EP2943560B1 - Low-water to water-free liquid cleaning agent - Google Patents

Description

The present invention relates to liquid low-water to water-free cleaning agents, in particular automatic dishwashing agents which contain at least one rinse aid surfactant, and their use.

Cleaning agents for hard surfaces, such as dishwashing detergents, are available to consumers in a variety of forms. In addition to the traditional solid detergents, flowable and in particular liquid to gel detergents have become increasingly important. Above all, the consumer appreciates the quick solubility and the associated quick availability of the ingredients in the cleaning liquor, particularly in short dishwashing programs and at low temperatures.

The importance of concentrated compositions, in which in particular the water content is reduced compared to conventional compositions, is increasing. Compositions whose water content is as low as possible, for example less than 20% by weight, are therefore particularly desirable for the consumer.

Furthermore, consumers have become accustomed to convenient dosing of pre-portioned machine dishwashing detergents and have so far mainly used these products in the form of tablets. In order to bring a liquid dishwashing detergent, which offers the above-mentioned advantages over solid compositions, into a pre-portioned supply form, the use of cold water-soluble films in the form of bags is common. However, there are limits to formula development because only a limited amount of water can be incorporated into the product. Exceeding the tolerable amount of water leads to premature dissolution of the enveloping water-soluble film. In order to ensure good storage stability of these water-soluble containers, water contents of less than 20% by weight are also desirable.

To ensure sufficient flowability of the formulation, organic solvents, in particular polyhydric alcohols, are therefore used instead of water. 1,2-Propylene glycol and glycerol and mixtures thereof have proven to be particularly advantageous here. However, a matrix of such organic solvents is only able to absorb sufficient amounts of a rinse aid surfactant to a limited extent, which can have a negative effect on the rinse aid performance of the product. The commonly used rinse aid surfactants include, in particular, alkoxylated nonionic surfactants, in particular fatty alcohol alkoxylates.

For adequate rinse aid performance, depending on the rest of the composition, at least 0.5% by weight of a rinse aid surfactant is generally required, usually at least 1-2% by weight.

The US 5981457 A describes a liquid, low-water dishwashing detergent which contains a nonionic surfactant and 0.2-1% by weight thickener, which consists of polyacrylates linked to polyalkyl ethers.

However, it has now been found that the use of rinse aid surfactants in compositions with low water contents, for example 20% by weight or less, either leads to an unacceptable thickening of the composition and / or, in the case of the use of organic solvents, to segregation in which the rinse aid and possibly parts of the organic solvents float on the rest of the composition, causing it to become an unacceptable thickening.

Surprisingly, it has now been found that the use of small amounts of hydrophobically modified acrylate polymers or acrylate / vinyl ester copolymers, which are usually used as thickeners, does not lead to thickening in such systems, but on the contrary leads to dilution and stabilization of the agents. This stabilizing effect can be seen in the fact that even with longer storage there is no longer an uncontrolled increase in viscosity, phase separation and solidification of the agents. In addition, the agents of this type have an unchanged good rinse aid performance.

In a first aspect, the invention is therefore directed to a liquid, low-water to water-free automatic dishwashing detergent with a water content of 20% by weight or less, which contains at least one rinse aid surfactant, which is a nonionic surfactant, characterized in that the agent further comprises at least one hydrophobically modified acrylic polymer or copolymer selected from C ₁₀ -C ₃₀ alkyl modified cross-linked polyacrylate, C ₁₀ -C ₃₀ alkyl modified acrylate / vinyl ester copolymer and mixtures thereof, in a concentration of 0.02 Contains up to 0.8 wt .-% based on the agent, characterized in that at least one C ₁₀ -C ₃₀ alkyl-modified acrylate / vinyl ester copolymer is included.

The term "low water" as used herein means that the composition so characterized contains 20% by weight of water or less. In particular, this term includes compositions which contain 1 to 20% by weight of water, 1 to 15% by weight of water, 5-15% by weight of water or 10 to less than 20% by weight of water.

"Anhydrous" as used herein means that a composition contains less than 5% by weight, especially less than 3% by weight, preferably less than 1% by weight of water.

The water content as defined herein relates to the water content determined by means of the Karl Fischer titration.

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

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

The polyacrylates and acrylate copolymers used according to the invention are distinguished by the fact that they are at least partially C ₁₀ -C ₃₀ -alkyl-modified crosslinked polyacrylates or at least partially hydrophobic, in particular C ₁₀ -C ₃₀ -alkyl, modified acrylate / vinyl ester copolymers. "Partially modified" in this context means that at least some, preferably at least 20, more preferably at least 40, particularly preferably at least 50% of the monomer units are each substituted with at least one C ₁₀ -C ₃₀ -alkyl radical. The polymers are therefore such as acrylate / C ₁₀ -C ₃₀ alkyl acrylate copolymers or acrylate / C ₁₀ -C ₃₀ alkyl acrylate / C ₁₀ -C ₃₀ alkyl Vinylester copolymers.

Such polymers are commercially available as thickeners and emulsifiers. Polygel DR (3V Sigma, Italy) and Pemulen® TR1 (Lubrizol, USA) are suitable, for example, without the invention being restricted to these polymers.

The amount of the at least one hydrophobically modified acrylate polymer or copolymer in the cleaning agent is 0.02 to 0.8, preferably 0.03 to 0.5, more preferably 0.05 to 0.15, most preferably 0.1% by weight .-% based on the detergent.

The cleaning agents according to the invention contain at least one rinse aid surfactant. The rinse aid surfactant is a nonionic surfactant. Although all nonionic surfactants known to the person skilled in the art can be used, low-foaming nonionic surfactants, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants are preferably used. In preferred embodiments, the dishwasher detergents contain nonionic surfactants from the group of the alkoxylated alcohols.

In various embodiments, nonionic surfactants can be used which have a melting point above room temperature. In such embodiments 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., particularly preferably.

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

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.Low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units are used as particularly preferred nonionic surfactants. Among these, surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Here are nonionic surfactants of the general formula

preferred, 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 represent integers from 1 to 6.

Thus, in particular nonionic surfactants are 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 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.

By adding the aforementioned nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w (A'O) _x - (A "O) _y - (A""O) _z -R ² , hereinafter also referred to as "hydroxy mixed ether", the cleaning performance of the preparations according to the invention can be significantly improved, both in comparison to a surfactant-free system and in comparison to systems which contain alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

Those end group-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 , are preferred in addition to a radical R ¹ which is saturated for linear or branched or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore have 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 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

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 with 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.
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 -hydroxydecyl ether.

End group-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 ¹ are also particularly preferred ² independently of one another represents a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} selected independently of one another 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 of 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, are aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical , x stand for values between 1 and 30, k and j stand 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 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, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . 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 here by way of example and may well be larger, the range of variation 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 group-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so 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 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 represents} H and x assumes values from 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 20 bis 40 steht

Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise die C_4-22 Fettalkohol-(EO)_10-80-2-hydroxyalkylether, insbesondere auch die C_8-12 Fettalkohol-(EO)₂₂-2-hydroxydecylether und die C_4-22 Fettalkohol-(EO)_40-80-2-hydroxyatkytether.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 represents} 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 20 to 40

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 ether and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyatkytether.

In various embodiments of the invention, the corresponding non-end-capped hydroxy mixed ethers can also be used instead of the end-capped hydroxy mixed ethers defined above. These can 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 liquid detergents of the invention preferably contain a nonionic surfactant from the group of hydroxy mixed ethers, the weight fraction of the nonionic surfactant in the total weight of the detergent preferably being 0.1 to 3.5, preferably 0.5 to 2.5, more preferably 1.0 to Is 2.0% by weight.

In various embodiments of the invention, the at least one rinse aid is a surfactant from the group of the polyalkoxylated fatty alcohols, in particular the hydroxy mixed ethers, preferably the endgroup-blocked hydroxy mixed ethers, and the at least one hydrophobically modified acrylate polymer or copolymer is an alkyl-modified polyacrylate or alkyl-modified one Acrylate / vinyl ester copolymer, in particular a partially C ₁₀ -C ₃₀ alkyl-modified cross-linked polyacrylate or a partially C ₁₀ -C ₃₀ alkyl modified acrylate / vinyl ester copolymer. In various embodiments, the weight fraction of the polyalkoxylated fatty alcohol, in particular the hydroxy mixed ethers, preferably the end-capped hydroxy mixed ethers, in such compositions can be 0.1 to 3.5, preferably 0.5 to 2.5, more preferably 1.0 to 2.0% by weight. % and the weight fraction of the alkyl-modified polyacrylate or alkyl-modified acrylate / vinyl ester copolymer, in particular of a partially C ₁₀ -C ₃₀ -alkyl modified cross-linked polyacrylate or of a partially C ₁₀ -C ₃₀ -alkyl modified acrylate / vinyl ester copolymer, 0, 02 to 0.9, preferably 0.05 to 0.5, more preferably 0.07 to 0.2, most preferably 0.1% by weight, in each case based on the total weight of the cleaning agent.

The cleaning agents according to the invention are machine dishwashing agents.

In a further aspect, the invention relates to cleaning agents of this type, which can be present in a water-insoluble, water-soluble or water-dispersible packaging, for example a film which contains a single portion.

Another object of the present invention is also a machine dishwashing method in which a cleaning agent according to the invention is used.

Machine dishwashing detergents that are commercially available today generally contain phosphates in the form of polyphosphates as the builder component. Polyphosphates which can be used according to the invention are, for example, tripolyphosphates, pyrophosphates and metaphosphates, and in particular their sodium or potassium salts. Tripolyphosphates are preferably used. In various preferred embodiments, the cleaning agent of the invention therefore contains at least one phosphate-containing builder component, preferably a polyphosphate, in particular a tripolyphosphate.

The tripolyphosphates (or triphosphates) which can be used according to the invention are condensation products of orthophosphoric acid (H ₃ PO ₄ ) with the empirical formula P ₃ O ₁₀ ^5- , which are usually in the form of their salts, preferably the alkali metal or alkaline earth metal, more preferably in the form of their Alkali metal salts are used. Tripolyphosphate salts are generally hygroscopic, white, odorless, non-flammable solids that are easily soluble in water. According to the invention, the sodium or potassium salt of tripolyphosphate (Na ₅ P ₃ O ₁₀ and K ₅ P ₃ O ₁₀ ) or a mixture thereof are used in particular.

The proportion by weight of the polyphosphates, in particular the tripolyphosphate, in the total weight of the cleaning agent according to the invention is preferably 0.1 to 40% by weight, in particular from 1 to 35% by weight, particularly preferably from 5 to 32% by weight, more preferably from 10 to 30% by weight.

As an alternative or in addition to the phosphates, in particular the polyphosphates, other builders, such as, for example, zeolites, silicates, carbonates, in particular the alkali carbonates, for example sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, and organic cobuilders can also be used.

The silicates used are, in particular, crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .y H ₂ O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred Values for x are 2, 3 or 4, and y stands for a number from 0 to 33, preferably from 0 to 20. Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are preferably delayed release and have secondary washing properties.

In preferred cleaning agents, the silicate content, 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. Particularly preferred cleaning agents are free of silicate.

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

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder action, the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Another important class of builders are aminocarboxylic acids and / or their salts. Particularly preferred representatives of this class are methylglycinediacetic acid (MGDA) or its salts and glutamine diacetic acid (GLDA) or its salts or ethylenediaminediacetic acid or its salts (EDDS). Iminodisuccinic acid (IDS) and iminodiacetic acid (IDA) are also suitable. Aminocarboxylic acids and their salts can be used together with the builders mentioned above, in particular also with the phosphate-free builders.

Polymeric polycarboxylates are also suitable as 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 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The cleaning agents can in particular also contain phosphonates as builders. A hydroxyalkane and / or aminoalkane phosphonate is preferably used as the phosphonate compound. Of the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are contained in the agents preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, in each case based on the total weight of the cleaning agent.

If the cleaning agents according to the invention contain phosphates, in particular tripolyphosphates, it is preferred that they contain, as a further constituent, preferably one or more builders (builders / cobuilders) in addition to the phosphate-containing builder component. The weight fraction of these additional builders other than the phosphate-containing builder component in the total weight of the agents according to the invention is preferably 0.1 to 10% by weight and in particular 2 to 7% by weight. These builders which differ from the phosphate-containing builder component include, in particular, those described above as further builders, preferably carbonates, citrates, phosphonates, MGDA, GLDA, iminodisuccinic acid, iminodiacetic acid, EDDS (ethylenediamine-N, N'-disuccinic acid) or the salts of the acids mentioned, other organic cobuilders and silicates.

Particularly preferred phosphate-containing cleaning agents contain citrate, for example sodium or potassium citrate, as one of their essential builders, which differ from the phosphate-containing builder component. Cleaning agents which contain 1 to 10% by weight, preferably 2 to 5% by weight, of citrate are preferred according to the invention. Additionally or alternatively, particularly preferred phosphate-containing cleaning agents can contain phosphonates, for example HEDP, as a builder different from the phosphate-containing builder component. Cleaning agents which contain 1 to 10% by weight, preferably 2 to 5% by weight, of phosphonate, in particular HEDP, are preferred according to the invention.

The cleaning agents according to the invention can also contain a sulfopolymer. The weight fraction of the sulfopolymer in the total weight of the cleaning agent according to the invention is preferably from 0.1 to 20% by weight, in particular from 0.5 to 18% by weight, particularly preferably 1.0 to 15% by weight, in particular from 4 to 14% by weight, especially from 6 to 12% by weight. The sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70% by weight, in particular 30 to 50% by weight, preferably about 35 to 40% by weight, of sulfopolymer (s).

A copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the sulfopolymer.

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

In addition to monomer (s) containing sulfonic acid groups, preferred copolymeric polysulfonates contain at least one monomer from the group of unsaturated carboxylic acids.

Unsaturated carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH are used as unsaturated carboxylic acid (s), 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 with -NH ₂ , -OH or -COOH 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, methylene malonic acid, sorbic acid, Cinnamic acid or mixtures thereof. Of course, the unsaturated dicarboxylic acids can also be used.

The monomers containing sulfonic acid groups are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

preferably 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, with - NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - , -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

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 selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , - CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ and X represents an optionally present spacer group 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-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl sulfopropyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.

The sulfonic acid groups in the polymers may be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

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

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

In a further preferred embodiment, in addition to the monomer containing carboxyl groups and monomer containing sulfonic acid groups, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer. By using these hydrophobically modified polymers, in particular the rinse aid performance of automatic dishwashing detergents according to the invention could be improved.

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

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

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, α -Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propyl ester, acrylic acid butyl ester, acrylate, methacrylate, acrylate - (Methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N - (2-ethylhexyl) acrylamide, octyl acrylate ster, Methacrylsäureoctylester, N - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N - (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N - (stearyl) acrylamide, behenyl acrylate, and Methacrylsäurebehenylester N- (Behenyl) acrylamide or mixtures thereof.

The monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably 5 to 80% by weight, based on the monomer containing sulfonic acid groups, the hydrophobic monomer and the monomer containing carboxylic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups and the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid-containing monomer 60 to 80 wt .-%, the monomers are preferably selected from the aforementioned.

In addition to the above-mentioned builders other than the phosphate-containing builder component, the cleaning agents can contain alkali metal hydroxides. These alkali carriers are preferably used in the cleaning agents 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, in each case based on the total weight of the cleaning agent. Alternative cleaning agents according to the invention are free from alkali metal hydroxides.

The cleaning agents according to the invention can contain at least one polyhydric alcohol. Such polyhydric alcohols can allow the incorporation of other constituents into a detergent formulation if the amount of water is small, in particular if the amount of water is limited to 20% by weight.

The amount of polyhydric alcohol used in washing or cleaning agents produced according to the invention is preferably at least 20% by weight, in particular at least 25% by weight, particularly preferably at least 28% by weight, especially at least 30% by weight. %. Preferred quantitative ranges are 20 to 50% by weight, in particular 25 to 45% by weight, especially 28 to 40% by weight.

The polyhydric alcohol is preferably selected from glycerol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol and mixtures thereof.

In a preferred embodiment, a mixture of at least two polyhydric alcohols is used.

A polyhydric alcohol which is particularly preferably used according to the invention is 1,2-propylene glycol. 1,2-propylene glycol is used in agents according to the invention preferably in an amount of 1 to 40% by weight, in particular in an amount of 2 to 35% by weight, particularly preferably in an amount of 5 to 30% by weight.

Another polyhydric alcohol which is particularly preferably used according to the invention is glycerol. Glycerin is used in agents according to the invention preferably in an amount of 1 to 40% by weight, in particular in an amount of 2 to 35% by weight, particularly preferably in an amount of 5 to 30% by weight.

In a particularly preferred embodiment, a mixture of glycerol and 1,2-propylene glycol is used.

The glycerin is preferably used in an amount of 0.1 to 40% by weight, in particular in an amount of 2 to 30% by weight, particularly preferably in an amount of 5 to 20% by weight. The 1,2-propylene glycol is preferably obtained in an amount of 1 to 40% by weight, in particular in an amount of 5 to 35% by weight, particularly preferably in an amount of 10 to 30% by weight to the total mass of the cleaning agent, the total amount of glycerol and 1,2-propylene glycol preferably at least 20% by weight, in particular at least 25% by weight, especially at least 30% by weight, particularly preferably 25 to 45% by weight .-%, in particular 30 to 42 wt .-%, especially 35 to 40 wt .-%. The mass ratios of glycerol: 1,2-propylene glycol can be in the range from 1: 7 to 7: 1, preferably in the range from 3: 1 to 1: 6. Depending on the other ingredients, it may be preferred that the alcohol mixture contain more glycerin than 1,2-propylene glycol. In such a case, the ratio of glycerol: 1,2-propylene glycol can range from 1: 1 to 3: 1 and / or the glycerol concentration is in the range 20-30% by weight and the 1,2-propylene glycol concentration is in the range 5-20% by weight. Alternatively, the ratio may be reversed and the detergent may contain large amounts of propylene glycol. In such embodiments, the ratio of glycerol: 1,2-propylene glycol is approximately 1: 7 to 1: 3 and / or the glycerol concentration is in the range 2-10% by weight and the 1,2-propylene glycol concentration is in the range 25-35 % By weight.

In general, the pH value of the cleaning agent can be adjusted using conventional pH regulators, the pH value being selected depending on the desired application. In various embodiments, the pH is in a range from 5.5 to 10.5, preferably 5.5 to 9.5, more preferably 7 to 9, in particular greater than 7, especially in the range 7.5 to 8.5 . Acids and / or alkalis, preferably alkalis, serve 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, 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, especially alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred. However, volatile alkali is particularly preferred, 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. The alkanolamine is preferably present in agents according to the invention in an amount of 0.5 to 10% by weight, in particular in an amount of 1 to 6% by weight.

To adjust and / or stabilize the pH, the agent according to the invention can contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid and citrates, in particular sodium and potassium citrates, for example trisodium citrate · 2H ₂ O and tripotassium citrate · H ₂ O.

The agents according to the invention preferably contain at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, bleaching agents, bleach activators, bleaching catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver preservatives, glass corrosion inhibitors, foam inhibitors, dyes, fragrances , Bitter substances, and antimicrobial agents.

Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzene sulfonates, olefin sulfonates, alkane sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates. Fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and -di-C ₈ -C ₁₈ alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkane sulfonates (fatty acid taurides), fatty acid carboxylic acid arcosinates, ether carboxylic acid arcosinates (ether carboxylic acid arcosinates), and ether carboxylic acid arcosinates (ether carboxylic acid arcosinates), are also usable within the scope of the present invention as well as α-sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

The anionic surfactants are preferably used as sodium salts, but can also be present as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form of their corresponding acid, e.g. Dodecylbenzenesulfonic acid.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R ^v ) N ⁺ CH ₂ COO ^- , in which R ^{iii is} an alkyl radical with 8 to 25, preferably 10 to 21, carbon atoms and R, which is optionally interrupted by heteroatoms or heteroatom groups ^iv and R ^{v are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyldimethylcarboxymethylbetaine and C ₁₁ -C ₁₇ -alkylamidopropyldimethylcarboxymethylbetaine.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^vi ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^- , in which R ^vi to R ^ix for four identical or different types, in particular two long and two short-chain, alkyl radicals and X ^- stand for an anion, in particular a halide ion, for example didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Further suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial active ingredients. By using quaternary surface-active compounds with an antimicrobial effect, the agent can be designed with an antimicrobial effect or its antimicrobial effect which may already be present due to other ingredients can be improved.

The enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are accordingly preferred. Cleaning agents ^according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5% by weight, based on active protein. The Protein concentration can be determined using known methods, for example the BCA method or the biuret method.

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

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

Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or developed further, in particular those with the amino acid exchange D96L.

Furthermore, enzymes can be used, 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, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenoloxidases, polyphenol oxidases) can be used according to the invention. Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of very different redox potentials between the oxidizing enzymes and the soiling.

A protein and / or enzyme can be protected against damage, such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage. When the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Detergents can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.

Proteases and amylases that are active in cleaning are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations. These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel form agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers or other auxiliaries.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or 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, bleaching agents or dyes, can additionally be applied in layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.

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

As can be seen from the previous explanations, 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.

Particularly preferred are cleaning agents which, based on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of enzyme preparations.

Zinc salts, in particular zinc acetate, are preferably used as glass corrosion inhibitors. Glass corrosion inhibitors are preferably contained in agents according to the invention in an amount of 0.05 to 5% by weight, in particular in an amount of 0.1 to 2% by weight.

In various embodiments, the cleaning agent has a viscosity above 2000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C.), in particular between 2000 and 10000 mPas, immediately after production. After storage, the viscosity can be higher, for example greater than 10000 mPas, such as in the range 10000-50000 mPas, (Brookfield Viscometer DV-II + Pro, spindle 25, 5 rpm, 20 ° C). It is preferred that the agent be flowable at room temperature.

The cleaning agent can be in a water-insoluble, water-soluble or water-dispersible packaging. The invention therefore also relates to kits which contain the cleaning agent together with such packaging. The cleaning agent can be made up in such a way that disposable portions are each packed separately.

The cleaning agent according to the invention is preferably contained in a water-soluble packaging. The water-soluble packaging allows the detergent to be portioned. The amount of cleaning agent in the portion pack is preferably 5 to 50 g, particularly preferably 10 to 30 g, especially 15 to 25 g.

The water-soluble covering is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures. The sheath can be formed from one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, can be the same or different. Films which, for example, can be glued and / or sealed to form packaging, such as hoses or pillows, are particularly preferred after they have been filled with an agent.

It is preferred that the water-soluble envelope contain polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings which contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with a sufficiently high water solubility, in particular cold water solubility.

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

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

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

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

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

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

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

The cleaning agents according to the invention are used as automatic dishwashing agents. The invention also relates to a dishwashing method, in particular machine dishwashing method, in which a cleaning agent according to the invention is used.

The cleaning agents according to the invention are distinguished by the fact that they are stable in storage and that there is no phase separation even after a long period of time.

embodiments

The cleaning agent formulation M1 according to the invention and the comparison formulations V1-V4 were produced. The compositions are shown in Table 1 below, the amounts given are in% by weight of active substance. Polygel DR (3V Sigma) was used as the hydrophobically modified acrylate / vinyl ester copolymer.

The rinse aid performance of the recipes was tested as follows: Various materials (glass, porcelain (black), stainless steel, plastic) with 20 g of the respective recipe and 100 g of greasy soiling were used in a Miele G 698 SC dishwasher at 50 ° C and 21 ° dH 4x rinsed and visually checked after the 2nd - 4th rinsing cycle. To do this, the machine is fully opened for 30 minutes after the end of the rinsing cycle and then in the black box (assessment room, which is painted matt black or lined and is light-shielded and equipped with artificial lighting with 2 fluorescent tubes (Philips TLD 36W / 965 Natural Daylight 6500) is determined visually. The results for the formulations tested are listed in Table 1. Table 1: Recipes M1 V1 V2 V3 V4 Potassium tripolyphosphate 27 27 27 27 27 Sodium tripolyphosphate 7.5 7.5 7.5 7.5 7.5 Sulfopolymer, sodium salt 9 9 9 9 9 Sodium citrate dihydrate 4 4 4 4 4 HEDP 4 4 4 4 4 glycerin 5 5 5 5 5 1,2-propylene glycol 30th 30th 30th 30th 30th Fatty alcohol alkoxylate 2 2 2 2 2 Acrylic acid polymer, Na salt 1 1 1 1 1 Ethanolamine 3.5 3.5 3.5 3.5 3.5 Enzymes 4 4 4 4 4 Zinc acetate 0.2 0.2 0.2 0.2 0.2 Hydrophobically modified acrylate / vinyl ester copolymer 0.1 - 1.0 0.01 - Unmodified polyacrylate - - - - 0.1 Perfume, dye, excipients, water Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Stability of the recipe ++ - - - - Viscosity after storage + O - - - Rinse aid + + n / A + + na = not applicable
++ = very good
+ = good
o = sufficient
- = bad
- = very bad

The stability of the formulation according to the invention was very good, in contrast the stability was poor or very poor in the comparison formulations, i.e. there was separation and phase separation of the individual components. Likewise, only in the formulation according to the invention did the viscosity remain constant over a longer storage period; in all comparison formulations there was an uncontrolled increase in viscosity, i.e. the recipes showed thixotropic behavior (o) or the recipe solidified (- and -).

In sum, the results of the investigation show that the recipe according to the invention is clearly superior to the comparison recipes in terms of stability and the change in viscosity after prolonged storage, while maintaining good rinse aid performance.

Claims (8)

1. A low-water to water-free liquid machine dishwashing agent having a water content of 20 wt.% or less, which agent contains at least one rinse aid, the rinse aid being a nonionic surfactant, characterized in that the agent further contains at least one hydrophobically modified acrylate polymer or copolymer, selected from C₁₀-C₃₀ alkyl-modified cross-linked polyacrylate, C₁₀-C₃₀ alkyl-modified acrylate/vinyl ester copolymer and mixtures thereof, in a concentration of from 0.02 to 0.8 wt.% based on the agent, characterized in that at least one C₁₀-C₃₀ alkyl-modified acrylate/vinyl ester copolymer is contained.
2. The machine dishwashing agent according to claim 1, characterized in that the amount of the at least one hydrophobically modified acrylate polymer or copolymer in the cleaning agent is in the range of from 0.03 to 0.5, more preferably 0.05 to 0.15, most preferably 0.1 wt.%, based on the agent.
3. The machine dishwashing agent according to claim 1 or 2, characterized in that the amount of the at least one rinse aid in the agent is in the range of from 0.1 to 3.5, preferably 0.5 to 2.5, more preferably 1 to 2.0 wt.%, based on the agent.
4. The machine dishwashing agent according to one of claims 1 to 3, characterized in that the at least one rinse aid is selected from the group of alkoxylated alcohols.
5. The machine dishwashing agent according to one of claims 1 to 4, characterized in that the agent further contains at least one builder or cobuilder, in particular a polyphosphate, preferably a tripolyphosphate, citrate and/or phosphonate.
6. The machine dishwashing agent according to one of claims 1 to 5, characterized in that the agent further contains one or more of the substances selected from the group consisting of complexing agents, pH adjusters, anionic, cationic and amphoteric surfactants, bleaching agents, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protecting agents, glass corrosion inhibitors, suds suppressors, dyes, fragrances, bitterns, and antimicrobial active ingredients.
7. The machine dishwashing agent according to one of claims 1 to 6, characterized in that it is in a water-insoluble, water-soluble or water-dispersible packaging, in particular in a film which contains polyvinyl alcohol.
8. A machine dishwashing method, characterized in that a machine dishwashing agent according to one of claims 1 to 7 is used.