DE102018133650A1 - Dishwashing liquid with improved rinse aid - Google Patents

Abstract

The present invention relates to a dishwashing detergent that A) at least one nonionic surfactant selected from fatty alcohol alkoxylates and B) at least one polymer that 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. Furthermore, the present invention 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 aid performance for plastic or stainless steel items in automatic dishwashing.

Description

The present invention relates to a dishwashing detergent that A) at least one nonionic surfactant selected from fatty alcohol alkoxylates and B) at least one polymer that 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. Furthermore, the present invention 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 aid performance for plastic or stainless steel items in automatic dishwashing.

A large number of dishwashing agents are known for dishwashers. These are commercially available as solid, powder, liquid and gel dishwashing detergents. Nevertheless, undesirable limescale deposits often remain on the wash ware, especially if the water hardness is high. In particular, these residues can be seen on glass and metal surfaces, which is not desired by the consumer.

There is therefore a need for dishwashing detergents which leave an improved rinse aid performance and thus less limescale deposits on the dishes being washed.

The inventors of the present invention surprisingly found that the above problems can be solved by a dishwashing detergent that A) at least one nonionic surfactant selected from fatty alcohol alkoxylates and B) at least one polymer selected by polymerizing itaconic acid with at least one co-monomer (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 for the combination of components A) and B) was found on the substrates plastic and stainless steel.

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.

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 that is 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.

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 detergent according to the present invention to improve the rinse aid performance for 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 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 specifying the amount of the individual compounds.

Unless stated otherwise, all of the quantities stated in connection with the dishwashing detergents described herein relate to% by weight, based in each case on the total weight of the dishwashing detergent. Furthermore, such quantities which relate to at least one constituent always relate to the total amount of this type of constituent which is 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 that are given here without decimal places each refer to the full specified value with one decimal place. For example, “99%” stands for “99.0%”.

The terms “approximately” “approx.” Or “approximately” in connection with a numerical value refer to a variance of ± 10% based on the numerical value given, preferably ± 5%, particularly preferably ± 1%.

The expression “essentially free of” means that the respective compound can be contained in principle, but is then present in an amount which does not impair the function of the other components. In the context of the present invention, therefore, the property “essentially free of” a particular compound preferably means 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 the detergent and cleaning agent.

Numerical ranges that are specified in the format "in / from x to y" include the values mentioned. If several preferred numerical ranges are specified in this format, it goes without saying that all ranges that result from the combination of the different endpoints are also covered.

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

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art upon studying the following detailed description and claims. Any feature or embodiment from one aspect of the invention may be used in any other aspect of the invention. For example, described features or embodiments of the dishwashing detergent can also be applied to the claimed uses, and vice versa. Furthermore, it goes without saying 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 restricted to these examples.

The dishwashing detergent according to the invention, hereinafter also 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 Alkylresten mit 3 bis 4 Kohlenstoffatomen oder unverzweigten Alkylrest mit 2 bis 4 Kohlenstoffatomen steht,
• - x und y unabhängig voneinander für Werte zwischen 1 und 70 stehen und
• - M für einen Alkylrest 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.

In one embodiment, the fatty alcohol alkoxylates have the formula R ¹ O (AlkO) _x M (OAlk) _y OR ² , where

• R ¹ and R ² independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms,
• Alk represents a branched alkyl radical with 3 to 4 carbon atoms or unbranched alkyl radical with 2 to 4 carbon atoms,
• - x and y independently of one another stand for values between 1 and 70 and
• - M represents an alkyl 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 of one another represent a branched or unbranched, saturated or unsaturated, cyclic or acyclic alkyl or alkenyl radical having 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 a further 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 of one another represent an alkyl radical or alkenyl radical having 6 to 16 carbon atoms and
• - R represents a linear, saturated alkyl radical having 2 to 12 carbon atoms, preferably 4 to 10 carbon atoms, and
• - x and y have values from 5 to 20 independently of one another.

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

• - 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 having 4 to 22 carbon atoms,
• R ² denotes a linear or branched hydrocarbon radical having 2 or 3 to 26 carbon atoms,
• - x and z for values between 0 and 40 and
• - y stands for 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 , in which

• R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms,
• - R ² denotes a linear or branched hydrocarbon radical having 2 or 3 to 26 carbon atoms and
• - y stands for 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 the hydroxy _mixed ethers of the general formula C _4-22 -CH (OH) CH ₂ O- (EO) _20-120 -C _2-26 . The composition very particularly preferably 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 under the trade names Dehypon® ^® E127 and Dehypon® ^® GRA by BASF.

• - 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 , where

• R ^{1 represents} a branched or unbranched alkyl radical having 8 to 16 carbon atoms,
• R ³ and R ⁴ independently of one another represent hydrogen or a branched or unbranched alkyl radical having up to 5 carbon atoms,
• R ^{2 represents} an unbranched alkyl radical having 5 to 17 carbon atoms,
• - x and z independently of one another have a value from 1 to 5 and
• - y stands for 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 , where

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

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

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the above-mentioned nonionic surfactants represent statistical mean values which can be an integer or a fraction for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which can result in mean values and fractional numbers for the C chain lengths as well as for 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 which is 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. In the following, this is also simply referred to as “polymer”.

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

In one embodiment, the polymer is selected 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 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, are obtained.

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 can 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, a random or a 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, in particular 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 the person 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, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms, and G that Is symbol which stands for a glucose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of component A), in particular not more than half of them.

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. 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, acylaminoalkane sulfonates (fatty acid taurides), alkyl ether carboxylic acids, fatty ether carboxylic acids, phosphates and α-sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

The composition may also include at least one alkyl sulfate, preferably selected from C8-18 fatty alcohol sulfates, more preferably C12-16 fatty alcohol sulfates, especially lauryl sulfates or myristyl sulfates, most preferably sodium lauryl sulfate.

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

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

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

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

These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably their mixtures. Enzymes can be present in the dishwashing detergent preferably in amounts from 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 wt .-%, each based on the total weight of the dishwasher detergent, are used.

The dishwashing detergent according to the invention may 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 contribute to the cleaning performance of the dishwashing detergent by, among other things, inhibiting the formation of limescale deposits on machine components and thus enabling the energy to be transferred efficiently to the water.

The weight fraction 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 hydrogen carbonate (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 wt .-%, each based on the total weight of the dishwashing detergent.

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

Alkali metal phosphate is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acid (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits on machine parts or scale 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). The 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% by weight .-%, preferably from 15 to 55 wt .-% and in particular from 20 to 50 wt .-%, each based on the total weight of the dishwashing detergent. In an alternative embodiment, there are essentially no phosphates.

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

If a polycarboxylic acid is used as the builder, it can be used in the form of the free acid and / or its alkali metal salts, in particular sodium salts, polycarboxylic acid being understood to mean carboxylic acid which carries more than one acid function. Examples include 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, and mixtures of these. In addition to their builder action, the free acids typically also have the property of an acidifying component and thus also serve to establish a lower and milder pH of dishwashing detergents.

The dishwashing detergent can contain citrate, preferably sodium citrate, particularly preferably as a builder. The dishwashing detergent may 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 agent.

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

A particularly preferred dishwashing detergent is characterized in that it contains at least two builders from the group of the phosphates, carbonates and citrates, the weight fraction of these builders, based on the total weight of the dishwashing detergent, preferably 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 above group 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 molar mass of 500 to 70,000 g / mol.

Suitable polymers are, in particular, polyacrylates, which preferably have a weight-average molar mass of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have a weight-average molar mass from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn 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, for. 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 e.g. B. Amidomethicone or Dow Corning, Dow Corning Co./US, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetrimamine (Carta retine®, Sandoz / CH), polyaminopolyamides such as, for. B. described in the FR A 22 52 840 and their crosslinked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally microcrystalline, 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 2,000 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 dishwasher detergent can be crystalline layered silicates of the general formula as builders NaMSi _x O _{2x +} 1y 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 for a number from 0 to 33, preferably from 0 to 20, stands.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are preferably delayed release and have secondary washing properties.

In a preferred dishwashing detergent, the silicate content, based on the total weight of the dishwashing detergent, is limited to amounts from 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 builders mentioned above, the dishwashing detergent may 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 .-%, each based on the total weight of the dishwashing detergent. An alternative preferred dishwashing detergent is free from 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, carboxymethyl cellulose, 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, carboxymethyl cellulose, locust bean gum, agar agar, tragacanth, gum arabic, pectins, starch, modified starch, dextrins, gelatins and casein, and modified Cellulose, most preferred is xanthan.

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.

The composition may also contain perfume oils and / or fragrances. In the context of the present invention, individual fragrance compounds, for example the synthetic ones, can be used as perfume oils or fragrances Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable 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. "Substantially phosphate-free," as used herein, means that the composition in question is essentially free of phosphates, i.e. contains in particular phosphates in quantities of less than 0.1% by weight, preferably less than 0.01% by weight, based on the total composition. Analogously, "essentially bleach-free" means that the composition in question is essentially free of bleaching agents, i.e. Contains bleaching agents in particular in quantities of less than 0.1% by weight, preferably less than 0.01% by weight, based on the total composition.

The composition may also contain corrosion inhibitors. (Glass) corrosion inhibitors prevent the appearance of cloudiness, streaks and scratches but also the iridescence of 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 stated otherwise, the pH is preferably measured at 25 ° C. in the undiluted composition, usually by means of a pH electrode. Acids and / or bases / alkalis are preferably used as pH adjusting agents.

Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid, most preferred is citric acid. In addition, the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used.

• -carbonate, insbesondere der Alkalimetallcarbonate, von denen Natriumcarbonat bevorzugt ist.

Suitable bases come from the group of alkali and alkaline earth metal hydroxides and

• carbonates, especially 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 at room temperature, i.e. about 20 ° C, in liquid form and in particular flowable and can thus 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 by means of water and / or at least one organic solvent.

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

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

In another preferred aspect, the compositions described herein can preferably be prefabricated into dosage units. These metering units preferably comprise 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 which contains a single portion. The cleaning agent can be packaged in such a way that disposable portions are packed 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 sheath can be formed from one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, can be the same or different. Films which, for example, can be glued and / or sealed to form packaging, such as hoses or pillows, are particularly preferred after they have been filled with an agent.

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

Suitable water-soluble films for the production of the water-soluble covering are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose weight-average molecular weight 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 is in particular from 40,000 to 80,000 g / mol.

Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct route of synthesis is not possible. The same applies to polyvinyl alcohol copolymers which are correspondingly 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 polymer material containing polyvinyl alcohol which is suitable for producing the water-soluble covering can additionally be a polymer selected from the group comprising (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers can be added. A preferred additional polymer is polylactic acid.

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

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

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

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

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

Another subject of the present application is a machine dishwashing method in which the dishwashing detergent 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 during the course of a dishwashing program, before the start of the main wash cycle or during the course of the main wash cycle. The dishwashing agent can be dosed or introduced into the interior of the dishwasher manually, but the dishwashing agent is preferably dosed into the interior of the dishwasher by means of the dosing chamber of the dishwasher. In the course of the cleaning process, preferably no additional water softener and no additional rinse aid are dosed into the interior of the dishwasher.

A preferred embodiment is a machine dishwashing process using the preferably liquid dishwashing detergent, in particular in the form of a molded article mentioned above, in particular for improved rinse aid performance for plastic or stainless steel items.

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 distinguished by an improved rinse aid performance compared to conventional dishwashing detergents. Another object of the present application is therefore the use of the dishwashing detergent according to the invention to improve the rinse aid performance for plastic or stainless steel items in automatic dishwashing.

Examples

The rinse aid 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). 28.5 g of test product were used per rinse cycle. The wash ware (stainless steel and plastic in each case) was evaluated visually by comparison with a reference scale (5 = no stains; 1 = very strong stains) and the arithmetic mean values (n = 3) were determined.

Example 1:

Tab. 1: Recipes of enzyme-containing gels according to the present invention, all of which had a rinse performance on stainless steel and plastic of 4-5. A B C. D % By weight % By weight % By weight % By weight Xanthan gum 0.4 0.4 0.4 0.4 Noverite AD 810G (88% polyacrylate-39) 4.5 4.0 3.0 5.0 Nonionic 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 had only one of the two components A) and B) or another nonionic surfactant. The following composition was used as the basic formulation: Frame formulation % By weight 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 Example 1 0% Dehypon E127 0% Noverite AD 810G 1.5 1.5 VBsp. 2nd 2% Dehypon E127 0% Noverite AD 810G 1.8 3.0 VBsp. 3rd 0% Dehypon E127 4% Noverite AD 810G 1.8 2.1 VBsp. 4th 2% Dehypon E127 4.5% Acusol 588 (acrylic / sulfate polymer) 2.3 3.7 Ex. 2 2% Dehypon E127 4% Noverite AD 810G 5.0 4.1 Ex. 3 2% Dehypon E127 2% Noverite AD 810G 4.7 4.0 VBsp. = 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 (example 2, 3 and example 3). All further experiments show greatly improved rinse aid properties compared to compositions with only the surfactant or polymer or Acusol 588 and the polymer.

QUOTES INCLUDE IN THE DESCRIPTION

This list of documents listed by the applicant has been generated automatically and is only included 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.

Patent literature cited

• WO 2014/143773 A1 [0029]
• FR 2252840 A [0071]

Claims (12)

Dishwashing detergent that A) at least one nonionic surfactant selected from fatty alcohol alkoxylates; B) at least one polymer that is 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; 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; contains or consists of. Dishwashing liquid after Claim 1 , wherein the at least one fatty alcohol alkoxylate is selected from i) 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 of one another for a branched or unbranched, saturated or unsaturated , optionally hydroxylated alkyl radical with 4 to 22 carbon atoms, - Alk stands for a branched alkyl radical with 3 or 4 carbon atoms or unbranched alkyl radical with 2 to 4 carbon atoms, - x and y independently of one another stand for values between 1 and 70 and - M stands for one Alkyl 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 of one another are a branched or unbranched, saturated or unsaturated, cyclic or acyclic alkyl or Alkenyl radical having up to 18 carbon atoms; and / or ii) at least one compound of 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 , in which - 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 is at least 15; and / or iii) at least one compound of 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 , where R ^{1 represents} a branched or unbranched alkyl radical having 8 to 16 carbon atoms, R ³ and R ⁴ independently of one another represent hydrogen or a branched or unbranched alkyl radical having 1 to 5 carbon atoms, R ^{2 represents} an unbranched alkyl radical having 5 to 17 Carbon atoms, - x and z independently of one another have a value from 1 to 5 and - y has a value from 13 to 35; or iv) at least one compound of 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 , in which - R ¹ and R ² independently of one another represent an alkyl radical or alkenyl radical having 6 to 16 carbon atoms and - R represents a linear, saturated alkyl radical having 2 to 12 carbon atoms, preferably 4 to 10 carbon atoms and - x and y independently of one another have values of Have 5 to 20; and / or v) at least one compound of the general formula R ¹ O [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms, R ² denotes a linear or branched hydrocarbon radical with 2 or 3 to 26 carbon atoms and y stands for a value between 15 and 120, preferably 20 to 100 and in particular 20 to 80; and / or vi) at least one compound selected from the group of the hydroxy _mixed ethers of the general formula C _4-22 -CH (OH) CH ₂ O- (EO) _20-120 -C _2-26 , in particular 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 / or vii) at least one compound of 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 , where R ^{1 represents} a branched or unbranched alkyl radical having 10 to 15 carbon atoms, R ³ and R ⁴ independently of one another represent hydrogen or a branched or unbranched alkyl radical having 2 or 3 carbon atoms, R ^{2 represents} an unbranched alkyl radical having 8 to 16 Carbon atoms, - x and z independently of one another have a value of 1 to 5 and - y has a value of 20 to 30. Dishwashing detergent according to one of the Claims 1 or 2nd , wherein at least one nonionic surfactant A) is present in 0.2 to 10% by weight or 0.5 to 9% by weight. 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 co-monomer selected from (meth) acrylic acid, salts, esters or anhydrides thereof or 2-acrylamido-2-methylpropanesulfonic acid or salts thereof, in particular the co-monomers are acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid or salts thereof; and or ii) has a number average molecular weight of 100 to 100,000 g / mol, in particular 500 to 50,000 g / mol; and or iii) based on 30 to 65 mol%, in particular 40 to 50 mol%, of acrylic acid monomers; and or iv) based on 0.1 to 20 mol%, preferably 0.5 to 10 mol%, of 2-acrylamido-2-methylpropanesulfonic acid monomers; and or v) is an alternating, a random or a block copolymer, preferably a terpolymer; and or vi) is etherified from 0.1 to 60%. Dishwashing detergent according to one of the preceding claims, wherein 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. Dishwashing detergent according to one of the preceding claims, wherein at least one surfactant different from A) is an anionic surfactant. Dishwashing detergent according to one of the preceding claims, wherein at least one enzyme comprises an amylase and / or a protease. Dishwashing agent according to one of the preceding claims, wherein the dishwashing agent is a liquid agent, in particular in gel form. Dishwashing detergent according to one of the preceding claims, wherein at least one additive comprises a thickener, preferably selected from polyacrylate thickeners, xanthan, gellan, guar, alginate, carrageenan, carboxymethyl cellulose, 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, carboxymethyl cellulose, locust bean gum, agar agar, tragacanth, gum arabic, p , Starch, modified starch, dextrins, gelatins and casein, and modified celluloses, most preferably xanthan. Method for cleaning dishes in a dishwasher, using a dishwasher detergent according to one of the Claims 1 to 9 . Procedure according to Claim 10 , characterized in that the dishwashing process is carried out at a liquor temperature below 60 ° C, preferably not above 50 ° C. Use of a dishwashing detergent according to one of the Claims 1 to 9 to improve the rinse aid performance for plastic or stainless steel items in automatic dishwashing.