EP3674386B1 - Dishwashing compositions with improved rinse performance - Google Patents

Description

The present invention relates to a dishwashing agent that A) at least one nonionic surfactant selected from fatty alcohol alkoxylates and B) at least one polymer that is selected by polymerizing itaconic acid with at least one co-monomer selected from (meth)acrylic acid, salts, esters or anhydrides thereof and 2 -Acrylamido-2-methylpropanesulfonic acid or salts thereof. The present invention further relates to a method for cleaning dishes in a dishwasher, using a dishwashing agent of the present invention, and the use of a dishwashing agent according to the present invention to improve the rinse performance of plastic or stainless steel items when washing dishes automatically.

A variety of dishwashing detergents are known for dishwashers. These are available for purchase as solid, powder, liquid and gel dishwashing detergents. However, unwanted lime deposits often remain on the items to be washed, especially when the water is hard. These residues are particularly visible on glass and metal surfaces, which is not something consumers want.

There is therefore a need for dishwashing detergents that provide improved rinsing performance and thus leave less limescale deposits on the washed items.

US 2017/022451 A1 discloses dishwashing detergent comprising a copolymer of itaconic acid and acrylic acid and an alkoxylated nonionic surfactant. The copolymer ensures better rinsing behavior on both glass and plastic surfaces.

EP 3 418 366 A1 discloses automatic dishwashing detergents comprising a copolymer of itaconic acid and a sulfomonomer selected from 2-acrylamidomethylpropanoic acid and/or styrene sulfonic acid. Specific example formulations also contain an ethoxylated nonionic surfactant.

WO 2017/167786 A1 discloses dishwashing detergent with improved rinse performance comprising 0.5 to 20% by weight of a surfactant mixture of an end-capped polyethoxylated nonionic surfactant and a specific hydroxy mixed ether.

DE 10 2007 042860 A1 discloses dishwashing detergent containing 10 to 60% by weight of builder, an alkoxylated fatty alcohol and an anionic copolymer. The copolymer is formed from an unsaturated carboxylic acid and a monomer with a sulfonic acid group. The weight ratio of the copolymer and the alkoxylated fatty alcohol is 3:1.

US 2018/223016 A1 discloses polyitaconic acid homo- and copolymers that do not have reactive tri-substituted vinyl monomers. It is further disclosed that such homo- or copolymers can be used as builders in detergents.

The inventors of the present invention have surprisingly found that the above problems can be solved by a dishwashing agent that A) at least one nonionic surfactant selected from specific fatty alcohol alkoxylates, as defined below, and B) at least one polymer that is made by polymerizing itaconic acid with at least a co-monomer selected from (meth)acrylic acid, salts, esters or anhydrides thereof and 2-acrylamido-2-methylpropanesulfonic acid or salts thereof. In this regard, it was particularly surprising that a synergistic effect was found for the combination of components A) and B) on the plastic and stainless steel substrates.

1. A) mindestens ein nichtionisches Tensid ausgewählt aus Fettalkoholalkoxylaten;
2. B) mindestens ein Polymer, dass durch Polymerisieren von Itaconsäure mit mindestens einem Co-Monomer ausgewählt aus (Meth)acrylsäure, Salzen, Ester oder Anhydriden davon oder 2-Acrylamido-2-methylpropansulfonsäure oder Salzen davon, erhalten wird;
3. C) gegebenenfalls mindestens ein von A) verschiedenes Tensid;
4. D) gegebenenfalls mindestens ein Enzym;
5. E) gegebenenfalls mindestens einen Komplexbildner; und
6. F) gegebenenfalls mindestens ein Additiv; umfasst oder daraus besteht,
   dadurch gekennzeichnet, dass das mindestens eine Fettalkoholalkoxylat ausgewählt ist aus mindestens einer Verbindung der allgemeinen Formel R¹O(AlkO)_xM(OAlk)_yOR², wobei
   • R¹ und R² unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten Alkylrest mit 4 bis 22 Kohlenstoffatomen stehen,
   • Alk für einen verzweigten Alkylenrest mit 3 oder 4 Kohlenstoffatomen oder unverzweigten Alkylenrest mit 2 bis 4 Kohlenstoffatomen steht,
   • x und y unabhängig voneinander für Werte zwischen 1 und 70 stehen und

- M für einen Alkylenrest aus der Gruppe CH₂, CHR³, CR³R⁴, CH₂CHR³ und CHR³CHR⁴ steht, wobei R³ und R⁴ unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, cyclischen oder acyclischen Alkyl- oder Alkenylrest mit bis zu 18 Kohlenstoffatomen stehen.Therefore, the invention relates in a first aspect to a dishwashing detergent that

1. A) at least one nonionic surfactant selected from fatty alcohol alkoxylates;
2. B) at least one polymer obtained by polymerizing itaconic acid with at least one co-monomer selected from (meth)acrylic acid, salts, esters or anhydrides thereof or 2-acrylamido-2-methylpropanesulfonic acid or salts thereof;
3. C) optionally at least one surfactant different from A);
4. D) optionally at least one enzyme;
5. E) optionally at least one complexing agent; and
6. F) optionally at least one additive; includes or consists of,
   characterized in that the at least one fatty alcohol alkoxylate is selected from at least one compound of the general formula R ¹ O(AlkO) _x M(OAlk) _y OR ² , where
   • R ¹ and R ² independently represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical with 4 to 22 carbon atoms,
   • Alk represents a branched alkylene radical with 3 or 4 carbon atoms or unbranched alkylene radical with 2 to 4 carbon atoms,
   • x and y independently represent values between 1 and 70 and

- M represents an alkylene radical from the group CH ₂ , CHR ³ , CR ³ R ⁴ , CH ₂ CHR ³ and CHR ³ CHR ⁴ , where R ³ and R ⁴ independently represent a branched or unbranched, saturated or unsaturated, cyclic or acyclic alkyl or alkenyl radical with up to 18 carbon atoms.

In a second aspect, the invention relates to a method for cleaning dishes in a dishwasher, using a dishwashing agent according to the present invention. Finally, in a third aspect, the invention relates to the use of a dishwashing agent according to the present invention to improve the rinse performance of plastic or stainless steel items in automatic dishwashing.

"At least one" as used herein refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with components of the compounds described herein, this information does not refer to the absolute amount of molecules, but rather to the type of component. “At least one surfactant” therefore means, for example, that only one type of surfactant or several different types of surfactant can be included, without providing information about the amount of the individual compounds.

Unless otherwise stated, all quantities given in connection with the dishwashing detergents described herein refer to % by weight based on the total weight of the dishwashing detergent. Furthermore, such quantities that relate to at least one component always refer to the total amount of this type of component contained in the dishwashing detergent, unless explicitly stated otherwise. This means that such quantities, for example in connection with "at least one surfactant", refer to the total amount of surfactants contained in the dishwashing detergent, unless explicitly stated otherwise.

Numerical values stated herein without decimal places refer to the full stated value with one decimal place. For example, "99%" stands for "99.0%".

The expressions “approximately” “approx.” or "about", in connection with a numerical value, refers to a variance of ±10% based on the specified numerical value, preferably ±5%, particularly preferably ±1%.

The expression “essentially free of” means that the respective compound can in principle be included, but is then present in an amount that does not impair the function of the other components. In the context of the present invention, the property “substantially free of” a particular compound is therefore preferably a total weight of less than 0.1% by weight, more preferably less than 0.001% by weight, in particular free of this, based on the total weight of detergents and cleaning agents.

Numerical ranges specified in the format "in/from x to y" include the stated values. When multiple preferred numerical ranges are specified in this format, it is understood that any ranges resulting from the combination of the various endpoints will also be captured.

Information about the molecular weight refers to the weight-average molecular weight in g/mol, unless the number-average molecular weight is explicitly stated. Molecular weights are preferably determined by GPC using polystyrene standards.

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from reading the following detailed description and claims. Any feature or embodiment from one aspect of the invention can be used in any other aspect of the invention. For example, described features or embodiments of the dishwashing detergents can also be applied to the claimed uses, and vice versa. Furthermore, 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 the invention is not limited to these examples.

The dishwashing detergent according to the invention, hereinafter referred to simply as a composition, contains at least one nonionic surfactant selected from fatty alcohol alkoxylates.

• R¹ und R² unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten Alkylrest mit 4 bis 22 Kohlenstoffatomen stehen,
• Alk für einen verzweigten Alkylenrest mit 3 bis 4 Kohlenstoffatomen oder unverzweigten Alkylenrest mit 2 bis 4 Kohlenstoffatomen steht,
• x und y unabhängig voneinander für Werte zwischen 1 und 70 stehen und
• M für einen Alkylenrest aus der Gruppe CH₂, CHR³, CR³R⁴, CH₂CHR³ und CHR³CHR⁴ steht, wobei R³ und R⁴ unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, cyclischen oder acyclischen Alkyl- oder Alkenylrest mit bis zu 18 Kohlenstoffatomen stehen.

According to the invention, the fatty alcohol alkoxylates have the formula R ¹ O(AlkO) _x M(OAlk) _y OR ² , where

• R ¹ and R ² independently represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical with 4 to 22 carbon atoms,
• Alk represents a branched alkylene radical with 3 to 4 carbon atoms or unbranched alkylene radical with 2 to 4 carbon atoms,
• x and y independently represent values between 1 and 70 and
• M represents an alkylene radical from the group CH ₂ , CHR ³ , CR ³ R ⁴ , CH ₂ CHR ³ and CHR ³ CHR ⁴ , where R ³ and R ⁴ independently represent a branched or unbranched, saturated or unsaturated, cyclic or acyclic Alkyl or alkenyl radical with up to 18 carbon atoms.

• R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 6 bis 16 Kohlenstoffatomen stehen und
• R für einen linearen, gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, vorzugsweise 4 bis 10 Kohlenstoffatomen steht und
• x und y unabhängig voneinander Werte von 5 bis 20 aufweisen.

In one embodiment, the fatty alcohol alkoxylates have the general formula

R ¹ -CH(OH)CH ₂ -O(CH ₂ CH ₂ O) _x CH ₂ CHR(OCH ₂ CH ₂ ) _y O-CH ₂ CH(OH)-R ²

on, in the

• R ¹ and R ² independently represent an alkyl radical or alkenyl radical with 6 to 16 carbon atoms and
• R represents a linear, saturated alkyl radical with 2 to 12 carbon atoms, preferably 4 to 10 carbon atoms and
• x and y independently have values from 5 to 20.

Such a nonionic surfactant is available, for example, from BASF under the trade name ^Dehypon® DA.

• R¹ für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen steht,
• R² einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 oder 3 bis 26 Kohlenstoffatomen bezeichnet,
• x und z für Werte zwischen 0 und 40 und
• y für einen Wert von mindestens 15 steht.

In a further embodiment, the fatty alcohol alkoxylates have the general formula

R ¹ O[CH ₂ CH(CH ₃ )O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH(CH ₃ )O] _z CH ₂ CH(OH)R ²

on, in the

• R ¹ represents a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms,
• R ² denotes a linear or branched hydrocarbon radical with 2 or 3 to 26 carbon atoms,
• x and z for values between 0 and 40 and
• y represents a value of at least 15.

• R¹ für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen steht,
• R² einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 oder 3 bis 26 Kohlenstoffatomen bezeichnet und
• y für einen Wert zwischen 15 und 120, vorzugsweise 20 bis 100 und insbesondere 20 bis 80 steht.

In a preferred embodiment, the fatty alcohol alkoxylates have the general formula

R ¹ O[CH ₂ CH ₂ O] _y CH ₂ CH(OH)R ²

on, in the

• R ¹ represents a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms,
• R ² denotes a linear or branched hydrocarbon radical with 2 or 3 to 26 carbon atoms and
• y represents a value between 15 and 120, preferably 20 to 100 and in particular 20 to 80.

The fatty alcohol alkoxylates are particularly preferably selected from the group of hydroxy mixed ethers of the general formula C _4-22 -CH(OH)CH ₂ O-(EO) _20-120 -C _2-26 . Very particularly preferably, the composition contains C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ether and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether. Such compounds are commercially available, for example, from BASF under the trade names ^Dehypon® E127 and ^Dehypon® GRA.

• R¹ für einen verzweigten oder unverzweigten Alkylrest mit 8 bis 16 Kohlenstoffatomen steht,
• R³ und R⁴ unabhängig voneinander für Wasserstoff oder einen verzweigten oder unverzweigten Alkylrest mit bis zu 5 Kohlenstoffatomen stehen,
• R² für einen unverzweigten Alkylrest mit 5 bis 17 Kohlenstoffatomen steht,
• x und z unabhängig voneinander für einen Wert von 1 bis 5 stehen und
• y für einen Wert von 13 bis 35 steht.

In a further embodiment, the fatty alcohol alkoxylates have the general formula

R ¹ O[CH ₂ CH(R ³ )O] _x [CH ₂ CHO] _y [CH ₂ CH(R ⁴ )O] _z C(O)R ²

on, where

• R ¹ represents a branched or unbranched alkyl radical with 8 to 16 carbon atoms,
• R ³ and R ⁴ independently represent hydrogen or a branched or unbranched alkyl radical with up to 5 carbon atoms,
• R ² represents an unbranched alkyl radical with 5 to 17 carbon atoms,
• x and z independently represent a value from 1 to 5 and
• y represents a value from 13 to 35.

• R¹ für einen verzweigten oder unverzweigten Alkylrest mit 10 bis 15 Kohlenstoffatomen steht,
• R³ und R⁴ unabhängig voneinander für Wasserstoff oder einen verzweigten Alkylrest mit 3 Kohlenstoffatomen oder unverzweigten Alkylrest mit 2 oder 3 Kohlenstoffatomen stehen,
• R² für einen unverzweigten Alkylrest mit 8 bis 16 Kohlenstoffatomen steht,
• x und z unabhängig voneinander für einen Wert von 1 bis 5 stehen und
• y für einen Wert von 20 bis 30. Diese sind beispielsweise unter dem Handelsnamen Plurafac^® LF 7319 von der Firma BASF erhältlich.

In a further embodiment, the fatty alcohol alkoxylates have the general formula

R ¹ O[CH ₂ CH(R ³ )O] _x [CH ₂ CHO] _y [CH ₂ CH(R ⁴ )O] _z C(O)R ²

on, where

• R ¹ represents a branched or unbranched alkyl radical with 10 to 15 carbon atoms,
• R ³ and R ⁴ independently represent hydrogen or a branched alkyl radical with 3 carbon atoms or unbranched alkyl radical with 2 or 3 carbon atoms,
• R ² represents an unbranched alkyl radical with 8 to 16 carbon atoms,
• x and z independently represent a value from 1 to 5 and
• y for a value of 20 to 30. These are available, for example, under the trade name ^Plurafac® LF 7319 from BASF.

In one embodiment, a mixture of the above-mentioned fatty alcohol alkoxylates may be included.

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

In a preferred embodiment, the at least one nonionic surfactant A) is present in 0.2 to 10% by weight or 0.5 to 9% by weight or 1 to 5% by weight.

The dishwashing detergent of the present invention further contains at least one copolymer obtained by polymerizing itaconic acid with at least one co-monomer selected from (meth)acrylic acid, salts, esters or anhydrides thereof, or 2-acrylamido-2-methylpropanesulfonic acid or salts thereof. This is referred to below simply as “polymer”.

These polymers are known to those skilled in the art and are commercially available, for example, under the trade name Noverite ^™ AD 810G from Lubrizol Advanced Materials, Inc. Suitable copolymers and their production methods are described, for example, in WO 2014/143773 A1 described.

In one embodiment, the polymer is made by polymerizing itaconic acid, in particular more than 25 mol%, in particular 35 to 60 mol%, itaconic acid monomers with less than 75 mol%, of at least one co-monomer selected from (meth)acrylic acid, salts, esters or Anhydrides thereof or 2-acrylamido-2-methylpropanesulfonic acid or salts thereof, in particular a mixture of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid or salts thereof.

In a further embodiment, the polymer has a number-average molecular weight of 100 to 100,000 g/mol, in particular 500 to 50,000 g/mol. Alternatively, the polymer may have a number average molecular weight of 100 to 500 g/mol.

In a further embodiment, acrylic acid is used in 30 to 65 mol%, in particular 40 to 50 mol%. In a further embodiment, 2-acrylamido-2-methylpropanesulfonic acid is used in 0.1 to 20 mol%, preferably 0.5 to 10 mol%.

The copolymer is preferably an alternating, random or block copolymer.

In particular, the copolymer is a terpolymer.

In one embodiment, the copolymer is etherified from 0.1 to 60%.

In a further embodiment, the copolymer is essentially free of citraconic acid and/or mesaconic acid monomers.

The polymerization is preferably carried out in the presence of a redox system, particularly preferably with a mixture of sodium persulfate, tert-butyl perpivalate or tert-butyl perbenzoate and a mixture of the sodium salt of 2-hydroxy-2-sulfinatoacetic acid and sodium sulfite. The polymers can preferably be polymerized by solution polymerization in an aqueous medium. Only water or a mixture of water and organic solvents such as alcohols, especially isoporopyl, can be used.

In a preferred embodiment, the at least one nonionic surfactant A) and the at least one polymer B) are present in a ratio of 1:1 to 1:5 or 1:2 to 1:3.

The dishwashing detergent can have at least one further surfactant different from A).

All nonionic surfactants known to those skilled in the art can be used as further nonionic surfactants.

Suitable further nonionic surfactants are, for example, alkyl glycosides of the general formula RO(G)x, in which R corresponds to a primary linear or methyl-branched, especially methyl-branched, aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms and G that Symbol that stands for a glucose unit with 5 or 6 carbon 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.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallow alkyl-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 component A), in particular not more than half of it.

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

In one aspect, the composition further comprises at least one anionic surfactant.

Suitable anionic surfactants are fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, olefin sulfonates, alkyl sulfates, alkyl sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates. Also usable within the scope of the present invention are fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and di-alkyl esters with 8 to 18 carbon atoms, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ethers). phosphates as well as α-sulfofatty acid salts, acyl glutamates, monoglyceride disulfates and alkyl ethers of glycerine disulfate.

The composition may further comprise at least one alkyl sulfate, preferably selected from C8-18 fatty alcohol sulfates, more preferably C12-16 fatty alcohol sulfates, in particular lauryl sulfates or myristyl sulfates, most preferred is sodium lauryl sulfate.

The at least one anionic surfactant can preferably be used in an amount of 0.1 to 10% by weight, in particular 0.5 to 3% by weight, based on the total weight of the composition.

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, as well as in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts.

In a preferred embodiment, the composition contains only nonionic surfactants.

The dishwashing detergent according to the invention can also preferably contain at least one enzyme.

These include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases and preferably mixtures thereof. Enzymes can be present in the dishwashing detergent preferably in amounts of 0.0001 to 10% by weight, preferably from 0.01 to 5% by weight, preferably from 0.1 to 4% by weight, particularly preferably between 0.2 and 4% by weight, based on the total weight of the dishwashing detergent, can be used.

The dishwashing detergent according to the invention can also preferably contain at least one complexing agent.

Preferred complexing agents are selected from β-alaninediacetic acid, methylglycinediacetic acid (MGDA), iminodisuccinate (IDS), glutamine-N,N-diacetic acid (GLDA), citrates and gluconates or mixtures thereof, in particular methylglycinediacetic acid (MGDA).

In a preferred embodiment, the at least one complexing agent is contained in 1.0 to 25.0% by weight, preferably in 5.0 to 20.0% by weight, based on the total weight of the composition.

The dishwashing detergent according to the invention can further comprise at least one additive. These can be all additives known to those skilled in the field of dishwashing detergents.

Particularly suitable additives are described below.

The dishwashing detergent can also contain builders. Builders are usually substances that help ensure the cleaning performance of the dishwashing detergent by, among other things, inhibiting the formation of limescale on machine components and thus enabling the energy to be transferred efficiently to the water.

The proportion by weight of the builders in the total weight of the dishwashing detergent is preferably 5 to 80% by weight and in particular 10 to 60% by weight. The builders include, in particular, carbonates, phosphates, citrates and silicates.

It is preferred to use carbonate(s) and/or bicarbonate(s), preferably alkali carbonate(s), particularly preferably sodium carbonate, in amounts of 2 to 30% by weight, preferably 4 to 28% by weight and in particular of 8 to 24% by weight, based on the total weight of the dishwashing detergent.

The use of phosphate(s) is also preferred. Among the large number of commercially available phosphates, alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphate is the general name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can differentiate between metaphosphoric acid (HPO ₃ ) _n and orthophosphoric acid H ₃ PO ₄ alongside higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent lime deposits on machine parts or lime incrustations on the objects to be cleaned and also contribute to cleaning performance.

Particularly preferred phosphates are pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate). Sodium potassium tripolyphosphates are also preferably used.

If phosphates are used as builders in the dishwashing detergent in the context of the present application, this contains phosphate(s), preferably alkali metal phosphate(s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 5 to 70 wt .-%, preferably from 15 to 55% by weight and in particular from 20 to 50% by weight, in each case based on the total weight of the dishwashing detergent. In an alternative embodiment, essentially no phosphates are present.

Polycarboxylates/polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals and dextrins are also used as preferred builders. This class of substances is also referred to as organic cobuilders and is described below.

If a polycarboxylic acid is used as a builder, it can be used in the form of the free acid and/or its alkali metal salts, in particular sodium salts, whereby polycarboxylic acid is understood to mean a carboxylic acid that carries more than one acid function. Citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, as well as mixtures of these can be mentioned as examples. In addition to their builder effect, the free acids typically also have the properties of an acidifying component and are therefore also used to adjust a lower and milder pH value of dishwashing detergents.

The dishwashing detergent can particularly preferably contain citrate as a builder, preferably sodium citrate. The dishwashing detergent can preferably contain 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 15% by weight of citrate, in particular sodium citrate, based on the total weight of the dishwashing detergent.

The citrates are preferably used together with carbonates and/or bicarbonates. Preferred dishwashing detergents therefore contain a builder combination of phosphate and carbonate/bicarbonate or of citrate and carbonate/bicarbonate or of phosphate, citrate and carbonate/bicarbonate.

A particularly preferred dishwashing agent is characterized in that it contains at least two builders from the group of phosphates, carbonates and citrates, the proportion by weight of these builders, based on the total weight of the dishwashing agent, preferably being 5 to 70% by weight, preferably 7 to 60 % by weight and in particular 10 to 25% by weight. The combination of two or more builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of the dishwashing detergent.

Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a weight-average molecular weight of 500 to 70,000 g/mol.

Suitable polymers are, in particular, polyacrylates, which preferably have a weight-average molecular weight of 2000 to 20,000 g/mol. Because of their superior solubility, the short-chain polyacrylates, which have a weight-average molecular weight of 2000 to 10,000 g/mol, and particularly preferably of 3000 to 5000 g/mol, can be preferred from this group.

In a preferred embodiment, the composition contains a cationic polymer. Suitable cationic polymers are, for example, cationic cellulose derivatives, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone/vinylimidazole polymers such as. B. Luviquate ^® (BASF AG, Ludwigshafen/FRG), condensation products of polyglycols and amines, quaternized collagen polypeptides such as Lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat ^® L, Grünau GmbH), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such as. B. Amidomethicone or Dow Corning, Dow Corning Co./US, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetrimamine (Carta ^retine® , Sandoz/CH), polyaminopolyamides such as. B. described in the FR A 22 52 840 as well as their cross-linked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally distributed in microcrystalline form, cationic guar gum such as. B. Jaguar ^® CBS, Jaguar ^® C-17, Jaguar ^® C-16 from Celanese/US, quaternized ammonium salt polymers such as. B. Mirapol ^® A-15, Mirapol ^® AD-1, Mirapol ^® AZ-1 from Miranol/US. Cationic polyacrylates are particularly suitable, preferably with a weight-average molecular weight of 2000 to 20,000 g/mol; such polymers are available, for example, under the trade name Mirapol Surf S 480 PF from Miranol/US. Cationic polyacrylates are preferably contained in 0.1 to 5% by weight, or 0.25 to 4% by weight or 0.5 to 1% by weight.

The content of (homo)polymeric polycarboxylates in the dishwashing detergent is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.

The dishwashing detergent can use crystalline layered silicates of the general formula as a builder

NaMSi _x O _2x+1 · y H ₂ O

contain, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferably 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, stands.

Amorphous sodium silicates with a modulus NazO:SiOz of 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and in particular from 1:2 to 1:2.6, which are preferably delayed in dissolution, can also be used and have secondary washing properties.

In a preferred dishwashing detergent, the content of silicates, based on the total weight of the dishwashing detergent, is limited to amounts of 0 to 10% by weight, preferably from 0 to 5% by weight and in particular from 0 to 2% by weight. A particularly preferred dishwashing detergent is free of silicates.

In addition to the aforementioned builders, the dishwashing detergent can contain alkaline agents, preferably alkali metal hydroxides, in particular sodium hydroxide. These alkaline agents are preferably used in the dishwashing detergent in amounts of 0 to 10% by weight, preferably 0 to 5% by weight, particularly preferably between 0.1 and 5% by weight and in particular between 0.5 and 5% by weight .-%, based on the total weight of the dishwashing detergent, used. An alternatively preferred dishwashing detergent is free of alkali metal hydroxides.

In a preferred embodiment, the dishwashing detergent contains at least one thickener. This is preferably selected from polyacrylate thickeners, xanthan, gellan, guar, alginate, carrageenan, carboxymethylcellulose, bentonites, welan gum, locust bean gum, agar-agar, tragacanth, gum arabic, pectins, polysaccharides, starch, modified starch, dextrins, gelatins and casein , modified celluloses, hydroxyethyl ether and hydroxypropyl ether, more preferably selected from xanthan, gellan, guar, alginate, carrageenan, carboxymethylcellulose, locust bean gum, agar-agar, tragacanth, gum arabic, pectins, starch, modified starch, dextrins, gelatins and casein, and modified Celluloses, most preferably xanthan gum.

The at least one thickener is preferably contained in 0.1 to 10% by weight or 0.25 to 5% by weight or 0.3 to 1% by weight.

Furthermore, the composition can contain perfume oils and/or fragrances. In the context of the present invention, individual fragrance compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. However, mixtures of different fragrances are preferably used, which together produce an appealing scent. Such perfume oils can also contain natural fragrance mixtures such as those available from plant sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

In preferred embodiments, the composition is essentially phosphate-free. In further preferred embodiments, the composition is bleach-free. "in the "Substantially phosphate-free", as used herein, means that the composition in question is essentially free of phosphates, ie in particular phosphates in amounts of less than 0.1% by weight, preferably less than 0.01% by weight, based on the entire composition contains. "Essentially bleach-free" means, analogously, that the composition in question is essentially free of bleaching agents, ie bleaching agent in particular in amounts of less than 0.1% by weight, preferably less than 0.01% by weight on the overall composition.

Furthermore, the composition may contain corrosion inhibitors. (Glass) corrosion inhibitors prevent the appearance of clouding, streaks and scratches as well as iridescence on the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and/or zinc salts and/or magnesium and/or zinc complexes.

The composition can preferably also contain dyes. Dyes are known to those skilled in the art and all common dyes can be used as long as they do not have a negative interaction with the other components of the composition.

The compositions can be in solid or liquid form.

In general, the pH of the liquid compositions described herein can be adjusted using conventional pH regulators. The pH of the composition is in a range from 9.0 to 13.0, preferably 10.0 to 12, in particular 10 to 11.5. Unless otherwise stated, the pH value is preferably measured at 25° C. in the undiluted composition, usually using a pH electrode. Acids and/or bases/alkalis are preferably used as pH adjusters.

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, most preferred is citric 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, in particular the alkali metal carbonates, of which sodium carbonate is preferred.

In preferred aspects according to one of the preceding aspects, the composition is in pre-portioned form and/or in particular in liquid form.

“Liquid” means that the composition is in liquid form and in particular flowable at room temperature, i.e. around 20 ° C, and can therefore be poured out of a container, for example. The term as used herein also includes gels.

The composition according to the invention can be added to 100% by weight with water and/or at least one organic solvent.

The liquid forms based on water and/or at least one organic solvent can be thickened, in the form of gels or pasty forms, i.e. non-solid compositions.

In a preferred aspect, the composition described herein is in liquid form, for example gel form, and is not pre-portioned. This allows the composition to be applied to the dirty parts and the composition to act.

In another preferred aspect, the compositions described herein can preferably be prepackaged into dosage units. These dosing units preferably include the amount of cleaning-active substances necessary for a cleaning cycle.

In a preferred aspect, the invention relates to a composition which can be present in a water-insoluble, water-soluble or water-dispersible packaging, for example a film containing a single-use portion. The cleaning agent can be formulated in such a way that single-use portions are each packaged separately.

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

It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings that 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 coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the weight-average molecular weight of which is in the range from 10,000 to 1,000,000 g/mol, preferably from 20,000 to 500,000 g/mol, particularly preferably from 30,000 to 100,000 g/mol and in particular from 40,000 to 80,000 g/mol.

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

A polyvinyl alcohol-containing film material suitable for producing the water-soluble coating can additionally contain 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 may be added. A preferred additional polymer is polylactic acids.

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

In addition to vinyl alcohol, also preferred polyvinyl alcohol copolymers include an ethylenically unsaturated carboxylic acid, its salt or its ester. In addition to vinyl alcohol, such polyvinyl alcohol copolymers particularly preferably contain acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.

It may be preferred that the film material contains further additives. The film material can, for example, contain 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, anti-blocking agents, anti-adhesive agents or mixtures thereof.

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

The composition and/or the film can preferably contain bitter substances. Bitter substances are known to those skilled in the art and all common bitter substances can be used. Denatonium benzoate is particularly preferred.

Another subject of the present application is an automatic dishwashing process in which the dishwashing agent according to the invention is used. In the method for cleaning dishes in a dishwasher using the dishwashing detergent, the dishwashing detergent is preferably metered or introduced into the interior of a dishwasher while running through a dishwashing program, before the start of the main wash cycle or during the course of the main wash cycle. The dishwashing detergent can be metered in or introduced into the interior of the dishwasher manually, but the dishwashing detergent is preferably dosed into the interior of the dishwasher using the dosing chamber of the dishwasher. During the cleaning process, no additional water softener and no additional rinse aid are preferably dosed into the interior of the dishwasher.

A preferred embodiment is a mechanical dishwashing process using the preferably liquid dishwashing agent, in particular in the form of a previously mentioned shaped body, in particular for improved final rinsing performance for plastic or stainless steel items to be washed.

For economic and ecological reasons, the dishwashing process is preferably carried out at a liquor temperature below 60 ° C, preferably not above 50 ° C, preferably at 35 to 45 ° C. In a preferred embodiment, the dishwashing process takes 5 to 90 minutes, in particular 10 to 75 minutes, particularly preferably 20 to 60 minutes. In alternative, particularly preferred embodiments, the dishwashing process takes a maximum of 50, 40 or 30 minutes.

As described at the beginning, the dishwashing detergent according to the invention is characterized by improved rinse performance compared to conventional dishwashing detergents. A further subject of the present application is therefore the use of the dishwashing detergent according to the invention to improve the rinse performance of plastic or stainless steel items in automatic dishwashing.

Examples

The final rinse tests were carried out in a Miele GSL with the program R50°C/8min/KI65°C 2 at a water hardness of 21°dH in the presence of ballast dirt (fat, egg, starch). 28.5g of test product was used per rinse cycle. The items to be washed (stainless steel and plastic) were evaluated visually by comparing them with a reference scale (5 = no stains; 1 = very strong stains) and the arithmetic mean values (n = 3) were determined.

Example 1:

Table 1: Recipes of enzyme-containing gels according to the present invention, all of which had a rinse performance of 4-5 on stainless steel and plastic. A b C D wt% wt% wt% wt% Xanthan gum 0.4 0.4 0.4 0.4 Noverite AD 810G (88% Polyacrylate-39) 4.5 4.0 3.0 5.0 Non-ionic surfactant (Dehypon E127) 2.0 3.5 1.5 1.5 Sodium citrate 9.5 9.5 9.5 9.5 Trilon M Max 18.5 18.5 18.5 18.5 citric acid 1.2 1.2 1.2 1.2 Cationic acrylate copolymer (Mirapol Surf S 480 PF) 0.67 0.67 0.67 0.67 Protease (% by weight of active enzyme) 0.3 0.3 0.3 0.3 Amylase (% by weight of active enzyme) 0.1 0.1 0.1 0.1 Perfume 0.2 0.2 0.2 0.2 Water Ad 100 Ad 100 Ad 100 Ad 100

Example 2:

Comparison of compositions according to the invention with compositions which only had one of the two components A) and B) or another nonionic surfactant. The following composition was used as a framework recipe: Framework recipe wt% Xanthan gum 0.4 Sodium citrate 9.5 Trilon M Max 18.5 citric acid 1.2 Cationic acrylate copolymer (Mirapol Surf S 480 PF) 0.67 Protease (% by weight of active enzyme) 0.3 Amylase (% by weight of active enzyme) 0.1 Perfume 0.2 Water Ad 100

The following combinations of surfactants and polymer were used: Table 2: Comparative Examples 1 to 4 and Examples 2 and 3 stainless steel plastic VEx.1 0% Dehypon E127 1.5 1.5 0% Noverite AD 810G VEx. 2 2% Dehypon E127 1.8 3.0 0% Noverite AD 810G VEx. 3 0% Dehypon E127 1.8 2.1 4% Noverite AD 810G VEx. 4 2% Dehypon E127 2.3 3.7 4.5% Acusol (acrylic/sulfate polymer) 588 Example 2 2% Dehypon E127 5.0 4.1 4% Noverite AD 810G Example 3 2% Dehypon E127 4.7 4.0 2% Noverite AD 810G VEx. = Comparative example, Example = Example according to the invention

As can be seen from the above experiments, there is a synergistic effect with the specific combination according to the invention on stainless steel (VEx.2, 3 and Example 3). All further tests show greatly improved rinse properties compared to compositions with only the surfactant or polymer or Acusol 588 and the polymer.

Claims (12)

1. A dishwashing detergent, that contains or consists of

   A) at least one non-ionic surfactant selected from fatty alcohol alkoxylates;

   B) at least one polymer that is obtained by polymerizing itaconic acid with at least one comonomer selected from (meth)acrylic acid, salts, esters, or anhydrides thereof or 2-acrylamido-2-methylpropane sulfonic acid or salts thereof;

   C) optionally at least one surfactant different from A);

   D) optionally at least one enzyme;

   E) optionally at least one complexing agent; and

   F) optionally at least one additive,
   characterized in that the at least one fatty alcohol alkoxylate is selected from at least one compound of the general formula R¹O(AlkO)_xM(OAlk)_yOR², where

   - R¹ and R² represent, independently of one another, a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl functional group having 4 to 22 carbon atoms,

   - Alk represents a branched alkyl functional group having 3 or 4 carbon atoms or an unbranched alkyl functional group having 2 to 4 carbon atoms,

   - x and y represent, independently of one another, values of between 1 and 70, and

   - M represents an alkyl functional group from the group CH₂, CHR³, CR³R⁴, CH₂CHR³ and CHR³CHR⁴, where R³ and R⁴ represent, independently of one another, a branched or unbranched, saturated or unsaturated, cyclic or acyclic alkyl or alkenyl functional group having up to 18 carbon atoms.
2. The dishwashing detergent according to claim 1, wherein the at least one fatty alcohol alkoxylate is selected from

   i) at least one compound of the general formula
   
           R¹O[CH₂CH(CH₃)O]_x[CH₂CH₂O]_y[CH₂CH(CH₃)O]_zCH₂CH(OH)R²,
   
   in which

   - R¹ represents a linear or branched aliphatic hydrocarbon functional group having 4 to 22 carbon atoms,

   - R² represents a linear or branched hydrocarbon functional group having 2 or 3 to 26 carbon atoms,

   - x and z values of between 0 and 40, and

   - y represents a value of at least 15; and/or

   ii) at least one compound of the general formula
   
           R¹O[CH₂CH(R³)O]_x[CH₂CHO]_y[CH₂CH(R⁴)O]_zC(O)R²,
   
   where

   - R¹ represents a branched or unbranched alkyl functional group having 8 to 16 carbon atoms,

   - R³ and R⁴ represent, independently of one other, hydrogen or a branched or unbranched alkyl functional group having 1 to 5 carbon atoms,

   - R² represents an unbranched alkyl functional group having 5 to 17 carbon atoms,

   - x and z represent, independently of one another, a value of from 1 to 5, and

   - y represents a value of from 13 to 35; or

   iii) at least one compound of the general formula
   
           R¹-CH(OH)CH₂-O(CH₂CH₂O)_xCH₂CHR(OCH₂CH₂)_yO-CH₂CH(OH)-R²,
   
   in which

   - R¹ and R², independently of one another, an alkyl functional group or alkenyl functional group having 6 to 16 carbon atoms, and

   - R represents a linear, saturated alkyl functional group having 2 to 12 carbon atoms, preferably 4 to 10 carbon atoms, and

   - x and y have, independently of one another, values of from 5 to 20; and/or

   iv) at least one compound of the general formula
   
           R¹O[CH₂CH₂O]_yCH₂CH(OH)R²,
   
   in which

   - R¹ represents a linear or branched aliphatic hydrocarbon functional group having 4 to 22 carbon atoms,

   - R² represents a linear or branched hydrocarbon functional group having 2 or 3 to 26 carbon atoms, and

   - y represents a value of between 15 and 120, preferably 20 to 100 and in particular 20 to 80; and/or

   v) at least one compound selected from the group of hydroxy mixed ethers of general formula C_4-22-CH(OH)CH₂O-(EO)_20-120-C_2-26, in particular the C_8-12 fatty alcohol-(EO)₂₂-2-hydroxydecyl ethers and the C_4-22 fatty alcohol-(EO)_40-80-2-hydroxyalkyl ethers; and/or

   vi) at least one compound of the general formula
   
           R¹O[CH₂CH(R³)O]_x[CH₂CHO]_y[CH₂CH(R⁴)O]_zC(O)R²,
   
   where

   - R¹ represents a branched or unbranched alkyl functional group having 10 to 15 carbon atoms,

   - R³ and R⁴ represent, independently of one another, hydrogen or a branched or unbranched alkyl functional group having 2 or 3 carbon atoms,

   - R² represents an unbranched alkyl functional group having 8 to 16 carbon atoms,

   - x and z represent, independently of one another, a value of from 1 to 5, and

   - y represents a value of from 20 to 30.
3. The dishwashing detergent according to one of claims 1 or 2, wherein
   that at least one non-ionic surfactant A) is present in 0.2 to 10 wt.% or 0.5 to 9 wt.%.
4. The dishwashing detergent according to one of the preceding claims, wherein the at least one polymer B)

   i) is obtained by polymerizing itaconic acid, in particular more than 25 mol.%, in particular 35 to 60 mol.%, itaconic acid monomers with less than 75 mol.% of at least one comonomer selected from (meth)acrylic acid, salts, esters or anhydrides thereof or 2-acrylamido-2-methylpropane sulfonic acid or salts thereof; in particular, the comonomers are acrylic acid and 2-acrylamido-2-methylpropane sulfonic acid or salts thereof; and/or

   ii) has a number-average molecular weight of 100 to 100,000 g/mol, in particular of 500 to 50,000 g/mol; and/or

   iii) is based on 30 to 65 mol.%, in particular 40 to 50 mol.%, acrylic acid monomers; and/or

   iv) is based on 0.1 to 20 mol.%, preferably 0.5 to 10 mol.%, 2-acrylamido-2-methylpropane sulfonic acid monomers; and/or

   v) is an alternating, statistical or block copolymer, preferably a terpolymer; and/or

   vi) is 0.1 to 60% etherified.
5. The dishwashing detergent according to one of the preceding claims, wherein
   that at least one non-ionic surfactant A) and the at least one polymer B) are present in a ratio of from 1:1 to 1:5 or 1:2 to 1:3.
6. The dishwashing detergent according to one of the preceding claims, wherein
   that at least one surfactant different from A) is an anionic surfactant.
7. The dishwashing detergent according to one of the preceding claims, wherein
   that at least one enzyme comprises an amylase and/or a protease.
8. The dishwashing detergent according to one of the preceding claims, wherein
   that the dishwashing detergent is a liquid agent, in particular a gel.
9. The dishwashing detergent according to one of the preceding claims, wherein
   that at least one additive comprises a thickener, preferably selected from polyacrylate thickeners, xanthan gum, gellan, guar, alginate, carrageenan, carboxymethyl cellulose, bentonites, welan gum, carob gum, agar-agar, tragacanth, gum arabic, pectins, polysaccharides, starch, modified starch, dextrins, gelatins, and casein, modified celluloses, hydroxyethyl ether, and hydroxypropyl ether, more preferably selected from xanthan gum, gellan, guar, alginate, carrageenan, carboxymethyl cellulose, carob gum, agar-agar, tragacanth, gum arabic, pectins, starch, modified starch, dextrins, gelatins, and casein, and modified celluloses, most preferably carob gum.
10. A method for cleaning dishes in a dishwasher using a dishwashing detergent according to one of the claims 1 to 9.
11. The method according to claim 10, characterized in that the dishwashing process is carried out at a liquor temperature of less than 60 °C, preferably no higher than 50 °C.
12. The use of a dishwashing detergent according to one of claims 1 to 9 for improving the rinsing performance of plastics or stainless steel washware during automatic dishwashing.