DE102008061858A1 - Machine dishwashing detergent - Google Patents

Abstract

Phosphate and bleach-free dishwashing detergent, containing: a) 10 to 60 wt .-% citrate b) 1 to 30 wt .-% polyphosphonic acid are characterized by a good cleaning performance, in particular improved Teereinigung.

Description

The present application describes automatic dishwashing detergents, automatic dishwashing process using this dishwashing detergent and the use of these dishwashing detergents to improve the Cleaning of dishes during automatic dishwashing.

At mechanically rinsed Dishes are becoming common higher Requirements placed as on manually rinsed dishes. So will be a tableware completely cleaned at first sight of leftovers then rated as not flawless if it still remains after machine dishwashing discoloration which, for example, on the attachment of vegetable dyes on the dish surface based.

Around To obtain spotless dishes are in automatic dishwashing detergents Bleach used.

to Activation of these bleaches and when cleaning at temperatures from 60 ° C and below to achieve an improved bleaching effect automatic dishwashing detergent usually bleach activators or bleach catalysts, in particular, the bleach catalysts are particularly effective have proven.

the Use of these bleaches are due to incompatibilities with other washing or cleaning active ingredients, such as Enzymes, or due to stability problems during storage Bleach-containing detergents and cleaners set limits. This applies in particular to liquid washing or detergent.

A technical possibility the cleaning performance of automatic dishwashing detergents, in particular bleach-free, automatic dishwashing detergents To improve is to increase the alkalinity of these Medium. While However, on the one hand with increasing alkalinity, the cleaning performance of automatic dishwashing detergents On the other hand, strong alkaline cleaners cause too damage in the silicate structure of glasses and can cause strong irritation on contact with skin.

When particularly effective builders to increase alkalinity have proved the alkali metal phosphates, for this reason the main component of the predominant Number of commercially available machines Dishwashing liquid form.

While the Phosphates with regard to their beneficial effect as a component automatic dishwashing detergent very appreciated their mission is from the perspective of environmental protection not unproblematic, since a substantial part of the phosphate over the Domestic waste water into the waters and especially in stagnant water (lakes, barrages) questionable role in their over-fertilization plays. As a result of this phenomenon also called eutrophication was the use of pentasodium triphosphate in laundry detergents in several countries, z. USA, Canada, Italy, Sweden, Norway, by law Regulations considerably reduces u. in Switzerland throughout prohibited. Allowed in Germany Detergents since 1984 at most 20% of this builder contain.

A Limitation of alkalinity as well as the phosphate content of the automatic dishwashing detergent that is from the point of view of the user and with a view to a sustainable one Product development desirable.

This Registration was therefore the object of a cleaning agent for the dishwashing to provide that opposite usual Dishwashing detergents even with low-temperature cleaning cycles or during cleaning cycles with low water consumption through improved cleaning performance distinguished. In particular, the Geschirreinigungsmittel should despite Phosphate and bleach free by a good cleaning performance characterized in that an improved cleaning performance, such as bleachable Soiling would be preferred without an increased at the same time damage of glass or ceramic surfaces to effect. The bleachable stains include stains, for example by tea or vegetable dyes, for example from vegetables or Fruit.

Surprisingly It was found that the above task is in a citrate-based, phosphate-free and bleach-free Basic recipe can be solved by the use of polyphosphonic acid.

• a) 10 bis 60 Gew.-% Citrat
• b) 1 bis 30 Gew.-% Polyphosphonsäure

A first subject of this application is a phosphate and bleach-free machine Ge dishwashing detergent containing:

• a) 10 to 60 wt .-% citrate
• b) 1 to 30 wt .-% polyphosphonic acid

The machine according to the invention Dishwashing liquid are preferably lower alkyl. Preferred machine according to the invention Dishwashing liquid are characterized in that the automatic dishwashing detergent 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.

One The first essential ingredient of the invention is the citrate. The term "citrate" includes as well as the citric acid as well as their salts, especially their alkali metal salts. Especially preferred machine according to the invention Dishwashing liquid contain citrate, preferably sodium citrate, in amounts of 12 to 50 wt .-%, preferably 15 to 40 wt .-% and in particular 15 to 30 wt .-%, each based on the total weight of the machine Dishwashing detergent. Citrate or citric acid have faced each other other builders in combination with the anionic copolymer in terms of tea cleaning proved to be particularly effective.

• * „-” bedeutet in dieser, wie in allen nachfolgenden Tabellen: die Rezeptur ist frei von diesem Bestandteil

Some exemplary formulations for preferred automatic dishwashing detergents according to the invention can be found in the following Table 1: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 12 to 50 15 to 40 15 to 30 15 to 30 polyphosphonic 1.0 to 30 1.0 to 30 1.0 to 30 1.0 to 30 phosphate - * - - - bleach - - - - PH value kA kA kA 9 to 11.5 Misc Add 100 Add 100 Add 100 Add 100

• * "-" means in this, as in all the following tables: the recipe is free from this ingredient

The machine according to the invention Dishwashing liquid can additional to the citrates Builders, especially carbonates or organic cobuilders.

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

Some exemplary formulations for preferred automatic dishwashing detergents according to the invention can be found in the following Table 2: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 12 to 50 15 to 40 15 to 40 15 to 30 polyphosphonic 1.0 to 30 1.0 to 30 1.0 to 30 1.0 to 30 carbonate 5 to 50 10 to 40 5 to 50 10 to 40 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100

When Organic cobuilders are in particular polycarboxylates / polycarboxylic acids, dextrins and to name phosphonates. These classes of substances are hereafter described.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, such polycarboxylic acids verifying such carboxylic acids be standing who 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, as well as mixtures of these. 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.

The Complexing phosphonates include, in addition to the 1-hydroxyethane-1,1-diphosphonic a series different compounds such as diethylenetriamine penta (methylenephosphonic acid) (DTPMP). In this application, in particular hydroxyalkane or Aminoalkanephosphonates. Among the hydroxyalkane phosphonates is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder. It is preferably used as the sodium salt, wherein the disodium salt is neutral and the tetrasodium salt is alkaline (pH 9) reacts. Ethylenediamine tetramethylene phosphonates are preferably used as aminoalkane phosphonates (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reacting Sodium salts, e.g. B. as hexasodium salt of EDTMP or hepta- and octa-sodium salt of DTPMP. As a builder will be there from the class of phosphonates preferred HEDP used. The aminoalkane phosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it may, especially if the means also bleach be preferred, Aminoalkanphosphonate, in particular DTPMP, to use or mixtures of the phosphonates mentioned.

• a) Aminotrimethylenphosphonsäure (ATMP) und/oder deren Salze;
• b) Ethylendiamintetra(methylenphosphonsäure) (EDTMP) und/oder deren Salze;
• c) Diethylentriaminpenta(methylenphosphonsäure) (DTPMP) und/oder deren Salze;
• d) 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) und/oder deren Salze;
• e) 2-Phosphonobutan-1,2,4-tricarbonsäure (PBTC) und/oder deren Salze;
• f) Hexamethylendiamintetra(methylenphosphonsäure) (HDPMP) und/oder deren Salze;
• 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

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

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

Of course, the machine according to the invention Dishwashing liquid contain two or more different phosphonates.

Of the Weight fraction of phosphonates in the total weight according to the invention by machine Dishwashing liquid is preferably 1 to 8 wt .-%, preferably 1.2 to 6 wt .-% and in particular 1.5 to 4 wt .-%.

Some exemplary formulations for preferred automatic dishwashing detergents according to the invention can be found in the following Table 3: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 polyphosphonic 1.0 to 30 1.0 to 30 1.0 to 30 1.0 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 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100

A another group of organic builders are the polymeric sulfonates. Contain preferred polysulfonates in addition to sulphonic acid group-containing (n) Monomer (s) at least one monomer from the unsaturated group Carboxylic acids.

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

Especially preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, Ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or their mixtures. Of course, the unsaturated can also be used Dicarboxylic acids.

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

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

Especially preferred sulfonic acid group-containing Monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of mentioned acids or their water-soluble Salts.

In the polymers can the sulfonic acid groups completely or partially in neutralized form, d. H. that the acidic acid atom of the sulfonic acid group in some or all of them Sulfonic acid groups against Metal ions, preferably alkali metal ions and in particular against Sodium ions, can be replaced. The use of partial or fully neutralized sulfonic acid group-containing Copolymer is preferred according to the invention.

The Monomer distribution of the polymers preferably used according to the invention Sulfonate is at Copolymers containing only monomers from the unsaturated groups carboxylic acids i) and the unsaturated sulfonic acids ii), preferably in each case 5 to 95% by weight of i) or ii), more preferably 50 to 90% by weight of monomer from group ii) and from 10 to 50% by weight of monomer from group i), in each case obtained on the polymer.

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molecular weights of 2,000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

In a further preferred embodiment include the polymeric sulfonates in addition to carboxyl group-containing monomer and sulfonic acid group-containing Monomer further at least one nonionic, preferably hydrophobic Monomer. Through the use of these hydrophobically modified polymers could in particular the rinse aid performance inventive machine Dishwashing liquid be improved.

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

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

• i) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Carbonsäuren
• ii) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Sulfonsäuren
• iii) optional weitere ionische oder nichtionische Monomere

enthält, werden erfindungsgemäß bevorzugt.Machine dishwashing detergent, characterized in that the automatic dishwashing agent, based on its total weight, contains 2.0 to 20% by weight, preferably 2.5 to 15% by weight and in particular 2.5 to 10% by weight of anionic copolymer, full

• i) one or more polyunsaturated monomers from the group of carboxylic acids
• ii) one or more polyunsaturated monomers from the group of sulfonic acids
• iii) optionally further ionic or nonionic monomers

contains are preferred according to the invention.

One second essential ingredient of the invention is the polyphosphonic b). The proportion by weight of the polyphosphonate b) on the total weight of the machine according to the invention Dishwashing detergent is preferably 2.0 to 28 wt .-%, preferably 4 to 26 wt .-% and in particular 8 to 24% by weight.

The homopolymers polyphosphonic acids have in relation to the means of the invention achieved Teereinigung as a simple homopolymer unsaturated Monocarboxylic acids or copolymers of unsaturated Monocarboxylic superior proved. The Teereinigung homopolymeric phosphonic acids turn is surpassed by the dough cleaning performance of copolymeric polyphosphonic acids. Preferred polyphosphonic acids comprising unsaturated Monocarboxylic acid (s) A and unsaturated Phosphonic acid (s) B are therefore preferred.

• i) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Carbonsäuren
• ii) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Phosphonsäuren
• iii) optional weitere ionische oder nichtionische Monomere

enthält.Preferred automatic dishwasher detergents according to the invention are characterized in that the automatic dishwashing agent comprises a polyphosphonic acid

• i) one or more polyunsaturated monomers from the group of carboxylic acids
• ii) one or more polyunsaturated monomers from the group of phosphonic acids
• iii) optionally further ionic or nonionic monomers

contains.

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

• i) 50 bis 90 Gew.-% ungesättigte Monocarbonsäure(n) A
• ii) 10 bis 50 Gew.-% ungesättigte Phosphonsäure(n) B.

enthält.Preferred automatic dishwasher detergents according to the invention are characterized in that the automatic dishwashing agent comprises as polyphosphonic acid b) a copolymer comprising

• i) 50 to 90% by weight of unsaturated monocarboxylic acid (s) A
• ii) 10 to 50% by weight of unsaturated phosphonic acid (s) B.

contains.

• i) 50 bis 90 Gew.-% Acrylsäure
• ii) 10 bis 50 Gew.-% Phosphonsäure.

Preferred machine dishwasher detergents according to the invention comprise as polyphosphonic acid b) a copolymer comprising

• i) 50 to 90 wt .-% acrylic acid
• ii) 10 to 50% by weight of phosphonic acid.

The polyphosphonic b) can in the machine according to the invention dishwashing detergent For example, be used as a powder or as an aqueous solution.

• ¹ Polyphosphonsäure b) ein Copolymer, umfassend 50 bis 90 Gew.-% Monocarbonsäure und 10 bis 50 Gew.-% Phosphonsäure

Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in the following Table 3a and 3b: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Polyphosphonic acid ¹ 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 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 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 Polyphosphonic acid ¹ 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 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 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100

• ¹ polyphosphonic acid b) a copolymer comprising 50 to 90 wt .-% monocarboxylic acid and 10 to 50 wt .-% phosphonic acid

Next the ingredients described above, the agents of the invention other washing or cleaning substances, preferably from the group of surfactants, enzymes, organic solvents, glass corrosion inhibitors, Corrosion inhibitors, fragrances and perfume carriers included. These preferred Ingredients are 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 corresponds to a primary straight-chain or methyl-branched, especially methyl-branched, 2-position 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.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half from that.

A another class of preferred nonionic surfactants, the 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 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 native origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 moles of EO per mole of alcohol. 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 _12-16 -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.

With particular preference are therefore ethoxylated nonionic surfactants, which consist of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per Mol of alcohol were used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _18-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

Especially preferred are nonionic surfactants which have a melting point above Have 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, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also with special Preference used.

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

Prefers Surfactants to be used come from the groups of the alkoxylated Nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants stand out about it out by good foam control.

Further particularly preferred nonionic surfactants with melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 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 nonionic surfactants of the general formula

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

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. When 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 native origin having 12 to 18 C atoms, eg. B. 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. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants 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 represent a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 -alkyl or alkenyl radical; A, A ', A''andA''' are independently of one another a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ - CH _{2 is} -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 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.

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 the use of the above-described nonionic surfactants with a free hydroxyl group on one of the two terminal alkyl radicals can be compared to conventional polyalkoxylated fatty alcohols without free hydroxyl group formation of coverings be significantly improved in the machine dishwashing.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, 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 specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned Nonionic surfactants represent statistical averages that are suitable for a specific Product can be a whole or a fractional number. by virtue of the manufacturing process consist of commercial products of the formulas mentioned mostly not from an individual representative, but from mixtures, which is responsible for both the C chain lengths as also for the degrees of ethoxylation or degrees of alkoxylation averages and resulting in fractional numbers.

• – R¹ und R² unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten Alkylrest mit 4 bis 22 Kohlenstoffatomen;
• – Alk für eine verzweigten oder unverzweigten Alkylrest mit 2 bis 4 Kohlenstoffatomen;
• – x und y unabhängig voneinander für Werte zwischen 1 und 70; und
• – M für einen Alkylrest aus der Gruppe CH₂, CHR³, CR³R⁴, CH₂CHR³ und CHR³CHR⁴, wobei R³ und R⁴ unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten Alkylrest mit 1 bis 18 Kohlenstoffatomen;

Another group of preferred nonionic surfactants are surfactants of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ² , in which

• 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 is a branched or unbranched alkyl radical having 2 to 4 carbon atoms;
• - x and y independently for values between 1 and 70; and
• M is 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 alkyl radical having 1 to 18 carbon atoms;

Of the Weight fraction of this nonionic surfactant in the total weight of machine according to the invention dishwashing detergent is in a preferred embodiment between 0.05 and 10% by weight, preferably between 0.1 and 8% by weight, preferably between 0.5 and 5 wt .-% and in particular between 1 and 3% by weight.

The group of nonionic surfactants of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ² comprises a number of particularly preferred compounds.

• – R, R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen;
• – x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen

In a first preferred embodiment, automatic dishwashing agents according to the invention contain as nonionic surfactant A a surfactant 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 is} used in the

• R, R ¹ and R ² independently represent an alkyl radical or alkenyl radical having 6 to 22 carbon atoms;
• - x and y independently represent values between 1 and 40

Particular preference is given to compounds 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 is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values of 20 to 30. Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH ₂ -OH with ethylene oxide, followed by reaction with an alkyle epoxide to close the free OH functions to form a dihydroxy ether.

• – R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen;
• – R³ und R4 unabhängig voneinander für H oder für einen Alkylrest oder Alkenylrest mit 1 bis 18 Kohlenstoffatomen und
• – x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen;

In a further preferred embodiment of machine dishwashing detergents according to the invention contain nonionic surfactant of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} O in which

• - R ¹ and R ² independently represent an alkyl radical or alkenyl radical having 4 to 22 carbon atoms;
• R ³ and R 4 independently of one another are H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and
• - x and y independently represent values between 1 and 40;

In particular compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, are in which R ³ and R ⁴ is H, and the subscripts x and y are preferably independently from each other assume values from 1 to 40, preferably from 1 to 15.

Especially preferred are compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, in which the radicals R ¹ and R ² are independently saturated alkyl groups having 4 to 14 Represent carbon atoms and the indices x and y independently of one another assume values of 1 to 15 and in particular of 1 to 12.

Also preferred are those compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which one of the radicals R ¹ and R ^{2 is} branched.

Very particularly preferred compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, in which the indices x and y are independently values 8-12 accept.

Of course, the aforementioned nonionic surfactants not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants be used. As surfactant mixtures are not mixtures nonionic surfactants referred to in their entirety one of the above general formulas, but rather such mixtures, the two, three, four or more nonionic Containing surfactants by different of the aforementioned general Formulas can be described.

Of the Weight fraction of the nonionic surfactant in the total weight of the inventive machine dishwashing detergent is in a preferred embodiment 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% by weight.

Some exemplary formulations for preferred automatic dishwashing detergents according to the invention can be found in the following Table 4a and 4b: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 polyphosphonic 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 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 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 polyphosphonic 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 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 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100

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.

Under Proteases are preferred to those of the subtilisin type. Examples therefor are the subtilisins BPN 'and Carlsberg and its advanced forms, the protease PB92, subtilisins 147 and 309, the Bacillus alkaline protease lentus, subtilisin DY and the subtilases, but not anymore the enzymes subtilisins in the strict sense, thermitase, Proteinase K and the proteases TW3 and TW7.

Examples for inventively usable Amylases are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as those for use in washing and Detergents improved developments of the aforementioned Amylases. Furthermore are for this purpose the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Usable according to the invention are still lipases or cutinases, especially because of their Triglyceride-splitting activities, but also to in situ peracids from suitable precursors produce. These include for example, the original one from Humicola lanuginosa (Thermomyces lanuginosus) available, respectively further developed lipases, in particular those with the amino acid exchange D96L.

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

to increase the bleaching effect oxidoreductases according to the invention, for example, oxidases, oxygenases, catalases, peroxidases, such as Halo, chloro, bromo, lignin, glucose or manganese peroxidases, Dioxygenases or laccases (phenol oxidases, polyphenol oxidases) be used. Advantageously, organic, particularly preferably aromatic, interacting with the enzymes Compounds added to the activity of the respective oxidoreductases to reinforce (Enhancer) or at very different redox potentials between the oxidizing enzymes and the soiling the electron flow to ensure (Mediators).

One Protein and / or enzyme may be particularly harmful during storage against damage such as inactivation, denaturation or decay, for example through physical influences, Oxidation or proteolytic cleavage are protected. In microbial Obtaining the proteins and / or enzymes is inhibiting the Proteolysis particularly preferred, especially if the means Contain proteases. Detergents or cleaners can contain stabilizers for this purpose; the provision of such funds represents a preferred embodiment of the present invention.

washing or purification-active proteases and amylases are usually not in the form of the pure protein but rather in the form of stabilized, storable and transportable Preparations provided. To these prefabricated preparations counting for example, by granulation, extrusion or lyophilization obtained solid preparations or, especially in liquid or gelatinous Means, solutions of Enzymes, advantageously as possible concentrated, low in water and / or with stabilizers or other aids added.

alternative can the enzymes for both the solid as well for the liquid Dosage form can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are as in enclosed in a solidified gel or in core-shell type, in which an enzyme-containing core with a water, air and / or Chemical-impermeable Protective layer coated is. In superimposed layers additional active ingredients, For example, stabilizers, emulsifiers, pigments, bleach or Dyes are applied. Such capsules are after known methods, for example by shaking or Roll granulation or applied in fluid-bed processes. Advantageously Such granules, for example by applying polymeric film-forming agents, low in dust and storage-stable due to the coating.

Farther Is it possible, to assemble two or more enzymes together, making one individual granules has several enzyme activities.

One preferred machine according to the invention Dishwashing liquid is characterized in that the dishwashing detergent, 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 .-%.

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

• a) 10 bis 40 Gew.-% Citrat
• b) 4 bis 26 Gew.-% Polyphosphonsäure
• c) 0,1 bis 8 Gew.-% Amylase- und/oder Protease Enzymzubereitung
• d) 2,0 bis 20 Gew.-% anionischen Copolymers, umfassend i) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Carbonsäuren ii) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Sulfonsäuren iii) optional weitere ionische oder nichtionische Monomere
• e) 0,2 bis 10 Gew.-% nichtionisches Tensid

A particularly preferred automatic dishwashing detergent according to the invention comprises

• a) 10 to 40 wt .-% citrate
• b) 4 to 26% by weight of polyphosphonic acid
• c) 0.1 to 8 wt .-% amylase and / or protease enzyme preparation
• d) 2.0 to 20% by weight of anionic copolymer comprising i) mono- or polyunsaturated monomers from the group of carboxylic acids ii) mono- or polyunsaturated monomers from the group of sulfonic acids iii) optionally further ionic or nonionic monomers
• e) 0.2 to 10% by weight of nonionic surfactant

Some further exemplary formulations for preferred automatic dishwasher detergents according to the invention can be found in the following Table 5a and 5b: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 polyphosphonic 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 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 Sulfocopolymer 0 to 20 0 to 20 0 to 20 0 to 20 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 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 polyphosphonic 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 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 Sulfocopolymer 0 to 20 2.0 to 20 2.0 to 20 2.5 to 15 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 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100

The machine according to the invention Dishwashing liquid can in the known in the art Konfektionsformen, so for example in solid or liquid But also as a combination of fixed and liquid forms of supply.

When Solid supply forms are particularly suitable powders, granules, Extrudates or compacts, in particular tablets. The liquid offer forms based on water and / or organic solvents can be thickened, in the form of gels.

Compositions according to the invention can be formulated as single-phase or multi-phase products. Prefers In particular, automatic dishwashing detergents with one, two, three or four phases.

Machinery Dishwashing liquid, characterized in that they are in the form of a prefabricated metering unit with two or more phases are particularly preferred.

The single phases of multiphasic agents may be the same or different Physical states exhibit. Machine dishwashing detergents, in particular, are preferred. the at least two different solid phases and / or at least two liquid ones Phases and / or at least one solid and at least one liquid phase exhibit. Especially preferred are two or more phases Tablets, for example two-layer tablets, in particular two-layer tablets with trough and a molded body located in the trough.

Mechanical machine according to the invention Dishwashing liquid are preferably prefabricated to dosage units.

These Dosing units preferably comprise those necessary for a cleaning cycle Amount of wash or cleaning-active substances. Preferred dosing 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 chosen with particular preference, that a meterability of the prefabricated units on the Dosing chamber of a dishwasher guaranteed is. 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 machine according to the invention Dishwashing liquid, in particular the prefabricated metering units have particular Preferably a water-soluble wrapping on.

Around the disintegration of prefabricated moldings to facilitate, it is possible Disintegration aids, so-called tablet disintegrants, in to incorporate these agents to reduce disintegration times.

These Substances which are also referred to as "explosives" due to their effect, enlarge with water access their volume, on the one hand increasing the intrinsic volume (swelling), on the other hand also about the Release of gases can create a pressure on the tablet can disintegrate into smaller particles. Well-known Disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can 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.

Prefers are disintegration aids in amounts of 0.5 to 10 wt .-%, preferably 3 to 7% by weight and in particular 4 to 6% by weight, respectively based on the total weight of the desintegrationshilfsmittelhaltigen By means of, used.

When preferred disintegrating agents become disintegrants Cellulose-based, so that preferred detergents or cleaning agents such cellulose-based disintegrant in amounts of 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-% included. The used as disintegration aids Cellulose is preferably not used in finely divided form, but before adding to the premixes to be pressed in a coarser one Transferred form, for example granulated or compacted. The particle sizes of such disintegrating agents are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90 wt .-% between 400 and 1200 microns.

preferred Disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are in disintegrating 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 disintegrant-containing agent.

According to the invention preferred can about that in addition, gas-evolving effervescent systems as tablet disintegration aids be used. However, preferred effervescent systems exist at least two constituents that react with one another to form gas, for example, alkali metal carbonate and / or bicarbonate and an acidifier suitable from the alkali metal salts in water solution Release carbon dioxide. An acidifier that is derived from the Alkali salts in aqueous solution carbon dioxide Release, for example, is the citric acid.

It it was found that the cleaning performance according to the invention by machine Dishwashing liquid by the addition of organic solvents can be improved.

These organic solvents are for example from the groups of mono-alcohols, diols, Triols or polyols, ethers, esters and / or amides. Especially preference is given to organic solvents which are water-soluble, being "water-soluble" solvents For the purposes of the present application, solvents are those at room temperature with water completely, d. H. without miscibility gap, are miscible.

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 but oxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.

When particularly effective in terms of cleaning performance and Here again with regard to the cleaning performance of bleachable Stains, especially on Teeanschmutzungen have the organic solvent from the group of organic amines and / or alkanolamines.

When organic amines are especially the primary and the secondary alkyl amines, the alkyleneamines and mixtures of these organic amines are preferred. To the group of preferred primary Include alkylamines Monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine and cyclohexylamine. To the group of preferred secondary alkylamines counts in particular Dimethylamine.

preferred Alkanolamines are especially the primary, secondary and tertiary alkanolamines as well as their mixtures. Particularly preferred primary alkanolamines are monoethanolamine (2-aminoethanol, MEA), monoisopropanolamine, Diethylethanolamine (2- (diethylamino) ethanol). Especially preferred secondary Alkanolamines are diethanolamine (2,2'-iminodiethanol, DEA, bis (2-hydroxyethyl) amine), N-methyl-diethanolamine, N-ethyl-diethanolamine. Diisopropanolamine and morpholine. Especially preferred tertiary Alkanolamines are triethanolamine and triisopropanolamine.

Combination products characterized in that it is an organic solvent contained, wherein the organic solvent is an organic Amine and / or an alkanolamine, preferably monoethanolamine, become particularly according to the invention prefers.

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

• a) 10 bis 40 Gew.-% Citrat
• b) 4 bis 26 Gew.-% Polyphosphonsäure
• c) 0,1 bis 8 Gew.-% Amylase- und/oder Protease Enzymzubereitung
• d) 2,0 bis 20 Gew.-% anionischen Copolymers, umfassend i) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Carbonsäuren ii) ein oder mehrfach ungesättigte Monomere aus der Gruppe der Sulfonsäuren iii) optional weitere ionische oder nichtionische Monomere
• e) 0,2 bis 10 Gew.-% nichtionisches Tensid
• f) 20 bis 70 Gew.-% Wasser

These solvent-containing automatic dishwashing agents are preferably in liquid form. A particularly preferred liquid automatic dishwashing detergent according to the invention comprises

• a) 10 to 40 wt .-% citrate
• b) 4 to 26% by weight of polyphosphonic acid
• c) 0.1 to 8 wt .-% amylase and / or protease enzyme preparation
• d) 2.0 to 20% by weight of anionic copolymer comprising i) mono- or polyunsaturated monomers from the group of carboxylic acids ii) mono- or polyunsaturated monomers from the group of sulfonic acids iii) optionally further ionic or nonionic monomers
• e) 0.2 to 10% by weight of nonionic surfactant
• f) 20 to 70 wt .-% water

Some exemplary formulations for preferred liquid automatic dishwashing detergents according to the invention can be found in the following Tables 5a and 5b: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 polyphosphonic 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 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 Sulfocopolymer 0 to 20 0 to 20 0 to 20 0 to 20 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 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 polyphosphonic 2.0 to 28 2.0 to 28 4.0 to 26 8.0 to 24 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 Sulfocopolymer 0 to 20 2.0 to 20 2.0 to 20 2.5 to 15 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 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100

Lie the agents according to the invention in liquid Form, these agents preferably contain from 20 to 80% by weight, preferably 30 to 70 wt .-% and in particular 40 to 60 wt .-% water. The dosing units of these liquid Offer forms preferably include those necessary for a cleaning cycle Amount of washing or cleaning substances. Preferred liquid dosage units have a weight between 25 and 60 g, preferably between 30 and 55 g and in particular between 55 and 50 g.

• a) ein erfindungsgemäßes maschinelles Geschirrspülmittel;
• 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

• a) a machine dishwashing detergent according to the invention;
• (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 Ge Dishwashing processes using agents according to the invention are therefore characterized in that the dishwashing processes are carried out at a liquor temperature below 60 ° C, preferably below 50 ° C.

As described above, are inventive means across from usual automatic dishwashing detergents through improved Teereinigung. Another item the present application is therefore the use of a machine according to the invention dishwashing detergent for improving the dough cleaning in automatic dishwashing.

Examples

• ¹⁾ 11,7 g Polyphosphonsäure „on top”

In a dishwasher 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 42.5 g ml of the automatic dishwashing detergent listed in the table below. ingredient V1 E1 Data in% by weight sodium citrate 9.0 9.0 potassium hydroxide 7.0 7.0 sodium 14 14 polyphosphonic - ¹⁾ sulfopolymer 4.2 4.2 HEDP 1.5 1.5 Nonionic surfactant 2.0 2.0 Protease preparation 2.0 2.0 Amylase preparation 0.8 0.8 alkanolamine 1.5 1.5 thickener 2.0 2.0 Water, Misc Add 100 Add 100

• ¹⁾ 11.7 g polyphosphonic acid "on top"

• (Bewertungsskala Reinigungsleistung: 10 = keine Verunreinigung bis 0 = starke Verunreinigung)

The tea cleaning performance of the automatic dishwashing detergents was evaluated by the IKW method. The results are given in the table below (The values given are average values from 3 experiments) cleaning performance V1 E1 tea 1 3

• (Evaluation scale cleaning performance: 10 = no contamination to 0 = heavy contamination)

Claims (15)

Phosphate and bleach-free machine Dishwashing liquid, including: a) 10 to 60 wt .-% citrate b) 1 to 30% by weight polyphosphonic Machine dishwashing detergent according to claim 1, characterized characterized in that the automatic dishwashing agent, based on its total weight, 12 to 50 wt .-%, preferably 15 to 40 wt .-% and in particular Contains 15 to 30 wt .-% citrate. Machine dishwashing detergent according to one of the previous ones Claims, characterized in that the automatic dishwashing detergent, based on its total weight, 2 to 28 wt .-%, preferably 4 to 26 wt .-% and in particular 8 to 24 wt .-% polyphosphonic acid. Machine dishwashing detergent according to one of the previous ones Claims, characterized in that the automatic dishwashing detergent a polyphosphonic acid, full i) one or more polyunsaturated monomers from the group the carboxylic acids ii) mono- or polyunsaturated Monomers from the group of phosphonic acids iii) optional others ionic or nonionic monomers contains. Machine dishwashing detergent according to one of the previous ones Claims, characterized in that the automatic dishwashing detergent, based on its total weight, 2.0 to 20 wt .-%, preferably 2.5 to 15 wt .-% and in particular 2.5 to 10 wt .-% anionic Copolymer comprising i) one or more polyunsaturated monomers from the group of carboxylic acids ii) mono- or polyunsaturated Monomers from the group of sulfonic acids iii) optional others ionic or nonionic monomers contains. Machine dishwashing detergent according to one of the previous ones Claims, characterized in that the automatic dishwashing detergent, based on its total weight, 1 to 8 wt .-%, preferably 1.2 contains up to 6 wt .-% and in particular 1.5 to 4 wt .-% phosphonate. Machine dishwashing detergent according to one of the previous ones Claims, characterized in that the dishwashing agent, based on its total weight, nonionic surfactant in amounts of from 0.1 to 15% by weight, preferably 0.2 to 10 wt .-%, particularly preferably 0.5 to 8 wt .-% and in particular from 1.0 to 6 wt .-%. Machine dishwashing detergent according to one of the preceding claims, characterized in that the dishwashing detergent contains a nonionic surfactant A of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ² , in which - R ¹ and R ² independently of one another are branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms; Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms; - x and y independently for values between 1 and 70; and M is an alkyl radical selected 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 alkyl radical having 1 up to 18 carbon atoms; Machine dishwashing detergent according to one of the previous ones Claims, characterized in that the automatic dishwashing detergent, based on its total weight, organic amine and / or an alkanolamine, preferably ethanolamine, in amounts of from 0.1 to 15% by weight, preferably 0.2 to 10 wt .-%, particularly preferably 0.5 to 8 wt .-% and in particular from 1.0 to 6 wt .-%. Machine dishwashing detergent according to one of the previous ones Claims, characterized in that the dishwashing agent, based on its total weight, Enzyme preparations in amounts of 0.1 to 12 wt .-%, preferably from 0.2 to 10 wt .-% and in particular from 0.5 to 8 wt .-%. Machine dishwashing detergent according to one of the previous ones Claims, containing a) 10 to 40 wt .-% citrate b) 4 to 26% by weight polyphosphonic c) 0.1 to 8% by weight of amylase and / or protease enzyme preparation d) 2.0 to 20% by weight of anionic copolymer comprising i) a or polyunsaturated Monomers from the group of carboxylic acids ii) one or more times unsaturated Monomers from the group of sulfonic acids iii) optional others ionic or nonionic monomers e) 0.2 to 10 wt .-% nonionic surfactant Liquid machine dishwashing detergent according to one of the preceding claims, comprising a) 10 to 40% by weight of citrate b) 4 to 26% by weight of polyphosphonic acid c) 0.1 to 8% by weight of amylase and / or protease enzyme preparation d) 2.0 to 20% by weight of anionic copolymer, comprising i) mono- or polyunsaturated monomers from the group of the carboxylic acids ii) one or more polyunsaturated monomers from the group of sulfonic acids iii) optionally further ionic or nonionic monomers e) from 0.2 to 10% by weight of nonionic surfactant f) from 20 to 70% by weight of water Method for cleaning dishes in a dishwasher, using a machine dishwashing detergent according to one of the preceding Claims. Method according to claim 13, characterized in that that the dishwashing process at a liquor temperature below 60 ° C is performed. Use of a machine dishwashing detergent according to one of the preceding claims for improving the dough cleaning in automatic dishwashing.