DE102016205344A1 - Dishwashing detergent with improved rinse performance - Google Patents

Abstract

The present invention relates to dishwashing detergent with improved rinse performance, based on the total weight of the dishwashing detergent, 0.5 to 20.0 wt .-% of a surfactant mixture as defined herein, the use of these dishwashing detergents and a method for dishwashing using these dishwashing detergents and the use the surfactant mixture to improve the rinse performance of a dishwashing detergent.

Description

The present invention relates to dishwashing detergents with improved rinse aid performance, the use of these dishwashing detergents, and a machine dishwashing method using these dishwashing detergents.

Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So even a completely cleaned of leftovers dishes is then rated as not flawless if it has after dishwasher washing whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets. Such staining and streaking is in principle observable on surfaces of all kinds (porcelain, glass, plastic, stainless steel), but especially on glass surfaces. This harness is the consumer - often by hand - post-treated, which is not very user-friendly. Therefore, there is a need for automatic dishwashing agents that reduce the formation of so-called spotting and filming stains and deposits.

In order to obtain glossy and spotless dishes, dishwashing agents are used in dishwashing formulations. Through a mediated by these agents film formation on the dishes, the water should run as completely as possible from the dishes, so that the surfaces are residue-free and flawless gloss at the end of the wash program. Although the use of such rinse aids is known in the art, there continues to be a need for dishwashing detergents which exhibit improved rinse performance.

The object underlying the present invention was therefore to provide a dishwashing detergent with improved rinsing performance.

It has now surprisingly been found that the combination of nonionic surfactants used in phosphate-free dishwashing formulations according to the invention bring about improved film formation on Spülgutoberflächen, whereby the water can run off the dishes in a thin, coherent film, so that during the subsequent drying process, no water droplets, stripes or Stay behind. As a result, the formation of streaks on items to be washed, in particular glass, is suppressed and the drying and rinsing performance is significantly improved, even with low-temperature cleaning cycles (≤50 ° C).

• (i) mindestens ein nichtionisches Tensid der Formel R¹O[CH₂CH₂O]_xCH₂CH(OH)R², wobei R¹ für einen linearen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten Kohlenwasserstoffrest mit 2 bis 30 Kohlenstoffatomen, vorzugsweise mit 4 bis 22 Kohlenstoffatomen, noch bevorzugter 8 bis 10 Kohlenstoffatomen steht, R² für einen linearen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten Kohlenwasserstoffrest mit 1 bis 30 Kohlenstoffatomen, vorzugsweise 2 bis 20 Kohlenstoffatomen, noch bevorzugter 6 bis 12 Kohlenstoffatomen steht, x für Werte von 1 bis 90, vorzugsweise für Werte von 10 bis 60 und insbesondere für Werte von 15 bis 40 steht; und
• (ii) mindestens ein nichtionisches Tensid der Formel R³O[CH₂CH₂O]_y[CH₂CH(R⁵)O]_zCH₂CH(OH)R⁴, wobei R³ und R⁴ unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen, vorzugsweise 6 bis 12 Kohlenstoffatomen stehen, jedes R⁵ unabhängig ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃ und -CH(CH₃)₂, vorzugsweise jedoch für -CH₃ steht, und y und z unabhängig voneinander für Werte von 1 bis 32 stehen, vorzugsweise y für Werte von 15 bis 32 und z für Werte von 1 bis 3 steht, wobei das Massenverhältnis des mindestens einen nichtionischen Tensids (i) zu dem mindestens einen nichtionischen Tensid (ii) im Bereich von 1:4 bis 4:1, vorzugsweise im Bereich von 1:1 bis 4:1 liegt.

A first aspect of the present invention therefore relates to a dishwashing detergent, in particular a machine phosphate-free dishwashing detergent, containing, based on the total weight of the dishwashing detergent, 0.5 to 20.0 wt .-%, preferably 1.0 to 10.0 wt. %, more preferably 2.0 to 5.0% by weight of a surfactant mixture comprising:

• (i) at least one nonionic surfactant of the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , wherein R ^{1 is} a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, more preferably 8 to 10 carbon atoms, R ^{2 is} a linear or branched, saturated or or polyunsaturated hydrocarbon radical having 1 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, x is from 1 to 90, preferably from 10 to 60 and especially from 15 to 40 ; and
• (ii) at least one nonionic surfactant of the formula R ³ O [CH ₂ CH ₂ O] _y [CH ₂ CH (R ⁵ ) O] _z CH ₂ CH (OH) R ⁴ , wherein R ³ and R ⁴ independently represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, preferably 6 to 12 carbon atoms, each R ^{5 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ and -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and y and z are independently from 1 to 32, preferably y is from 15 to 32, and z is from 1 to 3, wherein the mass ratio of the at least one nonionic surfactant (i) to the at least one nonionic surfactant (ii ) is in the range of 1: 4 to 4: 1, preferably in the range of 1: 1 to 4: 1.

Likewise provided by the present invention is the use of a dishwashing agent according to the invention in a machine dishwashing process, in particular the use for improving the rinsing performance when cleaning dishes in an automatic dishwashing machine.

Yet another object of the invention is a machine dishwashing process in which a dishwasher detergent according to the invention is used, in particular for the purpose of improving the rinse performance.

Finally, the use of the surfactant mixture used according to the invention for improving the final rinse performance of a machine dishwashing detergent is also the subject of the present invention.

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

"At least one" as used herein means 1 or more, i. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to an ingredient, the indication refers to the type of ingredient, not the absolute number of molecules. Thus, for example, "at least one nonionic surfactant" means at least one type of nonionic surfactant, i. that is, one type of nonionic surfactant or a mixture of several different nonionic surfactants may be meant. The term, together with weights, refers to all compounds of the type indicated which are included in the composition / mixture, i. that the composition does not contain any further compounds of this type beyond the stated amount of the corresponding compounds.

"Phosphate-free" as used herein means that the composition in question is substantially free of phosphates, i. in particular phosphates in amounts less than 1 wt .-%, preferably less than 0.1 wt .-% based on the total composition. Accordingly, as used herein, "free of" means that the respective fabric is present in amounts less than 1% by weight, preferably less than 0.1% by weight, more preferably less than 0.01% by weight of the Total composition is included. In particular, this also means that the corresponding substance is not deliberately added.

All percentages given in connection with the compositions described herein, unless explicitly stated otherwise, relate to% by weight, in each case based on the composition in question.

"Approximately" or "approximately" as used herein in connection with a numerical value refers to the numerical value ± 10%, preferably ± 5%.

Whenever alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.

The dishwashing compositions of the invention contain a surfactant mixture which comprises at least two low-foaming nonionic surfactants from the group of end-capped, poly (oxyalkylated) nonionic surfactants as defined above.

The surfactant mixture comprises at least one first nonionic surfactant from the group of end-capped, poly (ethoxylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ which is linear or branched, saturated or mono- or polyunsaturated, hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, more preferably 8 to 10 carbon atoms, furthermore a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical R ² having 1 to 30 carbon atoms, wherein x stands for values of 1 to 90, preferably for values of 10 to 60 and in particular for values of 15 to 40.

The hydrocarbon radicals R ¹ and / or R ² are preferably aliphatic hydrocarbon radicals, in particular linear or branched alkyl radicals. R ¹ is thus preferably an alkyl group having 2 to 30 carbon atoms, preferably 4 to 22 carbon atoms, more preferably 8 to 10 carbon atoms or a mixture of such groups, and R ² is preferably an alkyl group having 1 to 30 carbon atoms, preferably 2 to 20 Carbon atoms, more preferably 6 to 12 carbon atoms. In particularly preferred embodiments, R ^{2 is} an alkyl radical having 8 carbon atoms and thus forms a 2-hydroxydecyl radical etherified with the ethylene oxide units.

The group of these nonionic surfactants include, for example, the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ethers and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether. Most preferably, this nonionic surfactant (i) is a C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ether. "EO" in this context means "ethylene oxide", ie a group of the formula (CH ₂ CH ₂ O).

The surfactant mixture additionally comprises at least one second nonionic surfactant from the group of hydroxy mixed ethers of the formula R ³ O [CH ₂ CH ₂ O] _y [CH ₂ CH (R ⁵ ) O] _z CH ₂ CH (OH) R ⁴ , wherein R ³ and R ⁴ independently represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, preferably 6 to 12 carbon atoms, each R ^{5 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ and -CH (CH ₃ ) ₂ , but preferably is -CH ₃ , and y and z are independently from 1 to 32, preferably y, from 15 to 32 and z is from 1 to 3.

In various embodiments, the hydrocarbon radicals R ³ and / or R ^{4 are} aliphatic hydrocarbon radicals, in particular linear or branched alkyl radicals. R ³ is preferably a linear or branched, more preferably linear alkyl radical of 2 to 30 carbon atoms, preferably of 4 to 22 carbon atoms, more preferably 8 to 10 carbon atoms, or a mixture of such radicals, and R ⁴ is preferably a linear or branched one, especially preferably linear alkyl radical having 1 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. In particularly preferred embodiments, R ^{4 is} an alkyl group having 8 carbon atoms and thus forms an etherified with the alkylene oxide 2-hydroxydecyl.

R ⁵ is preferably -CH ₃ and thus forms a propylene oxide unit. It is preferred that z is 1 or 2, especially 1. In such embodiments, y is more preferably 20-24, most preferably 22.

The group of these nonionic surfactants include, for example, the C _2-26 fatty alcohol (EO) _15-40 - (PO) ₁ -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ - (PO) ₁ -2 -hydroxydecylether. Most preferably, this nonionic surfactant (ii) is a C _8-10 fatty alcohol (EO) ₂₂ - (PO) ₁ -2-hydroxydecyl ether. "PO" in this context means "propylene oxide", ie a group of the formula (CH ₂ CH (CH ₃ ) O).

Preferred surfactant mixtures in the dishwashing compositions according to the invention comprise as nonionic surfactant i) at least one C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ether, 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-hydroxyalkyl ether, and as nonionic surfactant (ii) at least the C _2-26 fatty alcohol (EO) _15-40 - (PO) ₁ -2-hydroxyalkyl ethers.

Particularly preferred surfactant mixtures contain at least one C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ether as nonionic surfactant (i) and at least one C _8-10 fatty alcohol (EO) ₂₂ - (PO) ₁ -2-hydroxydecyl ether as nonionic surfactant (ii).

Very particular preference is given to a surfactant mixture or a dishwasher detergent according to the invention comprising at least one C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ether as nonionic surfactant (i) and at least one C _8-10 fatty alcohol (EO) ₂₂ - ( PO) ₁ -2-hydroxydecyl ether as nonionic surfactant (ii).

The mass ratio of the at least one nonionic end-capped ethoxylated surfactant to the at least one hydroxy mixed ether, i. from the surfactant (i) to the surfactant (ii) is in the range of 1: 4 to 4: 1, preferably in the range of 1: 1 to 4: 1. The amount relative to the total weight of the composition for the surfactant (i) is preferably 1 to 5 wt .-%, preferably 2 to 3 wt .-% and for the surfactant (ii) preferably 0.2 to 2 wt .-%, preferably 0.5 to 1.5% by weight. The amounts mentioned or mass ratios in each case relate to the total amount of the surfactants according to (i) or (ii) in the dishwashing agents according to the invention.

Preferred surfactant mixtures in the dishwashing compositions according to the invention comprise as nonionic surfactant i) at least one C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ether, 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-hydroxyalkyl ether, and as nonionic surfactant (ii) at least the C _2-26 fatty alcohol (EO) _15-40 - (PO) ₁ -2-hydroxyalkyl ethers in a mass ratio in the range of 1: 1 to 4: 1.

Particularly preferred surfactant mixtures contain at least one C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ether as nonionic surfactant (i) and at least one C _8-10 fatty alcohol (EO) ₂₂ - (PO) ₁ -2-hydroxydecyl ether as nonionic surfactant (ii) in a mass ratio ranging from 1: 1 to 4: 1.

Particular preference is given to a surfactant mixture or a dishwasher detergent according to the invention comprising at least one C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ether as nonionic surfactant (i) and at least one C _8-10 fatty alcohol (EO) ₂₂ - (PO ) ₁ -2-hydroxydecyl ether as nonionic surfactant (ii) in a mass ratio ranging from 1: 1 to 4: 1.

Very particular preference is given to a surfactant mixture or a dishwasher detergent according to the invention comprising a C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ether as nonionic surfactant (i) and a C _8-10 fatty alcohol (EO) ₂₂ - (PO) ₁ -2-hydroxydecyl ether as nonionic surfactant (ii) in a mass ratio ranging from 1: 1 to 4: 1.

In the case of the abovementioned surfactant mixtures, the amount based on the total weight of the composition in a preferred embodiment of the surfactant (i) is 2 to 3% by weight and 0.5 to 1.5% by weight for the surfactant (ii).

In addition to the abovementioned nonionic surfactants, the compositions according to the invention may contain surfactants in the surfactant mixture, in particular further nonionic or else anionic surfactants, but also cationic or amphoteric surfactants.

Suitable further nonionic surfactants 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 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of useful nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

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

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

If further nonionic surfactants are used, however, preference is given to using further low-foaming nonionic surfactants from the group of the alkoxylated alcohols.

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. Somit 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. Preferred further nonionic surfactants are, for example, those which have alternating ethylene oxide and alkylene oxide (AO) units having 3 or more carbon atoms. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently stand for integers from 1 to 6. Thus, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.

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 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.

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

Suitable anionic surfactants are all anionic surfactants. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group. Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates. Also usable in the context of the present invention are fatty acid cyanamides, sulfosuccinates (sulfosuccinic esters), in particular sulfosuccinic mono- and di-alkyl esters having 8 to 18 carbon atoms, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and α-sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glyceryl disulfate.

Preferred anionic surfactants include those of the formula R ^{1 is} -O- (AO) n -SO ₃ ^- X ⁺ .

In this formula, R ^{1 is} a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms Atoms are preferred. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ oxo alcohols.

AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na ⁺ or K ⁺ including Na, with Na ^{+ being} extremely preferred. Other cations X ⁺ may be selected from NH ₄ ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ²⁺ , and mixtures thereof.

Additionally or alternatively, an anionic surfactant of formula R ³ -A-SO ₃ ^- Y ⁺ . be contained in the dishwashing detergent. In this formula, R ^{3 is} a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical and the grouping -A- for -O- or a chemical bond. In other words, sulfate (A = O) or sulfonate (A = chemical bond) surfactants can be described by the above formula. Depending on the choice of the group A, certain radicals R ^{3 are} preferred. In the sulfate surfactants (A = O), R ^{3 is} preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms Atoms are preferred. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ oxo alcohols. Y stands for a monovalent cation or the n-th part of an n-valent cation, the alkali metal ions being preferred, and Na ⁺ or K ⁺ being preferred, Na ^{+ being} extremely preferred. Other cations Y + may be selected from NH ₄ ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ²⁺ , and mixtures thereof.

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

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

In dishwashing detergents, the content of cationic and / or amphoteric surfactants is preferably less than 4% by weight, more preferably less than 2% by weight and in particular less than 1% by weight. Dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.

The agents according to the invention may contain at least one, preferably two or more further constituents, preferably selected from the group consisting of builders, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, polymers, bleaches, bleach activators, foam inhibitors, dyes, fragrances , Bitter substances and antimicrobial agents.

Builders which may be present in the dishwashing detergent are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, organic (co) builders, such as, for example, salts of organic di- and polycarboxylic acids, and mixtures of these substances.

It is possible, for example, to use crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, in which M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layer-form silicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O are for example sold by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite). Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O, in which x is 2. In particular, both .beta.- and δ-sodium Na ₂ Si ₂ O ₅ · yH ₂ O, and further in particular Na-SKS-5 (α-Na ₂ Si ₂ O _5), Na-SKS-7 _(.beta.-Na2 Si ₂ O _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t- Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

The dishwashing detergents in various embodiments contain a weight fraction of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} .yH ₂ O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular of 0 , 4 to 10 wt .-%, each based on the total weight of these agents. In various embodiments, the agents are free of such silicates.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.

In various embodiments, these silicate (s), preferably alkali metal silicates, more preferably crystalline or amorphous Alkalidisilikate, in the compositions in amounts of from 3 to 60 wt .-%, preferably from 8 to 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the automatic dishwashing detergent, be included. In other embodiments, the agents are free of these silicates.

Further builders are the alkali carriers. Suitable alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, it being possible to use the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, for the purposes of this invention. Particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. Because of their low chemical compatibility with the other ingredients of dishwasher detergents in comparison with other builders, the optional alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 % By weight and in particular below 2% by weight, in each case based on the total weight of the automatic dishwashing detergent. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.

In various embodiments, carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2 to 50 wt .-%, preferably from 5 to 40 wt .-% and in particular from 7 , 5 to 30 wt .-%, each based on the weight of the automatic dishwashing detergent are used.

The dishwashing detergents can contain as further builders in particular also phosphonates, which according to the invention are not subsumed under the phosphates. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are contained in the compositions preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.3 to 8 wt .-%, each based on the total weight of the dishwashing detergent.

Particularly suitable organic (co) builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and the phosphonates already mentioned above as builders. These classes of substances are described below.

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

The use of citric acid and / or citrates has proved to be particularly advantageous for the cleaning and rinsing performance. Therefore, machine dishwashing detergents are preferred according to the invention in that the automatic dishwashing agent contains citric acid or a salt of citric acid and the weight fraction of citric acid or citric acid salt is preferably from 1 to 40% by weight, preferably from 2 to 15% by weight in particular between 3 and 10 wt .-% is.

Another important class of phosphate-free builders are aminocarboxylic acids and / or their salts. Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts, and glutamic diacetic acid (GLDA) or its salts or ethylenediaminediacetic acid (EDDS) or its salts. Very particular preference is GLDA or its salts. The content of these aminocarboxylic acids or their salts, in particular GLDA sodium salt, may for example be between 0.1 and 25% by weight, preferably between 5 and 25% by weight and in particular between 15 and 25% by weight. Aminocarboxylic acids and their salts can be used, for example, together with the abovementioned builders, in particular together with citrate and the abovementioned phosphonates.

The compositions of the invention may further contain a sulfopolymer. The proportion by weight of the sulfopolymer in the total weight of the cleaning agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1.0 to 15 wt .-%, in particular from 4 to 14 wt .-%, especially from 6 to 12 wt .-%. The sulfopolymer is typically employed in the form of an aqueous solution, the aqueous solutions typically containing from 20 to 70 weight percent, more preferably from 30 to 50 weight percent, preferably from about 35 to 40 weight percent sulfopolymers.

The sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate. The copolymers may have two, three, four or more different monomer units. Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.

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

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.

In the sulfonic acid-containing monomers are those of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H preferred, in which R ⁵ to R ⁷ are independently -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 -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - , -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

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

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

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

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

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

In various embodiments, other polymers can be used in the compositions of the invention. The group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in automatic dishwashing detergents in addition to nonionic polymers. The sulfo (co) polymers described above are, for example, anionic polymers.

For the purposes of the present invention, "amphoteric polymers" furthermore have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be e.g. to act carboxylic acids, sulfonic acids or phosphonic acids.

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

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

"Cationic polymers" are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers are derived from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and 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 various embodiments of the present invention, the aforementioned amphoteric, zwitterionic or cationic polymers are in prefabricated form. For the preparation of the polymers is suitable inter alia

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

As enzymes, various enzyme preparations or enzyme compositions known in the art can be used. These enzyme preparations or enzyme compositions usually contain at least one protease and one or more other enzymes. Other suitable enzymes include, but are not limited to, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly. Agents ^according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5% by weight, based on active protein. The active protein concentration can be determined by known methods, for example the BCA method or the biuret method.

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

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

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

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

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Enzyme preparations preferably used according to the invention contain between 0.1 and 40 Wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and in particular between 0.8 and 10 wt .-% of the enzyme protein. Protease and amylase preparations preferably used according to the invention each contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and in particular between 0 , 8 and 10 wt .-% of the enzyme protein.

Particular preference is given to those agents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.1 to 10% by weight and in particular 0.2 to 5% by weight, of enzyme preparations.

The compositions described herein may also include enzyme stabilizers. One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned. Also, peptide aldehydes, that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose. Among the peptidic reversible protease inhibitors include ovomucoid and leupeptin. Also, specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Certain organic acids used as builders are capable of, as in WO 97/18287 discloses additionally stabilizing a contained enzyme.

Other enzyme stabilizers are known to those skilled in the art.

Bleaching agents are washing or cleaning substances. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. It is also possible to use all other inorganic or organic peroxy bleaches known to the person skilled in the art.

In various embodiments, the dishwashing agents can contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight of bleaching agent, preferably sodium percarbonate, contain.

In various embodiments of the invention, the dishwashing agents additionally contain at least one bleach activator. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Of all the bleach activators known to the person skilled in the art, polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are acylated Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used. Combinations of conventional bleach activators can also be used. As bleach activator TAED according to the invention, especially in combination with a percarbonate bleach, preferably sodium percarbonate, is very particularly preferred.

These bleach activators are preferably used in amounts of up to 10% by weight, in particular from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.

In general, the pH of the agent can be adjusted by means of customary pH regulators, the pH value being selected depending on the desired application. In various embodiments, the pH is in a range of 5.5 to 12, preferably 6 to 11, more preferably 7 to 10, especially greater than 7, especially in the range 7.5 to 9.5. The pH adjusting agents are acids and / or alkalis, preferably alkalis. Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or also Sulfamic acid. In addition, however, it is also possible to use the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof. Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred. However, particularly preferred is volatile alkali, for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule. The alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof. The alkanolamine is preferably contained in agents according to the invention in an amount of from 0.5 to 10% by weight, in particular in an amount of from 1 to 6% by weight.

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

Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors originate from the group of bismuth, magnesium and zinc salts as well as bismuth, magnesium and zinc complexes, in particular zinc acetate. As glass corrosion inhibitors are preferably used singly or in combination with the above-mentioned salts or complexes, alkoxylated or non-alkoxylated, particularly non-alkoxylated polyethyleneimines, such as available under the name Lupasol ^® from BASF used. In the context of the present invention, the content of zinc salt in dishwashing detergents is preferably between 0.1 and 5 wt.%, Preferably between 0.1 and 4 wt.% And in particular between 0.2 and 3 wt. the content of zinc in oxidized form (calculated as Zn ²⁺ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight. -%, in each case based on the total weight of the glass corrosion inhibitor-containing agent.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.

Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

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

Solvents which are suitable for the compositions used according to the invention are, in addition to water as the preferred solvent, generally water-miscible organic solvents, such as, without limitation, ethanol, propanol, 1,2-propanediol and glycerol. In various embodiments, the dishwashing detergent may be a low-water, liquid dishwashing detergent containing water in amounts up to a maximum of 25% by weight, preferably up to 20% by weight, based on the total weight of the composition.

The term "low in water" as used herein means that the composition thus characterized contains less than 25% by weight of water, preferably less than 20% by weight of water. In particular, this term covers compositions which contain from 1 to 20% by weight of water. The water content as defined herein refers to the water content determined by Karl Fischer titration.

In general, the formulation of dishwashing agents described herein can be carried out in different ways. The agents may be in solid or liquid form as well as in a combination of solid and liquid forms. Powder, granules, extrudates, compacts, in particular tablets, are particularly suitable as firm supply forms. The liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels. The agents can be formulated in the form of single-phase or multi-phase products. The individual phases of multiphase agents may have the same or different states of matter.

"Liquid" as used herein with respect to the agent of the invention therefore includes all flowable compositions and, in particular, also encompasses gels and pasty compositions.

The dishwashing agents described herein are preferably automatic dishwashing agents, which may be in solid or liquid form. However, the solid moldings described below are particularly preferably also liquid agents, in particular in the form of gels.

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

The dishwashing agents described herein are preferably prefabricated into dosage units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g. The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

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

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

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

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

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

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

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

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

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

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

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

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

The embodiments described in context with the agents according to the invention are readily transferable to the methods and uses of the invention and vice versa. EXAMPLES Example 1: Formulations Used Table 1: Composition of the automatic dishwashing detergent raw materials V1 V2 V3 e AS% AS% AS% AS% glycerol 2.5 2.5 2.5 2.5 Xanthan gum 0.50 0.50 0.50 0.50 sulfopolymer 7.60 7.60 7.60 7.60 GLDA-Na 4 18.2 18.2 18.2 18.2 Citric acid monohydrate 5.3 5.3 5.3 5.3 HEDP 0.60 0.60 0.60 0.60 Monoethanolamine 4.1 4.1 4.1 4.1 Cationic co-polymer based on polyacrylate 0.2 0.2 0.2 0.2 Nio-surfactant 1 - - 3.00 2.00 Nio-surfactant 2 2.70 - - 0.90 protease 0.2 0.2 0.2 0.2 amylase 0.0125 0.0125 0.0125 0.0125 Conservation Agent / Bittern / Perfume / Dye 0.5 0.5 0.5 0.5 water ad 100 ad 100 ad 100 ad 100 AS = active substance
Nio-surfactant 1 = C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ether
Nio-surfactant 2 = C _8-10 fatty alcohol (EO) ₂₂ - (PO) ₁ -2-hydroxydecyl ether

Example 2: rinse test

To determine the rinse effect, selected and defined dishes are rinsed 4 times and visually scrapped after the 2nd, 3rd and 4th rinse cycles. The first rinse is used to condition the dishes. Rinse-off grades based on the visual appearance of the dry items to be washed (porcelain, glasses, plastic parts) are assigned as parameters. 20 g each of the formulations mentioned above in Table 1 are metered in and, per rinse, 100 g of dirt are metered in to simulate a normally soiled load.

Filming is determined in the Miele G698 at 50 ° C. Water hardness 21 ° dH. After completion of the rinse cycle, the machine is fully opened for 30 minutes and then the clear rinse effect is visually determined in the black box (black-painted room, D6500 daylight lamp). On the crockery and cutlery remaining dried water drops, streaks, coverings and films are scored on a scale of 1-10. 10 means no drops / films, 1 means heavy drops / filming.

The following result was achieved: Table 2: Rinse aid result Glass porcelain plastic V1 6.1 3.3 5.9 V2 1.8 3.0 4.5 V3 6.6 6.6 5.3 E1 8.6 7.7 6.8

It can be clearly seen that the surfactant combination according to the invention leads to an improvement compared to the reference without surfactants (V2). However, compared to the particular individual surfactants (V1 and V3), the surfactant combination can achieve significant advantages.

QUOTES INCLUDE IN THE DESCRIPTION

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

Cited patent literature

• WO 97/18287 [0087]

Claims (11)

Dishwashing detergent, in particular automatic dishwashing detergent, containing, based on the total weight of the dishwashing detergent, from 0.5 to 20.0% by weight, preferably from 1.0 to 10.0% by weight, more preferably from 2.0 to 5.0% by weight % of a surfactant mixture comprising: (i) at least one nonionic surfactant of the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , wherein R ^{1 is} a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, more preferably 8 to 10 carbon atoms, R ^{2 is} a linear or branched, saturated or or polyunsaturated hydrocarbon radical having 1 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, x is from 1 to 90, preferably from 10 to 60 and especially from 15 to 40 ; and (ii) at least one nonionic surfactant of the formula R ³ O [CH ₂ CH ₂ O] _y [CH ₂ CH (R ⁵ ) O] _z CH ₂ CH (OH) R ⁴ , wherein R ³ and R ⁴ independently represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, preferably 6 to 12 carbon atoms, each R ^{5 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ and -CH (CH ₃ ) ₂ , but preferably is -CH ₃ , and y and z are independently from 1 to 32, preferably y, from 15 to 32 and z is from 1 to 3, wherein the mass ratio of the at least one nonionic surfactant (i) to the at least one nonionic surfactant (ii) is in the range of 1: 4 to 4: 1, preferably in the range of 1: 1 to 4 : 1 is. Dishwashing detergent according to claim 1, characterized in that the hydrocarbon radicals R ¹ and / or R ^{2 are} aliphatic hydrocarbon radicals, in particular linear or branched alkyl radicals. Dishwashing detergent according to claim 1 or 2, characterized in that the at least one nonionic surfactant (i) is selected from the group of C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular a C _8-12 fatty alcohol (EO) _{22 is} 2-hydroxydecyl ether. Dishwashing detergent according to one of claims 1 to 3, characterized in that the hydrocarbon radicals R ³ and / or R ^{4 are} aliphatic hydrocarbon radicals, in particular linear or branched alkyl radicals. A dishwashing detergent according to any one of claims 1 to 4, characterized in that (i) R ^{4 is} an alkyl radical having 8 carbon atoms; (ii) R ^{5 is} -CH ₃ ; (iii) z is 1 or 2, especially 1; and / or (iv) y is 20-24, preferably 22. Dishwashing detergent according to one of claims 1 to 5, characterized in that the at least one nonionic surfactant (ii) is selected from the group of C _2-26 fatty alcohol (EO) _15-40 - (PO) ₁ -2-hydroxyalkyl ether, in particular a C _8-10 fatty alcohol (EO) ₂₂ - (PO) ₁ -2-hydroxydecyl ether. Dishwashing detergent according to one of claims 1 to 6, characterized in that in each case based on the total weight of the composition, the surfactant (i) in an amount of 1 to 5 wt .-%, preferably 2 to 3 wt .-% and / or the surfactant (ii) in an amount of 0.2 to 2 wt .-%, preferably 0.5 to 1.5 wt.% Is contained. Dishwashing detergent according to one of claims 1 to 7, characterized in that the surfactant mixture further surfactants, in particular further nonionic, anionic, cationic and / or amphoteric surfactants, and / or at least one further constituent, preferably at least two further constituents selected from the group consisting from builders, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, especially silver protectants, glass corrosion inhibitors, polymers, bleaches, bleach activators, foam inhibitors, dyes, perfumes, bittering agents and antimicrobial agents.  Use of a dishwashing agent according to any one of claims 1 to 8 in a dishwashing process, in particular a machine dishwashing process. Dishwashing process, in particular automatic dishwashing process, characterized in that a dishwashing detergent according to one of claims 1 to 8 is used. Use of a surfactant mixture comprising: (i) at least one nonionic surfactant of the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , wherein R ^{1 is} a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, more preferably 8 to 10 carbon atoms, R ^{2 is} a linear or branched, saturated or or polyunsaturated hydrocarbon radical having 1 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, x is from 1 to 90, preferably from 10 to 60 and especially from 15 to 40 ; and (ii) at least one nonionic surfactant of the formula R ³ O [CH ₂ CH ₂ O] _y [CH ₂ CH (R ⁵ ) O] _z CH ₂ CH (OH) R ⁴ , wherein R ³ and R ⁴ independently represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, preferably 6 to 12 carbon atoms, each R ^{5 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ and -CH (CH ₃ ) ₂ , but preferably is -CH ₃ , and y and z are independently from 1 to 32, preferably y, from 15 to 32 and z is from 1 to 3, wherein the mass ratio of the at least one nonionic surfactant (i) to the at least one nonionic surfactant (ii) is in the range of 1: 4 to 4: 1, preferably in the range of 1: 1 to 4 : 1, for improving the rinsing performance of a dishwashing detergent, preferably a machine dishwashing detergent.