EP3325592B1 - Use of a combination of a complexing agent and a surfactant for improving rinsing power - Google Patents

Description

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

Machine-washed dishes are often subject to higher requirements than manually-washed dishes. For example, dishes that at first glance have been completely cleaned of food residues are rated as not flawless if they still show so-called "spotting" (drops) or "filming" (cloudy film) after machine dishwashing.

Plastics are particularly critical with regard to the rinsing performance, as they usually have a non-polar surface and have a lower heat capacity compared to porcelain and glass. The drainage and drying behavior of water droplets is poor, which means that water stains remain visible on the plastic surface. This effect is reinforced by high water hardness and is more noticeable on colored plastic items to be washed (e.g. Tupperware®).

WO 2014/139653 A2 discloses a dishwashing detergent in the form of a tablet comprising MGDA and nonionic surfactants.

The tableting of basic or core tablets (formulas) with a high content of MGDA (methylglycine diacetic acid) is difficult because the raw material MGDA is difficult to compress in large quantities and leads, for example, to considerable caking of the stamps and damage to the tablet surface.

Surprisingly, it has now been found that the addition of a combination of complexing agents and surfactants mentioned below to an automatic dishwashing detergent reduces so-called "spotting" on the dishes compared to a conventional automatic dishwashing detergent formulation, which makes the dishes (especially plastic) cleaner and, in particular, also for the consumer, creates a visually clean impression. Instead of the usual pressed core, a MGDA-containing melt core is used, in which larger amounts of MGDA and surfactant can be formulated compared to conventional pressed cores. Compared to a pressed core, about twice the amount of MGDA and about ten times the amount of surfactant can be used over a fused core. This is not possible with pressed cores, as this amount of surfactant and MGDA sticky non-compressible powders would result. Compared to the standard tablet with a compressed core, the disintegration time or the dissolution time of the entire tablet with an enamel core is not delayed, but rather shows a comparable dissolution profile.

In a first aspect, the present invention is therefore directed to a dishwashing detergent comprising at least one first solid, compacted phase and at least one second phase, the at least one second phase being a melt core comprising at least one surfactant, in particular a nonionic surfactant, in an amount of 10-40% by weight, based on the total weight of the melt core, and at least one complexing agent from the group of aminocarboxylic acids and their salts, in an amount of 30-60% by weight, based on the total weight of the melt core.

In a further aspect, the present invention is directed to the use of a dishwashing agent according to the invention for machine cleaning of dishes.

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

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 dishes. 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. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it goes without saying that the examples contained herein are intended to describe and illustrate the invention, but not to restrict it, and in particular the invention is not limited to these examples. Unless otherwise stated, all percentages are percentages by weight. Numeric ranges given in the format "from x to y" include the stated values. If several preferred numerical ranges are given in this format, it is understood that all ranges resulting from the combination of the various endpoints are also recorded.

"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 detergent according to the invention comprises at least two phases, the first phase being solid and compacted and the second phase being a melt. A "melt" is a composition that liquefies under the action of elevated temperatures (e.g.> 50 ° C), which solidifies again when it cools down to room temperature and forms a solid form.

For the purposes of the present invention, a phase is a spatial area in which physical parameters and the chemical composition are homogeneous. A phase differs from another phase by various features, for example ingredients, physical properties, external appearance, etc. Different phases can preferably be distinguished optically. For the consumer, the at least one first phase can be clearly distinguished from the at least one second phase. If the washing or cleaning agent according to the invention has more than one first phase, these can also be distinguished from one another with the naked eye because they differ from one another, for example, in terms of color. The same applies if there are two or more second phases. In this case, too, a visual differentiation of the phases is possible, for example on the basis of a color or transparency difference. Phases in the sense of the present invention are thus self-contained areas that can be visually distinguished from one another by the consumer with the naked eye. When used, the individual phases can have different properties, such as, for example, the speed with which the phase dissolves in water and thus the speed and the sequence in which the ingredients contained in the respective phase are released.

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 to either the at least one first phase, as defined herein, or the at least one second phase, as defined herein. The compositions of the phases corresponding to one another can differ to the extent that the respective definitions listed below allow both the at least one first phase and the at least one second phase. For example, it can be a three-phase dishwashing detergent which has 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 detergent is a melt core which contains at least one surfactant, in particular a nonionic surfactant in an amount of 10-40% by weight, based on the total weight of the melt core, and at least one Complexing agents from the group of aminocarboxylic acids and their salts in an amount of 30-60% by weight, based on the total weight of the melt core. The second phase is accordingly also referred to below as “fusible core” or “fusible core phase”.

All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants in this at least one melt core phase. In preferred embodiments, however, nonionic surfactants from the group of alkoxylated alcohols are used. One class of preferably usable nonionic surfactants, which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants as part of the melt core phase, are accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters.

In this context, preference is given in particular to those nonionic surfactants which are end-capped, poly (oxyalkylated) nonionic surfactants according to the formula R ¹ O [CH ₂ CH ₂ O] _x R ² , where R ^{1 stands} for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms and R ^{2 stands} for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, and where x stands for values between 1 and 80, preferably for values between 15 and 50 and in particular for values between 20 and 25. 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 _4-22 alkyl radical, are very particularly preferred. preferably a C _4-14 alkyl radical, more preferably a C _6-12 alkyl radical, in particular a linear or branched C _8-10 alkyl radical.

In preferred embodiments, the above-described end-group-capped, poly (oxyalkylated) nonionic surfactants of the fused core phase are used in amounts of 10-40% by weight, based on the fused core phase.

In a further embodiment, the above-described end-capped, poly (oxyalkylated) nonionic surfactants of the fused core phase are combined with a further surfactant from the group of non-end-capped, poly (oxyalkylated) nonionic surfactants according to the formula R ¹ O [CH ₂ CR ³ HO] _x H, where R ^{1 stands} for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, each R ³ independently for H, CH ₃ or CH ₂ -CH ₃ , preferably for H or CH ₃ and x stands for values between 1 and 80, preferably for values between 15 and 50 and in particular for values between 20 and 25. Fatty alcohol ethoxylates or fatty alcohol ethoxypropoxylates are very particularly preferred where 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 poly (oxyalkylated) non-end-capped poly (oxyalkylated) nonionic surfactants of the fused core phase described above are used in amounts of 10-30% by weight, based on the fused core phase. In general, the nonionic surfactants used in the surfactant melt phase have a melting point above room temperature. Nonionic surfactant (s) with a melting point above 25 ° C., preferably between 25 and 50 ° C. and in particular between 26.6 and 43.3 ° C., is / are particularly preferred.

The complexing agent is contained in the melt core phase in an amount of 30 to 60% by weight, based on the total weight of the melt core.

The complexing agents from the group of aminocarboxylic acids and their salts contained in the at least one second phase can be, for example, methylglycine diacetic acid (MGDA) or its salts, glutamine diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or its salts (EDDS). According to a preferred embodiment, the complexing agent is methylglycinediacetic acid.

In addition to the surfactants mentioned and the complexing agent, the fused core phase can also contain other ingredients. Preferably such ingredients include, for example, polyethylene glycol (PEG). PEG can be contained, for example, in amounts of 10 to 40% by weight, preferably 25-35% by weight, based on the weight of the fused core phase. Further polymers, in particular polycarboxylates, can likewise preferably be contained in the melt core phase.

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

Suitable nonionic surfactants in 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, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol that stands for a glycose unit with 5 or 6 carbon atoms, preferably for 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.

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 can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half that.

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

However, preference is given to using low-foaming nonionic surfactants in the first phase, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. The automatic dishwashing agents particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols.

One class of usable nonionic surfactants that can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

Surfactants to be used with preference come from the groups of ethoxylated primary alcohols and mixtures of these surfactants with structurally complex 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. Davon sind insbesondere nichtionische Tenside bevorzugt, die einen C_9-15-Alkylrest mit 1 bis 4 Ethylenoxideinheiten, gefolgt von 1 bis 4 Propylenoxideinheiten, gefolgt von 1 bis 4 Ethylenoxideinheiten, gefolgt von 1 bis 4 Propylenoxideinheiten aufweisen.Suitable nonionic surfactants are those which have alternating ethylene oxide and alkylene oxide units. Among these, surfactants with EO-AO-EO-AO blocks are again preferred, one to ten EO or AO groups being bonded to one another before a block from the other groups follows. Here are nonionic surfactants of the general formula

preferably 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 of one another stand for whole numbers from 1 to 6. Of these, nonionic surfactants are particularly preferred 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.

• 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 -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 represents} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A, A ', A "and A'" independently of one another for 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 stand for values between 0.5 and 120, where x, y and / or z can also be 0.

Particularly preferred are those end-capped, poly (oxyalkylated) nonionic surfactants which, according to 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 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² with 1 to 30 carbon atoms, where x stands for values between 1 and 90, preferably for values between 10 and 80 and in particular for values between 20 and 60. Surfactants of the above formula in which R ^{1 is} C ₇ to C ₁₃ , x is an integer natural number from 16 to 28 and R ^{2 is} Cs to C ₁₂ are particularly preferred.

Also 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 up to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15.

, Especially the C (EO) -2-hydroxyalkyl ether _{15-40 8-10} fatty alcohol (PO) ₁ - - to the group of these nonionic surfactants include the C _2-26 fatty alcohol, for example (PO) ₁ (EO) ₂₂ -2 hydroxydecyl ether. Also particularly preferred are 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 ² independently of one another represent 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 stands for -CH ₃ , and x and y independently of one another stand for values between 1 and 32, nonionic surfactants with R ³ = -CH ₃ and values for x from 15 to 32 and y from 0.5 and 1.5 being very particularly preferred are.

Further nonionic surfactants which can be used with preference are the end group-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 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2- Butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j for 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 can 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, 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 can be different if x 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if 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 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 x has been chosen as an example and can be larger, the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula becomes R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH ) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 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. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 have} 9 to 14 carbon atoms, R ³ stands for 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

• R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 -alkyl or -alkenyl radical;
• R ^{2 represents} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A represents 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 includes, 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 alcohols (EO) _40-80 -2-hydroxyalkyl ether.

In various embodiments of the invention, instead of the end-capped hydroxy mixed ethers defined above, it is also possible to use the corresponding non-end-capped hydroxy mixed ethers. These can satisfy the above formulas, but where R ² is hydrogen and R ¹ , R ³ , A, A ', A ", A'", w, x, y and z are as defined above.

The specified carbon chain lengths and degrees of ethoxylation or degrees of alkoxylation of the nonionic surfactants represent statistical mean values which, for a specific product, can be a whole number or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned mostly do not consist of an individual representative, but rather of mixtures, which can result in mean values and fractional numbers for both the carbon chain lengths and the degrees of ethoxylation or alkoxylation.

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. Surfactant mixtures are not mixtures of nonionic surfactants which in their entirety fall under one of the general formulas mentioned above, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different ones of the general formulas mentioned above .

The dishwashing detergents described herein, which in the at least one first phase comprise 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 agent of at least 2% by weight, preferably at least 5% by weight. The absolute amounts used per application can, for example, be in the range from 0.5-10 g / job, preferably in the range from 1-5 g / job. Those nonionic surfactants which have a melting point above room temperature are particularly preferred. Nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C., is / are particularly preferred .

Suitable nonionic surfactants which have melting points 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 can also contain the surfactants described above in connection with the second phase, in particular the optionally described end-group-capped fatty alcohol ethoxylates.

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

All anionic surface-active substances are suitable as anionic surfactants in dishwashing detergents. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 to 4 carbon 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 with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

Cationic and / or amphoteric surfactants, such as betaines or quaternary ammonium compounds, can also be used instead of the surfactants mentioned or in conjunction with them. However, it is preferred that no cationic and / or amphoteric surfactants are used.

In addition, in the at least one first phase, the dishwashing detergent can contain further ingredients which further improve the application-related and / or aesthetic properties of the dishwashing detergent. In the context of the present invention, the dishwashing detergent contains in various embodiments at least one or preferably several 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, can be advantageous.

In an embodiment preferred according to the invention, the use of phosphates (including polyphosphates) is largely or completely dispensed with. In this embodiment, the agent contains preferably less than 5% by weight, particularly preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s). In this embodiment, the agent is particularly preferably completely phosphate-free, i.e. the agent contains 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 agents according to the invention is preferably 15 to 80% by weight and in particular 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 as meaning 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. Thus, preferred polycarboxylic acids are dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids. The polycarboxylic acids can also carry other functional groups, such as hydroxyl or amino groups. For example, these are 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, such as, for example, nitro-tetracarboxylic acids diacetic acid (also known as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA), methylglycinediacetic acid (MGDA)) and their derivatives and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures of these.

Also suitable as organic builders are polymeric polycarboxylates (organic polymers with a large number of (in particular more than ten) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins.

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

Particularly preferred cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, contain one or more salts of citric acid, that is to say citrates, as one of their essential builders. These are preferably in a proportion of 2 to 40% by weight, in particular 5 to 30% by weight, particularly 7 to 28% by weight, particularly preferably 10 to 25% by weight, very particularly preferably 15 to Contain 20% by weight, each based on the total weight of the agent.

The use of carbonate (s) and / or hydrogen carbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate (soda), in amounts of from 2 to 50% by weight, preferably from 4 to 40% by weight, is also particularly preferred. -% and in particular from 10 to 30% by weight, very particularly preferably 10 to 24% by weight, each based on the weight of the agent.

Particularly preferred cleaning agents according to the invention, in particular dishwashing detergents, preferably machine dishwashing agents, are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, the proportion by weight of these builders, based on the total weight of the cleaning agent according to the invention, is preferably 5 to 70% by weight, preferably 15 to 60% by weight and in particular 20 to 50% by weight. The combination of two or more builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents. In addition to the builders mentioned here, one or more other builders can also be included.

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

In a 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% by weight, in particular 10 to 25% by weight, very particularly preferably 15 to 20% by weight, in each case based on the total amount of the cleaning agent, the total amount of these two Builders preferably 20 to 65% by weight, in particular 25 to 60% by weight, preferably 30 to 50% by weight. In addition, one or more other builders can also be included.

The cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, can in particular contain phosphonates as a further builder. A hydroxyalkane and / or aminoalkane phosphonate is preferably used as the phosphonate compound. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologs are preferred as aminoalkanephosphonates. Phosphonates are preferably used in the agents according to the invention in amounts from 0.1 to 10% by weight, in particular in amounts 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.

The combined use of citrate, (hydrogen) carbonate and phosphonate is particularly preferred. These can be used in the abovementioned amounts. In particular, amounts of, based on the total weight of the agent, 10 to 25% by weight of citrate, 10 to 30% by weight of carbonate (or hydrogen carbonate) and 2.5 to 7.5% by weight are used in this combination. Phosphonate used.

Further particularly preferred cleaning agents, in particular dishwashing detergents, preferably machine dishwashing 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, this is selected from the aminocarboxylic acids, the further phosphorus-free builder preferably being selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDSDS) and ethylenediamine disuccinate (preferably from 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 MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25% by weight. The use of MGDA or GLDA, in particular MGDA, as granules is particularly preferred. MGDA granulates 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 are advantageous. The combination of at least three, in particular at least four builders from the group mentioned above has proven particularly useful for the cleaning and rinsing performance of cleaning agents according to the invention Dishwashing detergents, preferably automatic dishwashing detergents, have proven advantageous. In addition, further builders can also be included.

Polymeric polycarboxylates are also suitable as organic builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol. Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates from this group, which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred.

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

Cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, can furthermore contain crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} · y H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x 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 module of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which are preferably delayed in dissolution and have secondary washing properties.

In certain cleaning agents according to the invention, in particular dishwashing detergents, preferably machine dishwashing detergents, the content of silicates, based on the total weight of the cleaning agent, 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 can also contain alkali metal hydroxides. These alkali carriers are used in the detergents or cleaning agents and in particular in the second phases preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5% by weight and in particular between 0.5 and 5% by weight, based in each case on the total weight of the detergent or cleaning agent, are used. Alternative cleaning agents according to the invention are free from alkali metal hydroxides.

The at least one first phase of the dishwashing detergents described herein can also contain various polymers.

According to the invention, homopolymers of α, β ethylenically unsaturated carboxylic acids, for example, can be used in various embodiments. The unsaturated carboxylic acid (s) used is / 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 represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or for -COOH or -COOR ⁴ , where 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 (methyl maleic acid), methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. Acrylic acid is very particularly preferred. In various embodiments of the invention, the homopolymer is therefore a polyacrylic acid.

In the polymers, the carboxylic acid groups can be wholly or partially in neutralized form, i.e. the acidic hydrogen atom of the carboxylic acid group in some or all carboxylic 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 polymers is preferred according to the invention.

The molar mass of the homopolymers used can be varied in order to adapt the properties of the polymers to the desired application. Preferred dishwashing detergents are characterized in that the homopolymers, in particular the polyacrylic acids, have molar masses M _n of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates from this group, which have molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1500 to 5000 g / mol, can in turn be preferred.

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

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

The monomers containing sulfonic acid groups are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

preferred, in which R ⁵ to R ⁷ independently of one another for -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, with - 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 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 -.

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 optionally present spacer group 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-hydroxy-propanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulphonic acid, 2-methyl-2-propen1-sulphonic acid, 3-sulphate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.

In the copolymers, too, the acid groups can be wholly or partly in neutralized form, ie the acidic hydrogen atom of the sulfonic and / or carboxylic acid group in some or all of the 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 used with preference is, in the case of copolymers which only contain monomers containing carboxylic acid groups and monomers containing sulphonic acid groups, preferably in each case from 5 to 95% by weight; the proportion of the monomer containing sulphonic acid groups is particularly preferably 50 to 90% by weight. and the proportion of the monomer containing carboxylic acid groups is 10 to 50% by weight, the monomers in this case being preferably selected from those mentioned above.

In various embodiments, the copolymers can contain, in addition to the above-described monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, further monomers, in particular unsaturated monomers containing carboxylic acid ester groups. In such terpolymers, the monomers containing carboxylic ester groups 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 defined as above and R ^{4 is} saturated or unsaturated, straight-chain or is a 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. _{C 1-8} alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate are very particularly preferred. Ethyl acrylate is very particularly preferred.

The molar mass of the copolymers used can be varied in order to adapt the properties of the polymers to the desired application. Preferred dishwashing detergents are characterized in that the copolymers have molar masses M _n from 2000 to 200,000 g / mol, preferably from 4000 to 25,000 g / mol and in particular from 5000 to 15,000 g / mol.

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

The dishwashing detergents can alternatively or additionally contain further polymers. The group of suitable polymers includes, in particular, the cleaning-active amphoteric, zwitterionic ones or cationic polymers, for example the rinse aid polymers and / or polymers that act as softeners.

Preferred amphoteric polymers that can be used come from the group of the alkyl acrylamide / acrylic acid copolymers, the alkyl acrylamide / methacrylic acid copolymers, the alkyl acrylamide / methyl methacrylic acid copolymers, the alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth ) acrylic acid copolymers, the alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.

Other zwitterionic polymers that can be used come from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts, acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts and methacroylethylbetaine / methacrylate copolymers.

Cationic polymers that can be used originate 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 methacrylate, 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 aforementioned amphoteric, zwitterionic or cationic polymers are present in prefabricated form. Among other things, it is suitable for the packaging of the polymers

• the encapsulation of the polymers by means of water-soluble or water-dispersible coating agents, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• the encapsulation of the polymers by means of water-insoluble, meltable coating agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins with a melting point above 30 ° C .;
• the cogranulation of the polymers with inert carrier materials, preferably with carrier materials from the group of detergent or cleaning-active substances, particularly preferably from the group of builders or co-builders.

Dishwashing detergents according to the invention preferably contain one or more enzyme (s) as a further component in the first phase. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are correspondingly preferred. Cleaning agents 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 with the aid of known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples are the subtilisins BPN 'and Carlsberg as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the subtilase enzymes, but no longer the subtilisins in the narrower sense of the term, thermitase, Proteinase K and the proteases TW3 and TW7.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, and the improved further 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 emphasized.

According to the invention, lipases or cutinases can also be used, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtained 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 substitutions D96L, T213R and N233R.

It is also possible to use enzymes which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

To increase the bleaching effect, according to the invention, 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. Advantageously, preferably organic, particularly preferably aromatic, compounds interacting with the enzymes are added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling. A protein and / or enzyme can be protected against damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage. In the case of microbial production of the proteins and / or enzymes, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Cleaning agents can contain stabilizers for this purpose; the provision of such means represents 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, storable and transportable preparations. These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or with stabilizers or other auxiliaries.

Alternatively, the enzymes for the first and / or second phase can be encapsulated, 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 in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Such granulates are advantageously low in dust, for example through the application of polymeric film-forming agents, and, owing to the coating, are stable in storage.

It is also possible to pack two or more enzymes together so that a single granulate has several enzyme activities.

As can be seen from the previous statements, 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% by weight of the enzyme protein. Are particularly preferred those cleaning agents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of the respective enzyme preparations.

The dishwashing detergent can also contain one or more enzyme stabilizers. Examples of suitable enzyme stabilizers include boron-containing compounds such as boric acid or boronic acids, and their salts and esters, polyols such as, for example, glycerol or 1,2-ethylene glycol, sugar, sugar alcohols, lactic acid or antioxidants.

In a preferred embodiment, dishwashing detergents according to the invention contain at least one zinc salt as a glass corrosion inhibitor as a further component. The zinc salt can 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, particularly preferably above 1 g / l and in particular 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 in cleaning agents according to the invention preferably in an amount of 0.01% by weight to 5% by weight, particularly preferably in an amount of 0.05% by weight to 3% by weight, in particular in an amount of 0.1% by weight to 2% by weight, based on the total weight of the cleaning agent.

In addition or as an alternative to the abovementioned zinc salts, polyethyleneimines, such as are available, for example, under the name Lupasol® (BASF), preferably in an amount of 0 to 5% by weight, in particular 0.01 to 2% by weight, can be used as glass corrosion inhibitors can be used.

The at least one first phase of the dishwashing detergent can furthermore contain a bleach, in particular an oxygen bleach and optionally a bleach activator and / or bleach catalyst. If available, these are only included in the first phase.

As a preferred bleaching agent, dishwashing agents according to the invention contain an oxygen bleaching agent from the group consisting of sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate. Other useful bleaching agents are, for example Peroxypyrophosphates, citrate perhydrates and _{peracid salts or peracids which provide H 2} O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. Furthermore, bleaches from the group of organic bleaches can also be used. Typical organic bleaching agents are the diacyl peroxides, such as, for example, dibenzoyl peroxide. Further typical organic bleaching agents are the peroxy acids, the alkyl peroxy acids and the aryl peroxy acids being mentioned as examples. Sodium percarbonate is particularly preferred because of its good bleaching performance. A particularly preferred oxygen bleach is sodium percarbonate.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances which carry 0- and / or N-acyl groups with the stated number of carbon atoms and / or optionally substituted benzoyl groups are suitable. Polyacylated alkylenediamines are preferred, tetraacetylethylenediamine (TAED) having proven particularly suitable.

The bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salen 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-amine complexes can also be used as bleach catalysts. Manganese complexes in the II, III, IV or IV oxidation state, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S, are used with particular preference. Ligands are preferably used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the agents according to the invention which have 1,4,7-trimethyl-1,4,7-triazacyclononane (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 ] (ClO 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 ] (ClO ₄ ) ₄ , [Mn ^III ₂ (µ-O) ₁ (µ-OAc) ₂ (Me-TACN ) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (µ-O) ₁ (µ-OAc) ₂ (Me-TACN) ₂ ] (ClO 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 conventional pH regulators, the pH being selected depending on the intended use. In various embodiments, the pH is in a range from 5.5 to 11, preferably 6 to 10.5, even more preferably 7 to 10.5, in particular greater than 7, especially in the range 8.5 to 10.5. Acids and / or alkalis, preferably alkalis, are used as pH adjusting agents. 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, the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used. Suitable bases come 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. Particularly preferred, however, is volatile alkali, for example in the form of ammonia and / or alkanolamines, which can contain up to 9 carbon atoms in the molecule. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and propanolamine and mixtures thereof.

To adjust and / or stabilize the pH, the dishwashing detergent according to the invention can also contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Preference is given to buffer substances which are also complexing agents or even chelating agents (chelators, INCI chelating agents). Particularly preferred buffer substances are 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.

In the context of the present invention, individual odoriferous compounds, e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type can be used as perfume oils or fragrances. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance note. Such perfume oils can also contain natural odorant mixtures, such as those obtainable from vegetable sources, e.g. pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

The dishwashing detergent according to the invention can also contain preservatives. For example, 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 and nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives are suitable 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'-methylene-bis- (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-tetraazatetradecanediimidamide, antimicrobial quaternary surface-active compounds, guanidines. Particularly preferred However, 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 prefabricated shaped bodies, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these agents in order to shorten the disintegration times. Tablet disintegrants or disintegration accelerators are understood as meaning auxiliaries which ensure the rapid disintegration of tablets in water or other media and the rapid release of the active ingredients. Disintegration aids can preferably be used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, based in each case on the total weight of the agent containing the disintegration aid.

As described above, the dishwashing detergent according to the invention consists of at least two phases, the first phase being solid and compacted and the second phase consisting of a melt core. To produce such a dishwashing detergent, the first phase is first produced in the form of a pressed powder phase using methods known in the prior art. After production, the first phase preferably has a depression or the like into which the second phase can be introduced as a melt. For this purpose, the components of the melt phase are mixed at temperatures at which the components of the melt phase are largely, preferably completely, liquefied, for example at temperatures above 50.degree. The melting temperature of this melt depends on the melting points of the respective components used. The hot liquid melt is then poured into the trough provided for the first solid phase of the dishwashing detergent so that it can harden. Alternatively, the hot, liquid melt of the second phase can also be pre-formed in any other form provided for this purpose, so that it can then be glued to a suitable point on the surface of the solid first phase provided for this purpose. Such a suitable location on the surface of the first solid phase can be, for example, a suitable depression or depression. The cured melt has more appealing optical properties compared to pressed powder phases.

In various embodiments, the dishwashing detergent according to the invention comprises several first phases, for example two first phases, these being independently of one another as defined above. For example, one of the first phases can contain bleach and other ingredients and the other enzymes and other ingredients. The several first phases are combined to form a multiphase basic tablet, for example by means of the method described above, which then has a depression or the like, into which the melting core is then introduced as described above.

According to a preferred embodiment, the multiphase dishwashing detergent is tightly wrapped in a water-soluble film or is contained in a water-soluble bag.

The water-soluble film or the water-soluble bag preferably comprises a water-soluble polymer. Some preferred water-soluble polymers, which are preferably used as water-soluble packaging, are polyvinyl alcohols, acetalized polyvinyl alcohols, polyvinylpyrrolidones, polyethylene oxides, celluloses and gelatins, polyvinyl alcohols and acetalized polyvinyl alcohols being particularly preferred.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten."Polyvinyl alcohols" (abbreviation PVAL, occasionally also PVOH) is the designation for polymers with the general structure

which in small proportions (approx. 2%) also have structural units of the type

contain.

Commercially available polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol), have degrees of hydrolysis of 87-99 mol%, i.e. they also contain one Residual content of acetyl groups.

In the context of the present invention, it is preferred that the water-soluble packaging at least partially comprises a polyvinyl alcohol whose degree of hydrolysis is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 mol% and above all 82 to Is 88 mole percent. In a preferred embodiment, the water-soluble packaging consists of at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least 80% by weight of a polyvinyl alcohol, its Degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%. Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the packaging, it being preferred according to the invention that the packaging material comprises a polyvinyl alcohol whose molecular weight is in the range from 5,000 gmol ^-1 to 100,000 gmol ^-1 , preferably 10,000 g.mol ^-1 to 90,000 g mol ^-1 , particularly preferably from 12,000 g mol ^-1 to 80,000 g mol ^-1 and in particular from 15,000 g mol ^-1 to 70,000 g mol ^-1 .

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, particularly preferably between about 240 to about 1680 and in particular between about 260 to about 1500.

The water solubility of polyvinyl alcohol can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols which are acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water. The reaction products of polyvinyl alcohol and starch are extremely advantageous. Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set to the desired values in a targeted manner.

The water-soluble bag is preferably from 10 μm to 500 μm, in particular from 20 μm to 400 μm, particularly preferably from 30 μm to 300 μm, especially from 40 μm to 200 μm, in particular from 50 μm to 150 μm. A particularly preferred polyvinyl alcohol is available, for example, under the trade name M8630 (Monosol).

The water-soluble film ((tight) envelope) particularly preferably comprises polyvinyl alcohol, as described above, the starting thickness preferably being from 10 μm to 100 μm, in particular from 12 μm to 60 μm, particularly preferably from 15 μm to 50 μm, above all from 20 µm to 40 µm, in particular from 22 µm to 35 µm, is used.

In the case of tight wrapping, a single portion of the detergent or cleaning agent is wrapped in each case. For the coated washing or cleaning agent single portion according to the invention, it is important that the coating lies tightly against the surface of the tablets at every point. Ideally, the envelope is even under tension, but this is not absolutely necessary. This tight fit of the cover is conducive to disintegration: the first time it comes into contact with water, a small amount of water will let through at some point, whereby it does not have to dissolve at all at first. At this point the disintegrant contained in the tablet begins to swell. This leads to the fact that the envelope is now due to the Increase in volume of the tablet suddenly tears open and the tablet is released. The mechanism described here does not work if the casing is not tightly fitting, since the tablet can swell without the casing being ruptured as a result. The use of a swellable disintegrant is superior to a gas-generating system, since its disintegrating effect always leads to the casing tearing open. In the case of a gas-generating system, the explosive effect can "fizzle out" as the gas escapes from a leak in the casing.

One-time detergent or cleaning agent portions preferred according to the invention are characterized in that the distance between the single portion and the water-soluble cover 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 µm.

In a preferred embodiment, the film wrapping is first placed loosely around a single portion of detergent or cleaning agent and welded and then shrunk onto it so that there is close contact between the film packaging and the cleaning agent concentrate. Accordingly, one-time detergent or cleaning agent portions according to the invention are characterized in that the envelope is a film packaging shrunk onto it.

For example, this wrapping can take place in that a water-soluble lower film is placed on a transport chain or a mold (s), then one or more detergent or cleaning agent portions are placed on the lower film; then a water-soluble upper film is placed on the detergent 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) Tube is placed around the disposable portions. This is followed by sealing and optional cutting of the foils. Then the film can then be shrunk on using hot air or infrared radiation, optionally with pressure applied.

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.

The dishwashing detergents described herein are preferably pre-packaged into metering units. These metering units preferably comprise the amount of washing or cleaning-active substances necessary for a cleaning cycle. Preferred dosing units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g. The volume of the aforementioned dosing units and their three-dimensional shape are shown with Particular preference is chosen so that the pre-assembled units can be metered 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 corresponding use of the dishwashing detergents according to the invention is also an object of the invention. The invention also relates to a method, in particular an automatic dishwashing method, in which a washing or cleaning agent according to the invention is used in at least one step of the method. The present application therefore also relates to a method for cleaning dishes in a dishwasher, in which the agent according to the invention is metered into the interior of a dishwasher while a dishwasher program is running before the start of the main wash cycle or during the main wash cycle. The dosing or introduction of the agent according to the invention into the interior of the dishwasher can take place manually, but the agent is preferably dosed into the interior of the dishwasher by means of the dosing chamber.

The embodiments described in the context of the agents according to the invention can easily be transferred to the methods and uses according to the invention, and vice versa.

Examples

Table 1 raw materials Standard formula - V1 Standard formula + surfactant / complexing agent combination E1 Standard formula + surfactant - V2 Standard formula + MGDA - V3 % * g / job addition addition addition from to from to g / job g / job g / job Na citrate 9.47 22.11 1.80 4.20 Citric acid 0.53 5.26 0.10 1.00 Phosphonate 4.21 7.89 0.80 1.50 Complexing agent (MGDA) 5.26 18.42 1.00 3.50 0.75 0.75 silicate 3.68 7.89 0.70 1.50 soda 16.84 26.32 3.20 5.00 Na percarbonate 13.16 18.42 2.50 3.50 Manganese bleach catalyst 0.01 0.11 0.002 0.02 TAED 2.11 3.16 0.40 0.60 Fatty alcohol ethoxylate C10 Endcapped 1.58 2.63 0.30 0.50 0.57 0.57 Fatty alcohol ethoxylate C12 Endcapped 1.05 2.63 0.20 0.50 Fatty alcohol ethoxypropoxylate 0.53 1.05 0.10 0.20 Benzotriazole 0.05 0.26 0.01 0.05 Sulfo polymer 5.26 9.47 1.00 1.80 cationic co-polymer 0.26 0.79 0.05 0.15 Polyethylene glycol 1.32 2.63 0.25 0.50 Protease 2.11 5.26 0.40 1.00 Amylase 0.42 1.05 0.08 0.20 Perfume 0.05 0.16 0.01 0.03 Dyes 0.53 1.32 0.10 0.25 Zn acetate 0.05 0.53 0.01 0.10 Na sulfate 0.53 2.63 0.10 0.50 water 0.05 0.53 0.01 0.10 69.06 140.53 13.12 26.70 * based on 19 g tablet weight E1 is a reference example.

Example 2: rinse test

To determine the rinsing effect, selected and defined items of crockery are washed 4 times and visually sampled after the 2nd, 3rd and 4th washing cycle. The first rinse is used to condition the dishes.

Rinse aid grades are assigned as parameters based on the visual appearance of the dry items to be washed (porcelain, glasses, plastic parts and stainless steel).

A tablet with the above-mentioned recipe is dosed and 100 g of dirt are dosed per wash cycle in order to simulate a normally soiled load.

"Spotting" is determined in two different dishwashers, on the one hand in the Bosch SMS 68M62 in the "50 ° C Eco Vario Speed" program, and on the other hand in a Miele G698 SC + in the "Normal 50 ° C" program. Water hardness: 21 ° dH.

After the end of the rinsing cycle, the machine is opened completely for 30 minutes and the rinsing effect is then visually determined in the black box (black painted room, D6500 daylight lamp). Any dried water droplets, streaks, deposits and films left on the dishes and cutlery are rated on a scale from 1-10. 10 means no films or no drops, 1 means strong film formation or strong droplet formation.

The following result was achieved by adding the surfactant-complexing agent combination according to the invention: <b> Table 3 </b> Spotting Miele Bosch melamine Tupperware melamine Tupperware V1 default 3.9 3.0 7.0 3.7 V2 Standard + surfactant 8.0 6.3 7.0 5.3 V3 Standard + complexing agent 4.1 3.5 6.9 4.0 E1 Standard surfactant / complexing agent combination 8.8 8.3 8.6 5.5 E1 is a reference example.

It can be clearly seen that the addition of the combination of surfactant and complexing agent leads to an improvement in "spotting" (droplet formation). The complexing agent alone has neither a positive nor a negative effect on the result. The surfactant has a positive effect on the result, which is, however, smaller than when using the combination of both substances.

Example 3: Manufacture

The production of an automatic dishwashing tablet according to the formula V1, which consists of two individual phases pressed one on top of the other and a third core phase, glued as a core in a cavity, does not represent any procedural difficulties. The combination of the formulas V3 and E1, however, lead to procedural difficulties in the Tabletting. A solution had to be found that made it possible to use a higher amount of MGDA in the overall formulation. A solution had to be found for this, in which an alternative to the separately pressed and glued-in core was found for a three-phase solid-phase tablet. The combination was made possible by an enclosed fusible core.

• hohe Konzentration von Wirksubstanzen
• Vorhalt als gießbare Masse
• rasche Aushärtung
• wieder aufschmelzbar, recyclebar

Due to the performance requirement combined with a corresponding process-related manufacturability, the following requirements arose for an active ingredient-containing formulation of the melt phase:

• high concentration of active substances
• Reservation as a pourable mass
• rapid hardening
• meltable again, recyclable

• geeignetes Lösemittel (Propylenglykol, Glycerin, Biodac, etc.)
• Lösemittelaufteilung
• Hilfsstoffe zur Verfestigung
• Rezeptur-Gehalt von MGDA-Pulver
• Einbringung weiterer Wirksubstanzen
• nötiges Temperaturprofil

Production of a pourable mass, implementation:
The basic idea is to produce a hardenable mass on the basis of MGDA powder. Suitable raw material combinations and manufacturing parameters have been checked through preliminary tests, e.g.

• suitable solvent (propylene glycol, glycerine, Biodac, etc.)
• Solvent distribution
• Solidifying auxiliaries
• Prescription content of MGDA powder
• Introduction of further active substances
• necessary temperature profile

The resulting basic formulation, which meets many requirements, is composed as follows: raw material MGDA powder 50% PEG 4000 20% nonionic surfactant 30%

To prepare the mass in a 20 L glass container with an anchor stirrer, PEG 4000, a non-ionic surfactant (Dehypon E127, already liquefied) was introduced and homogenized at 75.degree. MGDA powder was then stirred into the clear melt. The hot, beige-colored and easily flowable mass can be poured and solidified after a storage time of approx. 5 minutes at room temperature, provided moldings measuring 13.5 x 22.5 mm were cast (with h = 6-7 mm, arched). The molded bodies are haptically firm.

The advantage of this recipe is that it can be used to produce moldings which have a high proportion of MGDA and which avoid any problems with regard to compressibility. The rapid curing time of 5 minutes represents a further procedural advantage.

Claims (11)

1. A dishwashing detergent comprising at least one first solid, compacted phase and at least one second phase, characterized in that the at least one second phase is a melt core, comprising at least one surfactant, in particular a non-ionic surfactant, in an amount of 10-40 wt.%, based on the total weight of the melt core, and at least one complexing agent from the group of aminocarboxylic acids and the salts thereof, in an amount of 30-60 wt.%, based on the total weight of the melt core.
2. The dishwashing detergent according to claim 1, characterized in that the non-ionic surfactants contained in the at least one second phase are end-capped non-ionic surfactants of formula R¹O[CH₂CH₂O]_xR², wherein R¹ represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional groups having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, R² represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional groups having 1 to 30 carbon atoms, and x represents values between 1 and 80, preferably values between 15 and 50 and in particular values between 20 and 25.
3. The dishwashing detergent according to claim 2, characterized in that R¹ represents a linear or branched C_12-20 alkyl functional group, in particular a linear or branched C_16-18 alkyl functional group, and/or R² represents a linear or branched C_4-22 alkyl functional group, preferably a C_4-14 alkyl functional group, even more preferably a C_6-12 alkyl functional group, in particular a linear or branched C_8-10 alkyl functional group.
4. The dishwashing detergent according to one of claims 2 or 3, characterized in that the at least one second phase, in addition to the end-capped non-ionic surfactants, contains at least one non-end-capped, poly(oxyalkylated) non-ionic surfactant of formula R¹O[CH₂CH₂O]_xH, wherein R¹ represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional groups having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, and wherein x represents values between 1 and 80, preferably values between 15 and 50 and in particular values between 20 and 25.
5. The dishwashing detergent according to claim 4, characterized in that R¹ represents a linear or branched C_12-20 alkyl functional group, in particular a linear or branched C_16-18 alkyl functional group.
6. The dishwashing detergent according to one of claims 1 to 5, characterized in that the non-ionic surfactants of the at least one second phase have a melting point above 25 °C, preferably between 25 and 50 °C, more preferably between 26.6 and 43.3 °C.
7. The dishwashing detergent according to one of claims 1 to 6, characterized in that the complexing agent is methylglycine diacetic acid.
8. The dishwashing detergent according to one of claims 1 to 7, characterized in that the at least one first phase contains at least one surfactant, preferably at least one non-ionic surfactant.
9. The dishwashing detergent according to claim 8, characterized in that the at least one first phase contains at least one further ingredient selected from the group consisting of builders, polymers, bleaching agents, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, glass corrosion inhibitors, suds suppressors, dyes, additives for improving the flow and drying behavior, disintegration agents, preservatives, pH adjusters, fragrances, and perfume carriers.
10. The use of a dishwashing detergent according to one of claims 1 to 9 for automatically cleaning dishes.
11. A method for automatically cleaning dishes, characterized in that a washing or cleaning agent according to one of claims 1 to 9 is used in at least one method step.