EP2358853B1 - Machine 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 to improve drying in automatic dishwashing.

Dishwashing detergents are available to the consumer in a variety of forms. In addition to the traditional liquid hand dishwashing detergents, machine dishwashing detergents are particularly important with the spread of household dishwashers. These automatic dishwashing agents are typically offered to the consumer in solid form, for example as powders or as tablets, but increasingly also in liquid form.

One of the major objectives of the machine cleaners manufacturers is to improve the cleaning and rinse performance of these compositions, with more emphasis being placed recently on the cleaning and rinse performance in low temperature or reduced water consumption cleaning cycles.

To improve the rinsing performance and drying in automatic dishwashing, special rinse aids or rinse-active substances are usually used, which are dosed separately from the automatic dishwashing detergent in a first supply form.
A biodegradable, separately metered rinse aid based on specific polyalkoxylates is described for example in the European patent specification EP 1 682 643 B1 (Ecolab ).

In a second form of supply, the rinse aid or rinse-active substances are integrated into the automatic dishwashing detergent ("more than 1" dishwashing detergent).
Such a machine dishwashing detergent composition incorporating a specific surfactant for improving the rinsing properties is described in the European patent specification EP 1 524 313 B1 (Dalli ).

Developments in the field of machine rinse aid aim on the one hand at an improved formulation of the two forms of supply described above, and on the other hand at providing more effective rinse additives or additive combinations.

US7012052B1 (Procter & Gamble) discloses machine dishwashing detergents containing builders, enzymes, hydrophobically modified anionic polymers, and a mixture of nonionic surfactants. Also in DE4327327A1 (Henkel ) describes a machine dishwashing detergent, the builder, enzymes and contains a mixture of nonionic surfactants; Further, an acrylic / maleic acid copolymer is included. Mixtures of various nonionic surfactants and the use of these mixtures in detergents are disclosed in US Pat EP1764408A1 (Cognis ) DE19738866A1 (Henkel ) and DE4323252A1. (Handle ). These documents also show that the surfactant mixtures have good rinsing properties. The scale inhibition and the cleaning and rinsing performance of hydrophobically modified sulfonic acid group-containing copolymers in automatic dishwashing detergents is disclosed in US Pat WO2008 / 095563A1 (Henkel ) disclosed.

This application was based on the object to provide a machine dishwashing detergent with reduced deposit formation and improved drying and Klarspüleigenschaften, these improved drying and Klarspüleigenschaften especially in low-temperature cleaning cycles, ie in cleaning processes with Spülflottentemperaturen of 50 ° C or below should be achieved.

This object has been achieved by a machine dishwashing agent which, in addition to a specific surfactant combination, furthermore contains an anionic copolymer from the group of the polycarboxylic acids or the polysulfonic acids.

1. a) ein nichtionisches Tensid A der allgemeinen Formel
   
           R¹-CH(OH)CH₂-O(CH₂CH₂O)_xCH₂CHR(OCH₂CH₂)_yO-CH₂CH(OH)-R²,
   
   in der
   • R, R¹ und R² unabhängig voneinander für einen Alkylrest oder. Alkylenrest mit 6 bis 22 Kohlenstoffatomen;
   • x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen;
2. b) ein nichtionisches Tensid B, welches von dem nichtionischen Tensid A verschieden ist;
3. c) ein anionisches Polymer C.

A first subject of this application is a machine dishwashing detergent containing builder (s), enzyme (s) and

1. a) a nonionic surfactant A of the general formula
   
   R ^{1 is} -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 the
   • R, R ¹ and R ² independently represent an alkyl radical or. Alkylene radical having 6 to 22 carbon atoms;
   • x and y independently represent values between 1 and 40;
2. b) a nonionic surfactant B other than the nonionic surfactant A;
3. c) an anionic polymer C.

The present application relates to automatic dishwashing detergents. Automatic dishwashing detergents, according to this application, are compositions which can be used to clean soiled dishes in a dishwasher automatic dishwashing process. Thus, the automatic dishwasher detergents according to the invention differ, for example, from the machine rinse aid agents, which are always used in combination with automatic dishwashing detergents and do not develop their own cleaning action. Dishwashing compositions according to the invention contain builder (s) and enzyme (s) to ensure their cleaning action.

As a first component machine dishwashing detergents according to the invention contain one or more builders. The proportion by weight of the builders in the total weight of the machine according to the invention Dishwashing agent is preferably 15 to 80 wt .-% and in particular 20 to 70 wt .-%. The builders include in particular carbonates, phosphates, citrates, organic cobuilders and silicates.

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of from 2 to 30 wt .-%, preferably from 4 to 28 wt .-% and in particular from 8 to 24 wt .-%, each based on the weight of the automatic dishwashing detergent.
Preference is also the use of phosphate. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

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

If phosphates are used as washing or cleaning substances in automatic dishwasher detergents in the context of the present application, these contain phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in quantities from 5 to 60% by weight, preferably from 15 to 45% by weight, in particular from 20 to 40% by weight, in each case based on the weight of the automatic dishwashing detergent.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below.

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for environmental reasons, and 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, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Particularly preferred machine dishwasher detergents according to the invention contain citrate as one of their essential builders. Machine dishwashing detergents, characterized in that they contain 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight citrate, are preferred according to the invention.

The citrates, like the phosphates, are preferably used in combination with carbonates and / or bicarbonate. Preferred automatic dishwasher detergents are therefore characterized by a builder combination of phosphate and carbonate / bicarbonate or of citrate and carbonate / bicarbonate carbonate (compare Tables 1a and 1b below). Of course, however, builder combinations of phosphate, citrate and carbonate / bicarbonate can be realized.

Particularly preferred automatic dishwashing detergents are characterized in that the dishwashing detergent contains at least two builders from the group of the phosphates, carbonates and citrates, the weight fraction of these builders, based on its total weight of the automatic dishwashing agent, preferably from 5 to 80% by weight, preferably 15 to 75 wt .-% and in particular 30 to 70 wt .-% is. The combination of two or more builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.

Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which have 50 to 90% by weight of acrylic acid and 50 to 10 wt .-% maleic acid. Their 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.

The content of the automatic dishwashing agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.

Machine dishwashing detergents according to the invention may contain as builder crystalline layered silicates of the general formula NaMSi _x O _{2x +} 1yH ₂ O, wherein M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, where Particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.

In preferred machine dishwashing detergents according to the invention, the content of silicates, based on the total weight of the automatic dishwashing detergent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight. Particularly preferred automatic dishwasher detergents according to the invention are silicate-free.

In addition to the abovementioned builders, the agents according to the invention may contain alkali metal hydroxides. These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent used. Alternative automatic dishwashing detergents are free of alkali metal hydroxides.

Als zweiten Bestandteil enthalten erfindungsgemäße Geschirrspülmittel Enzym(e). Hierzu gehören insbesondere Proteasen, Amylasen, Lipasen, Hemicellulasen, Cellulasen, Perhydrolasen oder Oxidöreduktasen, sowie vorzugsweise deren Gemische. Diese Enzyme sind im Prinzip natürlichen Ursprungs; ausgehend von den natürlichen Molekülen stehen für den Einsatz in Wasch- oder Reinigungsmitteln verbesserte Varianten zur Verfügung, die entsprechend bevorzugt eingesetzt werden. Wasch- oder Reinigungsmittel enthalten Enzyme vorzugsweise in Gesamtmengen von 1 x 10^-6 bis 5 Gew.-% bezogen auf aktives Protein. Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren oder dem Biuret-Verfahren bestimmt werden.Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in the following Tables 1a and 1b:

Dishwashing agents according to the invention contain enzyme (s) as a second constituent. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or Oxidöreduktasen, 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 and improved for use in detergents and cleaners further developments of the aforementioned amylases. 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 generate in situ peracids from suitable precursors. 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 is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

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

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. 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.

Preference is given in particular to those automatic dishwashing detergents which contain, based in each case on their total weight, from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.5 to 8% by weight, of enzyme preparations ,

Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in Tables 2a and 2b below:

A first constituent of the active ingredient combination of nonionic surfactants A and B responsible for the improved drying of automatic dishwashing agents according to the invention and the anionic polymer is the nonionic surfactant A.

The proportion by weight of the nonionic surfactant A in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is between 0.05 and 10% by weight, preferably between 0.1 and 8% by weight, preferably between 0.5 and 5% by weight. % and in particular between 1 and 3 wt .-%.

• 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

Automatic dishwashing detergents according to the invention contain as nonionic surfactant A a surfactant of the general formula

R ^{1 is} -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 the

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

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] tripolyphosphate 5 to 50 15 to 40 - - citrate - * - 5 to 40 15 to 30 carbonate 2 to 45 2 to 35 2 to 45 2 to 35 Enzyme ** 0.2 to 10 0.2 to 10 0.5 to 8 0.5 to 8 Nonionic surfactant A ¹ 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10 Nonionic surfactant B ² 1 to 10 1 to 10 1 to 10 1 to 10 Anionic copolymer C ³ 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18 Misc Add 100 Add 100 Add 100 Add 100 ^{1 is} a nonionic surfactant A 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 the - R, R ¹ and R ² independently represent an alkyl or alkenyl radical having 6 to 22 carbon atoms;
- x and y are independently from each other values between 1 and 40 ^{2 are} a nonionic surfactant B, which is different from the nonionic surfactant A;
^{3 is} an anionic polymer C from the group of copolymeric polycarboxylates and copolymeric polysulfonates
** The weights are based on the weight of the enzyme preparation

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.

The automatic dishwashing compositions according to the invention contain as a further essential constituent a second nonionic surfactant B.

The proportion by weight of the nonionic surfactant B in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is between 0.1 and 30% by weight, preferably between 0.5 and 20% by weight; preferably between 1 and 10% by weight and in particular between 2 and 6% by weight.

Preferred nonionic surfactants B have the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _{x [} CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ² in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x and z are values between 0 and 40 and y for a value of at least 15 stands.
The addition of these nonionic surfactants has proved to be advantageous, in particular with regard to the rinse power and the drying. In a preferred embodiment, the automatic dishwashing detergent contains, based on its total weight, nonionic surfactant of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O ] _z CH ₂ CH (OH) R ² in amounts of from 0.1 to 15% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.5 to 8% by weight and in particular from 1, 0 to 6 wt .-%.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, according to the formula R ¹ O [CH ₂ CH ₂ O] _y, contain CH ₂ CH (OH) R ² in the R ^{1 group} for a linear or branched aliphatic hydrocarbon radical to 22 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures Hereby designated and y for a value between 15 and 120 preferably 20 to 100, in particular 20 to 80 stands. The group of these nonionic surfactants includes, for example, hydroxy _mixed ethers of the general formula C _6-22 -CH (OH) CH ₂ O- (EO) _20-120 -C _{2 -26} , for example the C _8-12 fatty alcohol (EO) ₂₂ - 2-hydroxydecyl ether and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ethers.

Automatic dishwashing detergent according to the invention, characterized in that the nonionic surfactant B is a surfactant of the general formula
R ¹ CH (OH) CH ₂ O- (CH ₂ CH ₂ O) _20-120 - R ^{2 is} used, wherein R ¹ and R ^{2 are} independently a linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms particularly preferred.

Some exemplary formulations for preferred automatic dishwashing detergents according to the invention can be found in Table 4 below: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] tripolyphosphate 5 to 50 15 to 40 - - citrate - * - 5 to 40 15 to 30 carbonate 2 to 45 2 to 35 2 to 45 2 to 35 Protease ** 0.2 to 10 0.2 to 10 0.5 to 8 0.5 to 8 Amylase ** 0.2 to 10 0.2 to 10 0.5 to 8 0.5 to 8 Nonionic surfactant A ¹ 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10 Nonionic surfactant B ² 1 to 10 1 to 10 1 to 10 1 to 10 Anionic copolymer C ³ 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18 Misc Add 100 Add 100 Add 100 Add 100 ^{1 is} a nonionic surfactant A 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 the - R, R ¹ and R ² independently represent an alkyl radical or alkylene radical having 6 to 22 carbon atoms; - x and y independently represent values between 1 and 40;
^{2 is} a nonionic surfactant B of the general formula R ¹ CH (OH) CH ₂ O- (CH ₂ CH ₂ O) _20-120 -R ² , where R ¹ and R ² independently of one another represent a linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms;
^{3 is} an anionic polymer C from the group of copolymeric polycarboxylates and copolymeric polysulfonates
** The weights are based on the weight of the enzyme preparation

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

Also preferred according to the invention are also surfactants of the general 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 having 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is a value between 1 and 40 and y is a value between 15 and 40, wherein the alkylene units [CH ₂ CH (CH ₃ ) O] and [CH ₂ CH ₂ O] randomized, ie in the form of a random random distribution.

The group of preferred end-capped poly (oxyalkylated) nonionic surfactants B also includes 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 are} independently 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 for x from 15 to 32 and y of 0.5 and 1.5 are most preferred.

By using the above-described nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals, the rinse performance and drying can be markedly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.

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. Surfactant mixtures are not mixtures of nonionic surfactants which in their entirety fall under one of the abovementioned general formulas, but rather those Mixtures containing two, three, four or more nonionic surfactants which may be described by different of the foregoing or other general formulas.

Particular preference is given to nonionic surfactants b) which have a melting point above room temperature. Nonionic surfactant (s) b) 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.

With regard to the optimization of the rinse aid and drying performance to be achieved by means of the automatic dishwashing compositions according to the invention, it has proved advantageous to use automatic dishwashing agents in which the weight ratio of nonionic surfactant A to nonionic surfactant B is between 0.05: 1 and 1: 2, preferably between 0.1: 1 and 1: 1.5 and in particular between 0.2: 1 and 1: 1.

The automatic dishwashing compositions according to the invention contain an anionic polymer C as a further essential constituent. Preferred anionic copolymers are the copolymeric polycarboxylates and the copolymeric polysulfonates.

The proportion by weight of the copolymeric anionic polymer C in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is between 0.1 and 20% by weight, preferably between 0.5 and 18% by weight, preferably between 1.0 and 15% by weight. -% and in particular between 4 and 14 wt .-%.

Automatic dishwashing detergents according to the invention, characterized in that the copolymeric anionic polymer C is selected from the group of hydrophobically modified polycarboxylates and polysulfonates, are particularly preferred because the hydrophobic modification of the anionic copolymers improves the rinsing and drying properties of these agents while at the same time causing low deposit formation can be achieved.

1. a) 0,5 bis 5 Gew.-% eines nichtionischen Tensids A der allgemeinen Formel
   
           R¹-CH(OH)CH₂-O(CH₂CH₂O)_xCH₂CHR(OCH₂CH₂)_yO-CH₂CH(OH)-R²,
   
   in der
   • 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
2. b) 1 bis 10 Gew.-% eines nichtionischen Tensids B, welches von dem nichtionischen Tensid A verschieden ist;
3. c) 1 bis 15 Gew.-% eines copolymeren anionisches Polymer C aus der Gruppe der hydrophob modifizierten Polycarboxylate und Polysulfonate

Particularly preferred automatic dishwasher detergents according to the invention contain

1. a) 0.5 to 5 wt .-% of a nonionic surfactant A of the general formula
   
   R ^{1 is} -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 the
   • R, R ¹ and R ² independently represent an alkyl group or alkenyl group having 6 to 22 carbon atoms;
   • x and y independently represent values between 1 and 40
2. b) 1 to 10% by weight of a nonionic surfactant B other than the nonionic surfactant A;
3. c) 1 to 15 wt .-% of a copolymeric anionic polymer C from the group of hydrophobically modified polycarboxylates and polysulfonates

1. a) 0,5 bis 5 Gew.-% eines nichtionischen Tensids A der allgemeinen Formel
   
           R¹-O(CH₂CH₂O)_xCH₂(OCH₂CH₂)_yO-R²,
   
   in der
   • R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen; und
   • x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen;
2. b) 1 bis 10 Gew.-% eines nichtionischen Tensids B, welches von dem nichtionischen Tensid A verschieden ist;
3. c) 1 bis 15 Gew.-% eines copolymeren anionisches Polymer C aus der Gruppe der hydrophob modifizierten Polycarboxylate und Polysulfonate

Further preferred automatic dishwasher detergents according to the invention contain

1. a) 0.5 to 5 wt .-% of a nonionic surfactant A of the general formula
   
   R ^{1 is} -O (CH ₂ CH ₂ O) _x CH ₂ (OCH ₂ CH ₂ ) _y OR ² ,
   
   in the
   • R ¹ and R ² independently represent an alkyl or alkenyl radical having 4 to 22 carbon atoms; and
   • x and y independently represent values between 1 and 40;
2. b) 1 to 10% by weight of a nonionic surfactant B other than the nonionic surfactant A;
3. c) 1 to 15 wt .-% of a copolymeric anionic polymer C from the group of hydrophobically modified polycarboxylates and polysulfonates

The copolymers C may have two, three, four or more different monomer units.

Preferred copolymeric polysulfonates C contain, in addition to sulfonic acid-containing (s) monomer (s) at least one monomer from the group of unsaturated carboxylic acids.

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

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

In the sulfonic acid-containing monomers are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

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, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH) ₃ 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 ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts. In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group ii) and from 10 to 50% by weight of monomer from group i), in each case based 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 agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

In a further preferred embodiment, the copolymers C further comprise at least one nonionic, preferably hydrophobic monomer in addition to carboxyl-containing monomer and sulfonic acid-containing monomer. The use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.

1. i) Carbonsäuregruppen-haltige Monomer(e)
2. ii) Sulfonsäuregruppen-haltige Monomer(e)
3. iii) nichtionische Monomer(e).

enthält, werden erfindungsgemäß bevorzugt.Automatic dishwashing detergent, characterized in that the automatic dishwashing detergent, as anionic copolymer C, comprises a copolymer

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

contains are preferred according to the invention.

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

Particularly 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-dimethylhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, α-olefins having 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-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N - (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate ter, Methacrylsäureoctylester, N - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N - (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N - (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and N- (behenyl) -acrylamide or mixtures thereof.

Some exemplary formulations for preferred automatic dishwashing agents according to the invention can be found in the following Table 5: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] tripolyphosphate 5 to 50 15 to 40 - - citrate - * - 5 to 40 15 to 30 carbonate 2 to 45 2 to 35 2 to 45 2 to 35 Nonionic surfactant A ¹ 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10 Nonionic surfactant B ² 1 to 10 1 to 10 1 to 10 1 to 10 Anionic copolymer C ³ 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18 Misc Add 100 Add 100 Add 100 Add 100 ^{1a is} a nonionic surfactant A 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 of 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
^2, a nonionic surfactant B other than the nonionic surfactant A;
^3, an anionic polymer C comprising
i) carboxylic acid group-containing monomer (s)
ii) sulfonic acid group-containing monomer (s)
iii) nonionic monomer (s).

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 bleaches, bleach activators and bleach catalysts, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.

Machine dishwashing detergents according to the invention may contain a bleaching agent as further constituent, with oxygen bleaches being preferred. Among the compounds which serve as bleaches and deliver H ₂ O ₂ in water are sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.

Preferred automatic dishwashing agents according to the invention are characterized in that they contain an oxygen bleaching agent, preferably sodium percarbonate, more preferably a coated sodium percarbonate. The proportion by weight of the bleaching agent, based on the total weight of the washing or cleaning agent, in preferred embodiments is between 2 and 30% by weight, preferably between 4 and 20% by weight and in particular between 6 and 15% by weight.

As bleach activators, the automatic dishwasher detergents according to the invention may contain bleach activators. These compounds give under perhydrolysis aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated carbon atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.

Automatic dishwashing detergent, characterized in that it contains as bleach activator a bleach activator from the group of the acetylated amines, which is preferably tetraacetylenediamine (TAED), are preferred according to the invention. These bleach activators, in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 10% by weight, especially 0.5 to 8% by weight and more preferably 1.0 to 6 Wt .-%, used.

In addition or as an alternative to the conventional bleach activators, the automatic dishwasher detergents according to the invention preferably contain at least one bleach catalyst. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used; having the nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are, for example, [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₂ (μ-OAc) ₁ (TACN ) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV ₄ (μ-O) ₆ (TACN) ₄ ] (ClO ₄ ) ₄ , [Mn ^III ₂ (μ-O) ₁ (μ-OAC) ₂ (Me-TACN ) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (μ-O) ₃ ( Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (μ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

Machine dishwashing detergent, characterized in that it further comprises a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me ₄ -TACN), are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.

The abovementioned bleach-enhancing transition metal complexes, in particular with the central atoms Mn and Co, are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight to 1% by weight and more preferably of 0, 01 wt .-% to 0.30 wt .-%, each based on the total weight of the bleach catalyst-containing agents used. In special cases, however, more bleach catalyst can be used.

Some exemplary formulations for preferred automatic dishwashing detergents according to the invention can be found in Table 6 below: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] tripolyphosphate 5 to 50 15 to 40 - - citrate - * - 5 to 40 15 to 30 carbonate 2 to 45 2 to 35 2 to 45 2 to 35 Nonionic surfactant A ¹ 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10 Nonionic surfactant B ² 1 to 10 1 to 10 1 to 10 1 to 10 Anionic copolymer C 3 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18 sodium 2 to 30 2 to 30 4 to 20 4 to 20 bleach catalyst 0 to 2 0.0025 to 1 0 to 2 0.0025 to 1 Misc Add 100 Add 100 Add 100 Add 100 ^{1a is} a nonionic surfactant A 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 which - R, R ¹ and R ² independently represent an alkyl or alkenyl radical having 6 to 22 carbon atoms; - x and y independently represent values between 1 and 40
^2, a nonionic surfactant B other than the nonionic surfactant A;
³ an anionic polymer C comprising i) monomer (s) containing carboxylic acid groups ii) monomer (s) containing sulfonic acid groups iii) nonionic monomer (s).

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

In particular, powders, granules, extrudates or compactates, in particular tablets, are suitable as firm supply sources. 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 disintegrates. 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 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m 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 in that 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 by an improved drying performance compared to conventional automatic dishwasher detergents. Another object of the present application is therefore the use of a machine dishwashing detergent according to the invention for improving the drying in automatic dishwashing.

Examples

To demonstrate the improved drying effect of dishwasher detergents according to the invention, the drying performance of various dishwashing detergents of different composition was determined

To this end, a machine load of crockery, comprising porcelain, glass, plastic and stainless steel, after adding a defined amount of dirt in a dishwasher (Bosch SGS 57M82; 50 ° normal without intensive drying) with 20 g of the automatic dishwashing detergent listed in the table below with a water hardness of 21 Rinsed ° dH. The dosage of the dishwashing agent was carried out in the main rinse of the dishwashing process. V1 [% by weight] V2 [% by weight] V3 [% by weight] E1 [% by weight] E2 [% by weight] potassium 37 37 37 37 37 Nonionic surfactant A ¹ - 6.1 2.0 2.0 2.0 Nonionic surfactant B ² 6.1 - 4.0 4.0 4.0 Anionic copolymer ³ 8.0 8.0 - 8.0 - Anionic copolymer ⁴ - - - - 8.0 sodium 14.0 14.0 14.0 14.0 14.0 TAED 2.5 2.5 2.5 2.5 2.5 sodium 20 20 20 20 20 protease 2.6 2.6 2.6 2.6 2.6 amylase 0.7 0.7 0.7 0.7 0.7 phosphonate 1.4 1.4 1.4 1.4 1.4 Water, Misc Add 100 Add 100 Add 100 Add 100 Add 100 ¹ 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 where - R, R ¹ and R ² independently represent an alkyl group or alkenyl group having 6 to 22 carbon atoms; - x and y independently represent values between 1 and 40
² hydroxy _mixed ethers of the general formula C _6-22 -CH (OH) CH ₂ O- (EO) _20-20 -C _2-26
³ anionic Coplymer from the group of copolymeric polysulfonates
⁴ anionic copolymer from the group of copolymeric hydrophobically modified polysulfonates

The drying index was determined 30 minutes after the end of the dishwashing process with the door of the dishwasher closed during these 30 minutes.
The maximum value for best drying is 0, for worst drying 6.0.
The deposit formation was determined together with the drying index.

The results of the experiment are given in the table below and are obtained as averages from three experiments: V1 V2 V3 E1 E2 porcelain 4.5 4.5 1.5 3.0 1.5 Glass 2.0 5.4 1.5 2.0 1.5 plastic 6.0 2.9 0.8 4.5 0.5 stainless steel 1.5 3.9 0.7 1.0 1.5 fouling Good Good insufficient Good Good

These results indicate that the drying performance of a dishwasher detergent can be significantly improved by the use of a surfactant combination according to the invention. A further improvement based on this surfactant system can be achieved by the simultaneous addition of a hydrophobically modified polysulfonic acid.

Claims (11)

1. An automatic dishwasher detergent containing builder(s), enzyme(s) and

   a) a non-ionic surfactant A of general formula
   
           R¹-CH(OH)CH₂-O(CH₂CH₂O)_xCH₂CHR(OCH₂CH₂)_yO-CH₂CH(OH)-R²,
   
   in which

   - R, R¹ and R² represent, independently of one another, an alkyl functional group or alkenyl functional group having from 6 to 22 carbon atoms;

   - x and y represent, independently of one another, values of between 1 and 40;

   b) a non-ionic surfactant B that is different from the non-ionic surfactant A;

   c) an anionic copolymer C.
2. The automatic dishwasher detergent according to claim 1, characterized in that the percentage by weight of the non-ionic surfactant A is between 0.05 and 10 wt.%, preferably between 0.1 and 8 wt.%, preferably between 0.5 and 5 wt.% and in particular between 1 and 3 wt.%.
3. The automatic dishwasher detergent according to either of the preceding claims, characterized in that a surfactant of general formula R¹CH(OH)CH₂O-(CH₂CH₂O)_20-120- R² is used as the non-ionic surfactant B, R¹ and R² representing, independently of one another, a linear or branched aliphatic hydrocarbon functional group having from 2 to 20 carbon atoms.
4. The automatic dishwasher detergent according to one of the preceding claims, characterized in that the percentage by weight of the non-ionic surfactant B is between 0.1 and 30 wt.%, preferably between 0.5 and 20 wt.%, preferably between 1 and 10 wt.% and in particular between 2 and 6 wt.%.
5. The automatic dishwasher detergent according to one of the preceding claims, characterized in that the copolymeric anionic polymer C is selected from the group of the hydrophobically modified polycarboxylates and polysulfonates.
6. The automatic dishwasher detergent according to one of the preceding claims, characterized in that the copolymeric anionic polymer C is selected from the group of the copolymers, comprising

   i) carbonic acid group-containing monomer(s)

   ii) sulfonic acid group-containing monomer(s)

   iii) non-ionic monomer(s).
7. The automatic dishwasher detergent according to one of the preceding claims, characterized in that the percentage by weight of the copolymeric anionic polymer C is between 0.1 and 20 wt.%, preferably between 0.5 and 18 wt.%, preferably between 1.0 and 15 wt.% and in particular between 4 and 14 wt.%.
8. The automatic dishwasher detergent according to one of the preceding claims, containing

   a) from 0.5 to 5 wt.% of a non-ionic surfactant A of general formula
   
           R¹-CH(OH)CH₂-O(CH₂CH₂O)_xCH₂CHR(OCH₂CH₂)_yO-CH₂CH(OH)-R²,
   
   in which

   - R, R¹ and R² represent, independently of one another, an alkyl functional group or alkenyl functional group having from 6 to 22 carbon atoms;

   - x and y represent, independently of one another, values of between 1 and 40;

   b) from 1 to 10 wt.% of a non-ionic surfactant B that is different from the non-ionic surfactant A;

   c) from 1 to 15 wt.% of a copolymeric anionic polymer C from the group of the hydrophobically modified polycarboxylates and polysulfonates.
9. A method for cleaning dishes in a dishwasher using an automatic dishwasher detergent according to one of the preceding claims.
10. The method according to claim 9, characterized in that the dishwashing process is carried out at a bath temperature of less than 60°C, preferably less than 50°C.
11. The use of an automatic dishwasher detergent according to one of the preceding claims for improving the drying process during automatic dishwashing.