EP3102659A1 - Use of amino carboxylic acids for stabilising low-water, liquid detergents or cleaning agents - Google Patents

Abstract

The invention relates to the use of at least one amino carboxylic acid for stabilising low-water, preferably substantially water-free, liquid detergent components or cleaning-agent components.

Description

 Use of aminocarboxylic acids for the stabilization of low-water liquid washing or

 detergents

The invention relates to the use of at least one aminocarboxylic acid for the stabilization of low-water, preferably substantially anhydrous liquid washing or

Detergent components.

Detergents or 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 especially appreciates the rapid solubility and the associated rapid availability of the ingredients in the cleaning liquor, especially in short-dishwashing programs and at low levels

Temperatures.

The importance of concentrated compositions, in which in particular the water content is reduced compared to conventional compositions, increases. Thus, for the consumer, compositions whose water content is as low as possible are particularly desirable.

Disposable portions, in particular water-soluble pouches or multi-chamber tablets made of water-soluble material, such as e.g. Containers made of PVA, produced by injection molding, 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. For the consumer, it is therefore a nuisance if the bags lose their attractive appearance.

This can be caused, for example, by the fact that, especially in low-water or substantially water-free compositions, the different components, for example dispersed solids or immiscible, non-aqueous

Liquids, disintegrate and a phase separation takes place. This phase separation perceived by the consumer as not aesthetically and in the worst case, he doubts the operational capability of the no longer appearing perfect product.

It is therefore the object of the present invention to provide a method which the phase separation in low-water, especially in substantially anhydrous washing or Detergent compositions counteracts and stability, in particular the

Storage stability of such compositions increased.

The object was achieved by the use of at least one aminocarboxylic acid for the stabilization of low-water, preferably substantially anhydrous, liquid detergent or cleaner components.

Aminocarboxylic acids are here to be understood as meaning the aminocarboxylic acids themselves and / or their salts, for example nitrilotriacetic acid, in particular 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). The aminodicarboxylic acids are preferably used. Particularly preferred representatives of this class are aminodiacetic acids,

According to a particularly preferred embodiment, the aminocarboxylic acid is selected from the group GLDA and MGDA, preferably MGDA.

According to a particular embodiment, the aminocarboxylic acid is present in amounts of from 2 to 25% by weight, in particular from 3 to 15% by weight, preferably from 4 to 10% by weight (based on the weight of the liquid washing or cleaning agent component) ,

It is also possible to use several aminocarboxylic acids, then the stated amount refers to all the aminocarboxylic acids used,

It is possible to use aminodicarboxylic acids, preferably in amounts of from 2 to 25% by weight, in particular from 3 to 15% by weight, preferably from 4 to 10% by weight (based on the weight of the liquid washing or cleaning agent component). contain.

Particularly preferred aminocarboxylic acids are exclusively aminodicarboxylic acids, in particular in an amount of from 2 to 25% by weight, in particular from 3 to 15% by weight, preferably from 4 to 10% by weight (based on the weight of the liquid washing or

Detergent component) is used.

In particular, preference is given to using MGDA or its salt, in particular in an amount of from 2 to 25% by weight, in particular from 3 to 15% by weight, preferably from 4 to 10% by weight (based on the weight of the liquid detergent). or detergent component). For the purposes of the present invention, low-water content means that a composition contains less than 20% by weight, in particular less than 15% by weight, preferably less than 13% by weight, particularly preferably less than 10% by weight of water.

"Substantially free of water" as used herein means that a composition contains less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight. The water content as defined herein refers to the water content determined by Karl Fischer titration.

According to a particular embodiment, the washing or cleaning agent is pre-portioned.

 In this connection, it is possible for the disposable portion to have one or more liquid phases which are located in a plurality of separate compartments. According to the invention, an amino carboxylic acid, in particular an amino dicarboxylic acid, in particular GLDA or MGDA, in particular MGDA, is then used in at least one, preferably in several, in particular in all liquid phases for phase stabilization.

According to the invention, the liquid phase is preferably "substantially free of water", this means that the liquid phase less than 7 wt .-%, in particular less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than The water content as defined herein refers to the water content determined by Karl Fischer titration.

In particular, all liquid phases and all solid phases of the cleaning agent used according to the invention are "substantially free of water", ie each of the individual phases contains less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight. -%, more preferably less than 1 wt .-% water (in each case based on the

Total weight of the respective phase).

"Liquid," as used herein with respect to the cleaning agent of the invention, includes all flowable compositions, and more particularly, includes gels and pasty compositions. In particular, the term also includes non-Newtonian

Liquids that have a yield point.

"At least one" as used herein means 1 or more, for example, 1, 2, 3, 4, 5, or more. "Solid" as used herein in reference to the detergent used in the invention includes all solid compositions, and includes in particular powdered, granular, amorphous, compressed, in particular pressed, tabletted compositions Powdered compositions may also contain, in addition to pulverulent constituents, some of the granules ,

The cleaning agent is preferably present in a water-soluble packaging.

The water-soluble packaging allows a portioning of the detergent. The amount of detergent in the sachet is preferably 5 to 50 g, more preferably 10 to 30 g, especially 15 to 25 g.

Preferably, this is a disposable portion, the detergent is preferably in an amount sufficient to carry out the cleaning, in machine dishwashing detergents in particular a cycle or a complete program run one

Dishwasher), before.

The water-soluble packaging in this case has at least two or more spatially separated compartments (chambers), in which spatially separated at least one solid, preferably pulverulent, and at least one liquid phase are filled.

Particularly suitable are two-chamber bags or two-chamber tablets which contain a solid and a liquid phase in separate compartments.

Furthermore, particularly multi-chamber packages (multi-chamber bags or multi-chamber shaped bodies) are suitable which contain a powdery phase in at least one of the separated compartments and a liquid phase in at least one other compartment. A phase is here understood to mean a detergent (partial) composition which, in combination with the other phase (s), results in a cleaning agent, in particular a machine dishwashing detergent.

The cleaning agent used according to the invention, in particular machine dishwashing detergent, can also be present in a water-soluble packaging which contains in particular more than two, for example three, four, five or six compartments.

Preferably, the package contains two, three or more chambers (compartments), wherein one, two or more of these chambers are filled with liquid phases, which are preferably different from each other, and in particular one or more mutually different ingredients. Preferred are pre-portioned detergents in which the water-soluble package has one, two or more chambers in addition to one, two or more liquid phases

(Compartments) with solid phases. When two or more solid phases are provided, it is preferred that they be of different composition and / or have a different solid form.

Particular preference is given to pre-portioned cleaning compositions which have at least one solid, preferably at least one pulverulent phase and at least one liquid phase in separate compartments.

Also preferred are pre-portioned detergents containing at least one solid, preferably at least one compressed phase and one liquid phase in separate

Have compartments.

It may also be preferable for the pre-portioned cleaning agent to have two or more solid phases, of which at least one powdery and at least one compressed and at least one, also two, three or more liquid phases are in each case separate compartments.

It is further preferred that the pre-portioned detergent, in particular the

Multi-chamber bag containing a solid, one of them different powdery and two liquid phases in each separate compartments.

 The pre-portioned detergents according to the invention, in particular machine dishwashing detergents, preferably comprise in the liquid phase, in one of the liquid phases, in particular in all liquid phases,

at least one, preferably two, three, four or more alkoxylated components 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) zR ⁶

 (Formula I)

 in which

R is selected from -H, -CH ₃ , straight-chain or branched, saturated or mono- or polyunsaturated, C2-24-alkyl or alkenyl radical;

R ² , R ³ , R ⁴ , R ^{5 are} each independently selected from -H, -CH ₃ , -

CH 2 CH ₃ , -CH 2 CH 2 CH ₃ , CH (CH ₃ ) 2, preferably -H or -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-24-alkyl or alkenyl, and

CH ₂ CH (OH) R ⁷

R ^{7 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C 6-26-alkyl or alkenyl radical; and

 w, x, y, z can each independently of one another assume values of 1 to 120 and where x, y and / or z = 0,

The liquid phase or the liquid phases of the cleaning agents according to the invention contain at least one component according to a).

Preferably, the liquid phase or contain the liquid phases of the cleaning agent according to the invention at least one component according to a), which is selected from the

Polyalkylene glycols according to formula (I) with

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) zR ⁶

(Formula I)

R = H, R ⁶ = H; R ² , R ³ , R ⁴ , R ⁵ , each independently selected from H, -Ch, and w, x, y, z = 1 to 50.

Under the o.g. Formula (I) are also a large part of the nonionic surfactants to grasp. Preference is given to weakly foaming alkoxylated nonionic surfactants, in particular ethoxylated,

low-foaming nonionic surfactants preferably used. In preferred embodiments, the automatic dishwashing agents contain nonionic surfactants from the group of alkoxylated alcohols.

According to a preferred embodiment, the water-poor, preferably substantially anhydrous, liquid washing or cleaning agent components comprise one or more nonionic surfactants in an amount of from 15 to 60% by weight, preferably from 20 to 50% by weight, in particular from 30 to 40% by weight. % (based on the weight of the liquid detergent or cleaner component).

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.

Particularly preferred nonionic surfactants used are low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula (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) zR ⁶ in which R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical; R ² , R ⁴ , R ⁶ each = -H; each group R ³ or R ^{5 is} independently selected from -Chta, -CH 2 CH 3, -CH 2 CH 2 -CH 3, CH (CH 3) 2 and the indices w, x, y, z independently represent 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.

Further preferred nonionic surfactants here are those of the general formula

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) zR ⁶ With

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

R ² , R ³ , R ⁴ , R ^{5 are} each independently selected from -H, -CH ₃ , -CH 2 CH ₃ , -CH 2 CH 2 CH ₃ , CH (CH ₃ ) 2, preferably -H or -CH ₃ ;

R ^{6 is} selected from -CH ₂ CH (OH) R ⁷

with R ⁷ for a straight-chain or branched, saturated or on or

 polyunsaturated C6-26 alkyl or alkenyl radical;

 and

 w, x, y and z are values between 1 and 120, where x, y and / or z can also be 0.

With these surfactants, hereinafter also referred to as "hydroxy mixed", the

Cleaning performance of the preparations according to the invention are significantly improved both in comparison to surfactant-free system as well as in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols

Finally, the nonionic surfactants of the general formula (I) have proven to be particularly effective.

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) zR ⁶ With

 R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

R ² = H,

R ^{6 is} selected from -CH ₂ CH (OH) R ⁷ with R ⁷ for a straight-chain or branched, saturated or on or

 polyunsaturated C6-26 alkyl or alkenyl radical;

 and

 w = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0.

The group of these nonionic surfactants include, for example, the C4-22 fatty alcohol (EO) io-so-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o 8o-2-hydroxyalkyl ethers.

Also preferred are also surfactants of the 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 in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, y, z = 0; R ² = CH ³ , R ³ = -H, R ⁶ = a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and w for values of 1 and 2 (for mixtures of such products also between 1 and 2, eg 1, 5) and x stands for a value of at least 15.

 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 ,

Preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula

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) zR ⁶

With y, z = 0 and R ² = H, R ⁶ = -CH ₂ CH (OH) R ⁷

R ^{7 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C 6-26-alkyl or alkenyl radical;

in the R independently of R ⁷ for a linear or branched, saturated or on 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 is -CH 3, and w and x independently represent values are between 1 and 32, with nonionic surfactants with R ³ = -CH ³ and values for w of 15 to 32 and x of 0 and 2 (in the case of mixtures of such products also numerical values between 0 and 2) being very particularly preferred.

According to a particular embodiment, in the case of the cleaning agent, in particular machine dishwashing detergent, in the liquid phase at least one, preferably at least two, in particular at least three of the components according to a) has a melting point (at 1 bar) of <30 ° C., preferably <25 ° C., in particular <20 ° C.

Thus, in particular, polyethylene glycols having an average molecular weight of from 180 to 600, and also nonionic surfactants of the general 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) zR ⁶ in which R is a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ -C 20 -alkyl or alkenyl radical; R ² , R ⁴ , R ⁶ each = -H; R ³ , R ⁵ = CH ₃ and the indices w, x, y, z independently represent integers from 1 to 6.

Preference may be given to one of the two or both o.g. Components with a melting point of <30 ° C, preferably <25 ° C, in particular <20 ° C (at 1 bar) additionally contain other components according to a), which have a higher melting point, in particular at least one of the above is particularly preferred said ethoxylated hydroxy mixed ethers.

According to a further particular embodiment, the cleaning agent, in particular machine dishwashing detergent in the liquid phase as one of the component according to a) at least one polyalkylene glycol, preferably at least one polyethylene glycol or at least one polypropylene glycol, in particular at least one polyethylene glycol, with a middle

Molecular weight between 180 and 6000, preferably 200 to 5000, in particular between 300 and 4000 is included.

It is particularly preferred if a component according to a) at least one

Polyalkylene glycol, preferably at least one polyethylene glycol, which is a middle

Molecular weight between 300 and 600 g / mol.

Furthermore, it is particularly preferred if the liquid phase (at least one of the liquid phases, preferably the liquid phases) is a component according to a) at least one further polyalkylene glycol, preferably at least one polyethylene glycol (PEG), which has an average molecular weight between 2000 and 6000 g / mol, preferably an average molecular weight between 3500 to 4500, in particular about 4000, (INCI: PEG 4000).

It is particularly preferred if the liquid phase (s) comprises a PEG having an average molecular weight of about 400 (INCI: PEG 400) and a PEG having a middle molecular weight

Molecular weight of about 4000 (INCI: PEG 4000) have.

The liquid phase or the at least one liquid phase or the liquid phases of the cleaning agent according to the invention preferably additionally contain at least one nonionic surfactant, preferably one which also represents a component according to a) according to formula I.

According to a further, particularly preferred embodiment, in the liquid phase as one of the components according to a) 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) zR ⁶

 in which

 R is selected from straight-chain or branched, saturated Ce-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 = 1 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, included.

These components according to a) are particularly advantageous, as they may optionally provide a basis for the liquid phase in addition to the liquid polyalkylene glycols, without causing organic components, in particular organic solvents, which

average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, must be used.

 It is particularly preferred in this case if in addition to one of the preferred components according to a) as a further preferred component according to a) at least one polyalkylene glycol, preferably at least one polyethylene glycol having an average molecular weight between about 300 and about 5000, in particular approx 4000 g / mol is used.

In this case, it is furthermore particularly preferred if the liquid phase (at least one of the liquid phases, preferably the liquid phases) additionally contains as a further component according to a) at least one further polyalkylene glycol, preferably at least one polyethylene glycol (PEG) which has an average molecular weight between 2000 and 6000 g / mol, in particular a PEG having an average molecular weight between 3500 to 4500, in particular about 4000 has.

It is particularly preferred if the liquid phase (s) comprises a PEG having an average molecular weight of about 400 (INCI: PEG 400) and a PEG having a middle molecular weight

Molecular weight of about 4000 (INCI: PEG 4000) have. It is particularly preferred if, in addition to the abovementioned

Components used as further component according to a) is at least one ethoxylated hydroxy mixed ether of the 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) zR ⁶ With

 R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

R ² = H,

R ^{6 is} selected from -CH ₂ CH (OH) R ⁷

with R ⁷ for a straight-chain or branched, saturated or on or

 polyunsaturated C6-26 alkyl or alkenyl radical;

 and

 w = 1 to 120, preferably 10 to 80, in particular 20 to 40; and x, y, z = 0.

Particularly preferred are in particular the C 4-22 fatty alcohol (EO) io-8o-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) 4-oxyalkyl ethers. 8o-2-hydroxyalkyl ethers.

In all the aforementioned embodiments, in particular the particular

highlighted combinations, it is preferred that the amount of all the components mentioned in accordance with a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,

According to a particularly preferred embodiment, the liquid phase (at least one of the liquid phase, if appropriate all liquid phases) in each case based on the respective

Total weight of (single) liquid phase:

0-40% by weight of at least one component a) 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) zR ^e where

 R is selected from straight-chain or branched, saturated Ce-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 = 1 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, is contained,

0-40% by weight of at least one ethoxylated hydroxy mixed ether of the 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) zR ⁶ with

 R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

o R ² = H,

o R ^{6 is} selected from -CH ₂ CH (OH) R ⁷

with R ⁷ for a straight-chain or branched, saturated or on or

 polyunsaturated C6-26 alkyl or alkenyl radical; and

 w = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0. and

 0-50% by weight of polyalkylene glycols;

It is preferred that the amount of all of the components referred to as preferred according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,

According to a particularly preferred embodiment, the liquid phase (at least one of the liquid phase, if appropriate all liquid phases) in each case based on the respective

Total weight of (single) liquid phase:

5 to 30% by weight of at least one component a) 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) zR ⁶ where

 R is selected from straight-chain or branched, saturated Ce-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 = 1 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, is contained,

5 to 30% by weight of at least one ethoxylated hydroxy mixed ether of the 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) zR ⁶ with o R for a linear or branched hydrocarbon radical with 2 to

 26 carbon atoms;

o R ² = H,

o R ^{6 is} selected from -CH ₂ CH (OH) R ⁷

with R ⁷ for a straight-chain or branched, saturated or on or

 polyunsaturated C6-26 alkyl or alkenyl radical; and

 w = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0. and

 5-40% by weight of polyalkylene glycols;

It is preferred that the amount of all of the components referred to as preferred according to a) in the liquid phase is between 15 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,

According to a particularly preferred embodiment, the liquid phase (at least one of the liquid phase, if appropriate all liquid phases) in each case based on the respective

Total weight of (single) liquid phase:

5 to 30% by weight of at least one component a) 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) zR ⁶ where

 R is selected from straight-chain or branched, saturated Ce-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 = 1 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, is contained,

5 to 30% by weight of at least one ethoxylated hydroxy mixed ether of the 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) zR ⁶ with

 R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

o R ² = H,

o R ^{6 is} selected from -CH ₂ CH (OH) R ⁷ with R ⁷ for a straight-chain or branched, saturated or on or

 polyunsaturated C6-26 alkyl or alkenyl radical; and

 w = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0. and

 5-30 wt.% Polyethylene glycols having an average molecular weight between 300 and 600 g / mol and

 1 -20 wt .-% polyethylene glycols having a molecular weight between 2000 and 6000

g / mol, comprising.

It is preferred that the amount of all of the components referred to as preferred according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,

In this case, it is preferred that the amount of all components mentioned as being preferred according to a) in the liquid phase is between 10 to 80% by weight, preferably between 20 and 70% by weight (in each case based on the total weight of the liquid phase) ,

According to a further embodiment, in the liquid phase (the liquid phases) additionally a end-capped nonionic surfactant according to formula I I

R ⁸ 0 [CH ₂ CH (R ⁹ ) O] h [CH ₂ ] kCH (OH) [CH 2] jOR °,

be contained, in particular poly (oxyalkylated) nonionic surfactants of the formula I I

in which R ⁸ and R ^{0 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{9 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, h are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value h> 2, then any R ⁹ in the formula above can

R ⁸ 0 [CH ₂ CH (R ⁹ ) 0] h [CH ₂ ] kCH (OH) [CH 2] jOR ° be different. R ⁸ and R ⁰ 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 ⁹ , H, -Chta or -CH 2 CH 3 are particularly preferred. Particularly preferred values for h are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ⁹ in the above formula may be different if h> 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when h is 3, the radical R ⁹ can be selected to form ethylene oxide (R ⁹ = H) or propylene oxide (R ⁹ = CH 3) units which may be joined together 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 h has been chosen here as an example and may be larger, with the range of variation increasing with increasing h values and including, for example, a large number of (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 ⁸ 0 [CH ₂ CH (R ⁹ ) 0] hCH ₂ CH (OH) CH ₂ OR ° simplified. In the latter formula, R ⁸ , R ⁰ and R ^{9 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and especially from 6 to 18. Particularly preferred are surfactants in which the radicals R ⁸ and R ^{0 have} 9 to 14 C atoms, R ^{9 is} H and h assumes values of 6 to 15.

According to a further preferred embodiment, the amount of all components according to a) in the liquid phase is between 10 and 80% by weight, preferably between 20 and 70% by weight (in each case based on the total weight of the liquid phase).

The ratio of the weight of one or more solid phases (of which preferably at least one solid phase is powdery, (in the case of several solid / powder phases the total weight of all solid and powder phases) to the weight of one or more liquid phases (in the case of several liquid phases According to the invention, preferably from 1:10 to 10: 1, particularly preferably from 1: 5 to 5: 1, very particularly preferably from 4: 1 to 1: 2.

According to a preferred embodiment, the cleaning agent, in particular

Machine dishwashing detergents, essentially free of anionic surfactants,

Substantially free of anionic surfactants as used herein means that a composition is less than 7% by weight, preferably less than 5% by weight, more preferably less than 3% by weight, most preferably less than 1% by weight. -%, particularly preferably less than 0.1 wt .-% anionic surfactant (based on the total weight of the composition). This preferably applies to all, in particular also the combinations according to the invention explicitly mentioned as preferred above.

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

Contains polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.

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

Molecular weight in the range of 10,000 to 1,000,000 gmol ^"1 , preferably from 20,000 to 500,000 gmol, 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 coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

In addition, a polymer selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath

(Meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added. A preferred additional polymer is polylactic acids.

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

Mixtures thereof, with itaconic acid being preferred.

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

It may be preferred that the film material contains further additives. The film material may 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 casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

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

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

According to a preferred embodiment, the pre-portioned cleaning agent used according to the invention, in particular machine dishwashing detergent, is essentially free of phosphates. This preferably applies to all, in particular also the combinations according to the invention explicitly mentioned as preferred above.

Substantially free of phosphates means that the total cleaning agent resulting from the addition of all phases (or all ingredients of all compartments) is preferably substantially free of phosphate-containing components. As phosphates or too

Phosphate-containing components in the context of the present invention are, in particular, phosphates, polyphosphates and pyrophosphates. However, phosphonates or hexafluorophosphate are not covered by this term. The total detergent thus contains less than 1% by weight, preferably 0.5% by weight, of phosphates, based on the total weight of the detergent (i.e., the total weight of all phases (i.e., all liquid and solid phases).

The detergents used according to the invention, in particular machine dishwashing detergents, contain builders, such as zeolites, silicates, carbonates, in particular the

Alkali carbonates, for example sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, and organic cobuilders. When silicates are, in particular crystalline layered silicates of general formula NaMSix02x + i ^■ y H2O 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 being 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 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.

In preferred cleaning agents, the content of silicates, based on the total weight of the cleaning agent, to amounts below 10 wt .-%, preferably below 5 wt .-%.

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.

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. The polyacrylate or the polyacrylates are used here in particular in a dried, more preferably in a dried and granulated (solid) form, which optionally may additionally be ground.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of about 1000 to 20,000, in particular 2,000 to 20,000 g / mol. Because of their superior solubility, this group can again be the short chain polyacrylates, the molecular weights of 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, be preferred.

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. 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. As Aminoalkanphosphonate are preferably

Ethylenediaminetetramethylenephosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. Phosphonate-containing components 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.

With respect to the proportion of the phosphonate unit (independently of the hydroxyalkane and / or

Aminoalkan portion) contain the compositions according to the invention from 0.01 to 25% by weight, preferably 5 to 20 wt .-%, 8 to 15 wt .-% phosphonate (each based on the

Total weight of the agent). According to the invention, the phosphonates are preferably contained in the solid phase (s).

The cleaning agents used according to the invention may further comprise a sulfopolymer. The proportion by weight of the sulfopolymer in the total weight of the cleaning agent used 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 .-%, most preferably 2.0 to 14 wt .-%, in particular from 4 to 14 wt .-%, especially from 4.5 to 12 wt .-%. The sulfopolymer is used here in particular in a dried, particularly preferably in a dried and granulated (solid) form, which optionally may additionally be ground.

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 (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another represent -H, -CH 3, a straight-chain or branched one 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 -NH 2, -OH or -COOH substituted alkyl or alkenyl radicals as defined above or for -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, alpha-chloroacrylic acid, alpha-cyanoacrylic acid, crotonic acid, alpha-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 - 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

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 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-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 molecular weights of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol and in particular from 5000 to 15,000 gmol ^-1 .

In another preferred embodiment, the copolymers include besides

Carboxyl-containing monomer and sulfonic acid-containing monomer further at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.

Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention. 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 1 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, ethylcyclohexyne, 1-octene, alpha-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22 alpha-olefin, 2-styrene, alpha 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) acry lamid,

Octyl acrylate, octyl acrylate, A / - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, A / - (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, A / - (stearyl) acrylamide, behenyl acrylate, Behenyl methacrylate and N- (behenyl) acrylamide or their mixtures.

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 various embodiments, the pH of an aqueous solution at 20 °, containing 10 wt .-% of the total cleaning agent, in a range of 7 to 14, in particular greater than 7, in particular in a range of 8 to 13, preferably 9 to 12 ,

The agents used according to the invention preferably contain at least one further constituent, preferably selected from the group consisting of cationic and amorphous 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 detergents, preferably dishwashing detergents, in particular machine

Dishwashing agents can also be used bleaching agents. Among the compounds which serve as bleaching agents in water H2O2, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. It is also possible to use all other inorganic or organic agents known to the person skilled in the art

Peroxy.

As a bleaching agent and chlorine or bromine releasing substances can be used. Examples of suitable chlorine or bromine releasing materials

heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid,

Tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

There are cleaning agents, preferably dishwashing detergents, in particular machine

Dishwashing agents which contain 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 25% by weight, very particularly preferably 4.0 to 20% by weight and in particular 5 to 18% by weight (based on the total weight of the cleaning agent) of bleaching agent, preferably sodium percarbonate.

Furthermore, the cleaning agents, preferably dishwashing detergents, in particular automatic dishwashing detergents, may contain bleach catalysts. Useful bleach catalysts include, but are not limited to, the group of bleach-enhancing transition metal salts and transition metal complexes, preferably Mn, Fe, Co, Ru or Mo complexes, more preferably from the group of manganese and / or cobalt salts and / or or complexes, in particular the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, the manganese sulfate and the complexes of manganese with 1, 4,7- trimethyl-1, 4,7-triazacyclononane (Mm-TACN) or 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane (Mm-TACN). Preference is given to detergents, preferably dishwashing agents, in particular automatic dishwasher detergents which contain from 0.001 to 1% by weight, preferably from 0.01 to 0.1% by weight (based in each case on the total weight of the cleaning agent) of bleach catalyst, preferably a Mn complex. in particular a complex of the manganese with 1, 4,7-trimethyl-1, 4,7-triazacyclononane (Mm-TACN) or 1, 2,4,7-tetramethyl-1, 4,7-tri-azacyclononane (Mm-TACN ), contain.

In various embodiments of the invention, the cleaning agents, preferably dishwashing agents, in particular automatic dishwasher detergents, additionally comprise at least one bleach activator. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. All of the bleach activators known to the person skilled in the art are acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT) Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used. Combinations of conventional bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight, based in each case on the total weight of the detergents used.

The bleaching agent and also bleach catalysts and / or bleach activators are preferably contained in the solid phase (s).

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ⁾ (R ^iv) (R ^v) N ⁺ CH2COO ^_ in which R ⁱ is an optionally interrupted by hetero atoms or hetero atom groups alkyl radical 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 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. 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.

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 used according to the invention preferably contain enzymes in total amounts of from 1 × 10 ^-6 to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

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

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and 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, 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 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. 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, more preferably between 0.4 and 20% by weight 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.

The enzymes, in particular the amylase (s) and / or protease (s), are preferably present in (one) of the solid phase (s), preferably as granules or granules.

Glass corrosion inhibitors used are metal salts, in particular zinc salts or bismuth salts, preferably zinc salts, in particular zinc acetate. Also preferred as glass corrosion inhibitors are polyethyleneimines and polyvinylamines, for example those obtainable under the name Lupasol® or Lupamin® from BASF, in particular nonalkoxylated

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

A further subject of the present invention is also a machine dishwashing process in which a cleaning agent according to the invention is used.

In yet another aspect, the invention also relates to the use of the cleaning agent according to the invention as a dishwashing detergent, in particular machine

Dishwashing liquid. Example:

 Surprisingly, it has been found that a liquid phase of the type mentioned can be stabilized by a specific amount of the builder MGDA, so that it shows no phase separation.

Table 1: liquid substantially anhydrous detergent component

Comparative formulation V1 shows visible phase separation on storage at 40 ° C., 1 bar within 4 weeks, while example E1 according to the invention had no visible phase separation under these conditions.

Also suitable is the following liquid formulation according to Tab. 2.

Table 2: liquid substantially anhydrous detergent component

 E2

 PEG 400 (Mr = about 400) 20

 PEG 4000 (Mr = approx. 4000) 6

 C10 - C14 fatty alcohol alkoxylate (10 EO + PO) 16

 Cio -Ci4 end caps locked Cs-do 20

 Fatty alcohol ethoxylate (18-30 EO)

 Methylglycinediacetic acid 5

 Sulfopolymer, (partially neutralized) Na salt 22

 Polyacrylate, Na salt 8

 Perfume, dye, auxiliaries, 3

 Total 100

Claims

claims 1. Use of at least one aminocarboxylic acid for the stabilization of  low in water, preferably of essentially anhydrous liquid washing or cleaning agent components. 2. Use according to claim 1, characterized in that the aminocarboxylic acid is selected from the group GLDA and MGDA, preferably MGDA. 3. Use according to one of the preceding claims, characterized in that the aminocarboxylic acid in amounts of 2 to 25 wt .-%, in particular from 3 to 15 wt .-%, preferably from 4 to 10 wt .-% (based on the weight the liquid detergent or cleaner component) is contained. 4. Use according to one of the preceding claims, characterized in that the water-poor, preferably substantially anhydrous liquid washing or  Detergent component is substantially free of phosphate. 5. Use according to one of the preceding claims, characterized in that the water-poor, preferably substantially anhydrous liquid washing or  Detergent component one or more nonionic surfactants in an amount of 15 to 60 wt .-%, preferably 20 to 50 wt .-%, in particular 30 to 40 wt .-% (based on the weight of the liquid detergent or cleaning agent component).