EP2350249B1 - Dishwasher detergent - Google Patents

Description

The present application describes automatic dishwashing detergents, automatic dishwashing processes using these dishwashing detergents, and the use of these dishwashing detergents for improving the dishwashing of machine dishwashing.

On machine-washed dishes are often made higher demands than manually rinsed dishes. Thus, a tableware that has been completely cleaned at first glance of food waste is then rated as not having any flaw if, after machine dishwashing, it still has discolorations which are based, for example, on the attachment of vegetable dyes to the dish surface.

In order to obtain spotless dishes, bleaching agents are used in automatic dishwashing detergents. In order to activate these bleaching agents and to achieve an improved bleaching effect during cleaning at temperatures of 60 ° C. and below, automatic dishwashing detergents generally also contain bleach activators or bleach catalysts, with the bleach catalysts in particular having proven to be particularly effective.

The use of these bleaches is limited due to incompatibilities with other detergent or cleaning active ingredients, such as enzymes, or because of stability issues in the storage of bleach-containing detergents and cleaners. This is especially true for liquid detergents or cleaning agents.

One technical option for improving the cleaning performance of automatic dishwashing detergents, in particular bleach-free automatic dishwasher detergents, is to increase the alkalinity of these detergents. While, on the one hand, with increasing alkalinity, the cleaning performance of automatic dishwashing detergents increases, on the other hand strongly alkaline cleaners also cause damage in the silicate structure of glasses and can cause strong irritation on contact with the skin.

Particularly effective builders for increasing the alkalinity have proved to be the alkali metal phosphates, which for this reason form the main constituent of the vast majority of commercially available automatic dishwashing detergents.

While the phosphates are highly valued for their beneficial effect as a component of automatic dishwashing detergents, their use is not unproblematic from an environmental point of view, since a substantial portion of the phosphate enters the water via domestic effluent and especially in stagnant water (lakes, barrages ) a questionable Role in their over-fertilization plays. As a result of this phenomenon, also referred to as eutrophication, the use of pentasodium triphosphate in laundry detergents in a number of countries, eg USA, Canada, Italy, Sweden, Norway, has been considerably reduced by law and regulations. completely prohibited in Switzerland. In Germany, detergents since 1984 may contain no more than 20% of this builder.

Limiting the alkalinity as well as the phosphate content of automatic dishwashing detergents is therefore desirable from the point of view of the user and with a view to sustainable product development.

This application was therefore based on the object to provide a detergent for dishwashing, which is distinguished from conventional dishwashing detergents even with low-temperature cleaning cycles or cleaning cycles with low water consumption by improved cleaning performance. In particular, the dishwashing detergent should be characterized by a good cleaning performance despite freedom from phosphates and bleach, with an improved cleaning performance, for example against bleachable stains, being preferred without at the same time causing increased damage to glass or ceramic surfaces. The bleachable stains include, for example, stains caused by tea or vegetable dyes, for example from vegetables or fruits.

Surprisingly, it has been found that the above object can be achieved in a citrate-based, basic formula by the use of specific polymers.

1. a) 10 bis 60 Gew.-% Citrat
2. b) 2,0 bis 30 Gew.-% anionisches Polymer, umfassend ungesättigte Dicarbonsäure(n) B,

dadurch gekennzeichnet, dass das maschinelle Geschirrspülmittel kein Silikat enthält.A first subject of this application is a low alkaline, phosphate and bleach-free machine dishwashing detergent having a pH (10% solution, 20 ° C) between 8 and 12, comprising:

1. a) 10 to 60 wt .-% citrate
2. b) 2.0 to 30% by weight of anionic polymer comprising unsaturated dicarboxylic acid (s) B,

characterized in that the automatic dishwashing agent does not contain silicate.

The automatic dishwashing compositions according to the invention are of low alkalinity. Preferred automatic dishwasher detergents according to the invention are characterized in that the automatic dishwasher detergent has a pH (10% solution, 20 ° C.) between 9 and 11.5, preferably between 9.5 and 11.5, in particular between 10.0 and 11.0.

A first essential ingredient of the composition of the invention is the citrate. The term "citrate" also encompasses citric acid as well as its salts, especially theirs

Alkali metal salts. Particularly preferred machine dishwasher detergents according to the invention contain citrate, preferably sodium citrate, in amounts of 12 to 50% by weight, preferably 15 to 40% by weight and in particular 15 to 30% by weight, in each case based on the total weight of the automatic dishwashing detergent. Citrate or citric acid has proven to be particularly effective over other builders in combination with the anionic copolymer in terms of tea cleaning.

Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in the following Tables 1a and 1b: ingredient Recipe 1a [% by weight] Recipe 2a [% by weight] Recipe 3a [% by weight] Recipe 4a [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Anionic copolymer ¹ 2.0 to 30 2.0 to 30 2.0 to 30 2.0 to 30 silicate - * - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 9 to 11.5 ingredient Recipe 1b [% by weight] Recipe 2b [% by weight] Recipe 3b [% by weight] Recipe 4b [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Maleic acid homopolymer 2.0 to 30 2.0 to 30 2.0 to 30 2.0 to 30 phosphate - * - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 9 to 11.5 9 to 11.5 ¹ anionic copolymer comprising unsaturated monocarboxylic acid (s) A and unsaturated dicarboxylic acid (s) B
* "-" means in this, as in all the following tables: the recipe is free from this ingredient

The automatic dishwashing compositions according to the invention may contain, in addition to the citrates, additional builders, in particular carbonates or organic cobuilders.

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 5 to 50 wt .-%, preferably from 10 to 40 wt .-% and in particular from 15 to 30 wt .-%, each based on the weight of the automatic dishwashing detergent.

Machine dishwashing detergents according to the invention are silicate-free.

Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in Tables 2a and 2b below: ingredient Recipe 1a [% by weight] Recipe 2a [% by weight] Recipe 3a [% by weight] Recipe 4a [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Anionic copolymer ¹ 2.0 to 30 2.0 to 30 2.0 to 30 2.0 to 30 carbonate 5 to 50 10 to 40 5 to 50 10 to 40 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 9 to 11.5 9 to 11.5 ingredient Recipe 1b [% by weight] Recipe 2b [% by weight] Recipe 3b [% by weight] Recipe 4b [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Maleic acid homopolymer 2.0 to 30 2.0 to 30 2.0 to 30 2.0 to 30 carbonate 5 to 50 10 to 40 5 to 50 10 to 40 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 9 to 11.5 9 to 11.5 ¹ anionic copolymer comprising unsaturated monocarboxylic acid (s) A and unsaturated dicarboxylic acid (s) B

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, dextrins and phosphonates. These classes of substances are described below.

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

In addition to the 1-hydroxyethane-1,1-diphosphonic acid, the complex-forming phosphonates comprise a number of different compounds, such as, for example, diethylenetriaminepenta (methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

1. a) Aminotrimethylenphosphonsäure (ATMP) und/oder deren Salze;
2. b) Ethylendiamintetra(methylenphosphonsäure) (EDTMP) und/oder deren Salze;
3. c) Diethylentriaminpenta(methylenphosphonsäure) (DTPMP) und/oder deren Salze;
4. d) 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) und/oder deren Salze;
5. e) 2-Phosphonobutan-1,2,4-tricarbonsäure (PBTC) und/oder deren Salze;
6. f) Hexamethylendiamintetra(methylenphosphonsäure) (HDTMP) und/oder deren Salze;
7. g) Nitrilotri(methylenphosphonsäure) (NTMP) und/oder deren Salze.

An automatic dishwashing agent preferred in the context of this application contains one or more phosphonate (s) from the group

1. a) aminotrimethylenephosphonic acid (ATMP) and / or salts thereof;
2. b) ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and / or salts thereof;
3. c) diethylenetriamine penta (methylenephosphonic acid) (DTPMP) and / or salts thereof;
4. d) 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or salts thereof;
5. e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or salts thereof;
6. f) hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and / or salts thereof;
7. g) nitrilotri (methylenephosphonic acid) (NTMP) and / or salts thereof.

Particularly preferred are automatic dishwashing detergents which contain as phosphonates 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).

Of course, the automatic dishwashing compositions of the invention may contain two or more different phosphonates.

The proportion by weight of the phosphonates in the total weight of automatic dishwashing detergents according to the invention is preferably from 1 to 8% by weight, preferably from 1.2 to 6% by weight and in particular from 1.5 to 4% by weight.

Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in Tables 3a and 3b below: ingredient Recipe 1a [% by weight] Recipe 2a [% by weight] Recipe 3a [% by weight] Recipe 4a [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Anionic copolymer ¹ 2.0 to 30 2.0 to 30 2.0 to 30 2.0 to 30 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12 ingredient Recipe 1b [% by weight] Recipe 2b [% by weight] Recipe 3b [% by weight] Recipe 4b [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Maleic acid homopolymer 2.0 to 30 2.0 to 30 2.0 to 30 2.0 to 30 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12 ¹ anionic copolymer comprising unsaturated monocarboxylic acid (s) A and unsaturated dicarboxylic acid (s) B

A second essential ingredient of the compositions of this invention is the anionic polymer b) comprising unsaturated dicarboxylic acid (s) B. In a first preferred embodiment, this anionic polymer is an anionic copolymer comprising unsaturated mono- and dicarboxylic acids.

1. a) 10 bis 60 Gew.-% Citrat
2. b) 2,0 bis 30 Gew.-% anionisches Copolymer, umfassend
   1. i) ungesättigte Monocarbonsäure(n) A
   2. ii) ungesättigte Dicarbonsäure(n) B.

Another preferred subject of this application is a low alkali, phosphate, silicate and bleach-free machine dishwashing detergent having a pH (10% solution, 20 ° C) between 8 and 12, comprising:

1. a) 10 to 60 wt .-% citrate
2. b) 2.0 to 30% by weight anionic copolymer comprising
   1. i) unsaturated monocarboxylic acid (s) A
   2. ii) unsaturated dicarboxylic acid (s) B.

The use of the anionic copolymer b), comprising unsaturated monocarboxylic acid (s) A and unsaturated dicarboxylic acid (s) B, has as a simple homopolymer of unsaturated monocarboxylic acids or copolymers of unsaturated monocarboxylic acids with monomers other than the unsaturated dicarboxylic acid with respect to the cleaning achieved with the inventive compositions proved superior.

1. i) 50 bis 90 Gew.-% ungesättigte Monocarbonsäure(n) A
2. ii) 10 bis 50 Gew.-% ungesättigte Dicarbonsäure(n) B.

enthält.Preferred automatic dishwashing detergents according to the invention are characterized in that the automatic dishwashing detergent comprises as anionic polymer b) a copolymer comprising

1. i) 50 to 90% by weight of unsaturated monocarboxylic acid (s) A
2. ii) from 10 to 50% by weight of unsaturated dicarboxylic acid (s) B.

contains.

Particularly suitable are copolymers of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable, preferred copolymers containing from 50 to 90% by weight of acrylic acid and from 50 to 10% by weight of maleic acid. The relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

1. i) 50 bis 90 Gew.-% Acrylsäure
2. ii) 10 bis 50 Gew.-% Maleinsäure

enthält.Preferred automatic dishwashing detergents according to the invention are characterized in that the automatic dishwashing detergent comprises as anionic polymer b) a copolymer comprising

1. i) 50 to 90 wt .-% acrylic acid
2. ii) 10 to 50% by weight of maleic acid

contains.

As an alternative to the previously described copolymers comprising unsaturated mono- and dicarboxylic acids, homopolymers of dicarboxylic acids may also be used as anionic polymers b), homopolymers of maleic acid being particularly preferred.

1. a) 10 bis 60 Gew.-% Citrat
2. b) 2,0 bis 30 Gew.-% Maleinsäure Homopolymer

Another preferred subject of this application is a low alkali, phosphate, silicate and bleach-free machine dishwashing detergent having a pH (10% solution, 20 ° C) between 8 and 12, comprising:

1. a) 10 to 60 wt .-% citrate
2. b) 2.0 to 30 wt .-% maleic homopolymer

The molecular weight of preferred maleic acid homopolymers is, based on free acids, between 2000 to 70000 g / mol, preferably 4000 to 50,000 g / mol and in particular 6000 to 40,000 g / mol.

The anionic copolymers b) can be used in the machine dishwasher according to the invention, for example as a powder or as an aqueous solution.

The proportion by weight of the anionic polymer b) in the total weight of automatic dishwasher detergents according to the invention is preferably from 2.0 to 20% by weight, preferably from 2.5 to 15% by weight and in particular from 2.5 to 10% by weight.

Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in Tables 4a to 4d below: ingredient Recipe 1a [% by weight] Recipe 2a [% by weight] Recipe 3a [% by weight] Recipe 4a [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Anionic copolymer ¹ 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 0 to 50 0 to 30 0 to 30 0 to 30 phosphonate 0 to 8 0 to 8 0 to 8 0 to 8 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12 ingredient Recipe 1b [% by weight] Recipe 2b [% by weight] Recipe 3b [% by weight] Recipe 4b [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Anionic copolymer ¹ 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12 ¹ anionic polymer b) a copolymer comprising from 50 to 90% by weight of acrylic acid and from 10 to 50% by weight of maleic acid ingredient Recipe 1c [% by weight] Recipe 2c [% by weight] Recipe 3c [% by weight] Recipe 4c [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Maleic acid homopolymer 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 0 to 50 0 to 30 0 to 30 0 to 30 phosphonate 0 to 8 0 to 8 0 to 8 0 to 8 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12 ingredient Recipe 1d [% by weight] Recipe 2d [% by weight] Recipe 3d [wt .-%] Recipe 4d [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Maleic acid homopolymer 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12

In addition to the ingredients described above, the compositions according to the invention may contain further washing or cleaning-active substances, preferably from the group of surfactants, enzymes, organic solvents, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.

In principle, all nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

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

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, washing or cleaning agents, in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and Mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Particular preference is therefore given to ethoxylated nonionic surfactants consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred ,

Nonionic surfactants from the group of alkoxylated alcohols, more preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also used with particular preference.

The nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol content of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.

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

More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

• bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.

In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nichionic surfactants of the general formula

• in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently stand for integers from 1 to 6.

The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Regardless of the type of alcohol used to make the nonionic surfactants used in the compositions Niotensides are preferred in which R ¹ in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or - CH (CH ₃ ) ₂ are suitable. Preference is given to using nonionic surfactants of the above formula in which R ² or R ^{3 is} a radical -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another are values of 1 or 2.

In summary, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , in which R ¹ and R ² independently of one another represents a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 -alkyl or -alkenyl radical; A, A ', A "and A"' independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Particularly preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched one Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is a value of at least 15.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

By using the above-described nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals, the formation of deposits in machine dishwashing can be markedly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₃ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.

Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,

The proportion by weight of the nonionic surfactant in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is between 0.1 and 15% by weight, preferably between 0.2 and 10% by weight, preferably between 0.5 and 8% by weight. and in particular between 1.0 and 6 wt .-%.

Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in Tables 5a to 5d below: ingredient Recipe 1a [% by weight] Recipe 2a [% by weight] Recipe 3a [% by weight] Recipe 4a [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Anionic copolymer ¹ 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 0 to 50 0 to 30 0 to 30 0 to 30 phosphonate 0 to 8 0 to 8 0 to 8 0 to 8 Nonionic surfactant 0.1 to 15 0.1 to 15 0.5 to 8 0.5 to 8 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12 ingredient Recipe 1b [% by weight] Recipe 2b [% by weight] Recipe 3b [% by weight] Recipe 4b [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Anionic copolymer ¹ 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 Nonionic surfactant 0.1 to 15 0.1 to 15 0.5 to 8 0.5 to 8 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12 ¹ anionic polymer b) a copolymer comprising from 50 to 90% by weight of acrylic acid and from 10 to 50% by weight of maleic acid ingredient Recipe 1c [% by weight] Recipe 2c [% by weight] Recipe 3c [% by weight] Recipe 4c [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Maleic acid homopolymer 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 0 to 50 0 to 30 0 to 30 0 to 30 phosphonate 0 to 8 0 to 8 0 to 8 0 to 8 Nonionic surfactant 0.1 to 15 0.1 to 15 0.5 to 8 0.5 to 8 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12 ingredient Recipe 1d [% by weight] Recipe 2d [% by weight] Recipe 3d [wt .-%] Recipe 4d [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Maleic acid homopolymer 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 Nonionic surfactant 0.1 to 15 0.1 to 15 0.5 to 8 0.5 to 8 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12

As a further constituent dishwashing agents according to the invention may contain enzyme (s). These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ⁶ to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

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

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the abovementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to obtain peracids in situ from suitable precursors produce. These include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

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

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

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

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

A preferred machine dishwashing detergent according to the invention is characterized in that the dishwashing agent, based on its total weight, enzyme preparation (s) in amounts of 0.1 to 12 wt .-%, preferably from 0.2 to 10 wt .-% and in particular from 0.5 to 8 wt .-% contains.

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

1. a) 10 bis 40 Gew.-% Citrat
2. b) 2,0 bis 10 Gew.-% anionisches Copolymer, umfassend
   1. i) Acrylsäure
   2. ii) Maleinsäure
3. c) 1 bis 8 Gew.-% Phosphonat
4. d) 0,2 bis 10 Gew.-% nichtionisches Tensid
5. e) 0,1 bis 8 Gew.-% Enzym-Zubereitung(en)

A particularly preferred automatic dishwashing detergent according to the invention comprises

1. a) 10 to 40 wt .-% citrate
2. b) 2.0 to 10% by weight of anionic copolymer comprising
   1. i) acrylic acid
   2. ii) maleic acid
3. c) 1 to 8 wt .-% phosphonate
4. d) 0.2 to 10% by weight of nonionic surfactant
5. e) 0.1 to 8% by weight of enzyme preparation (s)

1. a) 10 bis 40 Gew.-% Citrat
2. b) 2,0 bis 10 Gew.-% Maleinsäure Homopolymer
3. c) 1 bis 8 Gew.-% Phosphonat
4. d) 0,2 bis 10 Gew.-% nichtionisches Tensid
5. e) 0,1 bis 8 Gew.-% Enzym-Zubereitung(en)

Another particularly preferred automatic dishwashing detergent according to the invention comprises

1. a) 10 to 40 wt .-% citrate
2. b) 2.0 to 10 wt .-% maleic homopolymer
3. c) 1 to 8 wt .-% phosphonate
4. d) 0.2 to 10% by weight of nonionic surfactant
5. e) 0.1 to 8% by weight of enzyme preparation (s)

Some other exemplary formulations for preferred automatic dishwashing detergents according to the invention can be found in Tables 6a to 6d below: ingredient Recipe 1a [% by weight] Recipe 2a [% by weight] Recipe 3a [% by weight] Recipe 4a [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Anionic copolymer ¹ 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 0 to 50 0 to 30 0 to 30 0 to 30 phosphonate 0 to 8 0 to 8 0 to 8 0 to 8 Nonionic surfactant 0 to 15 0 to 15 0 to 8 0 to 8 Enzyme preparation (s) 0.1 to 12 0.1 to 12 0.5 to 8 0.5 to 8 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12 ingredient Recipe 1b [% by weight] Recipe 2b [% by weight] Recipe 3b [% by weight] Recipe 4b [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Anionic copolymer ¹ 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 Nonionic surfactant 0.1 to 15 0.1 to 15 0.5 to 8 0.5 to 8 Enzyme preparation (s) 0.1 to 12 0.1 to 12 0.5 to 8 0.5 to 8 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12 ingredient Recipe 1c [% by weight] Recipe 2c [% by weight] Recipe 3c [% by weight] Recipe 4c [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Maleic acid homopolymer 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 0 to 50 0 to 30 0 to 30 0 to 30 phosphonate 0 to 8 0 to 8 0 to 8 0 to 8 Nonionic surfactant 0 to 15 0 to 15 0 to 8 0 to 8 Enzyme preparation (s) 0.1 to 12 0.1 to 12 0.5 to 8 0.5 to 8 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12 ingredient Recipe 1d [% by weight] Recipe 2d [% by weight] Recipe 3d [wt .-%] Recipe 4d [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Maleic acid homopolymer 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 Nonionic surfactant 0.1 to 15 0.1 to 15 0.5 to 8 0.5 to 8 Enzyme preparation (s) 0.1 to 12 0.1 to 12 0.5 to 8 0.5 to 8 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12 ¹ anionic polymer b) a copolymer comprising from 50 to 90% by weight of acrylic acid and from 10 to 50% by weight of maleic acid

It has been found that the cleaning performance of automatic dishwashing detergents according to the invention can be improved by the addition of organic solvents.

These organic solvents are derived, for example, from the groups of the monoalcohols, diols, triols or polyols, the ethers, esters and / or amides. Particular preference is given to organic solvents which are water-soluble, "water-soluble" solvents in the sense of the present application being solvents which are completely miscible with water at room temperature, ie without a miscibility gap.

Organic solvents which can be used in the compositions according to the invention preferably originate from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the given concentration range. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, di ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t- Butyl ether and mixtures of these solvents.

The organic solvents from the group of the organic amines and / or the alkanolamines have proved to be particularly effective with regard to the cleaning performance and again with regard to the cleaning performance of bleachable soiling, in particular on tea stains.

Particularly preferred organic amines are the primary and secondary alkylamines, the alkyleneamines and mixtures of these organic amines. The group of preferred primary alkylamines include monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine and cyclohexylamine. The group of preferred secondary alkylamines includes in particular dimethylamine.

Preferred alkanolamines are in particular the primary, secondary and tertiary alkanolamines and mixtures thereof. Particularly preferred primary alkanolamines are monoethanolamine (2-aminoethanol, MEA), monoisopropanolamine, diethylethanolamine (2- (diethylamino) ethanol). Particularly preferred secondary alkanolamines are diethanolamine (2,2'-iminodiethanol, DEA, bis (2-hydroxyethyl) amine), N-methyl-diethanolamine, N-ethyl-diethanolamine. Diisopropanolamine and morpholine. Particularly preferred tertiary alkanolamines are triethanolamine and triisopropanolamine.

Combination products, characterized in that they contain an organic solvent, wherein the organic solvent is an organic amine and / or an alkanolamine, preferably monoethanolamine, are particularly preferred according to the invention.

A further subject of this application is a machine dishwashing detergent according to the invention, characterized in that the automatic dishwasher detergent, based on its total weight, organic amine and / or an alkanolamine, preferably ethanolamine, in Amounts from 0.1 to 15 wt .-%, preferably 0.2 to 10 wt .-%, particularly preferably 0.5 to 8 wt .-% and in particular from 1.0 to 6 wt .-%.

These solvent-containing automatic dishwashing agents are preferably in liquid form.

1. a) 10 bis 40 Gew.-% Citrat
2. b) 2,0 bis 10 Gew.-% anionisches Copolymer, umfassend
   1. i) Acrylsäure
   2. ii) Maleinsäure
3. c) 1 bis 8 Gew.-% Phosphonat
4. d) 0,1 bis 6 Gew.% Alkanolamin
5. e) 0,2 bis 10 Gew.-% nichtionisches Tensid
6. f) 0,1 bis 8 Gew.-% Enzym-Zubereitung(en)

A particularly preferred liquid automatic dishwashing detergent according to the invention comprises

1. a) 10 to 40 wt .-% citrate
2. b) 2.0 to 10% by weight of anionic copolymer comprising
   1. i) acrylic acid
   2. ii) maleic acid
3. c) 1 to 8 wt .-% phosphonate
4. d) 0.1 to 6 wt.% Alkanolamine
5. e) 0.2 to 10% by weight of nonionic surfactant
6. f) 0.1 to 8% by weight of enzyme preparation (s)

1. a) 10 bis 40 Gew.-% Citrat
2. b) 2,0 bis 10 Gew.-% Maleinsäure Homopolymer
3. c) 1 bis 8 Gew.-% Phosphonat
4. d) 0,5 bis 8 Gew.-% organisches Lösungsmittel
5. e) 0,2 bis 10 Gew.-% nichtionisches Tensid
6. f) 0,1 bis 8 Gew.-% Enzym-Zubereitung(en)

Another particularly preferred liquid automatic dishwashing detergent according to the invention comprises

1. a) 10 to 40 wt .-% citrate
2. b) 2.0 to 10 wt .-% maleic homopolymer
3. c) 1 to 8 wt .-% phosphonate
4. d) 0.5 to 8 wt .-% organic solvent
5. e) 0.2 to 10% by weight of nonionic surfactant
6. f) 0.1 to 8% by weight of enzyme preparation (s)

Some exemplary formulations for preferred automatic dishwashing detergents according to the invention can be found in Tables 7a to 7d below: ingredient Recipe 1a [% by weight] Recipe 2a [% by weight] Recipe 3a [% by weight] Recipe 4a [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Anionic copolymer ¹ 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 0 to 50 0 to 30 0 to 30 0 to 30 phosphonate 0 to 8 0 to 8 0 to 8 0 to 8 Nonionic surfactant 0 to 15 0 to 15 0 to 8 0 to 8 Enzyme preparation (s) 0 to 12 0 to 12 0 to 8 0 to 8 Org. Solvent 0.1 to 15 0.5 to 8 0.1 to 15 0.5 to 8 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12 ingredient Recipe 1b [% by weight] Recipe 2b [% by weight] Recipe 3b [% by weight] Recipe 4b [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Anionic copolymer ¹ 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 Nonionic surfactant 0.1 to 15 0.1 to 15 0.5 to 8 0.5 to 8 Enzyme preparation (s) 0.1 to 12 0.1 to 12 0.5 to 8 0.5 to 8 Org. Solvent 0.1 to 15 0.5 to 8 0.1 to 15 0.5 to 8 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12 ¹ anionic polymer b) a copolymer comprising from 50 to 90% by weight of acrylic acid and from 10 to 50% by weight of maleic acid ingredient Recipe 1c [% by weight] Recipe 2c [% by weight] Recipe 3c [% by weight] Recipe 4c [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Maleic acid homopolymer 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 0 to 50 0 to 30 0 to 30 0 to 30 phosphonate 0 to 8 0 to 8 0 to 8 0 to 8 Nonionic surfactant 0 to 15 0 to 15 0 to 8 0 to 8 Enzyme preparation (s) 0 to 12 0 to 12 0 to 8 0 to 8 Org. Solvent 0.1 to 15 0.5 to 8 0.1 to 15 0.5 to 8 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12 ingredient Recipe 1d [% by weight] Recipe 2d [% by weight] Recipe 3d [wt .-%] Recipe 4d [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Maleic acid homopolymer 2.0 to 20 2.0 to 20 2.5 to 10 2.5 to 10 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 Nonionic surfactant 0.1 to 15 0.1 to 15 0.5 to 8 0.5 to 8 Enzyme preparation (s) 0.1 to 12 0.1 to 12 0.5 to 8 0.5 to 8 Org. Solvent 0.1 to 15 0.5 to 8 0.1 to 15 0.5 to 8 silicate - - - - phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 8 to 12 8 to 12 8 to 12 8 to 12

The automatic dishwasher detergents according to the invention can be present in the ready-to-use form known to the person skilled in the art, that is to say, for example, in solid or liquid form but also as a combination of solid and liquid supply forms.

Powder, granules, extrudates or compactates, in particular tablets, are particularly suitable as firm supply forms. The liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.

Inventive agents can be formulated as single-phase or multi-phase products. In particular, automatic dishwashing detergents with one, two, three or four phases are preferred. Machine dishwashing detergents, characterized in that they are in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.

The individual phases of multiphase agents may have the same or different states of matter. Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase are preferred. Particularly preferred are in particular two- or multi-phase tablets, for example two-layer tablets, in particular two-layer tablets with a trough and a mold body located in the trough.

Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.

The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.

The automatic dishwasher detergents according to the invention, in particular the prefabricated metering units, have a water-soluble coating, with particular preference.

In order to facilitate the disintegration of preformed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times.

These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles can be cereal. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.

Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain. The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. The particle sizes of such Disintegrating agents are usually above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular at least 90 wt .-% between 400 and 1200 microns.

Preferred disintegration aids, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrating agent-containing agent.

Furthermore, according to the invention, gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries. However, preferred effervescent systems consist of at least two components which react with one another to form gas, for example alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution. An acidifying agent which releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.

1. a) ein erfindungsgemäßes maschinelles Geschirrspülmittel;
2. b) eine Anleitung, die den Verbraucher darauf hinweist, das maschinelle Geschirrspülmittel ohne Zusatz eines Klarspülers und/oder eines Enthärtersalzes zu verwenden ist, ist ein weiterer Gegenstand dieser Anmeldung.

The active substance combinations described above are particularly suitable for cleaning dishes in automatic dishwashing processes. Another object of the present application is a method for cleaning dishes in a dishwasher, using a dishwasher according to the invention, wherein the automatic dishwashing preferably during the passage of a dishwasher, before the main wash cycle or in the course of the main wash cycle in the interior of a dishwasher metered become. The metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered into the interior of the dishwasher by means of the metering chamber of the dishwasher. In the course of the cleaning process preferably no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher. A kit for a dishwasher, comprising

1. a) a machine dishwashing detergent according to the invention;
2. (b) instructions instructing the consumer to use the automatic dishwashing detergent without the addition of a rinse aid and / or a softening salt are another subject of this application.

The dishwasher detergents according to the invention exhibit their advantageous cleaning and drying properties, in particular also in low-temperature cleaning processes. Preferred dishwashing processes using agents according to the invention are therefore characterized the dishwashing processes are carried out at a liquor temperature below 60 ° C., preferably below 50 ° C.

As described at the beginning, agents according to the invention are distinguished from conventional automatic dishwasher detergents by improved tea cleaning. Another object of the present application is therefore the use of a machine dishwashing detergent according to the invention for improving the dough cleaning in automatic dishwashing.

Examples I. In a dishwasher machine, soiled dishes were rinsed in a dishwashing machine (Miele G 698) at a water hardness of 21 ° dH and a temperature of 50 ° C. with 42.5 g ml of the automatic dishwashing detergent listed in the table below.

ingredient V1 V2 V3 V4 E1 E2 E3 In% by weight potassium 18 - - - - - - silicate 18 sodium citrate - - 18 18 18 18 18 Acrylic acid homopolymer - - - 2.0 - - - Anionic copolymer ¹ - - - - 2.8 4.5 6.9 Sulfopolymer ² 4.2 - - - - - - Sulfopolymer ³ - 4.2 4.2 4.2 4.2 4.2 4.2 sodium 4.0 4.0 4.0 4.0 4.0 4.0 4.0 HEDP 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Nonionic surfactant 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Protease preparation 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Amylase preparation 0.8 0.8 0.8 0.8 0.8 0.8 0.8 alkanolamine 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Water, Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 pH (10% solution, 20 ° C) 10.3 10.6 10.5 10.4 10.4 10.4 10.3

1. i) ungesättigte Monocarbonsäure(n) A
2. ii) ungesättigte Dicarbonsäure(n) B.

² Sulfonsäure-haltiges Copolymer, umfassend

1. i) ungesättigte Carbonsäure(n)
2. ii) ungesättige Sulfonsäuregruppen-haltige(s) Monomer(e)

³ hydrophob modifiziertes Sulfonsäure-haltiges Copolymer, umfassend

1. i) ungesättigte Carbonsäure(n)
2. ii) ungesättige Sulfonsäuregruppen-haltige(s) Monomer(e)
3. iii) weitere(s) nichtionogene(s) Monome(e)

¹ anionic copolymer comprising

1. i) unsaturated monocarboxylic acid (s) A
2. ii) unsaturated dicarboxylic acid (s) B.

² sulfonic acid-containing copolymer comprising

1. i) unsaturated carboxylic acid (s)
2. ii) unsaturated sulfonic acid group-containing monomer (s)

³ hydrophobically modified sulfonic acid-containing copolymer comprising

1. i) unsaturated carboxylic acid (s)
2. ii) unsaturated sulfonic acid group-containing monomer (s)
3. iii) other nonionic monomers (s)

The cleaning performance of the automatic dishwashing detergents was assessed by the IKW method. The results are given in the table below (The values given are average values from 3 experiments) cleaning performance V1 V2 V3 V4 E1 E2 E3 tea 3.9 0.2 1.7 0.3 4.1 4.3 4.2 Strength 9.1 7.7 9.0 7.7 9.1 9.1 9.4 minced meat 10.0 9.5 10.0 10.0 10.0 10.0 10.0 (Evaluation scale cleaning performance: 10 = no contamination to 0 = heavy contamination)

II. In a dishwasher automatic dishwashing process, soiled dishes were rinsed in a dishwashing machine (Miele G 698) at a water hardness of 21 ° dH and a temperature of 50 ° C. with 41 g ml of the automatic dishwashing detergent listed in the table below.

ingredient V1 E1 Data in% by weight sodium citrate 8.0 8.0 Acrylic acid homopolymer 12 - Maleic acid homopolymer - 12 sulfopolymer 9.5 9.5 sodium 5.0 5.0 potassium hydroxide 9.5 9.5 HEDP 1.5 1.5 Nonionic surfactant 2.0 2.0 Protease preparation 2.4 2.4 Amylase preparation 0.6 0.6 1,2-propylene glycol 5.6 5.6 Water, Misc Add 100 Add 100 pH (10% solution, 20 ° C) 10.4 10.4

The cleaning performance of the automatic dishwashing detergents was assessed by the IKW method. The results are given in the table below (The values given are average values from 5 experiments) cleaning performance V1 E1 tea 0.2 2.0 (Evaluation scale cleaning performance: 10 = no contamination to 0 = heavy contamination)

Claims (14)

1. A low-alkali, phosphate- and bleaching agent-free automatic dishwashing agent with a pH value (10% solution; 20°C) of between 8 and 12, containing:

   a) 10 to 60 wt. % of citrate

   b) 2.0 to 30 wt.% of anionic polymer comprising unsaturated dicarboxylic acid(s) B,
   characterized in that the automatic dishwashing agent contains no silicate.
2. The automatic dishwashing agent according to claim 1, characterized in that the automatic dishwashing agent has a pH value (20°C) of between 9 and 11.5, preferably between 9.5 and 11.5.
3. The automatic dishwashing agent according to any one of the preceding claims, characterized in that the automatic dishwashing agent contains, relative to the total weight thereof, 12 to 50 wt.%, preferably 15 to 40 wt.% and in particular 15 to 30 wt.% of citrate.
4. The automatic dishwashing agent according to any one of the preceding claims, characterized in that the automatic dishwashing agent contains as anionic polymer b) a copolymer comprising

   i) unsaturated monocarboxylic acid(s) A, preferably 50 to 90 wt.% of unsaturated monocarboxylic acid(s) A, in particular acrylic acid

   ii) unsaturated dicarboxylic acid(s) B , preferably 10 to 50 wt.% of unsaturated dicarboxylic acid(s) B, in particular maleic acid.
5. The automatic dishwashing agent according to any one of claims 1 to 3, characterized in that the automatic dishwashing agent contains as anionic polymer b) a maleic acid homopolymer, preferably with a relative molecular mass, relative to free acids, of 2000 to 70000 g/mol, preferably 4000 to 50000 g/mol and in particular 6000 to 40000 g/mol.
6. The automatic dishwashing agent according to any one of the preceding claims, characterized in that the automatic dishwashing agent contains, relative to the total weight thereof, 2.0 to 20 wt.%, preferably 2.5 to 15 wt.% and in particular 2.5 to 10 wt.% of the anionic polymer b).
7. The automatic dishwashing agent according to any one of the preceding claims, characterized in that the automatic dishwashing agent contains, relative to the total weight thereof, organic solvent in quantities of 0.1 to 15 wt.%, preferably 0.2 to 12 wt.%, particularly preferably 0.5 to 10 wt.% and in particular of 2.0 to 8 wt.%, preferably organic amine and/or an alkanolamine, preferably ethanolamine, in quantities of 0.1 to 15 wt.%, preferably 0.2 to 10 wt.%, particularly preferably 0.5 to 8 wt.% and in particular of 1.0 to 6 wt.%.
8. The automatic dishwashing agent according to any one of the preceding claims, characterized in that the dishwashing agent contains, relative to the total weight thereof, nonionic surfactant in quantities of 0.1 to 15 wt.%, preferably 0.2 to 10 wt.%, particularly preferably 0.5 to 8 wt.% and in particular of 1.0 to 6 wt.%.
9. The automatic dishwashing agent according to any one of the preceding claims, characterized in that the dishwashing agent contains, relative to the total weight thereof, enzyme preparations in quantities of 0.1 to 12 wt.%, preferably of 0.2 to 10 wt.% and in particular of 0.5 to 8 wt.%.
10. A low-alkali automatic dishwashing agent according to any one of the preceding claims with a pH value (10% solution; 20°C) of between 8 and 12, containing

    a) 10 to 40 wt.% of citrate

    b) 2.0 to 10 wt.% of anionic copolymer, comprising

    i) acrylic acid

    ii) maleic acid

    c) 1 to 8 wt.% of phosphonate

    d) 0.2 to 10 wt.% of nonionic surfactant

    e) 0.1 to 8 wt.% of enzyme preparation(s)
11. The low-alkali automatic dishwashing agent according to any one of the preceding claims with a pH value (10% solution; 20°C) of between 8 and 12, containing

    a) 10 to 40 wt. % of citrate

    b) 2.0 to 10 wt.% of maleic acid homopolymer

    c) 1 to 8 wt.% of phosphonate

    d) 0.2 to 10 wt.% of nonionic surfactant

    e) 0.1 to 8 wt.% of enzyme preparation(s)
12. A method for cleaning dishes in a dishwashing machine using an automatic dishwashing agent according to any one of the preceding claims.
13. The method according to claim 12, wherein the dishwashing method is carried out at a liquor temperature of below 60°C.
14. Use of an automatic dishwashing agent according to any one of the preceding claims for improving tea cleaning in automatic dishwashing.