DE102015213939A1 - A multi-phase dishwashing detergent comprising a surfactant core - Google Patents

Abstract

The present invention relates to a solid, multi-phase dishwashing detergent comprising at least two phases and the use of such a dishwashing detergent and a method for cleaning dishes using such a dishwashing detergent.

Description

The present invention relates to a solid, multi-phase dishwashing detergent comprising at least two phases and the use of such a dishwashing detergent and a method for cleaning dishes using such a dishwashing detergent.

Manufacturers of automatic dishwashing agents advertise with increasingly efficient and thus more sustainable dishwashing detergents, in particular with regard to water and energy consumption. Along with this, rinsing programs with ever lower rinsing temperatures are offered and used. High temperatures in the cleaning cycle have a favorable effect on the removal of grease, since in this case edible fats can be liquefied and thus emulsified better. Lower dishwashing temperatures in the dishwasher lead to an accumulation of edible fat residues in the dishwasher sump / filter.

Customers prefer aesthetically pleasing cleaning agents. In particular, pressed powder phases, which in particular consisting of dishwasher tablets, do not satisfy the aesthetic requirements of the customers.

It is an object of the present invention to provide a dishwashing detergent whose composition, even at low rinsing temperatures, ensures efficient removal of edible fat residues from the dishwasher and, at the same time, has a more attractive aesthetics compared with current dishwashing detergents, in particular tabs made from pressed powder phases.

As has now surprisingly been found, the use of a surfactant melt of nonionic surfactants compared to current formulations, the fat from the filter of the dishwasher can be removed more efficiently. Moreover, the provision of the surfactant melt in the form of a surfactant core which is incorporated into a core well of a pressed powder dishwashing tablet may result in a visually appealing tablet.

In a first aspect, therefore, the present invention is directed to a dishwashing detergent comprising at least a first solid, compacted phase and at least one second phase, characterized in that the at least one second phase is a surfactant melt, comprising 10-100 wt .-%, preferably 20-100%, more preferably 50-100% by weight of surfactant (s), preferably nonionic surfactant (s).

In another aspect, the present invention is directed to the use of a dishwashing detergent according to the invention for machine dishwashing.

In a final aspect, the present invention is directed to a method for machine cleaning of dishes, characterized in that in at least one method step, a dishwashing agent according to the invention is applied.

According to the invention, a dishwashing detergent is to be understood as meaning all agents which are suitable for washing or cleaning hard surfaces, in particular crockery. Other suitable ingredients are described in detail below.

These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Further, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular that the invention is not limited to these examples. All percentages are by weight unless otherwise specified. Numeric ranges indicated in the format "from x to y" include the above values. If multiple preferred numeric ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints are also captured.

"At least one" as used herein refers to 1 or more, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.

The dishwashing agent according to the invention comprises at least two phases, wherein the first phase is solid and compacted and the second phase is a surfactant melt. As a "melt" is an under Exposure to elevated temperatures (eg> 50 ° C or> 60 ° C) refers to a liquefied composition which solidifies on cooling to room temperature and forms a solid form.

A phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous. A phase differs from another phase by various features, such as ingredients, physical properties, appearance, etc. Preferably, different phases can be visually distinguished. Thus, for the consumer, the at least one first phase is clearly distinguishable from the at least one second phase. If the washing or cleaning agent according to the invention has more than one first phase, then these can likewise be differentiated from one another by the naked eye, because they differ, for example, from one another in color. The same applies if two or more second phases are present. Also in this case, a visual differentiation of the phases, for example due to a color or transparency difference is possible. Phases in the sense of the present invention are thus self-contained areas that can be optically distinguished from the consumer by the naked eye. The individual phases may have different properties in use, such as the rate at which the phase dissolves in water and thus the rate and order of release of the ingredients contained in the respective phase.

 The phases are typically spatially separated. This can be done in various embodiments such that when one or both of the phases are liquid phases, the liquid phase is separate from the other phase in a separate, sealed area, for example the chamber of a pouch. Such Konfektionsformen are known in the art. For solid agents, i. Means in which both phases are solids, the two phases are also made up spatially separated from each other, for example in the form of a multi-chamber pouches, each of the phases is present in a separate chamber. Alternatively, in the case of compacted agents, such as tabs or tablets, in particular multi-phase tabs as known in the art, the two phases may be arranged directly adjacent to each other spatially in such a way that the phases are formulated separately and contact each other, but can not mix.

The dishwashing detergent according to the invention comprises at least two different phases. Both the at least one first phase and the at least one second phase are described below. In the event that the dishwashing detergent according to the invention has more than two phases, each further phase corresponds in each case either to the at least one first phase, as defined herein, or to the at least one second phase, as defined herein. In this case, the compositions of the respectively corresponding phases may differ to the extent permitted by the respective definitions given below of both the at least one first phase and the at least one second phase. For example, it may be a three-phase dishwashing detergent having two phases corresponding to the first phase as defined herein and one phase corresponding to the second phase as defined herein.

According to the present invention, the at least one second phase of the dishwashing agent is a surfactant melt comprising from 10 to 100% by weight, preferably from 20 to 100% by weight, more preferably from 50 to 100% by weight of surfactant ( en), in particular nonionic (m) surfactant (s). Accordingly, the second phase will hereinafter also be referred to as "surfactant melt" or "surfactant melt phase".

Nonionic surfactants which can be used in this at least one surfactant melt phase are all nonionic surfactants known to the person skilled in the art. In preferred embodiments, however, nonionic surfactants from the group of alkoxylated alcohols are used. A class of preferably usable nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants as constituent of the surfactant melt are accordingly alkoxylated (preferably ethoxylated or ethoxylated and propoxylated) fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain ,

Non-end-capped, poly (oxyalkylated) nonionic surfactants according to the formula R ¹ O [CH ₂ CH ₂ O] _x H are preferred in this context, where R ^{1 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 Carbon atoms, preferably having 4 to 22 carbon atoms, and x stands for values between 1 and 80, preferably for values between 15 and 50 and in particular for values between 25 and 50 stands. Very particular preference is given to fatty alcohol ethoxylates in which R ^{1 is} a linear or branched C _12-20 alkyl radical, in particular a linear or branched C _16-18 alkyl radical.

In preferred embodiments, the non-end-capped, poly (oxyalkylated) nonionic surfactants of the surfactant melt phase described above are used in amounts of from 5 to 100, preferably from 5 to 50, preferably from 10 to 30,% by weight, based on the surfactant melt. Phase used.

In further preferred embodiments, the above-described non-end-capped, poly (oxyalkylated) nonionic surfactants of the surfactant melt phase are combined with another surfactant from the group of end-capped, poly (oxyalkylated) nonionic surfactants. Preference is given in particular those endgruppenverschlossene, poly (oxyalkylated) nonionic surfactants, which, according to the formula R ¹ O [CH ₂ CH ₂ O] _x R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic Hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, further linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals R ² having 1 to 30 carbon atoms, wherein x for values between 1 and 80, preferably for values between 15 and 50 and especially for values between 25 and 50 stands. Very particular preference is given to end-capped fatty alcohol ethoxylates in which R ^{1 is} a linear or branched C _12-20 alkyl radical, in particular a linear or branched C _16-18 alkyl radical, and / or R ^{2 is} a linear or branched C _6-22 alkyl radical, in particular represents a linear or branched C _8-10 alkyl radical.

In preferred embodiments, the end-capped, poly (oxyalkylated) nonionic surfactants of the surfactant melt phase described above are used in amounts of 5-60% by weight, preferably 40-60% by weight, based on the surfactant melt phase.

In various embodiments, the mass ratio between the end capped nonionic surfactants described above and the non end capped nonionic surfactants in the surfactant melt phase is from 20: 1 to 1: 5, preferably from 10: 1 to 1: 1. In particularly preferred embodiments, the ratio is 3: 1 to 2: 1.

In general, the nonionic surfactants used in the surfactant melt phase have a melting point above room temperature. Nonionic surfactant (s) having a melting point above 25 ° C, preferably between 25 and 65 ° C and especially between 26.6 and 55 ° C, is / are particularly preferred.

In addition to the surfactants mentioned, the surfactant melt phase may contain other ingredients. Preferably, such ingredients include, for example, polyethylene glycols (PEG). Preference is given to polyethylene glycols having average molecular weights between 800 and 8000 g / mol, in particular between 1000 and 6000 g / mol, for example between 1500 and 5000 PEGs, for example in amounts of 10 to 40 wt.%, Preferably 25-35 wt. be contained based on the weight of the surfactant melt phase. Particularly preferred are between 20 to 35 wt .-% polyethylene glycols having an average molecular weight of 2000 to 5000 g / mol, for example, polyethylene glycols having an average molecular weight around 4000 g / mol (see INCI: PEG 4000) included. Other ingredients of the surfactant melt phase are other surfactants, in particular nonionic surfactants, polymers (polycarboxylates, especially homo- and / or copolymers of acrylic acid) and organic builders, in particular citric acid or citrates, are suitable. These ingredients are described in detail below.

The at least one first phase of the dishwashing agent according to the invention is a solid, compacted phase, typically a pressed powder phase. This at least one first phase of the dishwashing agent according to the invention usually contains at least one surfactant, preferably at least one nonionic surfactant. Suitable surfactants are described below.

Suitable nonionic surfactants of the first phase are, for example, alkyl glycosides of the general formula RO (G) _x in which R corresponds to a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants in the first phase of the dishwashing detergent are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

However, low-foaming nonionic surfactants are preferably used in the first phase, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. With particular preference, the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols.

A class of useful nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Preferably used surfactants come from the groups of 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 characterized by good foam control.

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen. Suitable nonionic surfactants are those 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

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 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 einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• – R² für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• – A, A’, A’’ und A’’’ unabhängig voneinander für einen Rest aus der Gruppe -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, -CH₂-CH(CH₂-CH₃) stehen,
• – w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.

Preferred nonionic surfactants here are those of the general formula R ^{1 is} -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A''O) _y - (A '''O) _z -R ² , in the

• R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• - A, A ', A''andA''' are independently a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ),
• - w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.

Preference is given in particular to those end-capped, poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Particularly preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.

The group of these nonionic surfactants 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. Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1 such that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH ) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

• – R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• – R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• – A für einen Rest aus der Gruppe CH₂CH₂, CH₂CH₂CH₂, CH₂CH(CH₃), vorzugsweise für CH₂CH₂ steht, und
• – w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 15 bis 50 steht.

Finally, the nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ^{2 have} proven to be particularly effective, in which

• R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A is a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH (CH ₃ ), preferably CH ₂ CH ₂ , and
• - w stands for values between 1 and 120, preferably 10 to 80, in particular 15 to 50.

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

In various embodiments of the invention, instead of the above-defined end-capped hydroxy mixed ethers, the corresponding non-end-capped ones may also be used Hydroxymischether be used. These may satisfy the above formulas, but R ² is hydrogen and R ¹ , R ³ , A, A ', A'',A''', w, x, y and z are as defined above.

The stated C chain lengths as well as degrees of ethoxylation or degree of alkoxylation of the nonionic surfactants represent statistical averages, which may be an integer or a fractional number for a specific product. Due to the production process commercial products of the formulas mentioned are usually not from an individual representative, but from mixtures, which can result in both the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation averages and resulting broken numbers.

Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,

The dishwashing compositions described herein, which comprise in the at least one first phase at least one surfactant, preferably a nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, contain the surfactant in various embodiments in an amount based on the total weight of the composition of at least 2% by weight, preferably at least 5% by weight. For example, the amounts used per application may be in the range of 0.5-10 g / job, preferably in the range of 0.5-5 g / job.

Particular preference is given in the at least one first phase to those nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred ,

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which are solid at room temperature.

In general, the first phase may also contain the surfactants described above in connection with the second phase, in particular the described optionally end-group-capped fatty alcohol ethoxylates.

In addition, the first phase of the dishwashing detergent according to the invention may also contain surfactants from the group of anionic, cationic and amphoteric surfactants.

Suitable anionic surfactants in dishwashing detergents are all anionic surfactants. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium as well as mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

Instead of or in combination with the surfactants mentioned, it is also possible to use cationic and / or amphoteric surfactants, such as betaines or quaternary ammonium compounds. However, it is preferred that no cationic and / or amphoteric surfactants are used.

In addition, the dishwashing detergent in the at least one first phase may contain further ingredients which further improve the performance and / or aesthetic properties of the dishwashing detergent. In the context of the present invention, the dishwashing detergent in various embodiments contains at least one or preferably more substances from the group of builders, Polymers, bleaches, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, glass corrosion inhibitors, foam inhibitors, dyes, additives to improve drainage and drying behavior, disintegration aids, preservatives, pH adjusters, fragrances and perfume carriers.

The use of builders (builders) such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders, may be advantageous.

In a preferred embodiment according to the invention, the use of phosphates (including polyphosphates) is largely or completely omitted. The agent in this embodiment preferably contains less than 5% by weight, more preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s). Most preferably, in this embodiment, the agent is completely phosphate-free, i. the agents contain less than 0.1% by weight of phosphate (s).

The builders include in particular carbonates, citrates, phosphonates, organic builders and silicates. The proportion by weight of the total builders in the total weight of compositions according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight.

Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which have more than one, in particular two to eight, acid functions, preferably two to six, in particular two, three, four or five acid functions carry throughout the molecule. Preferred polycarboxylic acids are thus dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids. The polycarboxylic acids may carry further functional groups, such as hydroxyl or amino groups. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, for example nitrilotriacetic acid (NTA), glutamine-N, N -diacetic acid (also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA), methylglycinediacetic acid (MGDA)) and their derivatives and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures thereof.

Also suitable as organic builders are polymeric polycarboxylates (organic polymers having a multiplicity of (in particular greater than 10) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins.

In addition to their builder effect, the free acids also typically have the property of an acidifying component and can thus, if desired, also serve to set a lower pH. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Particularly preferred cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwasher detergents, contain one or more salts of citric acid, ie citrates, as one of their essential builders. These are preferably in a proportion of 2 to 40 wt .-%, in particular from 5 to 30 wt .-%, particularly from 7 to 28 wt .-%, particularly preferably 10 to 25 wt .-%, most preferably 15 to Contain 20 wt .-%, each based on the total weight of the composition.

Also particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate (soda), in amounts of 2 to 50 wt .-%, preferably from 4 to 40 wt. -% and in particular from 10 to 30 wt .-%, most preferably 10 to 24 wt .-%, each based on the weight of the composition.

Particularly preferred cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, are characterized in that they comprise at least two builders from the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, the weight fraction of these builders, based on the total weight of the inventive detergent, preferably 5 to 70 wt .-%, preferably 15 to 60 wt .-% and in particular 20 to 50 wt .-% is. The combination of two or more builders from the above group has been proven for the Cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwasher detergents, have proven to be advantageous. In addition to the builders mentioned here, one or more other builders may additionally be present.

Preferred cleaning agents, in particular dishwashing agents, preferably automatic dishwasher detergents, are characterized by a builder combination of citrate and carbonate and / or bicarbonate.

In a very particularly preferred embodiment according to the invention, a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight. and the amount of citrate is preferably from 5 to 35 wt .-%, in particular 10 to 25 wt .-%, most preferably 15 to 20 wt .-%, each based on the total amount of the cleaning agent, wherein the total amount of these two Builders preferably 20 to 65 wt .-%, in particular 25 to 60 wt .-%, preferably 30 to 50 wt .-%, is. In addition, one or more further builders may additionally be included.

The detergents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, may in particular contain phosphonates as further builder. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are preferably present in compositions according to the invention in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight, very particularly preferably from 2.5 to 7.5% by weight, in each case based on the total weight of the agent.

Particularly preferred is the combined use of citrate, (hydrogen) carbonate and phosphonate. These can be used in the above quantities. In particular, in this combination amounts of, in each case based on the total weight of the composition, 10 to 25 wt .-% citrate, 10 to 30 wt .-% carbonate (or bicarbonate), and 2.5 to 7.5 wt .-% Phosphonate used.

Further particularly preferred cleaning agents, in particular dishwashing agents, preferably automatic dishwasher detergents, are characterized in that in addition to citrate and (hydrogen) carbonate and optionally phosphonate they contain at least one further phosphorus-free builder. In particular, it is selected from among the aminocarboxylic acids, wherein the further phosphorus-free builder is preferably selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), more preferably MGDA or GLDA. A particularly preferred combination is, for example, citrate, (hydrogen) carbonate and MGDA and optionally phosphonate.

The percentage by weight of the further phosphorus-free builder, in particular of the MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25% by weight. Particularly preferred is the use of MGDA or GLDA, in particular MGDA, as granules. Advantageous in this case are those MGDA granules which contain as little water as possible and / or have a lower hygroscopicity (water absorption at 25 ° C., normal pressure) compared to the non-granulated powder. The combination of at least three, in particular at least four, builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwasher detergents. In addition, other builders may be included.

As organic builders, polymeric polycarboxylates are furthermore suitable; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol. Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

The content of the cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwashing agents, of (homo) polymeric polycarboxylates is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight.

Detergents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, can furthermore comprise, as builder, crystalline stratiform 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, with particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20. 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 certain detergents according to the invention, in particular dishwashing detergents, preferably dishwasher detergents, the content of silicates, based on the total weight of the detergent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight ,

In addition to the abovementioned builders, the washing or cleaning agents according to the invention may furthermore comprise alkali metal hydroxides. These alkali carriers are preferably present only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably in the detergents or cleaners and in particular in the second phases 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the detergent or cleaning agent used. Alternative cleaning agents according to the invention are free of alkali metal hydroxides.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as builders.

The at least one first phase of the dishwashing detergent described herein may further contain various polymers.

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

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid (methylmaleic acid), methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. Very particular preference is given to acrylic acid. In various embodiments of the invention, the homopolymer is therefore a polyacrylic acid.

In the polymers, the carboxylic acid groups may be wholly or partially in neutralized form, i. in that the acidic carbon atom of the carboxylic acid group in some or all of the carboxylic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or completely neutralized polymers is preferred according to the invention.

The molecular weight of the homopolymers used can be varied in order to adapt the properties of the polymers to the desired end use. Preferred dishwashing detergents are characterized in that the homopolymers, in particular the polyacrylic acids, have molar masses M _{n of} from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1100 to 10 000 g / mol, and more preferably from 1200 to 5000 g / mol, may again be preferred from this group.

In various preferred embodiments of the invention, the agents further comprise at least one sulfopolymer. The polymers which can be used in this context are, in particular, copolymers which may have two, three, four or more different monomer units, where at least one monomer unit carries a sulfonic acid group. Preferred copolymers contain, in addition to sulfonic acid-containing (s) monomer (s) at least one monomer from the group of unsaturated carboxylic acids.

As the unsaturated carboxylic acid (s), the above-described unsaturated carboxylic acids are / are used with particular preference. Acrylic acid is very particularly preferred.

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 , where 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.

Also in the copolymers, the acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic and / or carboxylic acid group in some or all 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 copolymers is preferred according to the invention.

The monomer distribution of the copolymers preferably used 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 the proportion of the sulfonic acid group-containing monomer is from 50 to 90% by weight. and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.

In various embodiments, in addition to the above-described carboxylic acid group-containing monomers and sulfonic acid group-containing monomers, the copolymers may contain other monomers, particularly unsaturated carboxylic acid ester group-containing monomers. In such terpolymers, the carboxylic acid ester group-containing monomers are, for example, those of the formula R ¹ (R ² ) C =C (R ³ ) COOR ⁴ , in which R ¹ to R ^{3 are} as defined above and R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acid esters are alkyl esters of monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, sorbic acid, cinnamic acid or mixtures thereof. Very particular preference is given to C _1-8 -alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate. Very particular preference is given to ethyl acrylate.

The molecular weight of the copolymers used can be varied in order to adapt the properties of the polymers to the desired use. Preferred dishwashing detergents are characterized in that the copolymers have molar masses M _n of 2,000 to 200,000 g / mol, preferably of 4,000 to 25,000 g / mol and in particular of 5,000 to 15,000 g / mol.

The above-described homopolymers and copolymers may each be used in amounts of from 0.5 to 10% by weight, preferably from 1 to 5% by weight, based on the total weight of the composition. Absolute amounts are typically in the range of 0.1 to 2 g / job, preferably in the range of 0.2 to 1.0 g / job. The mass ratio of the polymers to each other, i. Homopolymer to copolymer, is in various embodiments, 5: 1 to 1: 5, preferably 2: 1 to 1: 2.

The dishwashing agents may alternatively or additionally contain other polymers. Suitable polymers include, in particular, the cleaning-active amphoteric, zwitterionic or cationic polymers, for example the rinse aid polymers and / or polymers which act as softeners.

Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth ) -acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Further usable zwitterionic polymers are from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.

Useful cationic polymers come from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and methacrylic acid and their esters and amides, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

• – die Verkapselung der Polymere mittels wasserlöslicher oder wasserdispergierbarer Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• – die Verkapselung der Polymere mittels wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30°C;
• – die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder (Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the abovementioned amphoteric, zwitterionic or cationic polymers are present in prefabricated form. For the preparation of the polymers is suitable inter alia

• The encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• - The encapsulation of the polymers by means of water-insoluble, fusible coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;
• - The cogranulation of the polymers with inert support materials, preferably with support materials from the group of washing or cleaning-active substances, particularly preferably from the group of builders (builders) or cobuilders.

As a further constituent dishwashing agents according to the invention in the first phase preferably contain one or more enzyme (s). These 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 % by weight 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 include the subtilisins BPN 'and Carlsberg and their advanced forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which are assigned to the subtilases but no longer to the subtilisins in the narrower sense.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens, from β. stearothermophilus, from Aspergillus niger and A. oryzae and the improved for use in detergents developments of the aforementioned amylases. 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 Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid substitution in positions D96L, T213R and / or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.

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

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils. A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In the case of microbial recovery of the 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 the first and / or second phase, 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 entrapped as in a solidified gel or in of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

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

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein. Preference is given in particular to those cleansers which, based in each case on their total weight, are 0, 1 to 12 wt .-%, preferably 0.2 to 10 wt .-% and in particular 0.5 to 8 wt .-% of the respective enzyme preparations.

The dishwashing detergent may further contain one or more enzyme stabilizer (s). Examples of suitable enzyme stabilizers include boron-containing compounds such as boric acid or boronic acids, and their salts and esters, polyols such as glycerol or 1,2-ethylene glycol, sugars, sugar alcohols, lactic acid or antioxidants.

Dishwashing agents according to the invention contain in a preferred embodiment as further constituent at least one zinc salt as glass corrosion inhibitor. The zinc salt may be an inorganic or organic zinc salt. The zinc salt to be used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and especially above 5 g / l (all solubilities at 20 ° C. water temperature). The inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate. The organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate. In a particularly preferred embodiment according to the invention, zinc acetate is used as the zinc salt.

The zinc salt is preferably present in the detergent according to the invention in an amount of from 0.01% by weight to 5% by weight, more preferably in an amount of from 0.05% by weight to 3% by weight, in particular in an amount of 0.1 wt .-% to 2 wt .-%, based on the total weight of the cleaning agent.

Additionally or alternatively to the above-mentioned salts (especially zinc salts) may polyethyleneimines described, for example, under the name Lupasol ^® (BASF) can be obtained, preferably in an amount of 0 to 5 wt .-%, particularly 0.01 to second %, are used as glass corrosion inhibitors.

The at least one first phase of the dishwashing agent may further comprise a bleaching agent, in particular an oxygen bleaching agent and optionally a bleach activator and / or bleach catalyst. These are, if available, only included in the first phase.

Dishwashing agents according to the invention contain as preferred bleaching agent an oxygen bleaching agent from the group of sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate. 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. Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Because of its good bleaching performance, sodium percarbonate is particularly preferred. A particularly preferred oxygen bleach is sodium percarbonate.

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. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.

The bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salene complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts. It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are, for example, [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (CIO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₂ (μ-OAc) ₁ (TACN ) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV ₄ (μ-O) ₆ (TACN) ₄ ] (CIO ₄ ) ₄ , [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (Me-TACN ) ₂ ] (CIO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (CIO ₄ ) ₃ , [Mn ^IV ₂ (μ-O) ₃ ( Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (μ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (with OAc = OC (O) CH ₃ ).

In general, the pH of the dishwashing detergent can be adjusted by means of customary pH regulators, the pH value being chosen as a function of the desired intended use. In various embodiments, the pH is in a range of 5.5 to 11, preferably 6 to 10.5, more preferably 7 to 10.5, especially greater than 7, especially in the range 8.5 to 10.5. The pH adjusting agents are acids and / or alkalis, preferably alkalis. Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, however, it is also possible to use the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof. Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred. However, particularly preferred is volatile alkali, for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule. The alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.

To adjust and / or stabilize the pH, the dishwasher detergent according to the invention may also contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents). Particularly preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate.2H ₂ O and tripotassium citrate H ₂ O.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

Furthermore, preservatives may be contained in the dishwashing detergent according to the invention. Suitable examples are preservatives from the groups of alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides. Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2 Benzyl 4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4- Chlorophenyl) -3,12-diimino-2,4,11,13-tetraazatetradecandiimidamide, antimicrobial quaternary surface active compounds, guanidines. However, particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.

In order to facilitate the disintegration of preformed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times. By tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients. Desintegration aids may preferably be used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.

As described above, the dishwasher according to the invention consists of at least two phases, wherein the first phase is solid and compacted and the second phase of a Surfactant melt exists. To prepare such a dishwashing detergent, the first phase is first prepared by methods known in the art in the form of a pressed powder phase. After preparation, the first phase preferably has a depression or the like, into which the second phase can be introduced as surfactant melt. For this purpose, the components of the surfactant melt are mixed at temperatures at which the components of the surfactant melt for the most part, preferably completely, liquefied, for example at temperatures above 50 ° C. The melting temperature of the surfactant melt depends on the melting points of the particular components used. Subsequently, the liquid surfactant melt is poured hot into the designated well of the first solid phase of the dishwashing detergent so that it can harden. Alternatively, the second phase hot liquid surfactant melt may also be preformed in any other suitable form as desired to be subsequently adhered to a designated and suitable location on the surface of the solid first phase. Such a suitable location on the surface of the first solid phase may, for example, be a suitable depression or depression. The cured surfactant melt has more attractive optical properties compared to pressed powder phases.

The dishwashing agents described herein are preferably prefabricated into dosage units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a total weight of between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g. The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

The weight ratio of the first, preferably compacted phase to the second phase (surfactant melt phase) is preferably 20: 1 to 1: 1, preferably 15: 1 to 5: 1, in particular 12: 1 to 7: 1, for example 10: 1 to 8: 1.

The automatic dishwashing agents, in particular the prefabricated metering units, have a water-soluble coating, with particular preference.

The water-soluble coating 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.

The water soluble package may have one or more chambers. The agent may be contained in one or more chambers, if any, of the water soluble envelope. The amount of agent preferably corresponds to the full or half dose needed for a rinse.

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 5,000 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 comprising (meth) acrylic acid-containing (co) may additionally be used for a polyvinyl alcohol-containing film material which is suitable for producing the water-soluble coating. Polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added. A preferred additional polymer is polylactic acids.

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

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

It may be preferred that the film material contains further additives. The film material may 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.

According to a preferred embodiment, the multi-phase dishwashing detergent is closely enveloped by a water-soluble film

The water-soluble film, which is preferably used in the narrow envelope, particularly preferably comprises polyvinyl alcohol, as described above, wherein as starting thickness preferably a thickness of 10 .mu.m to 100 .mu.m, in particular from 12 .mu.m to 60 .mu.m, particularly preferably from 15 .mu.m to 50 μm, especially from 20 microns to 40 microns, in particular from 22 microns to 35 microns is used.

In the case of a tight envelope, a disposable portion of the washing or cleaning agent is wrapped in each case. For the coated detergent or cleaning agent portion according to the invention, it is important that the coating rests close to its surface at any point of the tablets. Ideally, the envelope is even under tension, which is not absolutely necessary. This dense covering of the envelope is conducive to disintegration: upon first contact with water, the envelope will pass a small amount of water at some point, and at first it does not need to dissolve at all. At this point, the disintegrant contained in the tablet begins to swell. As a result, the wrapper suddenly ruptures as a result of the volume increase of the tablet and releases the tablet. If the wrapper is not tight, the mechanism described here will not work as the tablet can swell without bursting the wrapper. In this case, the use of a swellable disintegrating agent is superior to a gas-developing system, since its explosive effect in each case leads to a rupture of the casing. In a gas-evolving system, the explosive effect may "fizzle out" of the enclosure by leakage of the gas from a leak.

Preferred detergent or cleaning agent portions according to the invention are characterized in that the distance between the disposable portion and water-soluble coating over the entire surface is 0.1 to 1000 μm, preferably 0.5 to 500 μm, particularly preferably 1 to 250 μm and in particular 2.5 to 100 microns, is.

In a preferred embodiment, the film wrapping is first loosely wrapped around a detergent or cleaning agent portion and sealed and then shrunk onto it so that there is close contact between the film package and the detergent concentrate. Accordingly, washing or cleaning agent disposable portions according to the invention are characterized in that the wrapping is a film packaging shrunk onto the latter.

For example, this wrapping can be done by a water-soluble lower film is placed on a transport chain or a mold (s) tool, then one or more washing or Detergent portion (s) are placed on the lower film; then a water-soluble upper film is placed on the washing or cleaning agent portion (s) on the lower film and this is then fixed on the lower film, including the washing or cleaning agent portion (s),

Alternatively, this step can also be done by a single-stranded film, which is then placed around the disposable portions as a tube. This is followed by sealing and optional cutting of the films. Subsequently, then the shrinking of the film by the use of hot air or infrared radiation, optionally with pressing done.

Such water-soluble coatings are also in the patent applications WO 2004/031338 A such as WO 2003/099985 A , the disclosure of which is hereby incorporated by reference, already described. Table 1: Basic formulation of the cleaning agents according to the invention (base tablets without surfactant-melting core), in particular dishwashing detergent, preferably automatic dishwashing detergent; Unless indicated otherwise, the following information relates to% by weight of active substance, based on the total weight of the composition: Wt .-% preferably wt.% Citrate, Na salt 10-25 15-20 Phosphonate (eg HEDP) 0-10 2.5-7.5 MGDA, Na salt 0-40 0-25 Disilicate, Na salt 0-40 5-35 soda 10-30 10-25 Percarbonate, Na salt 5.0-20.0 10-15 Bleach catalyst (preferably Mn-based) 0.0 to 0.8 0.02-0.5 Bleach activator (eg TAED) 1.0-4.0 1-3 Nonionic surfactant (s), eg fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 1.5 to 15.0 2.5-10 polycarboxylate 0.5-15 4-10 Cationic copolymer 0.0-1.0 0-0.75 Disintegrant - (eg Crosslinked PVP) 0.0-3.0 0.0-3.0 Protease preparation (tq) 1.0 to 7 1.5-5 Amylase preparation (tq) 0.2-6 0.5-3 Silver protection (benzotriazole) 0.0-1.0 0-0.5 Perfume 0.0-0.5 0.05-0.25 dye solution 0.0 to 1.5 0.0 to 1 Zn salt (eg acetate) 0.01-0.5 0.1-0.3 sodium sulphate 0.0 to 25 0.0 to 10 water 0.0 to 3 0.0 to 1.5 pH-adjusting agent (eg citric acid) 0.0-5 0-1.5 processing aids 0-10 0-5 Table 2: Frame formulation of the surfactant melt core according to the invention for combination with cleaning agents, in particular dishwashing agents, preferably mechanically Dishwashing agents according to Table 1; Unless indicated otherwise, the following information relates to% by weight of active substance, based on the total weight of the core: Wt .-% preferably wt.% Fatty alcohol ethoxylate (s) without endcap, 10-80 EO 5.0 to 100 5-50 Fatty alcohol ethoxylate (e) endcapped 0.0 to 70 5-60 PEG 0.0 to 70 10-50 Citrate, Na salt 0.0 to 20 0.0 to 10 sulfopolymer 0.0 to 15 0.0 to 10 polyacrylate 0.0 to 15 0.0 to 10 dyes 0.0-5.0 0.0-2.0

The corresponding use of the dishwashing compositions according to the invention is likewise an object of the invention. The invention likewise relates to a method, in particular a machine dishwashing method, in which a washing or cleaning center according to the invention is used in at least one step of the method. The subject matter of the present application is therefore furthermore a process for the cleaning of dishes in a dishwashing machine, in which the agent according to the invention is metered into the interior of a dishwasher during the passage of a dishwashing program before the main wash cycle or during the main wash cycle. The metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher.

The embodiments described in context with the agents according to the invention are readily transferable to the methods and uses of the invention and vice versa.

Examples

Example 1: Preparation of a tablet with a surfactant melt core

The enamel body consists for example of 10-50% PEG (average Mr 1000 to 8000 g / mol), 5-60% fatty alcohol ethoxylate endcap, preferably C ₈ -C ₁₀ endcap, 5-50% fatty alcohol ethoxylate with 10-80 EO, preferably 25 -50 EO.

The components are mixed at temperatures> 50 ° C and poured hot into the well of a dishwasher tab (preferably according to the base tablet, Table 3). The mass is allowed to cure in the trough. Preforming and subsequent gluing of such a melt is also conceivable. Table 3: raw materials based tablet fusible core Addition g / job % * g / job from to from to Na citrate 12.90 51.61 2.00 8th soda 19.35 32.26 3.00 5 Na Percarbonate 12.90 22.58 2.00 3.5 Manganese-containing bleach catalyst 0.01 0.32 0.001 0.05 TAED 3.23 6.45 0.50 1 Fatty alcohol ethoxylate C10 Endcapped 1.29 3.87 0.20 0.6 0.85 Fatty alcohol ethoxylate C12 endcapped 0.65 3.23 0.10 0.5 benzotriazole 0.06 0.65 0.01 0.1 sulfopolymer 1.94 6.45 0.30 1 Polyethylene glycol average. Mr 4000 g / mol 0.65 3.23 0.10 0.5 0.5 Protease (tq) 0.45 1.42 0.07 0.22 Amylase (tq) 0.13 0.65 0.02 0.1 Perfume 0.06 0.13 0.01 0.02 dyes 0.65 1.29 0.10 0.2 Zn acetate 0.06 0.26 0.01 0.04 Na sulphate 3.23 9.68 0.50 1.5 water 0.00 1.29 0.00 0.2 phosphonate 0.00 32.26 0.00 5 silicate 0.00 32.26 0.00 5 C _16-18 fatty alcohol ethoxylate 25 EO - - - - 0.35 * based on a base tablet weight of 15.5 g

Example 2: Fat Cleaning Trial

To determine the removal of grease, in a Bosch SMS68 dishwasher in the 40 ° C Gentle program, in each case 10 g fat (5 g butter + 5 g margarine) with a dishwashing tablet (composition according to basic tablet (15.5 g, without surfactant melt core This is used to build up fat on the filter The amount of fat in the filter is determined gravimetrically.

Subsequently, without adding fat with a dishwasher tablet gem. Rinsed base composition (15.5 g) without or with surfactant melt core (according to Example 1) and weighed the sieve again. Differential weighing gives the amount of grease removed and is given as a percentage (Table 4). Table 4 Trial 1 Trial 2 Average Removal in% Basic tablet without surfactant melt core 22.1 16.2 19.2 Basic tablet with surfactant melt core 60.3 52.3 56.3

It can be clearly seen that the tablet with surfactant melt core leads to a significantly better removal of grease in the filter.

QUOTES INCLUDE IN THE DESCRIPTION

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

Cited patent literature

• WO 2004/031338 A [0142]
• WO 2003/099985 A [0142]

Claims (14)

A dishwashing detergent comprising at least a first solid, compacted phase and at least one second phase, characterized in that the at least one second phase is a surfactant melt comprising 10-100 wt.%, Preferably 20-100%, more preferably 50-100 wt. % Surfactants, preferably nonionic surfactants. Dishwashing detergent according to claim 1, characterized in that the nonionic surfactants contained in the at least one second phase are not end-capped, poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x H, characterized in that R ^{1 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, and wherein x for values between 1 and 80, preferably for values between 15 and 50 and in particular for values between 25 and 50 stands. Dishwashing detergent according to claim 2, characterized in that R ^{1 represents} a linear or branched C _12-20 alkyl radical, in particular a linear or branched C _16-18 alkyl radical. Dishwashing composition according to one of claims 2 or 3, characterized in that the at least one second phase, the non-endgruppenverschlossenen, poly (oxyalkylated) nonionic surfactants in amounts of 5 to 50 wt .-%, preferably 10 to 30 wt .-%, based on the second phase, contains. A dishwashing detergent according to any one of claims 2 to 4, characterized in that the at least one second phase contains, in addition to the non-end-capped poly (oxyalkylated) nonionic surfactants, at least one end-capped nonionic surfactant of formula R ¹ O [CH ₂ CH ₂ O] _x R ² , wherein R ^{1 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, R ^{2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms and x stands for values between 1 and 80, preferably for values between 15 and 50 and in particular for values between 20 and 50. Dishwashing detergent according to claim 5, characterized in that R ^{1 is} a linear or branched C _12-20 alkyl radical, in particular a linear or branched C _16-18 alkyl radical, and / or R ^{2 is} a linear or branched C _6-22 alkyl radical , in particular a linear or branched C _8-12 alkyl radical. Dishwashing agent according to one of claims 5 or 6, characterized in that the end-capped poly (oxyalkylated) nonionic surfactants in amounts of 5-60 wt .-%, preferably 40-60 wt .-%, based on the second phase, are included. Dishwashing composition according to one of claims 5 to 7, characterized in that the mass ratio between the end-capped nonionic surfactants and non-end-capped nonionic surfactants in the at least one second phase from 20: 1 to 1: 5, preferably from 10: 1 to 1: 1, in particular from 3: 1 to 2: 1. Dishwashing detergent according to one of claims 1 to 8, characterized in that the nonionic surfactants of the at least one second phase have a melting point above 25 ° C, preferably between 25 and 65 ° C, more preferably between 26.6 and 55 ° C. Dishwashing agent according to one of claims 1 to 9, characterized in that the at least one second phase contains at least one further ingredients, preferably polyethylene glycols (PEG), preferably having an average molecular weight between 800 and 8000 g / mol, in an amount of 10 to 40 Wt .-%, preferably 25-35 wt .-% based on the weight of the second phase. Dishwashing composition according to one of claims 1 to 10, characterized in that the at least one first phase contains at least one surfactant, preferably at least one nonionic surfactant. Dishwashing composition according to claim 11, characterized in that the at least one first phase comprises at least one further ingredient selected from the group consisting of builders, polymers, bleaches, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, glass corrosion inhibitors, foam inhibitors, dyes, Additives to Improvement of drainage and drying behavior, Disintegrationshilfsmitteln, preservatives, pH Stellmittenl, fragrances and perfume carriers contains.  Use of a dishwashing detergent according to any one of claims 1 to 12 for mechanically cleaning dishes. A process for the automatic cleaning of dishes, characterized in that in at least one process step, a wax or cleaning agent according to any one of claims 1 to 12 is applied.