DE102014202221A1 - Multi-phase pre-portioned detergent - Google Patents

Abstract

The present invention relates to pre-portioned multi-phase detergents, in particular automatic dishwashing detergents and their use.

Description

The present invention relates to pre-portioned multi-phase detergents, in particular automatic dishwashing detergents and their use.

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

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.

Further, consumers have become accustomed to conveniently dosing pre-portioned automatic dishwashing detergents and have been using these products primarily in the form of tablets. In order to bring a multi-phase dishwashing detergent, which combines the above-mentioned advantages of solid and liquid compositions, into a pre-portioned form, the use of water-soluble films in the form of bags or multi-chamber shaped bodies lends itself.

Disposable portions, in particular water-soluble bags or multi-chamber tablets made of water-soluble material, 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 may be caused, for example, by ingredients migrating between the various chambers (compartments) during the usual household storage period, especially when the different phases of the pre-portioned detergent present in a water-soluble package having a plurality of separate compartments , In particular, it often happens that the solid phase from the liquid phase absorbs solvent or migrating liquid components.

 In the case of a solid phase, in particular in the case of a pulverulent phase, this often leads to clumping visible to the consumer, which no longer offers appealing optics and / or can change the dissolution behavior of the solid, in particular pulverulent, phase during use. In compressed, in particular pressed, for example, tableted solid phases, the compressed phase may be dissolved by the liquid components of the other phase, resulting in unsightly optics, e.g. also color changes, leads.

Accordingly, the liquid phase loses volume in the mentioned migration processes, even if the pre-portioned detergents are stored in a sealed outer packaging. This volume loss is visually so clearly visible for longer storage times that the consumer can perceive this. Frequently, the consumer concludes from such observed loss of volume on a leakage of the detergent molding or at least on a deterioration in the function of the detergent itself.

The object of the present invention was therefore to provide a pre-portioned multiphase cleaning agent which is stable in form and storage and in which there is no appreciable migration of components between the various chambers.

• a) mindestens eine, bevorzugt zwei, drei, vier oder mehr alkoxylierte Komponenten gemäß Formel I enthält R¹-O-(CH₂-CH(R²)-O)_w-(CH₂-CH(R³)-O)_x-(CH₂-CH(R⁴)-O)_y-(CH₂-CH(R⁵)-O)_z-R⁶ (Formel I) wobei R¹ ausgewählt ist aus -H, -CH₃, geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten,C_2-24-Alkyl- oder -Alkenylrest steht; R², R³, R⁴, R⁵, jeweils unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, CH(CH₃)₂, vorzugsweise -H oder -CH₃; R⁶ ausgewählt ist aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂, -CH₂-CH₂-CH₂CH₃, -CH₂CH(CH₃)₂, -C(CH₃)₃, C_5-24-Alkyl- oder -Alkenyl, sowie -CH₂CH(OH)R⁷ mit R⁷ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-26-Alkyl- oder -Alkenylrest; und w, x, y, z jeweils unabhängig voneinander Werte von 1 bis 120 annehmen können und wobei x, y und/oder z = 0 sein können,
• b) im wesentlichen frei von organischen Komponenten, welche ein durchschnittliches Molekulargewicht von kleiner 175 g/mol, bevorzugt von kleiner als 150 g/mol aufweisen, ist; und
• c) im wesentlichen frei von Wasser ist.

The object was achieved by a pre-portioned detergent, preferably machine dishwashing detergent, in a water-soluble packaging having at least two compartments, comprising at least one solid, preferably pulverulent phase and at least one liquid phase,
characterized in that the liquid phase (or the liquid phases)

• a) contains at least one, preferably two, three, four or more alkoxylated components according to formula I. R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ (Formula I) wherein R ^{1 is} selected from -H, -CH ₃ , straight-chain or branched, saturated or mono- or polyunsaturated, C _2-24 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 , C _5-24 alkyl or alkenyl, and -CH ₂ CH (OH) R ⁷ with R ^{7 is} a straight-chain or branched, saturated or on 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,
• b) substantially free of organic components having an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol; and
• c) is substantially free 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. Contains% water. The water content as defined herein refers to the water content determined by Karl Fischer titration.

According to the invention, the liquid phase according to c) is "substantially free of water", this means that the liquid phase is less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, particularly preferred contains less than 1% by weight of water. 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 detergent of the invention are "substantially free of water", i. each of the individual phases contains in each case less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, particularly preferably less than 1% by weight of 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 present invention includes all flowable compositions and, in particular, also encompasses gels and pasty compositions. In particular, the term also includes non-Newtonian fluids having a yield point.

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

"Solid" as used herein with respect to the cleaning composition of the invention includes all solid compositions, and includes in particular powdered, granulated, amorphous, compressed, in particular pressed, tabletted compositions.

The detergent is 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.

This is preferably a disposable portion, the cleaning agent is preferably present in a sufficient amount for performing the cleaning, in machine dishwashing detergents in particular a cycle or a complete program cycle of a 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 containing a solid and a liquid phase in separate compartments.

Particularly suitable are multichamber packaging which contains 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 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 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 wherein the water soluble package contains one, two or more solid phase chambers in addition to one, two or more liquid 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 which have at least one solid, preferably at least one compressed phase and one liquid phase in separate 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, contains a solid, one of which is different powdery and two liquid phases in each separate compartments.

The at least one liquid phase in the cleaning agent according to the invention is essentially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol;

Essentially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, means that in the liquid phase (in the case of several liquid phases in each individual liquid phase) less than 5 Wt .-%, preferably less than 3 wt .-% of such organic compounds are contained, which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol.

In particular, according to the invention, the presence of usually short-chain organic solvents having an average molecular weight of less than 175 g / mol, such as dipropylene glycol dimethyl ether, preferably less than 150 g / mol, such as decane, octane, dipropylene glycols, glycerol, propanediols, monoethanolamine, diethanolamine be avoided, which are particularly prone to migration between the compartments.

In the (or the liquid phase (s)), said organic components, preferably organic solvents, which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, in each case only to a proportion of less be contained as 5 wt .-%, preferably of less than 3 wt .-% (each based on the composition of the individual liquid phase).

The total amount of the organic components contained in the liquid phase or the liquid phases, preferably organic solvents, which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, is at most 20 wt .-% (relative on the total weight of each liquid phase).

If the pre-portioned cleaning agent, in particular machine dishwashing detergent, comprises several liquid phases in separate compartments, it is very particularly preferred according to the invention for each of the liquid phases to be essentially free of organic components having an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol (except the components mentioned under a), since otherwise there is a migration of the components between the individual liquid phases in the separate compartments.

According to a preferred embodiment, the liquid phase (are the liquid phases) of the cleaning agent according to the invention, in particular machine dishwashing, substantially free of organic components having an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol and at 20 ° C and 1 bar are liquid.

The pre-portioned detergents according to the invention, in particular machine dishwashing detergents, 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 ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ (Formula I) in which
R ^{1 is} selected from -H, -CH ₃ , straight-chain or branched, saturated or mono- or polyunsaturated, C _2-24 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 , C _5-24 alkyl or alkenyl, and -CH ₂ CH (OH) R ⁷
R ^{7 is} 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 of formula (I) with R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ (Formula I) R ¹ , R ⁶ = H, R ² , R ³ , R ⁴ , R ⁵ , each independently selected from H, -CH ₃ , 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. Low-foaming alkoxylated nonionic surfactants, in particular ethoxylated, low-foaming nonionic surfactants, are preferably used with preference. In preferred embodiments, the automatic dishwashing agents contain nonionic surfactants from the group of alkoxylated alcohols.

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 ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ in which R ^{1 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 -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently stand for integers from 1 to 6.

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

• – R¹ für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• – R², R³, R⁴, R⁵, jeweils unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, CH(CH₃)₂, vorzugsweise -H oder -CH₃;
• – R⁶ ausgewählt ist aus -CH₂CH(OH)R⁷ mit R⁷ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-26-Alkyl- oder -Alkenylrest; und

w, x, y und z für Werte zwischen 1 und 120 stehen, wobei x, y und/oder z auch 0 sein können. Further preferred nonionic surfactants here are those of the general formula R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ With

• R ^{1 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 being} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-26 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 rinse performance of the preparations according to the invention can be significantly improved, both compared to surfactant-free system and compared to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols contain

• – R¹ für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• – R² = H,
• – R⁶ ausgewählt ist aus -CH₂CH(OH)R⁷ mit R⁷ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-26-Alkyl- oder -Alkenylrest; und
• – w = 1 bis 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40; und x, y, z = 0 ist.

Finally, the nonionic surfactants of general formula (I) have proven to be particularly effective. R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ With

• R ^{1 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 being} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-26 alkyl or alkenyl radical; and
• W = 1 to 120, preferably 10 to 80, in particular 20 to 40; and x, y, z = 0.

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

Also preferred are also surfactants of the formula (I) R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ wherein R ^{1 is} 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 numerical values between 1 and 2, eg 1.5) and x stands for a value of at least 15.

The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ - (EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2 -hydroxydecylether.

Preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula (I) R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ With y, z = 0 and R ² = H, R ⁶ = -CH ₂ CH (OH) R ⁷
R ^{7 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-26 alkyl or alkenyl radical;
in which R ¹ independently of R ^{7 is} a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably represents -CH ₃ , and w and x independently of one another represent values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values for w of 15 to 32 and x of 0.5 and 1.5 are very particularly preferred.

According to a particular embodiment, 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 ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-20 -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 above-mentioned components having a melting point of ≦ 30 ° C., preferably ≦ 25 ° C., in particular ≦ 20 ° C. (at 1 bar), in addition to other components according to a) which have a higher melting point , in particular at least one of the ethoxylated hydroxy mixed ethers mentioned above as being particularly preferred.

According to a particular embodiment, the cleaning agent, in particular machine dishwashing detergent in the liquid phase, as one of the components 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 an average molecular weight between 180 and 6000, preferably 200 to 5000, especially 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 has an average molecular weight between 300 and 600 g / mol.

Furthermore, it is particularly preferred if the liquid phase (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, in particular PEG 4000, having.

It is particularly preferred if the liquid phase (s) comprise a PEG having an average molecular weight of 400 and a PEG having an average molecular weight of 4000.

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

According to a particularly preferred embodiment, in the liquid phase as one of the components according to a) a component according to formula (I) R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ in which
R ^{1 is} selected from straight-chain or branched, saturated C _8-16 -alkyl radicals;
R ² and R ⁴ are -H, R ³ and R ⁵ are -CH ₃ ,
R ^{6 is} selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ -CH ₂ -CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ , C _5-20 alkyl (linear or branched), and are independently selected
w = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
x = 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 included.

These components according to a) are particularly advantageous because they may optionally provide a basis for the liquid phase in addition to the liquid polyalkylene glycols, without organic components, in particular organic solvents having an average molecular weight of less than 175 g / mol, preferably from 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 300 and 4000 g / mol, is used , Furthermore, it is particularly preferred if the liquid phase (the liquid phases) is additionally 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, in particular PEG 4000 , having.

• – R¹ für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• – R² = H,
• – R⁶ ausgewählt ist aus -CH₂CH(OH)R⁷ mit R⁷ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-26-Alkyl- oder -Alkenylrest; und
• – w = 1 bis 120, vorzugsweise 10 bis 80, insbesondere 15 bis 40; und x, y, z = 0 ist.

It is particularly preferred if the liquid phase (s) has a 400 molecular weight PEG and a 4000 molecular weight PEG. It is very particularly preferred if, in addition to the abovementioned components, use is made of at least one ethoxylated hydroxy mixed ether of the formula (I) as further component according to a) R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ With

• R ^{1 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 being} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-26 alkyl or alkenyl radical; and
• W = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0.

Particular preference is given in particular to the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ethers and the C _4-22 fatty alcohol (EO ) _40-80 -2-hydroxyalkyl ether. The combinations mentioned according to this particular embodiment can be used in an amount of

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 and 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 II R ⁸ O [CH ₂ CH (R ⁹ ) O] _h [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ¹⁰ , in particular poly (oxyalkylated) nonionic surfactants of the formula II in which R ⁸ and R ^{10 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, h for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5 stand. When the value h ≥ 2, each R ⁹ in the above formula R ⁸ O [CH ₂ CH (R ⁹ ) O] _h [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{10 may be} different. R ⁸ and R ¹⁰ 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 are H, -CH ₃ or - CH ₂ CH _{3 is} 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 x 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 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 by way of example and may well be greater, with the variation range increasing with increasing h values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1 such that the above formula is R ⁸ O [CH ₂ CH (R ⁹ ) O] _h CH ₂ CH (OH ) CH ₂ OR ¹⁰ simplified. In the latter formula, R ⁸ , R ¹⁰ 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 ^{10 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 to 80 wt .-%, preferably between 20 to 70 wt .-% (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 1:10 to 10: 1, particularly preferably 1: 5 to 5: 1, very particularly preferably 4: 1 to 1: 2.

In a preferred embodiment, the detergent, especially machine dishwashing detergent, is substantially free of anionic surfactants. Essentially free of anionic surfactants as used herein means that a composition is less than 7% by weight, preferably less than 5% by weight. , in particular less than 3 wt .-%, most preferably less than 1 wt .-%, particularly preferably less than 0.1 wt .-% anionic surfactant (based on the total weight of the composition).

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

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

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

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

In addition, a polymer selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above can be additionally used as a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating Be added polymers. A preferred additional polymer is polylactic acids.

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

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

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

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

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

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

According to a preferred embodiment, the pre-portioned detergent according to the invention, in particular machine dishwashing detergent, is substantially free of phosphates.

Substantially free of phosphates means that the total cleaning agent, which results from the addition of all phases (or all ingredients of all compartments), is preferably substantially free of phosphate-containing components. Phosphates or else 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 according to the invention, in particular machine dishwashing detergents, comprise builders, such as, for example, zeolites, silicates, carbonates, in particular the alkali metal carbonates, for example sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, and organic cobuilders.

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

In preferred cleaning agents, the content of silicates, based on the total weight of the cleaning agent, 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), if such use is not objectionable for ecological reasons, and mixtures thereof. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

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

Particularly preferred is the use of MGDA or GLDA, in particular MGDA, as granules. Particular preference is given to those MGDA granules which contain as little as possible water and / or in particular and have a low hygroscopicity.

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, particularly preferably in a dried and granulated (solid) form, which may optionally additionally be ground.

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. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. 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 regard to the proportion of the phosphonate unit (independently of the hydroxyalkane and / or aminoalkane portion), the compositions according to the invention contain from 0.01 to 25% by weight, preferably from 5 to 20% by weight, from 8 to 15% by weight. % Phosphonate (in each case based on the total weight of the composition). According to the invention, the phosphonates are preferably contained in the solid phase (s).

The cleaning agents of the invention may further contain a sulfopolymer. The proportion by weight of the sulfopolymer in the total weight of the cleaning agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1.0 to 15 wt .-%, in particular from 4 to 14 wt .-%, especially from 6 to 12 wt .-%. The sulfopolymer is used here in particular in a dried, particularly preferably in a dried and granulated (solid) form, this 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 not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.

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

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

Preferred among these monomers are those of the formulas H ₂ C = CH-X-SO ₃ H H ₂ C = C (CH ₃ ) -X-SO ₃ H HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, - C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

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

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

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

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

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

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

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

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexene, 1-octene, olefins having 10 or more carbon atoms, such as, for example, 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, acrylic acid pentyl ester, hexyl acrylate, methyl methacrylate, N-butyl (Methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, acrylic acid oct yl ester, octyl acrylate, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, methacrylic acid stearyl ester, N- (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and N- (behenyl) acrylamide or mixtures thereof.

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

In 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 compositions according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of cationic and amphoteric 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 automatic dishwashing detergents, bleaching agents can also be used. Among the compounds which serve as bleaches and deliver H ₂ O ₂ in water, the sodium percarbonate, the sodium perborate tetrahydrate and the Sodium perborate monohydrate particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. It is also possible to use all other inorganic or organic peroxy bleaches known to the person skilled in the art.

As a bleaching agent and chlorine or bromine releasing substances can be used. Among the suitable chlorine or bromine releasing materials are, for example, 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. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

Preference is given to detergents, preferably dishwashing agents, in particular automatic dishwasher detergents, which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight. % (based on the total weight of the cleaning agent) bleach, 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 (Mn ₃ -TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Mn ₄ -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 manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Mn ₃ -TACN) or 1,2,4,7-tetramethyl-1,4,7-tri-azacyclononane (Mn ₄ -TACN).

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. Of all the bleach activators known to the person skilled in the art, polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are acylated 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 from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 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 ⁺ CH ₂ COO ^- , in which R ^{iii is} an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R ^iv and R ^{v are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -Alkyldimethylcarboxymethylbetain and C ₁₁ -C ₁₇ -Alkylamidopropyl-dimethylcarboxymethylbetain.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^vi ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^- , in which R ^vi to R ^{ix are} four identical or different, in particular two long and two short-chain, alkyl radicals and X ^{- are} an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Further suitable cationic surfactants are the quaternary surface-active compounds, in particular 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.

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

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

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

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

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

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

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

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

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

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

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

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

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.

The glass corrosion inhibitors used are 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 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.

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 automatic dishwashing detergent.

embodiments

There were prepared the detergent formulation according to the invention with a solid phase according to Table 1 and a liquid phase according to Table 2, E1 and a comparative formulation V1 with a solid phase according to Table 1 and a liquid phase according to Table 2, V1. The amounts indicated in the tables are in% by weight of active substance. 15 g each of the solid phase were each sealed in a first bag of polyvinyl alcohol and 5 g each of the liquid phase (E1 or V1) were sealed in each second bag of polyvinyl alcohol. Table 1: Formulation of the solid phase Fixed phase Sodium carbonate peroxyhydrate 20 Sodium citrate dihydrate 18 Sodium carbonate (anhydrous) 20 Methylglycinediacetic acid, sodium salt 18 Bleach catalyst (containing MnTACN) 2.5 Bleach activator (TAED) 2.5 Enzyme preparation (amylase, protease) 4 Perfume, dye, auxiliaries 5 HEDP 10 total quantity 100 Table 2: Formulations of the liquid phases E1 V1 PEG 400 (Mr = 400) 20 - PEG 4000 (Mr = 4000) 6 - C ₁₀ -C ₁₄ fatty alcohol alkoxylate (10 EO + PO) 17 - C ₁₀ -C _{14 end} caps capped C ₈ -C ₁₀ fatty alcohol ethoxylate (18-30 EO) 20 - glycerin - 25 1,2-propylene glycol - 18 water - 20 methylglycine 4 4 Sulfopolymer, (partially neutralized) Na salt 24 24 Polyacrylate, Na salt 8th 8th Perfume, dye, auxiliaries, 1 1 total quantity 100 100

The pre-portioned detergent according to the invention (liquid phase = E1) exhibited a good stability and a weight loss of less than 5% by weight of the liquid phase (based on the initial weight of the liquid phase) with closed outer packaging (glass container) after a storage time of 2 weeks at 25 ° C. ).

The other pre-portioned detergent (Comparative Example, liquid phase = V1) showed a weight loss of the liquid phase of 20% by weight when the packaging was closed after a storage time of 2 weeks at 25 ° C. The chamber containing the solid phase was significantly more filled, gravimetric weight gain equivalent to weight loss of the fluid chamber was observed.

Claims (13)

Preportioned detergent, preferably machine dishwashing detergent, in a water-soluble packaging with at least two compartments, comprising at least one solid, preferably pulverulent phase and at least one liquid phase, characterized in that the liquid phase (or liquid phases) a) at least one, preferably two , three, four or more alkoxylated components according to formula I. R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ (Formula I) wherein R ^{1 is} selected from -H, -CH ₃ , straight-chain or branched, saturated or mono- or polyunsaturated, C _2-24 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 , C _5-24 alkyl or alkenyl, and -CH ₂ CH (OH) R ⁷ with R ^{7 is} a straight-chain or branched, saturated or on 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 can be 0, b) essentially free of organic components which have an average molecular weight of less than 175 g / mol , preferably of less than 150 g / mol, is; and c) is substantially free of water. Detergent according to claim 1, characterized in that in the liquid phase at least one, preferably several, in particular all of the components according to a) a melting point (at 1 bar) of ≤ 30 ° C, preferably ≤ 25 ° C, in particular ≤ 20 ° C. exhibit. Cleaning agent according to one of the preceding claims, characterized in that 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, having an average molecular weight between 160 and 6000, is preferred 200 to 5000, in particular between 300 and 4000 is included. Cleaning agent according to one of the preceding claims, characterized in that in the liquid phase as one of the component according to a) a component according to formula (I) wherein R ^{1 is} selected from straight-chain or branched, saturated C _8-16 -alkyl radicals; R ² and R ⁴ are -H, R ³ and R ⁵ are -CH ₃ , R ^{6 is} selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ -CH ₂ -CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ , C _5-20 alkyl (linear or branched), and independently selected w = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3; x = 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 included. Cleaning agent according to one of the preceding claims, characterized in that in the liquid phase as one of the component according to a) at least one end-capped nonionic surfactant according to formula I. R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ with - R ^{1 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 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-26 alkyl or alkenyl radical; and w = 1 to 120, preferably 10 to 80, in particular 20 to 40; and x, y, z = 0 is included. Cleaning agent according to one of the preceding claims, characterized in that the amount of all components according to a) in the liquid phase between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) is. Cleaning agent according to one of the preceding claims, characterized in that the organic components according to b) are liquid at 20 ° C and 1 bar. Cleaning agent according to one of the preceding claims, characterized in that the cleaning agent is preferably substantially free of phosphates. Cleaning agent according to one of the preceding claims, characterized in that the cleaning agent preferably phosphonate (based on the proportion of phosphonate) in amounts of 0.01 to 25 wt .-%, preferably 5 to 20 wt .-%, 8 to 15 wt .-% phosphonate (in each case based on the total weight of the composition). Cleaning agent according to one of the preceding claims, characterized in that it is a multi-chamber package, preferably a multi-chamber bag, in particular with two, three, four or more chambers, is. Cleaning agent according to one of the preceding claims, characterized in that it is a water-soluble or packaging of a polyvinyl alcohol or polyvinyl alcohol copolymer-containing film.  Use of a cleaning agent according to one of the preceding claims 1 to 11 in a cleaning process in a machine dishwasher. Process for the cleaning of dishes, preferably in a machine dishwasher, characterized in that a cleaning agent according to one of claims 1 to 11 is used.