight of the first liquid preparation).

Description

Pre-portioned detergents comprising at least two separate liquid preparations

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

Consumers are available 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. To make a liquid dishwashing detergent that has the advantages mentioned above

Compositions to provide in a pre-portioned form offers the use of water-soluble films in the form of bags. Disposable portions, especially water-soluble bags enjoy the consumer not only therefore

Increasing popularity because the consumer no longer comes into contact with the chemical composition, 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 MetaSilikaten can not be used, since the water-soluble packaging by such

Ingredients can be at least partially attacked. 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 in reference to the cleaning agent of the present invention includes all flowable compositions and more particularly includes gels and pastes

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

Portion pack 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. As preparation (phase) becomes Here, a detergent (partial) composition understood that in combination with the other preparations / phases, a detergent, especially a machine dishwashing detergent results.

It may be particularly preferred that the pre-portioned

Detergent contains in addition to the two mentioned preparations one or two further preparations in other 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.

Preferably, a packaging according to the invention with two compartments can be present, wherein the first and the second liquid preparation separated from each other in each one of

Compartments are present.

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 one or more different from each other

Have ingredients.

"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, respectively,

for example 2, 3, 4, 5, 6 or more.

The first liquid preparation contains 20 to 60 wt .-% alkali metal carbonate, in particular sodium carbonate (a2C03). 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 alkali metal hydrogencarbonates, such as, for example, Sodium bicarbonate, or

Alkali metal sesquicarbonates, to be construed. The alkali metal carbonates, depending on their amount and the water content of the first preparation in solution or as a dispersion available. 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 any 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, separated 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 serving 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 detergent used in a complete dishwasher cleaning program).

According to a preferred embodiment, the ratio of alkali metal carbonate to water in the first liquid preparation is based in each case on the total amount of the first liquid Preparation 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) The water content as defined herein refers to the water content determined by the 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 separation 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, in particular between 6: 1 and 2.5: 1, more 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 furthermore contained 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 the formation of a stable and storage-stable dispersion of the large

Alkalimetallcarbonatmenge reach without segregation during storage of the agent 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 phyllosilicates are lithium-magnesium-sodium phyllosilicates, for example available under the trade name Laponite® RD, which are particularly suitable for ensuring the stability of the dispersion of the alkali metal carbonates in the first liquid preparation over an extended 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 concentrations mentioned are low enough to be stronger

To avoid formation of deposits on the surfaces to be cleaned, for example the dishes or the 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 produces the rinse aid result (after the end of the

Dishwasher cleaning program) positively influenced.

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 more 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 contain alternating ethylene oxide (EO) and

Alkylene oxide units (AO) have. 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 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 ) -0) z R ⁶ wherein R 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, Cs-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 C9-alkyl group with 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.

Preferred nonionic surfactants here are those of the general formula R -CH (OH) CH20- (AO) w- (AO) x- (A "0) y- (A '" 0) zR ² , in which

R is a straight-chain or branched, saturated or mono- or polyunsaturated Ce-24-alkyl or alkenyl radical;

R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A, Α ', 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 abovementioned nonionic surfactants of the general formula R ¹ -CH (OH) CH 2 O- (AO) w- (AO) x- (A "0) y- (A '" 0) zR ² , hereinafter also referred to as "hydroxy mixed ether ", the performance, in particular the rinsing performance, according to the invention prepared compared to surfactant-free system as well as compared to systems containing only alternative nonionic surfactants, for example from the 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 0 [CH ₂ CH ₂ O] xCH ₂ CH (OI-1) R ² , in addition to a radical R 1 which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 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 between 1 and 90, preferably Values between 30 and 80 and especially for values between 30 and 60 stands.

Particular preference is given to surfactants of the formula RO [CH ₂ CH (CH ₃ ) O] x [CH ₂ CH ₂ O] _y CH ² CH (OH) R ² , in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ^{2 is} one linear or branched

Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15 stands.

The group of these nonionic surfactants include, for example, the C2-26 fatty alcohol (PO) i- (EO) is-4o-2-hydroxyalkyl ethers, in particular the coco fatty alcohol (PO) i (EO) 22-2-hydroxydecyl ethers ,

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH ₂ CH ₂ O] x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² in which R and R ² independently of one another are linear or branched , saturated or single or multiple

unsaturated 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 is -CH 3, and x and y independently of each other for between values 1 and 32, with nonionic surfactants with R ³ = -CH ³ and values for x of 15 to 32 and y of 0.5 and 1.5 being very particularly preferred.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH ₂ CH (R ³ ) O] _x [CH ₂ ] kCH (OH) [CH ₂ ] jOR ² where R 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 is 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 RO [CH ₂ CH (R ³ ) O] x [CH ₂ ] _k CH (OH) [CH ₂ ] jOR ^{2 may be} different. R 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 are particularly preferred. For the radical R ³ , H, -Ch 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, the range of variation 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, so that the above formula zu

R 0 [CH ₂ CH (R ³ ) O] x CH ₂ CH (OH) CH ² CO ² simplified. In the last-mentioned 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 have} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

Finally, the nonionic surfactants of the general formula R -CH (OH) CH ₂ O- (AO) wR ^{2 have} proven to be particularly effective, in which

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 values between 1 and 120, preferably 10 to 80, especially 20 to 40. The group of these non-ionic surfactants include, for example _C4-22 fatty alcohol (EO) io-so-2-hydroxyalkyl ethers, in particular, the _Cs-i2 fatty alcohol - (EO) ₂₂ -2-C4 hydroxydecylether and ₂₂ fatty alcohol (EO) 4o-8o-2-hydroxyalkyl ether. In various embodiments of the invention, instead of the above-defined end-capped hydroxy mixed ethers, the corresponding ones can not

end-capped hydroxy mixed ethers. These may satisfy the above formulas, but R ² is hydrogen and R, R ³ , A, Α ', 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 on

Total weight of the total cleaning agent is 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 from 25 to 50% by weight.

Alkali metal carbonate, preferably sodium carbonate, and 10 to 50 wt .-% 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-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 ) -0) z R ⁽ wherein R is selected from straight-chain or branched, saturated Ce-ie-alkyl radicals;

R ² and R ⁴ are -H, R ³ and R ⁵ are -CH ₃ ,

CH 2 CH ₃ , -CH 2 CH (CH ₃ ) 2, -C (CH ₃ ) 3, Cs-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.

Alkali metal carbonate, preferably sodium carbonate, and 10 to 50 wt .-% of at least one of the preceding paragraph as particularly preferred according to formula (I) described

contains nonionic surfactants. If a plurality of nonionic surfactants contain the surfactants mentioned as preferred in the preceding paragraph, then the stated amounts relate in each case to the total amount of the nonionic surfactants falling under the preferred formula.

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, such as in particular monoethanolamine and triethanolamine, are likewise suitable, although it is preferred that these be present only in small amounts, in particular up to about 5% by weight. otherwise it may impair the integrity of the enveloping package (especially in PVA-containing films).

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 volatility or

Evaporation number mentioned) 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 more particularly 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 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 conspicuous migrations can cause one of the chambers to continue to inflate more fluid is filled 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.

Preferably, crystalline layered silicates of general formula NaMSi _x are 02x + i ^■ y H2O used, wherein 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 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layered silicates of the formula NaMSi be _x 02x + i ^■ y H2O, for example, by Clariant GmbH

(Germany) under the trade name Na-SKS. Examples of these silicates are sodium SKS-1 (Na ₂ Si ₂ x 2045 ^■ H2O, kenyaite), Na-SKS-2 _(Na2 Sii ₄₀₂₉ ^■ x H2O, magadiite), Na-SKS-3 ^(■ x Na2Si80i7 H2O) or Na-SKS-4 (Na2Si409 ^■ x H2O, makatite). Particularly suitable for the purposes of the present invention are crystalline sheet silicates of the formula NaMSix02x + i ^■ y H2O, where x is the second In particular, both .beta.- and δ-sodium Na2Si20s ^■ y H2O and further especially Na-SKS-5 (a-Na ₂ Si ₂ 0 _5), Na-SKS-7 _(.beta.-Na2 _Si2 05, natrosilite) , Na-SKS-9 (NaHSi20s ^■ H2O), Na-SKS-10 (NaHSi ₂ 0 ₅ ^■ 3 H ₂ 0, kanemite), Na-SKS-11 _(t-Na2 Si20 ₅₎ and Na-SKS-13 (NaHSi ₂ 0 ₅ ), but especially Na-SKS-6 (5-Na ₂ Si20 ₅ ) is preferred.

Machine dishwashing detergents preferably contain a weight proportion of crystalline layered silicate of the formula NaMSi _x 02x + y i ^■ H2O of 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular from 0.4 to 10 Wt .-%, each based on the total weight of these agents.

It is also possible to use amorphous sodium silicates having a modulus Na 2 O: SiO 2 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 are preferably delayed in dissolution and secondary wash properties. The dissolution delay compared to conventional amorphous sodium silicates can in various ways, for example by surface treatment, compounding, compaction compaction or by

Overdrying caused. 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.

Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids in which one

Metaphosphoric acids (HP03) n and orthophosphoric acid H3PO4 can distinguish 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 important phosphates are the pentasodium triphosphate, NasPsO-io

(Sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K5P3O10 (potassium tripolyphosphate) and corresponding mixed salts (sodium potassium tripolyphosphates).

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 alkali hydrogencarbonates and / or -sequicarbonates

Sodium hydrogen carbonate or sodium sesquicarbonate can be used. 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. Preferably, the agent is free of water-insoluble builders and contains

in particular, no zeolites are preferred.

Particularly suitable silicates are crystalline layered silicates of the general formula NaMSixO 2 + + H 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, 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 having a modulus Na 2 O: SiO 2 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 are preferably delayed in dissolution and secondary wash 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. Especially preferred for phosphate-free detergents are the builders or co-builders selected from the group formed from citrate, aminocarboxylates (in particular MGDA and / or GLDA) and also

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), provided such use is not objectionable for environmental reasons, and mixtures thereof. In addition to their builder effect, the free acids typically also have the property of a

Acidification and thus also serve to set a lower and milder pH of the automatic dishwashing detergent. In particular, here are citric acid,

Succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof.

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. 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 detergents may contain, in particular, phosphonates as builder. As the phosphonate compound is preferably a hydroxyalkane and / or aminoalkane phosphonate used. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. As Aminoalkanphosphonate are preferably

Ethylenediaminetetramethylenephosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. 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 of the phosphate-containing builder component

various builders on the total weight of the compositions according to the invention

preferably 0.1 to 10 wt .-% and in particular 2 to 7 wt .-%. 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 cleaning agents can be used as one of the phosphate-containing

Builder component different builder phosphonates, such as HEDP included. 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 sulfonic acid group-containing (s)

Monomer (s) at least one monomer from the group 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, with -NH2, -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -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 is -H, -CH 3, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with - 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- where n = 0 to 4, -COO- (CH ₂ ) k- where 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

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H in which R ⁶ and R ^{7 are} independently selected

of -H, -CH _3, -CH ₂ CH _3, -CH ₂ CH 2 CH ₃ and -CH (CH ₃₎ ₂ and X is an optionally present

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-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfo - Propylmethacrylat, 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 inventively preferred.

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 share of

Carboxylic acid-containing monomers 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 in particular the performance, in particular the

Rinse performance of automatic dishwashing detergent according to the invention can be improved.

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.

As nonionic monomers are preferably monomers of the general formula

R (R ² ) C = C (R ³ ) -XR ^{4 is} used, in which R to R ^3, independently of one another, is -H, -CH ₃ or -C 2 H 5, X is an optionally present spacer group which is 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 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, a 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, A / (2-ethylhexyl) acrylamide,

Octyl acrylate, octyl acrylate, A / - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, A / - (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 Monomers 60 to 80 wt .-%, the monomers are hereby 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 contain at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphorous surfactants, bleaching agents, 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 adjusting agents (in particular

Alkali metal bicarbonate (s)), dye (s), perfumes and / or preservatives.

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 of the substances selected from the group consisting of pH adjusters, anionic, cationic and amphoteric surfactants, enzymes, thickeners,

Sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, perfumes, 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 acid esters), in particular sulfosuccinic acid mono- and di-Cs-Os-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 ''')(R' ^v ) (R ^v ) N ⁺ CH 2 COO ^' , in which R ^{i is} an alkyl radical having 8 to 25, preferably 10 to 21, carbon atoms and optionally interrupted by hetero atoms or heteroatom groups R ^iv and R ^{v are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetain.

Suitable cationic surfactants are i.a. the quaternary ammonium compounds of the formula

(R ^VI ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^" , in which R ^vi to R ^ix for four identical or different, in particular two long and two short-chain, alkyl radicals and X ^" for an anion , in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Other suitable cationic surfactants are the quaternary

surface-active compounds, in particular with 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 contain enzymes

preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% 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 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, those originally from Humicola lanuginosa

(Thermomyces lanuginosus), or in particular those with one or more of the following amino acid exchanges starting from said lipase in positions D96L, T213R and / or N233R, more preferably all of the exchanges D96L, T213R and N233R.

Furthermore, enzymes can be used which are termed hemicellulases

be summarized. 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. be used. Advantageously, it is additionally preferable to add organic, more preferably aromatic, enzyme-interacting compounds to enhance the activity of the respective oxidoreductases (enhancers) or to react at greatly varying redox potentials between the oxidizing enzymes and the

Stains to ensure the flow of electrons (mediators).

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 with a water, air and / or

Chemical-impermeable protective layer is coated. 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 former, low-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. Preferably used according to the invention Protease and amylase preparations contain between 0.1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and

in particular between 0.8 and 10% by weight of the enzyme protein.

Preference is given in particular to those detergents which, in each case 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.

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 various 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 also

Sulfamic 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 and alkaline earth metal hydroxides and carbonates, in particular the

Alkalimetallhydrogencarbonate, of which potassium bicarbonate and especially

Sodium hydrogencarbonate is preferred.

It may also be volatile alkali, for example in the form of ammonia and / or

Alkanolamines, which can contain up to 9 C-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 at the same time complexing agents or even

Chelating agents (chelators, INCI chelating agents) are. Particularly preferred buffer substances are citric acid or citrates, in particular the sodium and potassium lead,

for example, trisodium citrate 2H20 and tripotassium citrate Ή2Ο.

Suitable thickeners are all viscosity regulators customarily used in detergents and cleaners, to which, 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, core flour 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) or 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), for example the copolymers of Methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and

Methyl methacrylate (CAS 25852-37-3) and which are obtainable for example from Messrs. Rohm & Haas under the trade names Aculyn ^® and Acusol ^®, and from Degussa (Goldschmidt) under the trade name Tego ^® polymer, 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 Cio-30-alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with Ci-4-alkanols formed, esters (INCI Acrylates / C 10-30 alkyl acrylate crosspolymer) and the example of the Fa. BFGoodrich are available under the trade name Carbopol ^®, eg hydrophobic the

Carbopol ^® ETD 2623 and Carbopol ^® 1382 (INCI Acrylates / C 10-30 Alkyl Acrylate Crosspolymer) and Carbopol AQUA ^® 30 (formerly Carbopol ^® EX 473). In the international application

WO 97/38076 lists a number 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, e.g. propoxylated guar, as well as their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, may be used alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g. Hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropyl methyl 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 Kelco under the trade names Keltrol ^® and Kelzan ^® or by the company Rhodia under the trade name Rhodopol ^{® is} available.

In various embodiments, the second liquid preparation directly after production has a viscosity above 1000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C), in particular between 2000 and 10,000 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 (also referred to as water-soluble wrapping) water-soluble packaging of

Detergent is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The packaging may consist of one or two or more layers of the water-soluble

Foil material are formed. 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 a good stability with a sufficiently high water solubility, in particular water solubility on.

Suitable water-soluble films for producing the water-soluble packaging are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose

Molecular weight in the range of 10,000 to 1,000,000 gmol ^_1 , preferably from 20,000 to 500,000 gmol ¹ , more preferably from 30,000 to 100,000 gmol ^-1 and in particular 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 comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble packaging

(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 include, 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, detackifiers, 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 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 detergents, in particular automatic dishwashing detergents (machine dishwashing detergents). The corresponding

Use is also the subject of the invention. Likewise, the invention relates to a

Dishwashing process, in particular automatic dishwashing process, in which a detergent 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).

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 when used in a conventional Dishwasher a good cleaning performance on burnt stains compared to a commercial 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 hydrogencarbonate 0,5 -

Synthetic Li-Na-Mg Phyllosilicate - -

C10-C12 alcohol with EO / PO 40

(Nonionic surfactant)

Potassium tripolyphosphate - 20

Hydroxymix ether - 2

Acrylic acid polymer, Na salt - 0.5

Sulfopolymer - 8

Sodium citrate (dihydrate) - 4

Glycerol - 25

Ethanolamine - 3

Phosphonate - 2

Enzyme preparations, liquid 5

(containing protease, amylase)

Zinc acetate (anhydrous) - 0.2

Perfume, dye, excipients, 0,5 0,5

preservative

Water 100% 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).

Claims

claims

1. Pre-portioned detergent, preferably machine dishwashing, in one

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 ) contains.

2. Cleaning agent according to claim 1, characterized in that in the first liquid preparation further comprises a layered silicate, in particular magnesium-containing phyllosilicate.

3. Cleaning agent according to claim 2, characterized in that the layered silicate in the first liquid preparation to 0.01 to 10 wt .-%, preferably 0.1 to 8 wt .-%, in particular 0.3 to 5 wt .-% , very particularly preferably 0.6 to 3 wt .-% (in each case based on the total weight of the first liquid preparation) is included.

4. 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.

5. Cleaning agent according to claim 4, characterized in that the first liquid

Preparation contains 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) of nonionic surfactant.

6. Cleaning agent according to one of claims 4 or 5, characterized in that the first liquid preparation as a nonionic surfactant, a component according to formula (I)

R-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 ) -0) z R ⁶ wherein R ^{1 is} selected from straight-chain or branched, saturated Ce-ie- 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 , Cs-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,

contains.

7. 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, glycerol, and / or mixture thereof, in particular 1, 2- Propanediol and / or glycerin included.

8. Cleaning agent 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 (each based on the total weight of the respective liquid preparation) is between 5: 1 and 1: 5.

9. Cleaning agent 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 (in particular MGDA and or GLDA), polyphosphates, preferably a tripolyphosphate), as well as phosphonates and mixtures thereof.

10. 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, Bleaching catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, bitter substances, fragrances and antimicrobial agents.

11. A detergent according to any 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).

12. Cleaning agent according to one of claims 1 to 1 1, characterized in that it is a water-soluble packaging of a Polyvinylalkohol- or

Polyvinyl alcohol copolymer-containing film is.

13. Use of the cleaning agent according to any one of claims 1 to 12 as a dishwashing detergent, in particular automatic dishwashing detergent.

14. Machine dishwashing process, characterized in that a cleaning agent according to one of claims 1 to 12 is used.