EP2129761B1 - Cleaning agents - Google Patents

Description

The present patent application relates to detergents for the automatic cleaning of dishes.

Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So the dishes after machine cleaning should not only be completely free from food debris but also, for example, have no whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets.

After machine dishwashing, the dishes are often still wet. If the dishes are not immediately removed from the machine and dried with a kitchen towel, but left in the machine, ugly limescale on the dishes - especially plastic dishes - the result, which can then be removed only by polishing the dishes with a cloth , There is no satisfactory solution to this problem so far. Although automatic dishwashing detergents usually contain so-called rinse aid surfactants, which are intended to prevent the formation of unsightly limescale and limescale deposits. These rinse aid surfactants usually work differently on different hydrophilic / hydrophobic surfaces; However, plastic surfaces are usually critical and often still come with lime stains or -belagen from the machine.

The patent application DE 100 50 622 A1 relates to automatic dishwashing detergents containing from 1 to 94.9% by weight of builders, from 5 to 30% by weight of nonionic surfactants and from 0.1 to 70% by weight of copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionic monomers contain

Surprisingly, it has now been found that certain polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compounds when used in a dishwasher detergent both cause excellent rinse performance and lead to a significantly better drying of the dishes.

• wobei jedes A unabhänging ausgewählt wird aus S, O und NR¹,
• Y ausgewählt wird aus zwei- bis mehrwertigen, insbesondere vierwertigen, geradkettigen, cyclischen oder verzweigten, gesättigten, ungesättigten oder aromatischen, substituierten oder unsubstituierten Kohlenwasserstoffresten mit bis zu 1000 Kohlenstoffatomen (wobei die Kohlenstoffatome einer gegebenenfalls enthaltenen Polyorganosiloxaneinheit nicht mitgezählt werden), die eine oder mehrere Gruppen, ausgewählt aus -O-, -(CO)-, -NH-, -NR²-, -(N⁺R²R³)- und einer Polyorganosiloxaneinheit mit 2 bis 1000 Siliciumatomen enthalten können,
• R¹ Wasserstoff oder ein geradkettiger, cyclischer oder verzweigter, gesättigter, ungesättigter oder aromatischer Kohlenwasserstoffrest mit bis zu 40 Kohlenstoffatomen ist, der eine oder mehrere Gruppen, ausgewählt aus -O-, -(CO)-, -NH- und -NR²- enthalten kann,
• R² ein geradkettiger, cyclischer oder verzweigter, gesättigter, ungesättigter oder aromatischer Kohlenwasserstoffrest mit bis zu 40 Kohlenstoffatomen ist, der eine oder mehrere Gruppen, ausgewählt aus -O-, -(CO)- und -NH- enthalten kann,
• R³ ein geradkettiger, cyclischer oder verzweigter, gesättigter, ungesättigter oder aromatischer Kohlenwasserstoffrest mit bis zu 100 Kohlenstoffatomen ist, der eine oder mehrere Gruppen, ausgewählt aus -O-, -(CO)- und -NH- enthalten kann, oder ein zweiwertiger Rest ist, der cyclische Strukturen innerhalb des Restes Y ausbildet,
• oder einer oder beide zu Y nachbarständige Reste A mit dem zwischen ihnen stehenden Rest Y einen stickstoffhaltigen heterocyclischen Rest bilden können,
• und in der gesamten Verbindung nicht alle in Formel (I) angegebenen Reste A bzw. Y bzw. R¹ bzw. R² bzw. R³ gleich sein müssen mit der Maßgabe, dass in der gesamten Verbindung mindestens einer der Reste Y eine Polyorganosiloxaneinheit mit 2 bis 1000 Siliciumatomen umfasst, und mindestens eine der Y-Einheiten gemäß Strukturelement der Formel (I) eine Gruppierung -(N⁺R²R³)- aufweist, oder deren Säureadditionsverbindung und/oder Salz.

The present invention therefore relates, in a first embodiment, to an automatic dishwashing detergent which comprises a polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound containing at least one structural element of the formula (I):

-YA- (C = O) -A- (I),

• where each A independently is selected from S, O and NR ¹ ,
• Y is selected from bivalent to polyvalent, especially tetravalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic, substituted or unsubstituted hydrocarbon radicals having up to 1000 carbon atoms (excluding the carbon atoms of any polyorganosiloxane unit optionally included) containing one or more May contain groups selected from -O-, - (CO) -, -NH-, -NR ² -, - (N ⁺ R ² R ³ ) - and a polyorganosiloxane unit having 2 to 1000 silicon atoms,
• R ^{1 is} hydrogen or a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms and having one or more groups selected from -O-, - (CO) -, -NH- and -NR ² - can contain
• R ^{2 is} a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms and which may contain one or more groups selected from -O-, - (CO) - and -NH-,
• R ^{3 is} a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms, which may contain one or more groups selected from -O-, - (CO) - and -NH-, or a bivalent radical is that forms cyclic structures within the remainder Y,
• or one or both of the radicals A which may be adjacent to Y may form, with the radical Y between them, a nitrogen-containing heterocyclic radical,
• and in the entire compound not all radicals A or Y or R ¹ or R ² or R ³ given in formula (I) must be identical, with the proviso that in the entire compound at least one of the radicals Y is a polyorganosiloxane unit 2 to 1000 silicon atoms, and at least one of the Y units according to the structural element of the formula (I) has a grouping - (N ⁺ R ² R ³ ) -, or their acid addition compound and / or salt.

Compounds of the general formula (I) can be obtained by reacting diisocyanates, bis-chloroformic acid esters or amides or phosgene with thiols, alcohols or amines containing the structural element Y. In order to obtain polymeric structures, these starting compounds having the structural element Y have at least 2 of the said functional groups. Suitable end groups are compounds which otherwise correspond to the structural element Y but are only monofunctional.

• in denen A und Y die oben genannten Bedeutungen haben und
• Z ausgewählt wird aus den zweiwertigen, geradkettigen, cyclischen oder verzweigten, gesättigten oder ungesättigten, gegebenenfalls substituierten Kohlenwasserstoffresten mit 1 bis 12 Kohlenstoffatomen. Diese Strukturelemente können durch Ringöffnung von cyclischen Carbonaten (Kohlensäureestern von vicinalen Diolen) mit das Strukturelement Y enthaltenden Thiolen, Alkoholen oder Aminen erhalten werden.

Among the preferred polycarbonate and / or polyurethane-polyorganosiloxane compounds are those which contain at least one structural element of the formula (II) or (III):

-AYA- (CO) -OZ- (CHOH) -ZO- (CO) - (II),

-AYA- (CO) -O- (CHCH ₂ OH) -ZO- (CO) - (III),

• in which A and Y have the meanings mentioned above and
• Z is selected from the divalent, straight-chain, cyclic or branched, saturated or unsaturated, optionally substituted hydrocarbon radicals having 1 to 12 carbon atoms. These structural elements can be obtained by ring opening of cyclic carbonates (carbonic acid esters of vicinal diols) with the thiols, alcohols or amines containing the structural element Y.

The polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound preferably has the structural element of the formula (I) several times in succession, the multiply occurring in each case corresponding radicals A or Y or Z or R ¹ or R ² or R ^{3 may be the} same or different.

The term acid addition compound means a salt-like compound which can be obtained by protonation of basic groups in the molecule, such as in particular the optionally present amino groups, for example by reaction with inorganic or organic acids. The acid addition compounds may be used as such or may optionally form under conditions of use of the compounds defined above.

For the groupings - (N ⁺ R ² R ³ ) - are usual Gegenanionionen, such as halide, hydroxide, sulfate, carbonate, in the charge neutrality ensuring amount present.

When in the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compounds present polyorganosiloxane structural element is preferably the structure - (SiR ⁴ ₂ O) _p - (SiR ⁴ ₂₎ -, wherein R ⁴ is a straight chain, cyclical or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 20 carbon atoms, and p = 1 to 999. The polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compounds preferably contain on average at least two, in particular at least three, of said polyorganosiloxane structural elements. R ⁴ is preferably a straight-chain or cyclic or branched, saturated or unsaturated or aromatic C ₁ - to C ₂₀ -, in particular C ₁ -C ₉ hydrocarbon radical, particularly preferably methyl or phenyl, and p is preferably 1 to 199, particularly preferably 1 to 99. In a preferred embodiment, all radicals R ^{4 are the} same.

Preferred polycarbonate, polyurethane and / or polyurea polyorganosiloxane compounds used according to the invention are linear, ie all Y units in the structural element of the formula (I) are in each case divalent radicals. However, according to the invention, branched compounds are also included in which at least one of the radicals Y is trivalent or polyvalent is tetravalent, so that branched structures with linear repeating structures of structural elements of formula (I) form.

In the groupings -NR ² - and - (N ⁺ R ² R ³ ) - R ² and R ^{3 are} preferably methyl groups.

A further embodiment relates to the multiple regular occurrence of -O-groupings in at least one of the units Y, R ¹ , R ² and / or R ³ according to the structural element of the formula (I), preferably in the form of oligoethoxy and / or oligopropoxy groups their degrees of oligomerization are preferably in the range of 2 to 60.

In a further preferred embodiment, at least one of the units Y, R ¹ , R ² and / or R ³ according to the structural element of the formula (I) contains oligoethylenimine groups whose degrees of oligomerization are in particular in the range from 10 to 15 000.

Reactive cyclic carbonates and ureas, processes for their preparation and their reaction with polymeric substrates are described in the international patent application WO 2005/058863 described.

Compositions according to the invention preferably contain from 0.01% by weight to 5% by weight, in particular from 0.5% by weight to 3% by weight, of such active ingredient described here (the polycarbonate, polyurethane and / or polyurea polyorganosiloxane -Connection).

Compositions according to the invention can moreover contain all ingredients conventionally contained in such compositions, in particular builder (s), bleach and surfactant (s), provided that they do not unduly interact negatively with the active substance essential to the invention during storage and / or application of the composition.

• R⁶ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• R⁷ für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht; A, A', A" und A'" unabhängig voneinander für einen Rest aus der Gruppe -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, -CH₂-CH(CH₂-CH₃) stehen,
• w, x, y und z unabhängig voneinander für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.

Machine dishwashing agents according to the invention preferably contain nonionic surfactant, including in particular nonionic surfactants of the general formula

R ^{6 is} -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ⁷ ,

in the

• R ^{6 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{7 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ),
• w, x, y and z independently represent values between 0.5 and 120, where x, y and / or z can also be 0.

Preferred automatic dishwasher detergents according to the invention have a weight fraction of nonionic surfactant of from 1% by weight to 10% by weight, preferably from 2% by weight to 8% by weight and in particular from 2% by weight to 6% by weight.

• R⁶ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• R⁷ für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht; A, und A' unabhängig voneinander für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) stehen, und
• w und x unabhängig voneinander für Werte zwischen 0,5 und 120 stehen.

Nonionic surfactants of the general formula R ⁶ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x -R ^{7 have} proven to be particularly advantageous with respect to the cleaning and rinsing performance, in which

• R ^{6 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{7 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, and A 'independently represent a radical from the group CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), and
• w and x independently represent values between 0.5 and 120.

• R⁶ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• R⁷ für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A für einen Rest CH₂CH₂ und A' für einen Rest -CH₂CH₂-CH₂ oder -CH₂-CH(CH₃) steht, und
• w für Werte zwischen 2 und 40 steht, während x für Werte zwischen 0,5 und 2 steht.

Automatic dishwashing agents in which the nonionic surfactant has the general formula R ⁶ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x -R ⁷ , in which

• R ^{6 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{7 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A is a radical CH ₂ CH ₂ and A 'is a radical -CH ₂ CH ₂ -CH ₂ or -CH ₂ -CH (CH ₃ ), and
• w stands for values between 2 and 40, while x stands for values between 0.5 and 2.

• R⁶ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• R⁷ für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A für einen Rest aus der Gruppe CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃) steht, und
• w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht.

In a further preferred embodiment, the nonionic surfactant has the general formula R ⁶ -CH (OH) CH ₂ O- (AO) _w -R ⁷ in which

• R ^{6 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{7 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A is a radical from the group CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), and
• w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40.

The stated C chain lengths and degrees of alkoxylation or degrees of ethoxylation of the stated nonionic surfactants represent statistical averages which may be an integer or a fractional number for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, resulting in both the C chain lengths as also give average values for the degrees of ethoxylation or degrees of alkoxylation and, consequently, fractional numbers.

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

As a further essential constituent, automatic dishwasher detergents preferred according to the invention contain one or more builders. The builders include in particular phosphates, silicates, carbonates and organic cobuilders.

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

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. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, 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.

One embodiment of preferred automatic dishwashing detergents according to the invention contains citrate as one of its essential builders. Automatic dishwashing agents according to the invention which contain 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 45% by weight, of citrate are preferred according to the invention.

With preference, automatic dishwashing agents according to the invention contain as builder crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is 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 module of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably delayed release and have secondary washing properties.

Machine dishwashing detergents preferred in the context of the present invention comprise from 2 to 15% by weight, preferably from 3 to 12% by weight and in particular from 4 to 8% by weight, of silicate (s).

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

If this is unobjectionable for ecological reasons, the known alkali metal phosphates, in particular trisodium polyphosphate, can also be used as builders. Alkaliphosphat is the summary term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to high 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. Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 ° C) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and pass on Madrell's salt. NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33 gcm ^-3 , has a melting point of 253 ° C (decomposition to form (KPO ₃ ) _x , potassium polyphosphate) and is easily soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 mol (density 2.066 gcm ^-3 , water loss at 95 ° C), 7 mol (density 1.68 gcm ^-3 , melting point 48 ° C with loss of 5 H ₂ O) and 12 moles of water (density 1.52 gcm ^-3 , melting point 35 ° C with loss of 5 H ₂ O), becomes anhydrous at 100 ° C and goes on stronger heating in the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) has a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° C and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry. Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 ° C, also indicated 880 ° C) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° C. under water loss). For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° C or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° C is 10.4. Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Madrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water at room temperature dissolve about 17 g, at 60 ° C about 20 g, at 100 ° C about 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° C by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two applicable; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used.

An inventive composition contains in a preferred embodiment, up to 60 wt .-%, in particular 35 wt .-% to 50 wt .-% phosphate. In further preferred embodiments, it contains from 5% to 60%, preferably from 10% to 50% and more preferably from 15% to 45% by weight citrate and is phosphate free or contains 15% Wt .-% to 25 wt .-% phosphate.

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 contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. 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 (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. 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.

Preferred automatic dishwashing agents according to the invention also contain one or more bleaching agents. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or Peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.

Machine dishwashing detergents which contain from 1 to 20% by weight, preferably from 2 to 15% by weight and in particular from 4 to 12% by weight, of sodium percarbonate are preferred according to the invention.

If desired, chlorine or bromine-releasing substances can also be used as the bleaching agent. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

In order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C. and below, the automatic dishwasher detergents according to the invention may additionally contain bleach activators. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.

Bleach activators, in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight, in each case based on the total weight of the bleach activator-containing agents used.

In addition to or instead of such conventional bleach activators, so-called bleach catalysts can also be used. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salene complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can be used as bleach catalysts.

It is particularly preferred to use complexes of manganese in the oxidation state II, III 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 which have 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 ).

Automatic dishwashing detergent containing 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 aforementioned 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 agents used. In special cases, however, more bleach catalyst can be used.

Preferred automatic dishwashing agents according to the invention additionally comprise a complexing agent, preferably a phosphonic acid or a phosphonate and / or an aminocarboxylic acid, among these preferably methylglycinediacetic acid (MGDA) and / or nitrilotriacetic acid (NTA), provided their use is not objectionable for ecological reasons.

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

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

A preferred automatic dishwashing detergent contains one or more phosphonates from the group

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

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

If desired, automatic dishwashing agents according to the invention may also contain two or more different phosphonates and / or aminicarboxylic acids. Particular preference is given to those automatic dishwashing compositions which contain as phosphonates both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta (methylenephosphonic acid) (DTPMP), the weight ratio of HEDP to DTPMP being between 20: 1 and 1:20, preferably between 15: 1 and 1:15 and in particular between 10: 1 and 1:10.

The proportion by weight of these complexing agents, in particular the sum of the proportions by weight of 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and methylglycinediacetic acid (MGDA) is preferably 0.5 to 14% by weight, preferably 1 to 12% by weight and in particular 2 to 8 wt .-%. In In a particularly preferred embodiment, an agent according to the invention contains up to 5% by weight, in particular from 0.5% by weight to 2% by weight, of phosphonate.

In addition to these ingredients, preferred automatic dishwasher detergents contain further ingredients, preferably active ingredients from the group of polymers, enzymes, corrosion inhibitors and fragrances and / or dyes.

The group of washing- or cleaning-active polymers includes, for example, the polymers and rinse-aid polymers which act as softeners and, if desired, can be used in addition to the active ingredient used according to the invention. In general, cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.

1. i) Monomere aus der Gruppe der ein- oder mehrfach ungesättigten Carbonsäuren der allgemeinen Formel
   
           R⁸(R⁹)C=C(R¹⁰)COOH,
   
   in der R⁸ bis R¹⁰ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist.
2. ii) Monomere der allgemeinen Formel
   
           R¹¹(R¹²)C=C(R¹³)-X-R¹⁴,
   
   in der R¹¹ bis R¹³ unabhängig voneinander für -H, -CH₃ oder -C₂H₅ steht, X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -CH₂-, -C(O)O- und -C(O)-NH-, und R¹⁴ für einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 22 Kohlenstoffatomen oder für einen ungesättigten, vorzugsweise aromatischen Rest mit 6 bis 22 Kohlenstoffatomen steht
3. iii) Sulfonsäuregruppen-haltigen Monomere der allgemeinen Formel
   
           R¹⁵(R¹⁶)C=C(R¹⁷)-X'-SO₃H,
   
   in der R¹⁵ bis R¹⁷ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste oder für - COOH oder -COOR¹⁸ steht, wobei R¹⁸ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X' für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-.
4. iv) weiteren ionischen und/oder nichtionogenen Monomere.

The optionally present additional rinse aid polymer is preferably a copolymer comprising monomers of at least two of the following groups

1. i) monomers from the group of mono- or polyunsaturated carboxylic acids of the general formula
   
   R ⁸ (R ⁹ ) C = C (R ¹⁰ ) COOH,
   
   in the R ⁸ to R ^{10 are} independently of one another -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 as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
2. ii) monomers of the general formula
   
   R ¹¹ (R ¹² ) C = C (R ¹³ ) -XR ¹⁴ ,
   
   in which R ¹¹ to R ¹³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is an optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and - C (O) -NH-, and R ^{14 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms
3. iii) sulfonic acid group-containing monomers of the general formula
   
   R ¹⁵ (R ¹⁶ ) C = C (R ¹⁷ ) -X'-SO ₃ H,
   
   in R ¹⁵ to R ¹⁷ 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 Or -COOH or -COOR ¹⁸ , where R ^{18 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X 'is an optional existing 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 ) -.
4. iv) further ionic and / or nonionic monomers.

In the polymers, the carboxylic acid and / or sulfonic acid groups may be wholly or partially in neutralized form, i. The acidic acid hydrogen atom may be exchanged in some or all of the acid groups for metal ions, preferably alkali metal ions and especially sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

"Cationic polymers" in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

"Amphoteric polymers" in the sense of the present invention have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids. Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth ) -acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Preferred zwitterionic polymers are from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.

In the context of the present application, particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula

H ₂ C = (CR ¹⁹ ) - (CH ₂ ) _x - (N ⁺ R ²⁰ R ²¹ ) - (CH ₂ ) _y - (CR ²² ) = CH ₂ G ^-

in which R ¹⁹ and R ²² independently of one another are H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ²⁰ and R ²¹ independently represent an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl radical is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. G ^- represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumenesulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹⁹ and R ²² in the above formula are selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH , -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H. Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹⁹ and R ^{22 are} H, R ²⁰ and R ²¹ are methyl and x and y are each 1.

Detergents contain the abovementioned cationic and / or amphoteric polymers, preferably in amounts of up to 10% by weight, in particular between 0.01 and 10% by weight, in each case based on the total weight of the composition. For the purposes of the present application, preference is given to detergents in which the weight fraction of the cationic and / or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing agent is.

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

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

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

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to 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, for example, the cutinases can be used, which have been originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.

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.

The enzymes can be used in any form known in the art. These 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 stabilizers.

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.

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.

Preferred are one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, in amounts of from 0.1 to 5 wt .-%, preferably from 0.2 to 5 wt .-% and in particular of 0.4 to 5 wt .-%, each based on the total enzyme-containing agent used.

1. a) 35 bis 50 Gew.-% Phosphat oder 15 bis 45 Gew.-% Citrat
2. b) 2 bis 8 Gew.-% nichtionische(s) Tensid(e)
3. c) 4 bis 16 Gew.-% Polymer(e)
4. d) 2 bis 15 Gew.-% Natriumpercarbonat
5. e) 1 bis 6 Gew.-% Enzym

umfassen.In summary, dishwashing detergents according to the invention are preferred which, in addition to the active ingredient according to the invention

1. a) 35 to 50% by weight of phosphate or 15 to 45% by weight of citrate
2. b) 2 to 8% by weight of nonionic surfactant (s)
3. c) 4 to 16% by weight of polymer (s)
4. d) 2 to 15 wt .-% sodium percarbonate
5. e) 1 to 6 wt .-% enzyme

include.

Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes. The spectrum of the invention preferred zinc salts, preferably organic acids, particularly preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 have mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C. water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

With particular preference is used as the glass corrosion inhibitor at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

In the context of the present invention, the content of zinc salt in detergents or cleaners is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight. , or the content of zinc in oxidized form (calculated as Zn ²⁺ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 0, 5 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.

Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. According to the invention, preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, these substances being particularly preferably used in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 Wt .-%, particularly preferably 0.01 to 0.04 wt .-% are used.

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.

Preference is given to using disintegration aids in amounts of from 0.5 to 10% by weight, preferably from 1 to 7% by weight and in particular from 1 to 5% by weight, based in each case on the total weight of the disintegration assistant-containing agent.

Disintegrating agents based on cellulose are used as preferred disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 1 to 7% by weight and in particular from 1 to 5% 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 .mu.m and 1600 .mu.m and in particular at least 90 wt .-% between 400 .mu.m and 1200 .mu.m.

Preferred disintegration aids, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are present in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 1 to 7% by weight and in particular from 1 to 5 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. The gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water. However, preferred effervescent systems consist of at least two components which react with one another to form gas, for example of 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. As Acidifizierungsmittel which release carbon dioxide from the alkali metal salts in aqueous solution, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil. The fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic dishes do not stain them.

The automatic dishwashing compositions according to the invention can be formulated in solid or liquid form but can also be present, for example, as a combination of solid and liquid forms.

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

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

The individual phases of multiphase agents may have the same or different states of matter. Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase are preferred.

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 6 g and 30 g, preferably between 14 g and 26 g and in particular between 15 g 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 ml and 35 ml, preferably between 12 ml 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.

The present application further relates to a method for cleaning dishes in a dishwasher using automatic dishwashing agents according to the invention, wherein the automatic dishwashing agents are preferably metered into the interior of a dishwasher during the passage of a dishwashing program, before the main wash cycle or during the main wash cycle. The dosing or the entry of the agent according to the invention in the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the dosing of the dishwasher in the interior of the dishwasher. In the course of the cleaning process preferably no additional rinse aid and no additional water softening is metered into the interior of the dishwasher.

As described at the outset, compositions according to the invention are distinguished from conventional automatic dishwasher detergents by an improved rinsing action and an improved drying action. The use of a dishwasher detergent according to the invention as a rinse aid in automatic dishwashing and the use of a dishwasher detergent according to the invention as a drying accelerator in automatic dishwashing are therefore further objects of the present application.

Examples

Stained dishes were rinsed in a dishwasher with 21 g of a commercially available phosphate-containing machine dishwashing detergent V1 or 21 g of the phosphate-free machine dishwashing detergent V2 or the same amount respectively of the invention compound E1 to E4 at a water hardness of 21 ° dH.

The composition (in each case in% by weight) of the dishwashing agents used can be taken from the following table: composition V1 E1 E2 V2 E3 E4 phosphate 33 33 33 - - - citrate - - - 23 23 23 phosphonate 2.0 2.0 2.0 2.0 2.0 2.0 copolymer 12.0 12.0 12.0 12.0 12.0 12.0 soda 28.0 28.0 28.0 28.0 28.0 28.0 sodium 10.0 10.0 10.0 10.0 10.0 10.0 TAED 2.4 2.4 2.4 2.4 2.4 2.4 Protease / amylase granules 4.0 4.0 4.0 4.0 4.0 4.0 Nonionic surfactant 5.0 5.0 5.0 5.0 5.0 5.0 Active substance I - 2.0 - - 2.0 - Active ingredient II - - 2.0 - - 2.0 other Add 100 Add 100 Add 100 Add 100 Add 100 Add 100

• Bewertungsskala Klarspülen: 10 = keine Tropfenbildung bis 0 = starke Tropfenbildung.
• Bewertungsskala Trocknung: 0 = keine Tropfen bis 6 = mehr als 5 Tropfen

The overall appearance of the dishes (made of plastic, glass, porcelain and stainless steel) was assessed on the basis of the following rating scales:

• Rating scale rinsing: 10 = no dripping up to 0 = heavy dripping.
• Rating Scale Drying: 0 = no drops to 6 = more than 5 drops

It has been found that the formulations E1 and E2 according to the invention compared with the formulation V1 without active ingredient according to the invention lead to a significant reduction in the formation of limescale as well as the improvement in the drying, in particular of the plastic crockery. The formulations according to the invention E3 and E4 compared with the recipe V2 without active ingredient according to the invention lead to a significant reduction of Kalkbelagsbildung and to improve the drying of the plastic dishes in particular.

Claims (13)

1. Automatic dishwashing agent, characterised in that it comprises a polycarbonate-, polyurethane- and/or polyurea-polyorganosiloxane compound, comprising at least one structural element of Formula (I):
   
           -Y-A-(C=O)-A-     (I)
   
   

   wherein each A is independently selected from S, O and NR¹,

   Y is selected from divalent to polyvalent, in particular tetravalent, linear, cyclic or branched, saturated, unsaturated or aromatic, substituted or unsubstituted hydrocarbon groups with up to 1000 carbon atoms (not counting the carbon atoms of a polyorganosiloxane unit that is optionally also present), which may comprise one or more groups selected from -O, -(CO)-, -NH-, -NR²-, -(N⁺R²R³)- and a polyorganosiloxane unit with 2 to 1000 silicon atoms,

   R¹ is hydrogen or a linear, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon group with up to 40 carbon atoms, which may comprise one or more groups selected from -O-, -(CO)-, -NH- and -NR²-, R² is a linear, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon group with up to 40 carbon atoms, which may comprise one or more groups selected from -O-, -(CO)- and -NH-,

   R³ is a linear, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon group with up to 100 carbon atoms, which may comprise one or more groups selected from -O-, -(CO)- and -NH- or is a divalent group, which forms cyclic structures within the group Y,

   or one or both groups A vicinal to Y, together with the group Y between them, may form a nitrogen-containing heterocyclic group,

   and not all the groups A and/or Y and/or R¹ and/or R² and/or R³ indicated in Formula (I) within the entire compound must be the same, with the proviso that at least one of the groups Y in the entire compound includes a polyorganosiloxane unit with 2 to 1000 silicon atoms, and at least one of the Y-units according to the structural element of Formula (I) possesses a -(N⁺R²R³)- group or its acid addition compound and/or salt.
2. Agent according to claim 1, characterised in that the polyorganosiloxane structural element present in the polycarbonate-, polyurethane- and/or polyurea-polyorganosiloxane compounds is the structure -(SiR⁴ ₂O)_p-(SiR⁴ ₂)-, in which R⁴ is a linear, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon group with up to 20 carbon atoms and p = 1 to 999.
3. Agent according to claim 2, characterised in that the polycarbonate-, polyurethane- and/or polyurea-polyorganosiloxane compound in the agent comprises at least two, in particular at least three, of the aforementioned polyorganosiloxane structural elements.
4. Agent according to one of claims 1 to 3, characterised in that in at least one of the units Y, R¹, R² and/or R³ according to the structural element of Formula (I), oligoethoxy and/or oligopropoxy groups are present whose degrees of oligomerisation are in particular in the range 2 to 60.
5. Agent according to any one of claims 1 to 4, characterised in that in at least one of the units Y, R¹, R² and/or R³ according to the structural element of Formula (I), oligoethylene-imine groups are present whose degrees of oligomerisation are in particular in the range 10 to 15 0000.
6. Agent according to one of claims 1 to 6, characterised in that the compound of Formula (I) is a polycarbonate- and/or polyurethane-polyorganosiloxane compound comprising at least one structural element of Formula (II) or Formula (III):
   
           -A-Y-A-(CO)-O-Z-(CHOH)-Z-O-(CO)-     (II)
   
           -A-Y-A-(CO)-O-(CHCH₂OH)-Z-O-(CO)-     (III)
   
   

   in which A and Y have the meanings given above for Formula (I), and Z is selected from divalent, linear, cyclic or branched, saturated or unsaturated, optionally substituted hydrocarbon groups with 1 to 12 carbon atoms.
7. Agent according to one of claims 1 to 6, characterised in that it comprises 0.01 wt % to 5 wt %, in particular 0.5 wt % to 3 wt % of the active substance.
8. Agent according to one of claims 1 to 7, characterised in that it comprises a non-ionic surfactant of the general formula:
   
           R⁶-CH(OH)CH₂O-(AO)_w-(A'O)_x-(A"O)_y-A("'O)_z-R⁷,
   
   in which

   R⁶ stands for a linear or branched, saturated or a mono- or polyunsaturated C_6-24 alkyl or alkenyl group;

   R⁷ stands for a linear or branched hydrocarbon group with 2 to 26 carbon atoms;

   A, A', A" and A"', independently of one another, stand for a group from the group
   
           -CH₂CH₂,
   
           -CH₂CH₂-CH₂,
   
           -CH₂CH(CH₃),
   
           -CH₂-CH₂-CH₂-CH₂,
   
           -CH₂-CH(CH₃)-CH₂-,
   
           -CH₂-CH(CH₂CH₃),
   
   w, x, y and z, independently of one another, stand for values between 0.5 and 120, wherein x, y and/or z may also be 0.
9. Agent according to one of claims 1 to 8, characterised in that it comprises 1 wt % to 10 wt %, preferably 2 wt % to 8 wt % and in particular 2 wt % to 6 wt % non-ionic surfactant and/or up to 60 wt %, in particular 35 wt % to 50 wt % phosphate.
10. Agent according to one of claims 1 to 9, characterised in that it comprises 5 wt % to 60 wt %, preferably 10 wt % to 50 wt % and in particular 15 wt % to 45 wt % citrate and is phosphate-free or comprises 15 wt % to 25 wt % phosphate.
11. Agent according to one of claims 1 to 10, characterised in that it comprises an additional clear rinse polymer, selected from the copolymers that comprise monomers from at least two of the following groups of

    i) monomers from the group of mono or polyunsaturated carboxylic acids of the general formula
    
            R⁸(R⁹)C=C(R¹⁰)COOH,
    
    in which R⁸ to R¹⁰, independently of one another, stand for -H, -CH₃, a linear or branched, saturated alkyl group with 2 to 12 carbon atoms, a linear or branched, mono or polyunsaturated alkenyl group with 2 to 12 carbon atoms, alkyl or alkenyl groups, as defined above, substituted with -NH₂, -OH or -COOH or stand for -COOH or -COOR⁴, wherein R⁴ is a saturated or unsaturated, linear or branched hydrocarbon group with 1 to 12 carbon atoms,

    ii) monomers of the general formula
    
            R¹¹(R¹²)C=C(R¹³)-X-R¹⁴,
    
    in which R¹¹ to R¹³, independently of one another, stands for -H, -CH₃ or -C₂H₅, X stands for an optional spacer group that is selected from -CH₂-, -C(O)O- and -C(O)-NH-, and R¹⁴ stands for a linear or branched, saturated alky group with 2 to 22 carbon atoms or for an unsaturated, preferably aromatic group, with 6 to 22 carbon atoms;

    iii) sulfonic acid group-containing monomers of the general formula R¹⁵(R¹⁶)C=C(R¹⁷)-X'-SO₃H, in which R¹⁵ to R¹⁷, independently of one another, stands for -H, -CH₃, a linear or branched, saturated alkyl group with 2 to 12 carbon atoms, a linear or branched, mono or polyunsaturated alkenyl group with 2 to 12 carbon atoms, alkyl or alkenyl groups substituted with -NH₂, -OH or -COOH, or stands for -COOH or -COOR¹⁸, wherein R¹⁸ is a saturated or unsaturated, linear or branched hydrocarbon group with 1 to 12 carbon atoms, and X' stands for an optional spacer group that is selected from -(CH₂)_n-, where n = 0 to 4, -COO-(CH₂)_k-, where k = 1 to 6, -C(O)-NH-C(CH₃)₂- and -C(O)-NH-CH(CH₂CH₃)-,

    iv) other ionic and/or non-ionogenic monomers.
12. Method for cleaning dishes in a dishwashing machine, using automatic dishwashing agents according to one of claims 1 to 11.
13. Use of an automatic dishwashing agent according to any one of claims 1 to 11 as a clear rinse agent and/or as a drying accelerator in automatic dishwashing.