Multi-phase pre-portioned cleaning agent

Abstract

The invention relates to pre-portioned multi-phase cleaning agents, in particular dishwasher detergents in a water-soluble packaging having at least two compartments, comprising at least one solid, preferably powder phase and at least one liquid phase, characterized in that the liquid phase (or the liquid phases) a) contains at least one alkoxylated component, preferably two, three, four, or more alkoxylated components, according to formula 1, R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2- CH(R5)-O)z-R6, R1 being selected from -H, -CH3, straight-chain or branched, saturated or mono- or polyunsaturated, C2-24 alkyl group or alkenyl group; R2, R3, R4, and R5 being selected independently of each other from -H, -CH3, -CH2CH3, -CH2CH2CH3, CH(CH3)2, preferably -H or - CH3; R6 being selected from -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2-CH2-CH2CH3, -CH2CH(CH3)2, -C(CH3)3, C5-24 alkyl or alkenyl, and -CH2CH(OH)R7, R7 being a straight-chain or branched, saturated or mono- or polyunsaturated C6-26 alkyl group or alkenyl group; and w, x, y, and z being able to assume values from 1 to 120 independently of each other and x, y, and / or z being able to equal 0, b) is substantially free of organic components that have an average molecular weight of less than 175 g / mol, preferably of less than 150 g / mol; and c) is substantially free of water. The invention further relates to the use of said cleaning agents.

Description

[0001] The present invention relates to pre-portioned multi-phase cleaning agents, in particular automatic dishwashing detergents, and their use.

[0002] Cleaning agents for hard surfaces, such as dishwashing detergents, are available to consumers in a wide variety of forms. In addition to traditional solid detergents, free-flowing and especially liquid to gel-like cleaning agents have recently gained increasing importance. Consumers particularly value the rapid solubility and the resulting rapid availability of the ingredients in the cleaning solution, especially in short dishwashing cycles and at low temperatures.

[0003] The importance of concentrated formulations, in particular those with a reduced water content compared to conventional formulations, is increasing. For consumers, formulations with the lowest possible water content are therefore particularly desirable.

[0004] Furthermore, consumers have become accustomed to the convenient dosing of pre-portioned dishwasher detergents and have so far primarily used these products in tablet form. To offer a multi-phase dishwashing detergent, which combines the aforementioned advantages of solid and liquid formulations, in a pre-portioned form, the use of water-soluble films in the form of pouches or multi-chamber molded articles, particularly those made of water-soluble material, such as PVA containers, manufactured by injection molding, is a suitable option.

[0005] Single-serve packages, especially water-soluble pouches or multi-chamber molded containers made of water-soluble material, are enjoying increasing popularity among consumers not only because they eliminate contact with the chemical composition, but also because of their attractive appearance. Therefore, it is a nuisance for consumers when the pouches lose their attractive appearance.

[0006] This can be caused, for example, by ingredients migrating between the different compartments during the usual storage period of the product in the home, especially when the different phases of the pre-portioned cleaning product, which are contained in a water-soluble package with several separate compartments, migrate between the different compartments. In particular, it often occurs that the solid phase absorbs solvents or migrating liquid components from the liquid phase.

[0007] In the case of a solid phase, especially a powdered phase, this often leads to clumping visible to the consumer, which no longer offers an appealing appearance and / or can alter the dissolving behavior of the solid, especially powdered, phase during use. In the case of compressed, especially pressed, such as tabletted, solid phases, the liquid ingredients of the other phase can dissolve the compressed phase, resulting in an unsightly appearance and, for example, discoloration.

[0008] Accordingly, the liquid phase loses volume during the aforementioned migration processes, even if the pre-portioned cleaning agents are stored in a sealed outer package. This volume loss is so noticeable over longer storage periods that the consumer can detect it. Consumers often conclude from such an observed volume loss that the pouch or detergent tablet is leaking, or at least that the detergent itself is deteriorating in function.

[0009] The object of the present invention was therefore to provide a pre-portioned multi-phase cleaning agent which is dimensionally and storage-stable and in which no significant migration of components between the different chambers occurs.

[0010] The object was achieved by a pre-portioned cleaning agent, preferably machine dishwashing detergent, in a water-soluble package with at least two compartments, comprising at least one solid, preferably powdered phase and at least one liquid phase, characterized in that the liquid phase (or the liquid phases) a) at least one, preferably two, three, four or more alkoxylated components according to formula I contains R 1< -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) where 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 mono- or di-alkyl group.polyunsaturated C 6-26 alkyl or alkenyl radical; and w, x, y, z can each independently assume values ​​from 1 to 120 and where x, y and / or z can be =0, b) contains less than 5 wt.% of those organic compounds which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol; and c) contains less than 7 wt.% water, . wherein the pH of an aqueous solution at 20°C, containing 10% by weight of the total cleaning agent, is in a range from 7 to 14, in particular greater than 7, in particular in a range from 8 to 13, preferably from 9 to 12, and 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 160 and 6000 is contained.

[0011] "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, and most preferably less than 1% by weight of water. The water content as defined herein refers to the water content determined by Karl Fischer titration.

[0012] According to the invention, the liquid phase according to c) is "essentially free of water," meaning that the liquid phase contains less than 7 wt.%, in particular less than 5 wt.%, preferably less than 3 wt.%, particularly preferably less than 1 wt.% water. The water content, as defined herein, refers to the water content determined by Karl Fischer titration.

[0013] In particular, all liquid phases and all solid phases of the cleaning agent according to the invention are "essentially 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, particularly preferably less than 1% by weight of water (in each case based on the total weight of the respective phase).

[0014] "Liquid," as used herein in relation to the cleaning agent according to the invention, includes all flowable compositions, and in particular also encompasses gels and pasty compositions. In particular, the term also includes non-Newtonian liquids that have a yield point.

[0015] "At least one" as used herein means 1 or more, for example 1, 2, 3, 4, 5, or more.

[0016] "Solid," as used herein in relation to the cleaning agent according to the invention, includes all solid compositions and in particular encompasses powdered, granulated, amorphous, compressed, especially pressed, and tabletted compositions. Powdered compositions may also contain granules in addition to powdered components. The cleaning agent according to the invention is presented in a water-soluble package. The water-soluble packaging allows for portioning of the cleaning agent. The amount of cleaning agent in the portion pack is preferably 5 to 50 g, particularly preferably 10 to 30 g, especially 15 to 25 g.

[0017] This is preferably a single portion, and the cleaning agent is preferably present in a sufficient quantity to carry out the cleaning, in the case of machine dishwashing detergents, in particular one cycle or one complete program run of a dishwasher.

[0018] The water-soluble packaging has at least two or more spatially separated compartments (chambers) into which at least one solid, preferably powdery, and at least one liquid phase are filled in a spatially separated manner.

[0019] Particularly suitable are two-chamber bags or two-chamber molded bodies that contain a solid and a liquid phase in separate compartments.

[0020] Furthermore, multi-chamber packaging (multi-chamber bags or multi-chamber molded bodies) are particularly suitable, which contain a powdered phase in at least one of the separate compartments and a liquid phase in at least one other compartment. The "phase" here is understood to be a cleaning agent (partial) composition, which, in combination with the other phase(s), results in a cleaning agent, in particular a dishwasher detergent.

[0021] The cleaning agent according to the invention, in particular automatic dishwashing detergent, can also be present in a water-soluble package which in particular contains more than two, for example three, four, five or six compartments.

[0022] The packaging preferably contains three or more chambers (compartments), wherein one, two or more of these chambers are filled with liquid phases which are preferably different from one another and in particular have one or more ingredients which are different from one another.

[0023] Preferred are pre-portioned cleaning agents in which the water-soluble package contains, in addition to one, two, or more liquid phases, one, two, or more compartments with solid phases. If two or more solid phases are provided, it is preferred that they have a different composition and / or a different solid form.

[0024] According to the invention, pre-portioned cleaning agents have at least one solid phase, preferably at least one powdered phase, and at least one liquid phase in separate compartments.

[0025] According to the invention, pre-portioned cleaning agents have at least one solid phase, preferably at least one compressed phase, and a liquid phase in separate compartments.

[0026] It may also be preferred that the pre-portioned cleaning agent comprises two or more solid phases, of which at least one is powdered and at least one is compressed and at least one, also two, three or more liquid phases in separate compartments.

[0027] It is further preferred that the pre-portioned cleaning agent, in particular the multi-chamber bag, contains a solid phase, a different powder phase and two liquid phases in separate compartments.

[0028] The at least one liquid phase in the cleaning agent according to the invention is substantially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol; Substantially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, means that the liquid phase (in the case of several liquid phases, in each individual liquid phase) contains in each case less than 5% by weight, preferably less than 3% by weight, of such organic compounds which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol.

[0029] In particular, according to the invention, the presence of usually short-chain organic solvents which have 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, which have a particularly strong tendency to migrate between the compartments, should be avoided.

[0030] In the liquid phase(s), the above-mentioned organic components, preferably organic solvents, which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, should each be present in a proportion of less than 5 wt.%, preferably less than 3 wt.% (in each case based on the composition of the individual liquid phase).

[0031] If the pre-portioned cleaning agent, in particular automatic dishwashing detergent, comprises a plurality of liquid phases in separate compartments, it is very particularly preferred according to the invention that each of the liquid phases is substantially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol (except for the components mentioned under a), since otherwise migration of the components between the individual liquid phases in the separate compartments occurs.

[0032] According to a preferred embodiment, the liquid phase (are the liquid phases) of the cleaning agent according to the invention, in particular machine dishwashing detergent, is substantially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol and are liquid at 20 °C and 1 bar.

[0033] The pre-portioned cleaning agents according to the invention, in particular automatic dishwashing detergents, contain 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< -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) where 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< representing 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 assume values ​​from 1 to 120 and where x, y and / or z can be =0,

[0034] The liquid phase or the liquid phases of the cleaning agents according to the invention contain at least one component according to a).

[0035] The liquid phase or the liquid phases of the cleaning agents according to the invention preferably contain or contain at least one component according to a), which is selected from the polyalkylene glycols according to formula (I) with R 1< -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) R1, R6=H, R 2< , R 3< , R 4< , R 5< , each independently selected from H, -CH 3 , and w, x, y, z= 1 to 50.

[0036] A large proportion of nonionic surfactants are also included in the above-mentioned formula (I). Low-foaming alkoxylated nonionic surfactants, especially ethoxylated low-foaming nonionic surfactants, are preferred. In preferred embodiments, the automatic dishwashing detergents contain nonionic surfactants from the group of alkoxylated alcohols.

[0037] Preferred surfactants come from the group of alkoxylated nonionic surfactants, especially ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

[0038] Particularly preferred nonionic surfactants are low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, surfactants with EO-AO-EO-AO blocks are preferred, wherein one to ten EO or AO groups are bonded to one another before a block composed of the other groups follows. Nonionic surfactants of the general formula (I) R1<-O-(CH2-CH(R2<)-O)w-(CH2-CH(R3<)-O)x-(CH2-CH(R4<)-O)y-(CH2-CH(R5<)-O)z-R6< are preferred, in which R1< is a straight-chain or branched, saturated or mono- or polyunsaturated C6-24 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 represent integers from 1 to 6.

[0039] Thus, nonionic surfactants which have a C 9-15 alkyl radical 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 are particularly preferred.

[0040] Further preferred non-ionic surfactants are those of the general formula R 1< -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< represents 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< represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-26 alkyl or alkenyl radical; and w, x, y and z represent values ​​between 1 and 120, where x, y and / or z can also be 0.

[0041] With these surfactants, hereinafter also referred to as "hydroxy mixed ethers", the rinse performance of the preparations according to the invention can be significantly improved, both in comparison to surfactant-free systems and in comparison to systems containing alternative non-ionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

[0042] Finally, the non-ionic surfactants of the general formula (I) R 1< -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< have proven to be particularly effective. R 1< represents 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< representing 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.

[0043] The group of these non-ionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.

[0044] Also preferred are surfactants of the formula (I) R 1< -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 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 is a value of 1 and 2 (in the case of mixtures of such products also between 1 and 2, e.g. 1.5) and x is a value of at least 15.

[0045] The group of these non-ionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 -(EO) 15 - 40 -2-hydroxyalkyl ethers, in particular the C 8-10 fatty alcohol (PO) 1 -(EO) 22 -2-hydroxydecyl ethers.

[0046] Preference is also given to end-capped poly(oxyalkylated) nonionic surfactants of the formula (I) R 1< -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< with R 7< representing a straight-chain or branched, saturated or mono- or polyunsaturated C 6-26 alkyl or alkenyl radical; in the R 1 independent of R 7 represents 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 for-CH 3 and w and x independently represent values ​​between 1 and 32, where nonionic surfactants with R 3 = -CH 3 and values ​​for w of 15 to 32 and x of 0.5 and 1.5 are particularly preferred.

[0047] According to a particular embodiment, in the cleaning agent, in particular automatic dishwashing detergent, at least one, preferably at least two, in particular at least three of the components according to a) have a melting point (at 1 bar) of ≤ 30 °C, preferably ≤ 25 °C, in particular ≤ 20 °C in the liquid phase.

[0048] In particular, polyethylene glycols having an average molecular weight of 180 to 600, and nonionic surfactants of the general formula (I) R 1< -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< are preferred, in which R 1< stands for 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 of one another stand for integers from 1 to 6.

[0049] Preferably, in addition to one of the two or both of the above-mentioned components having a melting point of ≤ 30 °C, preferably ≤ 25 °C, in particular ≤ 20 °C (at 1 bar), 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, may additionally be present.

[0050] The cleaning agent, in particular automatic dishwashing detergent, comprises 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 160 and 6000, preferably 200 to 5000, in particular between 300 and 4000.

[0051] It is particularly preferred if a component according to a) is at least one polyalkylene glycol, preferably at least one polyethylene glycol, which has an average molecular weight between 300 and 600 g / mol.

[0052] 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 and 4500, in particular about 4000, (INCI: PEG 4000).

[0053] It is particularly preferred if the liquid phase(s) comprise a PEG with an average molecular weight of approximately 400 (INCI: PEG 400) and a PEG with an average molecular weight of approximately 4000 (INCI: PEG 4000).

[0054] 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 non-ionic surfactant, preferably one which is also a component according to a) according to formula I.

[0055] According to a further, particularly preferred embodiment, in the liquid phase as one of the components according to a) is a component according to formula (I) R 1< -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< where 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 of one another 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.

[0056] These components according to a) are particularly advantageous since they can optionally provide a basis for the liquid phase in addition to the liquid polyalkylene glycols, without having to use organic components, in particular organic solvents which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol.

[0057] It is particularly preferred if, in addition to one of the components according to a) preferred here, at least one polyalkylene glycol, preferably at least one polyethylene glycol, which has an average molecular weight between approximately 300 and approximately 5000, in particular approximately 4000 g / mol, is used as a further preferred component according to a).

[0058] It is further particularly preferred if the liquid phase (at least one of the liquid phases, preferably the liquid phases) additionally comprises, 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 with an average molecular weight between 3500 and 4500, in particular approximately 4000.

[0059] It is particularly preferred if the liquid phase(s) comprise a PEG with an average molecular weight of approximately 400 (INCI: PEG 400) and a PEG with an average molecular weight of approximately 4000 (INCI: PEG 4000).

[0060] It is very particularly preferred if, in addition to the above-mentioned components, at least one ethoxylated hydroxy mixed ether of the formula (I) R 1< -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< represents 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< representing 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.

[0061] Particularly preferred are the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.

[0062] In all the above-mentioned embodiments, in particular the particularly highlighted combinations, it is preferred that the amount of all components mentioned 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).

[0063] According to a particularly preferred embodiment, the liquid phase (at least one of the liquid phases, optionally all liquid phases) contains, based on the respective total weight of the (individual) liquid phase: 0-40% by weight of at least one component a) according to formula (I) R 1< -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< where 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 of one another 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, 0-40 wt.-% of at least one ethoxylated hydroxy mixed ether of the formula (I) R 1< -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< represents 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< represents 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, especially 15 to 40; and x,y,z=0. and 0-50% by weight of polyalkylene glycols;

[0064] It is preferred that the amount of all the components mentioned as 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).

[0065] According to a particularly preferred embodiment, the liquid phase (at least one of the liquid phases, optionally all liquid phases) contains, based on the respective total weight of the (individual) liquid phase: 5 to 30 wt.% of at least one component a) according to formula (I) R 1< -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< where 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 of one another 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, 5 to 30 wt.-% of at least one ethoxylated hydroxy mixed ether of the formula (I) R 1< -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< represents 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< represents 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. and 5-40 wt.% polyalkylene glycols; .

[0066] It is preferred that the amount of all the components mentioned as preferred according to a) in the liquid phase is between 15 and 80% by weight, preferably between 20 and 70% by weight (in each case based on the total weight of the liquid phase).

[0067] According to a particularly preferred embodiment, the liquid phase (at least one of the liquid phases, optionally all liquid phases) contains, based on the respective total weight of the (individual) liquid phase: 5 to 30 wt.% of at least one component a) according to formula (I) R 1< -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< where 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 of one another 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, 5 to 30 wt.-% of at least one ethoxylated hydroxy mixed ether of the formula (I) R 1< -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< represents 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< represents 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. and 5-30 wt.% polyethylene glycols with an average molecular weight between 300 and 600 g / mol and 1-20 wt.% polyethylene glycols with a molecular weight between 2000 and 6000 g / mol.

[0068] It is preferred that the amount of all the components mentioned as 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).

[0069] According to a further embodiment, the liquid phase (the liquid phases) may additionally contain an end-capped non-ionic 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) non-ionic 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, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, h is between 1 and 30, k and j are between 1 and 12, preferably between 1 and 5. If 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< can 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 C atoms being particularly preferred. For the radical R 9<, H, -CH 3 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 can be different if h ≥ 2. This allows the alkylene oxide unit in the square brackets to 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 can 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 as an example and can be larger, whereby the range of variation increases with increasing h values ​​and includes, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa.

[0070] Particularly preferred end-capped poly(oxyalkylated) alcohols of the above formula have values ​​of k = 1 and j = 1, so that the above formula is simplified to R 8< O[CH 2 CH(R 9< )O] h CH 2 CH(OH)CH 2 OR 10<. In the latter formula, R 8< , R 10< and R 9< are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particular preference is given to surfactants in which the radicals R 8< and R 10< have 9 to 14 C atoms, R 9< stands for H and h assumes values ​​from 6 to 15.

[0071] 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).

[0072] 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 / powdery phases the total weight of all solid and powdery phases) to the weight of one or more liquid phases (in the case of several liquid phases) is 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.

[0073] According to a preferred embodiment, the cleaning agent, in particular automatic dishwashing detergent, is substantially free of anionic surfactants. As used herein, substantially free of anionic surfactants means that a composition contains less than 7% by weight, preferably less than 5% by weight, in particular less than 3% by weight, very particularly preferably less than 1% by weight, especially preferably less than 0.1% by weight of anionic surfactant (based on the total weight of the agent). This preferably applies to all combinations according to the invention, in particular also to the combinations explicitly mentioned above as preferred.

[0074] The water-soluble wrapping 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 wrapping can be formed from one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the additional layers, if present, can be the same or different. Films that can be glued and / or sealed, for example, to form packages such as tubes or pillows after they have been filled with an agent are particularly preferred.

[0075] It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer exhibit good stability with sufficiently high water solubility, particularly cold water solubility.

[0076] 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 from 10,000 to 1,000,000 gmol -1< , preferably from 20,000 to 500,000 gmol -1< , particularly preferably from 30,000 to 100,000 gmol -1< and in particular from 40,000 to 80,000 gmol -1<.

[0077] Polyvinyl alcohol is typically produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and especially 82 to 88 mol%.

[0078] A polymer selected from the group comprising (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above polymers can additionally be added to a polyvinyl alcohol-containing film material suitable for producing the water-soluble wrapping. A preferred additional polymer is polylactic acid.

[0079] Preferred polyvinyl alcohol copolymers comprise, 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.

[0080] Likewise preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt, or its ester. Particularly preferably, such polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, or mixtures thereof.

[0081] It may be preferred for the film material to contain further additives. The film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol, or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-adhesive agents, or mixtures thereof.

[0082] Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packages according to the invention are films sold by MonoSol LLC, for example, under the designation M8630, C8400, or M8900. Other suitable films include films designated Solublon®< PT, Solublon®< GA, Solublon®< KC, or Solublon®< KL by Aicello Chemical Europe GmbH, or VF-HP films by Kuraray.

[0083] The cleaning agents according to the invention can be used as dishwashing agents, in particular automatic dishwashing agents. The corresponding use is also the subject of the invention. The invention also relates to a dishwashing process, in particular an automatic dishwashing process, in which a cleaning agent according to the invention is used. The particular embodiments described above also apply to the use and the process.

[0084] The cleaning agents according to the invention are preferably a dishwashing detergent, in particular an automatic dishwashing detergent.

[0085] According to a preferred embodiment, the pre-portioned cleaning agent according to the invention, in particular automatic dishwashing detergent, is essentially free of phosphates. This preferably applies to all combinations according to the invention, in particular also to the combinations explicitly mentioned above as preferred.

[0086] Essentially free of phosphates means that the entire cleaning agent resulting from the addition of all phases (or all ingredients of all compartments) is preferably essentially free of phosphate-containing components. Phosphates or phosphate-containing components within the meaning of the present invention are, in particular, phosphates, polyphosphates, and pyrophosphates. However, phosphonates or hexafluorophosphate are not encompassed by this term. The entire cleaning agent thus contains less than 1% by weight, preferably 0.5% by weight, of phosphates, based on the total weight of the cleaning agent (i.e., the total weight of all phases (i.e., all liquid and solid phases).

[0087] The cleaning agents according to the invention, in particular automatic dishwashing detergents, contain builders such as zeolites, silicates, carbonates, in particular the alkali carbonates, for example sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, and organic cobuilders.

[0088] Particularly suitable silicates are crystalline layered silicates of the general formula NaMSi x O 2x+1 y H 2 O, in which M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values ​​for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. Also suitable are amorphous sodium silicates with a modulus Na 2 O : SiO 2 of 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 have secondary washing properties.

[0089] In preferred cleaning agents, the content of silicates, based on the total weight of the cleaning agent, is limited to amounts below 10 wt.%, preferably below 5 wt.%.

[0090] Organic cobuilders include, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders, and phosphonates. These classes of substances are described below.

[0091] Useful organic builders include, for example, polycarboxylic acids, which can be used in the form of the free acid and / or their sodium salts. Polycarboxylic acids are understood to be carboxylic acids that have more than one acid function. Examples include 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 acceptable for ecological reasons, and mixtures thereof. In addition to their builder effect, the free acids typically also have the property of an acidifying component and thus also serve to adjust a lower and milder pH value of automatic dishwashing detergents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof are particularly suitable.

[0092] Another important class of builders is aminocarboxylic acids and / or their salts. Particularly preferred representatives of this class are methylglycinediacetic acid (MGDA) or its salts, glutamic diacetic acid (GLDA) or its salts, or ethylenediamine diacetic acid or its salts (EDDS). Iminodisuccinic acid (IDS) and iminodiacetic acid (IDA) are also suitable. Aminocarboxylic acids and their salts can be used together with the aforementioned builders, especially with phosphate-free builders.

[0093] The use of MGDA or GLDA or their salts is particularly preferred. MGDA is used in particular. MGDA can preferably be used as granules, and especially preferably in the solid phase. Particularly preferred are MGDA granules that contain as little water as possible and / or have low hygroscopicity.

[0094] Particularly preferred is the use of MGDA or its salts in a total amount of 3 to 50 wt.% based on the total weight of the cleaning agent.

[0095] Polymeric polycarboxylates are also suitable as builders. These include, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 to 70,000 g / mol. The polyacrylate(s) are used here in particular in a dried, particularly preferably dried and granulated (solid) form, which may optionally be additionally ground.

[0096] Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of approximately 1000 to 20,000, in particular 2000 to 10,000 g / mol. Due to their superior solubility, short-chain polyacrylates, which have molecular weights of 2000 to 10,000 g / mol, and particularly preferably 3000 to 5000 g / mol, may be preferred from this group.

[0097] Also suitable are copolymeric polycarboxylates, especially 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 wt.% acrylic acid and 50 to 10 wt.% maleic acid, have proven particularly suitable. Their relative molecular weight, based on free acids, is generally 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol, and especially 30,000 to 40,000 g / mol.

[0098] The cleaning agents can also contain phosphonates as builders. A hydroxyalkane and / or aminoalkanephosphonate is preferably used as the phosphonate compound. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and their higher homologues are preferred as aminoalkanephosphonates. Phosphonate-containing components are preferably present in the agents in amounts of 0.1 to 10 wt.%, in particular in amounts of 0.5 to 8 wt.%, based in each case on the total weight of the cleaning agent. With regard to the proportion of the phosphonate unit (independent of the hydroxyalkane and / or aminoalkane proportion), the agents according to the invention contain from 0.01 to 25% by weight, preferably 5 to 20% by weight, 8 to 15% by weight of phosphonate (in each case based on the total weight of the agent).According to the invention, the phosphonates are preferably contained in the solid phase(s).

[0099] The cleaning agents according to the invention can further contain a sulfopolymer. The weight fraction 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 from 1.0 to 15 wt. %, very particularly preferably from 2.0 to 14 wt. %, in particular from 4 to 14 wt. %, above all 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 may optionally be additionally ground. The sulfopolymer used is preferably a copolymeric polysulfonate, b a hydrophobically modified copolymeric polysulfonate.

[0100] The copolymers can have two, three, four or more different monomer units.

[0101] Preferred copolymeric polysulfonates contain, in addition to monomer(s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.

[0102] As unsaturated carboxylic acid(s) it is / are particularly preferred to use 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 represent -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 represents -COOH or -COOR 4<, where R 4< is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

[0103] Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, alpha-cyanoacrylic acid, crotonic acid, alpha-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid, or mixtures thereof. Unsaturated dicarboxylic acids can, of course, also be used.

[0104] Among the sulfonic acid group-containing monomers, those of the formula R 5< (R 6< )C=C(R 7< )-X-SO 3 H are preferred, in which R 5< to R 7< independently of one another represent -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 or represent -COOH or -COOR 4<, where R 4< is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group which is selected from -(CH 2 ) n - with n = 0 to 4, -COO-(CH 2 ) k - with k = 1 to 6, -C(O)-NH-C(CH 3 ) 2 -, -C(O)-NH-C(CH 3 ) 2 -CH 2 - and -C(O)-NH-CH(CH 3 )-CH 2 -.

[0105] 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 represents an optionally present spacer group 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 -.

[0106] 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-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-soluble salts.

[0107] In the polymers, the sulfonic acid groups can be present entirely or partially in neutralized form, i.e., the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and especially sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

[0108] The monomer distribution of the copolymers preferably used according to the invention is, for copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, preferably in each case 5 to 95 wt.%, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90 wt.% and the proportion of the monomer containing carboxylic acid groups is 10 to 50 wt.%, the monomers are preferably selected from those mentioned above.

[0109] The molecular weight of the sulfo-copolymers preferably used according to the invention can be varied to adapt the properties of the polymers to the desired application. Preferred cleaning agents are characterized by the copolymers having molecular weights of 2000 to 200,000 gmol -1 , preferably of 4000 to 25,000 gmol -1 , and in particular of 5000 to 15,000 gmol -1 .

[0110] In a further preferred embodiment, the copolymers comprise, in addition to the carboxyl-containing monomer and the sulfonic acid-containing monomer, at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has been shown to improve, in particular, the rinse performance of automatic dishwashing detergents according to the invention.

[0111] Anionic copolymers comprising carboxylic acid group-containing monomers, sulfonic acid group-containing monomers and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.

[0112] Monomers of the general formula R 1< (R 2< )C=C(R 3< )-XR 4< are preferably used as non-ionic monomers, in which R 1< to R 3< independently of one another represent -H, -CH 3 or -C2H5, 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 1 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

[0113] Particularly preferred non-ionic 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, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4,4-dimehtylhexane-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-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N-(methyl)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N-(2-Ethylhexyl)acrylamide, octyl acrylate, octyl methacrylate, N -(Octyl)acrylamide, acrylic acid lauryl ester, methacrylic acid lauryl ester, N -(Lauryl)acrylamide, stearyl acrylate, stearyl methacrylate, N -(Stearyl)acrylamide, behenyl acrylate, behenyl methacrylate and N-(behenyl)acrylamide or mixtures thereof.

[0114] The monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably 5 to 80 wt.% in relation to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, particularly preferably the proportion of the sulfonic acid group-containing monomer and the hydrophobic monomer is 5 to 30 wt.% in each case and the proportion of the carboxylic acid group-containing monomer is 60 to 80 wt.%, the monomers are preferably selected from those mentioned above.

[0115] The pH of an aqueous solution at 20°C, containing 10% by weight of the total cleaning agent, is in a range from 7 to 14, in particular greater than 7, in particular in a range from 8 to 13, preferably 9 to 12.

[0116] The agents according to the invention preferably contain at least one further component, 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, bittering agents, and antimicrobial agents.

[0117] Bleaching agents can also be used in cleaning agents, preferably dishwashing detergents, especially automatic dishwashing detergents. Among the compounds used as bleaching agents that release H2O2 in water, sodium percarbonate, sodium perborate tetrahydrate, and sodium perborate monohydrate are particularly important. Other useful bleaching agents include peroxypyrophosphates, citrate perhydrates, and H2O2-releasing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid, or diperdodecanedioic acid. All other inorganic or organic peroxy bleaching agents known to those skilled in the art from the prior art can also be used.

[0118] Chlorine- or bromine-releasing substances can also be used as bleaching agents. Suitable chlorine- or bromine-releasing materials include heterocyclic N-bromo- and N-chloroamides, such as 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-dimethylhydanthoin are also suitable.

[0119] Cleaning agents, preferably dishwashing agents, in particular automatic dishwashing agents, are preferred 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.

[0120] Furthermore, the cleaning agents, preferably dishwashing detergents, in particular automatic dishwashing detergents, can contain bleach catalysts. The usable 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, particularly preferably from the group of manganese and / or cobalt salts and / or complexes, in particular cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, cobalt or manganese chlorides, manganese sulfate, and 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).

[0121] Cleaning agents, preferably dishwashing agents, in particular automatic dishwashing agents, are preferred which contain 0.001 to 1% by weight, preferably 0.01 to 0.1% by weight (in each case based on the total weight of the cleaning agent) of bleaching 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-triazacyclononane (Mn 4 -TACN).

[0122] In various embodiments of the invention, the cleaning agents, preferably dishwashing detergents, in particular automatic dishwashing detergents, additionally contain at least one bleach activator. Compounds that, under perhydrolysis conditions, yield aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, can be used as bleach activators. Of all the bleach activators known to the person skilled in the art from the prior art, polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), 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 wt.%, in particular 0.1 wt.% to 8 wt.%, particularly 2 to 8 wt.%, and particularly preferably 2 to 6 wt.%, based in each case on the total weight of the cleaning agents.

[0123] The bleaching agent as well as bleach catalysts and / or bleach activators are preferably contained in the solid phase(s).

[0124] 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 heteroatoms 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 -alkyldimethylcarboxymethylbetaine and C 11 -C 17 -alkylamidopropyldimethylcarboxymethylbetaine.

[0125] 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< represent four identical or different, in particular two long-chain and two short-chain, alkyl radicals and X -< represents an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride and mixtures thereof. Other suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. By using quaternary surface-active compounds with antimicrobial effect, the agent can be given an antimicrobial effect or its already existing antimicrobial effect due to other ingredients can be improved.

[0126] The enzymes include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, or oxidoreductases, and preferably mixtures thereof. These enzymes are essentially of natural origin; based on the natural molecules, improved variants are available for use in cleaning agents and are therefore preferably used. Cleaning agents according to the invention preferably contain enzymes in total amounts of 1 x 10 -6 to 5 wt.% based on active protein. The protein concentration can be determined using known methods, for example, the BCA method or the biuret method.

[0127] Among the proteases, those of the subtilisin type are preferred. Examples include subtilisins BPN' and Carlsberg and their further developed forms, protease PB92, subtilisins 147 and 309, alkaline protease from Bacillus lentus,Subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the narrower sense.

[0128] Examples of amylases that can be used according to the invention are the α-amylases from Bacillus licheniformis, out of B . amyloliquefaciens, out of B. stearothermophilus, out of Aspergillus niger and A. oryzae as well as the improved developments of the aforementioned amylases for use in cleaning agents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) should be highlighted.

[0129] Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-cleaving activities, but also to produce from suitable precursors in situ These include, for example, the peracids originally from Humicola lanuginosa ( Thermomyces lanuginosus) available or further developed lipases, in particular those with one or more of the following amino acid substitutions starting from the said lipase in the positions D96L, T213R and / or N233R, particularly preferably all of the substitutions D96L, T213R and N233R.

[0130] Enzymes collectively referred to as hemicellulases can also be used. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectinesterases, xyloglucanases (=xylanases), pullulanases, and β-glucanases.

[0131] To increase the bleaching effect, 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. Advantageously, organic compounds, particularly aromatic ones, that interact with the enzymes are also added to enhance the activity of the respective oxidoreductases (enhancers) or to ensure electron flow in the event of significantly different redox potentials between the oxidizing enzymes and the soils (mediators).

[0132] A protein and / or enzyme can be protected, particularly during storage, against damage such as inactivation, denaturation, or degradation, for example, due to physical influences, oxidation, or proteolytic cleavage. In the case of microbial extraction of the proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Cleaning agents can contain stabilizers for this purpose; the provision of such agents represents a preferred embodiment of the present invention.

[0133] Cleaning-active proteases and amylases are generally not supplied in the form of pure proteins, but rather in the form of stabilized, storable, and transportable preparations. These prefabricated preparations include, for example, solid preparations obtained by granulation, extrusion, or lyophilization or, particularly in the case of liquid or gel-like products, solutions of the enzymes, preferably as concentrated as possible, with little water content, and / or containing stabilizers or other additives.

[0134] Alternatively, the enzymes can be encapsulated for both solid and liquid dosage forms, for example by spray-drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, for example those in which the enzymes are enclosed as if in a solidified gel, or in those of the core-shell type, in which an enzyme-containing core is coated with a water-, air-, and / or chemical-impermeable protective layer. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Such capsules are applied using methods known per se, for example by shake or roll granulation or in fluid-bed processes. Such granules, for example by applying polymeric film formers, are advantageously low in dust and, due to the coating, are stable during storage.

[0135] Furthermore, it is possible to package two or more enzymes together so that a single granulate has multiple enzyme activities.

[0136] As can be seen from the above, the enzyme protein constitutes 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 wt.%, preferably between 0.2 and 30 wt.%, particularly preferably between 0.4 and 20 wt.%, and especially between 0.8 and 10 wt.% of the enzyme protein.

[0137] Particularly preferred cleaning agents are those which, based 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.

[0138] Preferably, the enzymes, in particular the amylase(s) and / or protease(s), are contained in (one of) the solid phase(s), preferably as granules.

[0139] Metal salts, especially zinc or bismuth salts, preferably zinc salts, especially zinc acetate, are used as glass corrosion inhibitors. Polyethyleneimines and polyvinylamines, such as those available from BASF under the name Lupasol® or Lupamin®, are also preferably used as glass corrosion inhibitors, especially non-alkoxylated polyethyleneimines. Glass corrosion inhibitors are preferably present in the compositions according to the invention in an amount of 0.05 to 5 wt.%, in particular in an amount of 0.1 to 2 wt.%.

[0140] The cleaning agents according to the invention are characterized by the fact that they are storage-stable and no phase separation occurs even after a longer period of time.

[0141] The present invention also relates to a machine dishwashing process in which a cleaning agent according to the invention is used.

[0142] In another aspect, the invention also relates to the use of the cleaning agent according to the invention as a dishwashing detergent, in particular an automatic dishwashing detergent. Examples of implementation

[0143] The cleaning agent formulation according to the invention with a solid phase according to Table 1 and a liquid phase according to Table 2, E1, as well as a comparative formulation V1 with a solid phase according to Table 1 and a liquid phase according to Table 2, V1, were prepared. The amounts stated in the tables are in wt. % active ingredient. 15 g of the solid phase were sealed into a first polyvinyl alcohol bag, and 5 g of the liquid phase (E1 or V1) were sealed into a second polyvinyl alcohol bag. Table 1: Formulation of the solid phase Solid phase Natri and mca rbonat-peroxohyd rat 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, excipients 5 HEDP 10 Total amount 100 Table 2: Recipes of the liquid phases E1 V1 PEG 400 (Mr = approx. 400) 20 - PEG 4000 (Mr = approx. 4000) 6 - C 10- -C 14 fatty alcohol alkoxylate (10 EO+PO) 17 - C 10- -C14 end-capped C 8 -C 10 fatty alcohol ethoxylate (18-30 EO) 20 - Glycerin - 25 1,2-propylene glycol - 18 Water - 20 Methylglycinediacetic acid 4 4 Sulfopolymer, (partially neutralized) Na salt 24 24 Polyacrylate, sodium salt 8 8 Perfume, dye, excipients, 1 1 Total amount 100 100

[0144] The pre-portioned cleaning agent according to the invention (liquid phase = E1) showed good stability and a weight loss of less than 5 wt.% of the liquid phase (based on the initial weight of the liquid phase) after a storage time of 2 weeks at 25 °C in a closed outer packaging (glass container).

[0145] The other pre-portioned cleaning agent (comparative example, liquid phase = V1) showed a weight loss of 20 wt% in the liquid phase after a storage period of 2 weeks at 25 °C in a closed package. The compartment containing the solid phase was significantly more densely packed, and gravimetrically determined a weight gain equivalent to the weight loss in the liquid compartment.

[0146] Similar results were obtained with pre-portioned cleaning agents of the following composition (E2). 12 g of the solid phase (E2) were sealed in a first polyvinyl alcohol bag, and 4 g of the liquid phase (E2) were sealed in a second polyvinyl alcohol bag. Table 3: Formulation of the solid phase Solid phase E2 Sodium carbonate peroxohydrate 22 Sodium citrate dihydrate 8 Sodium carbonate (anhydrous) 22 Methylglycinediacetic acid, sodium salt 20 Bleach catalyst (containing MnTACN) 2,5 Enzyme preparation (amylase, protease) 4 Perfume, dye, excipients 7,5 HEDP sodium salt 11 C 10 -C 14 -end-capped C 8 -C 10 fatty alcohol ethoxylate (18-30 EO) 3 Total amount 100 Table 4: Recipes of the liquid phases E2 PEG 400 (Mr = approx. 400) 20 PEG 4000 (Mr = approx. 4000) 6 C 10- -C 14 fatty alcohol alkoxylate (10 EO+PO) 16 C 10 -C 14 -end-capped C 8 -C 10 fatty alcohol ethoxylate (18-30 EO) 20 Methylglycinediacetic acid 5 Sulfopolymer, (partially neutralized) Na salt 22 Polyacrylate, sodium salt 8 Perfume, dye, excipients, 3 Total amount 100

Claims

1. A pre-portioned cleaning agent, preferably a dishwashing agent, in a water-soluble packaging having at least two compartments, comprising at least one solid, preferably powdered 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         R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6     (Formula I) in which R1 is selected from -H, -CH3, a straight-chain or branched, saturated or mono- or polyunsaturated C2-24 alkyl or alkenyl group; R2, R3, R4, R5 are each selected, independently of one another, from -H, -CH3, - CH2CH3, -CH2CH2CH3, CH(CH3)2, preferably -H or -CH3; R6 is selected from -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2-CH2-CH2CH3, - CH2CH(CH3)2, -C(CH3)3, C5-24 alkyl or alkenyl, and -CH2CH(OH)R7 where R7 represents a straight-chain or branched, saturated or mono- or polyunsaturated C6-26 alkyl or alkenyl group; and w, x, y and z can, independently of one another, each assume values of 1 to 120 and in which x, y and / or z can be 0, b) contains less than 5 wt.% of organic compounds of the kind which have an average molecular weight of less than 175 g / mol, preferably of less than 150 g / mol; and c) contains less than 7% by weight of water, wherein the pH of an aqueous solution at 20°C, containing 10% by weight of the total cleaning agent, is in a range from 7 to 14, in particular greater than 7, in particular in a range from 8 to 13, preferably from 9 to 12, and 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 160 and 6000.

2. The cleaning agent according to claim 1, characterized in that in the liquid phase, at least one, preferably a plurality of, in particular all of the components according to a) have a melting point (at 1 bar) of ≤ 30 °C, preferably ≤ 25 °C, in particular ≤ 20 °C.

3. The cleaning agent according to one of the preceding claims, characterized in that the liquid phase contains, 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, having a mean molecular weight between 200 to 5000, in particular between 300 and 4000.

4. The cleaning agent according to one of the preceding claims, characterized in that the liquid phase contains, as one of the components according to a), a component according to formula (I)         R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6 in which R1 is selected from straight-chain or branched, saturated C8-16 alkyl groups; R2 and R4 are -H, R3 and R5 are -CH3, R6 is selected from -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2-CH2- CH2CH3, - CH2CH(CH3)2, -C(CH3)3, C5-20 alkyl (linear or branched), and, selected independently of one another, 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.

5. The cleaning agent according to one of the preceding claims, characterized in that the liquid phase contains, as one of the components according to a), at least one end-capped non-ionic surfactant according to formula I         R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6 in which - R1 represents a linear or branched hydrocarbon group having 2 to 26 carbon atoms; - R2 = H, - R6 is selected from -CH2CH(OH)R7 where R7 represents a straight-chain or branched, saturated or mono- or polyunsaturated C6-26 alkyl or alkenyl group; and - w = 1 to 120, preferably 10 to 80, in particular 20 to 40; and x, y and z = 0.

6. The cleaning agent according to one of the preceding claims, characterized in that the amount of all the components according to a) in the liquid phase is between 10 to 80 wt.%, preferably between 20 to 70 wt.% (based in each case on the total weight of the liquid phase).

7. The 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.

8. The cleaning agent according to one of the preceding claims, characterized in that the cleaning agent preferably contains less than 1 wt.% phosphate, based on the total weight of the cleaning agent.

9. The cleaning agent according to one of the preceding claims, characterized in that the cleaning agent preferably contains phosphonate (based on the proportion of the phosphonate group) in amounts of 0.01 to 25 wt.%, preferably 5 to 20 wt.%, 8 to 15 wt.% phosphonate (based in each case on the total weight of the agent).

10. The cleaning agent according to one of the preceding claims, characterized in that it is a multi-chamber packaging, preferably a multi-chamber pouch, in particular having two, three, four or more chambers.

11. The cleaning agent according to one of the preceding claims, characterized in that it is a water-soluble packaging or packaging made of a film containing polyvinyl alcohol or polyvinyl alcohol copolymer.

12. The use of a cleaning agent according to one of the preceding claims 1 to 11 in a cleaning method in an automatic dishwasher.

13. A method for cleaning dishes, preferably in an automatic dishwasher, characterized in that a cleaning agent according to one of claims 1 to 11 is used.