DE102007038482A1 - Machine dishwashing agents, useful as clear rinsing agents and/or as drying accelerator in machine dishwasher, comprises polycarbonate, polyurethane and/or polyurea-polyorganosiloxane compounds or their acid addition compounds and/or salts - Google Patents

Abstract

Machine dishwashing agents comprises a polycarbonate-, polyurethane- and/or polyurea-polyorganosiloxane compounds (I) or their acid addition compounds and/or salts. Machine dishwashing agents comprises a polycarbonate-, polyurethane- and/or polyurea-polyorganosiloxane compounds of formula (-Y 1>-A-(C=O)-A-) (I) or their acid addition compounds and/or salts. Either A : S, O or NR 1>; and Y 1>bivalent to polyvalent, preferably tetravalent, optionally saturated up to 1000C aromatic hydrocarbon containing one or more NR 2>, N +>R 2>R 3> (both preferred), O, (CO), NH, 2-1000 polyorganosiloxane unit with silicon atom (optionally substituted), preferably oligoethoxy and/or oligopropoxy (where its oligomerization degree is preferably 2-60) or oligoethylene imine (where its oligomerization degree is preferably 10-150000); or Y 1>A : nitrogen containing heterocyclic ring; R 1>H, optionally saturated up to 40C aromatic hydrocarbon containing one or more O, (CO), NH, NR 2>, preferably oligoethoxy and/or oligopropoxy (where its oligomerization degree is preferably 2-60) or oligoethylene imine (where its oligomerization degree is preferably 10-150000); R 2>optionally saturated up to 40C aromatic hydrocarbon containing one or more O, (CO), NH, preferably oligoethoxy and/or oligopropoxy (where its oligomerization degree is preferably 2-60) or oligoethylene imine (where its oligomerization degree is preferably 10-150000); and R 3>optionally saturated up to 100C aromatic hydrocarbon containing one or more O, (CO), NH, a bivalent residue, which form cyclic structures within the Y 1>, preferably oligoethoxy and/or oligopropoxy preferably oligoethoxy and/or oligopropoxy (where its oligomerization degree is preferably 2-60) or oligoethylene imine (where its oligomerization degree is preferably 10-150000). Provided that: in formula (I), A, Y 1>, R 1>, R 2> and R 3> are not same, when at least one of the residues of Y 1> is polyorganosiloxane unit with 2-1000 silicon atom. An independent claim is included for the machine dishwashing agents comprising [1,3]-dioxolan-2-one compound of formula (IV) or [1,3]-diazepan-2-one compound of formula (V) and/or a polymer, which is obtained by the reaction of a polymer substrate (that modifies the functional groups of hydroxy-, primary and secondary amino- group) with (IV) or (V). R : 1-12C-alkyl; X : CO-CH=CH 2, CO-C(CH 3)=CH 2, CO-O-aryl, 2-6C-alkylene-SO 2-CH=CH 2 or CO-NH-R1a; R1a : 1-30C-alkyl, 1-30C-haloalkyl, 1-30C-hydroxyalkyl, 1-6C-alkyloxy-1-30C-alkyl, 1-6C-alkylcarbonyloxy-1-30C-alkyl, amino-1-30C-alkyl, mono- or di(1-6C-alkyl)amino-1-30C-alkyl, ammonio-1-30C-alkyl, polyoxyalkylene-1-30C-alkyl, polysiloxanyl-1-30C-alkyl, (meth)acryloyloxy-1-30C-alkyl, sulfono-1-30C-alkyl, phosphono-1-30C-alkyl, di(1-6C-alkyl)-phosphono-1-30C-alkyl, phosphonato-1-30C-alkyl, di(1-6C-alkyl) phosphonato-1-30Calkyl or a saccharide; and k : greater than 0. Provided that: in formula (IV), when k is 1, X has the above variable or when k is greater than 1, X is: (i) polyamine bonded with ((CO)-NH), (ii) polymer skeleton bonded with (CO)-, NH-2-6C-alkylene-O(CO)- or (CO)-O-2-6C-alkylene-O(CO)- or (iii) polymer skeleton bonded with (CO)-polysiloxanyl-1-30C-alkyl-groups. [Image] .

Description

The This patent application relates to cleaning agents for the machine cleaning of dishes.

At machine-washed dishes become common today higher requirements than manually flushed Dishes. So the dishes after machine cleaning should not only be completely free from food waste but for example also no whitish, on water hardness or other have mineral salts based stains that lack of wetting agents come from dried water drops.

To The automatic dishwashing is the dishes often still wet. If the dishes are not immediately out of the Machine removed and dried with a kitchen towel, but leave in the machine, are ugly limescale on the dishes - especially plastic dishes - the Follow that only by polishing the dishes with a cloth can be removed. There is this problem so far no satisfactory solution. Machine dishwashing detergent although usually contain so-called rinse aid surfactants, making unsightly limescale and limescale deposits should prevent. These rinse aid surfactants act in the Usually on different hydrophilic / hydrophobic surfaces different good; especially plastic surfaces but mostly critical and often still come with limescale respectively coverings from the machine.

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

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 of 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 radical Y, or one or both of Y may form adjacent radicals Y 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, or their acid addition compound and / or salt.

links of the general formula (I) can be obtained by reacting diisocyanates, Bis-chloroformates or amides or Phosgene containing the structural element Y thiols, alcohols or amines. To obtain polymeric structures have these structural element Y having starting compounds at least 2 of the said functional groups. As end groups compounds come into consideration that are otherwise the structural element Y, but only monofunctional.

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- (CHORO) -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.

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

If the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound contains moieties - (N ⁺ R ² R ³ ) -, common counter anion ions, such as halide, hydroxide, sulfate, carbonate, are present in order to ensure charge neutrality.

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 - to C ₉ -hydrocarbon radical, particularly preferably methyl or phenyl, and p is especially 1 to 199, particularly preferred 1 to 99. In a preferred embodiment, all radicals R ^{4 are the} same.

preferred polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compounds are linear, that is, there are all Y units in the structural element of the formula (I) each divalent radicals. According to the invention but also includes branched compounds wherein at least one Y is trivalent or polyvalent, preferably tetravalent, then that branched structures with linear repeating structures form from structural elements of the formula (I).

In a further embodiment, in the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound used according to the invention, at least one of the Y units according to the structural element of the formula (I) has a grouping -NR ² - and / or at least one of the Y units according to structural element of the formula (I) a grouping - (N ⁺ R ² R ³ ) - on. 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.

The preparation of compounds having structural elements of the formula (I) starting from diisocyanates is disclosed in a German Patent Application filed on the same day by the Momentive Performance Materials. 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.

invention Agents preferably contain from 0.01% by weight to 5% by weight, in particular 0.5 wt .-% to 3 wt .-% of such active ingredient.

invention In addition, funds can all In such agents conventionally containing ingredients, in particular builder (s), bleach and surfactant (s), provided that they are stored and / or applied during use not unreasonably negative with the invention essential Active substance interact.

Machine dishwashing detergents according to the invention preferably contain nonionic surfactant, including in particular nonionic surfactants of the general formula R ⁶ -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''andA''' are independently of one another a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ - CH _{2 is} -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ),
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 dishwashing detergent according to the invention have a weight fraction of nonionic surfactant of 1% by weight to 10 wt .-%, preferably 2 wt .-% to 8 wt .-% and in particular 2 wt .-% to 6 wt .-% on.

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.

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.

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 specified C chain lengths and degrees of alkoxylation or Make ethoxylation of said nonionic surfactants statistical averages for a specific product may be an integer or a fractional number. by virtue of the manufacturing process consist of commercial products of the formulas mentioned mostly not from an individual representative, but from mixtures, resulting in both the C chain lengths as also for the degrees of ethoxylation or degrees of alkoxylation Mean values and resulting broken numbers result.

The mentioned nonionic surfactants can not only as individual substances, but also as Ten sidgemische from two, three, four or more surfactants are used. 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 ,

When further essential constituents contain according to the invention preferred automatic dishwashing detergent one or more builders. The builders include in particular phosphates, Silicates, carbonates and organic cobuilders.

When Organic co-builders are in particular polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and to name other organic cobuilders. These substance classes will be described below.

useful Organic builders are, for example, those in Usable form of the free acid and / or its sodium salts Polycarboxylic acids. 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. The free Acids typically also have, in addition to their builder effect the property of an acidifying component and thus serve also for setting a lower and milder pH of Detergents or cleaners. In particular, here are citric acid, Succinic acid, glutaric acid, adipic acid, Gluconic acid and any mixtures of these.

A Embodiment of preferred inventive automatic dishwashing detergent contains as one their essential builders citrate. invention automatic dishwashing detergents containing from 5 to 60% by weight, preferably 10 to 50 wt .-% and in particular 15 to 45 wt .-% citrate, are preferred according to the invention.

With preference, automatic dishwasher detergents according to the invention comprise as builder crystalline layer-form silicates of the general formula NaMSi _x O ₂ × _{+ 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 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 the For the purposes of the present invention, preferred automatic dishwashing detergents contain from 2 to 15 wt .-%, preferably 3 to 12 wt .-% and in particular 4 to 8 wt .-% silicate (s).

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

If this is harmless for ecological reasons, can also be used as builders the known alkali metal phosphates, in particular trisodium polyphosphate.

Alkaliphosphat 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 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 moles (density 2.066 gcm ^-3 , loss of water at 95 ° C), 7 moles (density 1.68 gcm ^-3 , enamel point 48 ° C with loss of 5H ₂ O) and 12 moles of water (density 1.52 gcm ^-3 , melting point 35 ° C with loss of 5H ₂ O), becomes anhydrous at 100 ° C and goes on stronger heating in the diphosphate Na ₄ P ₂ O ₇ over. 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 ) have 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 z. 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: fused or annealed 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 6H 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 dissolve at room temperature about 17 g, at 60 ° C about 20 g, at 100 ° C about 32 g of the salt water free of water; 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 + 2KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

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

One Inventive agent contains in one preferred embodiment up to 60 wt .-%, in particular From 35% to 50% by weight of phosphate. In further preferred embodiments it contains 5% by weight to 60% by weight, preferably 10% by weight to 50 wt .-% and in particular 15 wt .-% to 45 wt .-% citrate and is phosphate-free or contains 15% by weight to 25% by weight of phosphate.

When Builders are also suitable polymeric polycarboxylates, These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70000 g / mol. suitable Polymers are in particular polyacrylates, which preferably have a molecular weight from 2000 to 20,000 g / mol. Because of their superior Solubility can turn out of this group the short-chain polyacrylates, the molecular weights of 2,000 to 10,000 g / mol, and more preferably from 3000 to 5000 g / mol, be preferred.

Suitable are furthermore copolymeric polycarboxylates, especially those of Acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special suitable copolymers of acrylic acid with maleic acid proven, the 50 to 90 wt .-% acrylic acid and 50 to 10 Wt .-% maleic acid. Your molecular weight, based on free acids, is generally 2000 to 70000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol. The (co) polymeric polycarboxylates can either used as a powder or as an aqueous solution become. The content of automatic dishwashing detergents of (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-% and in particular 3 to 10 wt .-%.

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 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

Farther can also bleach from the group of organic Bleaching agents are used. Typical organic bleach are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical Organic bleaches are the peroxyacids, wherein as Examples especially the alkylperoxy acids and the aryl peroxyacids to be named.

Machinery Dishwashing detergent containing 1 to 20% by weight, preferably 2 to 15% by weight and in particular from 4 to 12% by weight of sodium percarbonate contained are preferred according to the invention.

When If desired, bleaching agents can also be chlorine or bromine-releasing substances are used. Among the suitable For example, chlorine or bromine releasing materials are used heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, Tribromoisocyanuric acid, dibromoisocyanuric acid and / or Dichloroisocyanuric acid (DICH) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Around when cleaning at temperatures of 60 ° C and below one To achieve improved bleaching effect, the inventive automatic dishwashing detergent additionally bleach activators contain. As bleach activators, compounds which under perhydrolysis conditions, aliphatic peroxycarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, be used. Suitable substances are the O- and / or N-acyl groups said C atomic number and / or optionally substituted benzoyl groups wear. Preference is given to polyacylated alkylenediamines, where Tetraacetylethylenediamine (TAED) proved to be particularly suitable Has.

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

additionally to such conventional bleach activators or in their place can also be used so-called bleach catalysts become. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline 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 are known as Bleach catalysts usable.

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 ).

Machine 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 in common Quantities, preferably in an amount up to 5 wt .-%, in particular of 0.0025% to 1% by weight, and more preferably 0.01% by weight to 0.30% by weight, based in each case on the total weight of the agents, used. In special cases, however, more can be done Bleaching catalyst can be used.

preferred Automatic dishwashing detergent according to the invention additionally contain 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), if their Use for environmental reasons not to complain about is.

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

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

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

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

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

invention Machine dishwashing detergents can be added if desired also two or more different phosphonates and / or aminicarboxylic acids contain. Particular preference is given to such automatic dishwasher detergents, which as phosphonates both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) as well as diethylenetriaminepenta (methylenephosphonic acid) (DTPMP), the weight ratio of HEDP to DTPMP between 20: 1 and 1:20, preferably between 15: 1 and 1:15 and especially between 10: 1 and 1:10.

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

In addition to these ingredients, preferred automatic dishwashing agents contain other ingredients Fe, preferably active ingredients from the group of polymers, enzymes, corrosion inhibitors and fragrances and / or dyes.

to Group of washing or cleaning active polymers count for example, the effective as a softener polymers and Rinse aid polymers, if desired in addition to the active ingredient used in the invention can be used. Generally are in washing or Detergents in addition to nonionic polymers also cationic, anionic and amphoteric polymers can be used.

• 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.
• 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
• 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)-.
• 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

• 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 which R ⁸ to R ¹⁰ independently of one another represent -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 , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
• 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 a 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
• iii) sulfonic acid group-containing monomers of the general formula R ¹⁵ (R ¹⁶ ) C = C (R ¹⁷ ) -X'-SO ₃ H in which 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 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ¹⁸ stands where R ^{18 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X 'is an optionally present spacer group which is selected from - (CH ₂ ) _n - where 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 ) -.
• iv) further ionic and / or nonionic monomers.

In The polymers may contain the carboxylic acid and / or Sulfonic acid groups in whole or in part in neutralized Form, d. H. the acidic acid atom of the acid group can in some or all acid groups against metal ions, preferably alkali metal ions and in particular against sodium ions, be exchanged. The use of partially or fully neutralized Sulfonsäuregruppenhaltigen copolymers is inventively preferred.

"Cationic Polymers "in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can for example, by (alkyl) ammonium groups present in the polymer chain or other positively charged groups. Especially preferred cationic polymers are from the groups of the quaternized Cellulose derivatives containing 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 acrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymer, the quaternized Polyvinyl alcohols or under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 Polymers.

For the purposes of the present invention, "amphoteric polymers" 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 the linear or branched, saturated or unsaturated sulfonates Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylic acid , allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or allylphosphonic acids Preferred amphoteric polymers sta 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 / Al kylaminoalkyl (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 ,

Prefers usable 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 Methacroylethylbetain / 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.

cleaning supplies contain the aforementioned cationic and / or amphoteric polymers preferably in amounts of up to 10% by weight, in particular between 0.01 and 10 wt .-%, each based on the total weight of the composition. In the context of the present application, such cleaning agents are preferred those of the weight fraction of the cationic and / or amphoteric polymers between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4 wt .-%, more preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, respectively based on the total weight of the automatic dishwashing detergent, 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.

Under Proteases are preferred to those of the subtilisin type. Examples these are the subtilisins BPN 'and Carlsberg and their more advanced forms, the protease PB92, the subtilisins 147 and 309, the Bacillus lentus alkaline protease, subtilisin Dy and the subtilases, but not the subtilisins in the In the narrower sense, enzymes thermitase, proteinase K and the proteases TW3 and TW7.

Examples for amylases usable according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as those for use in detergents and cleaners improved developments of the aforementioned amylases. Furthermore For this purpose Bacillus α-amylase is used sp. A 7-7 (DSM 12368) and 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. For this For example, include the lipases originally available 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 solani.

Farther enzymes can be used under the term Hemicellulases are summarized. These include for example mannanases, xanthan lyases, pectin lyases (= pectinases), Pectinesterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

to Increasing the bleaching effect according to the invention oxidoreductases, for example, oxidases, oxygenases, catalases, peroxidases, such as Halo, chloro, bromo, lignin, glucose or manganese peroxidases, Dioxygenases or laccases (phenol oxidases, polyphenol oxidases) be used. Advantageously, in addition preferably organic, particularly preferably aromatic, with the Enzyme-interacting compounds added to the activity the oxidoreductases in question (Enhancer) or at strongly different redox potentials between the oxidizing enzymes and soiling the electron flow to ensure (mediators).

The Enzymes can be established in any of the prior art Form are used. These include, for example, the obtained by granulation, extrusion or lyophilization solid Preparations or, in particular in liquid or gel agents, solutions of enzymes, advantageously as concentrated as possible, low in water and / or mixed with stabilizers.

alternative The enzymes can be used both for the solid as well be encapsulated for the liquid dosage form, for example, by spray drying or extrusion of the Enzyme solution together with a preferably natural Polymer or in the form of capsules, for example those in which the enzymes are included as in a solidified gel or in those of the core-shell type in which an enzyme-containing core with a water, air and / or chemical impermeable Protective layer is coated. In superimposed layers In addition, other active ingredients, for example Stabilizers, emulsifiers, pigments, bleaching or dyes applied become. Such capsules are prepared by methods known per se, for example, by shaking or rolling granulation or applied in fluid-bed processes. Advantageously, such Granules, for example by applying polymeric film formers, low in dust and storage-stable due to the coating.

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

One Protein and / or enzyme may be especially during storage against damage such as inactivation, denaturation or decay by physical influences, oxidation or proteolytic cleavage. In microbial Obtaining the proteins and / or enzymes is inhibiting the Proteolysis particularly preferred, especially if the means Contain proteases. Washing or cleaning agents. can contain stabilizers for this purpose; the provision of such funds represents a preferred embodiment of the present invention Invention.

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

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

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

include.

Glass corrosion inhibitors also prevent the occurrence of turbidity, streaks and scratches the iridescence of the glass surface of mechanically 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 given as a glass corrosion inhibitor at least one Zinc salt of an organic carboxylic acid, particularly preferred a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, Zinc acetate, zinc lactate and zinc citrate used. Also zinc ricinoleate, Zinc abietate and zinc oxalate are 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, wherein in the field of automatic dishwashing, especially silver protectants have a special meaning. It is possible to use the known substances of the prior art. In general, especially silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metal salts or complexes used become. Particularly preferred to use are benzotriazole and / or Alkylaminotriazole. According to the invention are preferred 3-amino-5-alkyl-1,2,4-triazoles or their physiologically acceptable Salts used, these substances with particular preference in a concentration of 0.001 to 10 wt .-%, preferably 0.0025 used to 2 wt .-%, particularly preferably 0.01 to 0.04 wt .-% become.

Around to facilitate the disintegration of prefabricated moldings is it is possible disintegration aids, so-called disintegrants, to work into these remedies to reduce disintegration times.

These Substances which are also referred to as "explosives" due to their effect increase their volume when they enter the water, on the one hand, increasing the intrinsic volume (swelling), on the other hand also on the release of gases pressure can be generated, which disintegrate the tablet into smaller particles leaves. Well-known disintegration aids are, for example Carbonate / citric acid systems, although other organic Acids can be used. Swelling disintegration aids are for example synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as Cellulose and starch and their derivatives, alginates or casein derivatives.

Prefers are disintegration aids in amounts of 0.5 to 10 wt .-%, preferably 1 to 7 wt .-% and in particular 1 to 5 wt .-%, respectively based on the total weight of the desintegrationshilfsmittelhaltigen By means of, used.

When preferred disintegrating agents become disintegrants Cellulose-based, so that preferred detergents or cleaning agents such cellulose-based disintegrant in amounts of 0.5 to 10 wt .-%, preferably 1 to 7 wt .-% and in particular 1 to 5 wt .-% included. The used as disintegration aids Cellulose is preferably not used in finely divided form, but before adding to the premixes to be pressed in a coarser shape, for example granulated or compacted. The particle sizes such disintegrating agents are usually above 200 μm, preferably at least 90 wt .-% between 300 microns and 1600 microns and in particular at least 90 wt .-% between 400 μm and 1200 μm.

preferred Disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are in disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 1 to 7% by weight and in particular from 1 to 5 wt .-%, each based on the total weight of the disintegrant-containing agent.

According to the invention preferred In addition, gases can continue to evolve Effervescent systems used as Tablettenendesintegrationshilfsmittel become. The gas-developing effervescent system can consist of a single Substance that releases a gas on contact with water. Among these compounds is in particular the magnesium peroxide to call, which releases oxygen on contact with water. preferred Effervescent systems, however, consist of at least two components, the react with each other to form gas, for example, alkali metal carbonate and / or bicarbonate and an acidifier, the is suitable from the alkali metal salts in aqueous solution Release carbon dioxide. As Acidifizierungsmittel, from the Alkali salts in aqueous solution carbon dioxide are, for example, boric acid and alkali metal hydrogen sulfates, Alkali metal dihydrogen phosphates and other inorganic salts. However, preference is given to using organic acidifiers, the citric acid being a particularly preferred acidifying agent is. Preference is given to acidifying agents in the effervescent system from Group of organic di-, tri- and oligocarboxylic acids or mixtures.

When Perfume oils or fragrances may be in the frame the individual invention fragrance compounds, for. B. the synthetic products of the ester type, ethers, aldehydes, ketones, Alcohols and hydrocarbons are used. To be favoured However, mixtures of different fragrances are used together create an appealing scent. Such perfume oils may also contain natural fragrance mixtures, as they are accessible from plant sources, eg. B. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil. The fragrances can be processed directly, it can but also be beneficial to apply the perfumes on carriers, by a slower release of fragrance for long-lasting Provide scent. As such carrier materials, for example Cyclodextrins proven to be effective, with the cyclodextrin-perfume complexes additionally be coated with other excipients can.

preferred Dyes whose selection does not present any difficulty to the skilled person have a high storage stability and insensitivity compared to the other ingredients of the funds and against light as well as no pronounced substantivity compared to those to be treated with the dye-containing agents Substrates such as textiles, glass, ceramics or plastic crockery, so as not to stain them.

The automatic dishwashing detergent according to the invention can be made up in solid or liquid form but also as a combination of solid and liquid Offer forms.

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

invention Agents may be single-phase or multi-phase products be made up. In particular, mechanical machines are preferred Dishwashing detergent with one, two, three or four phases. Machine dishwashing detergent, characterized that they are in the form of a prefabricated dosing unit with two or three more phases are present, are particularly preferred.

The individual phases of multiphasic agents may be the same or different states of aggregation. Prefers are in particular automatic dishwashing detergents, the at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least have a liquid phase.

invention Machine dishwashing detergents are preferably dosing units prefabricated. These dosing units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred dosing 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 selected with particular preference so that a dosing the pre-assembled units via the metering chamber a dishwasher is guaranteed. 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 dishwashing detergent according to the invention, in particular the prefabricated metering units have particular Preferably a water-soluble wrapper.

The present application further relates to a method for cleaning dishes in a dishwasher, using automatic dishwashing detergent according to the invention, wherein the ma schinellen dishwashing detergent are preferably metered during the passage of a dishwashing program before the main wash cycle or in the course of the main wash cycle in the interior of a dishwasher. 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 rinse aid and no additional water softening is metered into the interior of the dishwasher.

As described above, are characterized inventive Means compared to conventional automatic dishwashing detergents by an improved rinse action and an improved Drying effect off. The use of an inventive automatic dishwashing detergent as rinse aid in the automatic dishwashing and the use of a automatic dishwashing detergent according to the invention as a drying accelerator in automatic dishwashing are therefore further objects of the present application.

Examples

soiled Dishes were 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 in each case of the composition according to the invention E1 to E4 are rinsed 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

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 showed that the formulations of the invention E1 and E2 compared to the recipe V1 without inventive Active ingredient to a significant reduction of Kalkbelagsbildung as well as the improvement of the drying, especially of the plastic dishes to lead. The formulations according to the invention E3 and E4 compared with the recipe V2 without active ingredient according to the invention to a significant Reduction of limescale formation and improvement of Drying in particular of the plastic dishes.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• WO 2005/058863 [0016]

Claims (23)

Machine dishwashing detergent, characterized in that it contains a polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound containing at least one structural element of the formula (I): -YA- (C = O) -A- (I), wherein each A independently is selected from S, O and NR ¹ , Y is selected from bi- to polyvalent, especially tetravalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic, substituted or unsubstituted hydrocarbon radicals having up to 1000 carbon atoms (the Not counting carbon atoms of an optionally contained polyorganosiloxane unit) containing one or more groups selected from -O-, - (CO) -, -NH-, -NR ² -, - (N ⁺ R ² R ³ ) - and a polyorganosiloxane unit 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 can-Provide ^2, R ² is a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical m it is up to 40 carbon atoms, 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 is a bivalent radical which forms cyclic structures within the radical Y, or one or both of the Y adjacent radicals A with the radical Y between them can form 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 to In that in the entire compound at least one of the radicals Y comprises a polyorganosiloxane unit having 2 to 1000 silicon atoms, or their acid addition compound and / or salt. Composition according to Claim 1, characterized in that the polyorganosiloxane structural element present in the polycarbonate, polyurethane and / or polyurea polyorganosiloxane compounds is the structure - (SiR ⁴ ₂ O) _p - (SiR ⁴ ₂ ) in which R ^{4 is} a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 20 carbon atoms, and p = 1 to 999. Means according to claim 2, characterized in that the polycarbonate, polyurethane and / or polyurea polyorganosiloxane compounds on average at least two, in particular at least three of said Contains polyorganosiloxane structural elements. Composition according to one of claims 1 to 3, characterized in that in the polycarbonate, polyurethane and / or polyurea polyorganosiloxane compound at least one of the Y units according to structural element of formula (I) a grouping -NR ² - and / or at least one of the Y units according to the structural element of the formula (I) has a grouping - (N ⁺ R ² R ³ ) -. Agent according to one of claims 1 to 4, characterized in that in at least one of the units Y, R ¹ , R ² and / or R ³ according to structural element of formula (I) Oligoethoxy- and / or Oligopropoxygruppen are present whose degrees of oligomerization in particular Range from 2 to 60 are. Agent according to one of claims 1 to 5, characterized in that Oligoethylenimingruppen are present in at least one of the units Y, R ¹ , R ² and / or R ³ according to structural element of the formula (I) whose degrees of oligomerization in particular in the range of 10 to 15 0000 lie. Agent according to one of claims 1 to 6, characterized in that it is 0.01 wt .-% to 5 wt .-%, in particular Contains 0.5 wt .-% to 3 wt .-% of the active ingredient. Agent according to one of Claims 1 to 7, characterized in that it contains nonionic surfactant of the general formula R ⁶ -CH (OH) CH ₂ O- (AO) _w - (A'O) _w - (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''andA''' are independently of one another a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ - CH ₂ -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. Agent according to one of claims 1 to 8, characterized in that it is 1 wt .-% to 10 wt .-%, preferably 2 wt .-% to 8 wt .-% and in particular 2 wt .-% to 6 wt .-% nonionic Contains surfactant. Agent according to one of claims 1 to 9, characterized in that it contains up to 60% by weight, in particular 35 Wt .-% to 50 wt .-% phosphate. Agent according to one of claims 1 to 9, characterized in that it is 5 wt .-% to 60 wt .-%, preferably 10% by weight to 50% by weight and in particular 15% by weight to 45% by weight Contains citrate and is phosphate-free or 15 wt .-% to 25 wt .-% phosphate. Composition according to one of claims 1 to 11, characterized in that it contains an additional rinse aid polymer selected from the copolymers comprising 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 R. ⁸ (R ⁹ ) C =C (R ¹⁰ ) COOH, in which R ⁸ to R ¹⁰ 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, one 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 , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical with 1 to 12 carbon atoms. 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 a 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 iii) sulfonic acid group-containing monomers of the general formula R ¹⁵ (R ¹⁶ ) C = C (R ¹⁷ ) -X'-SO ₃ H in which R ¹⁵ to R ^{17 are} independently -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 ¹⁸ , wherein R ^{18 is} a saturated or unsaturated, geradkettigter od it is a branched hydrocarbon radical having 1 to 12 carbon atoms, and X 'is an optional spacer group which is selected from - (CH ₂ ) - 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 ) -. iv) further ionic and / or nonionic monomers. Agent according to one of claims 1 to 12, characterized in that it is 1 to 20 wt .-%, preferably 2 to 15% by weight and in particular from 4 to 12% by weight of sodium percarbonate contains. Agent according to one of claims 1 to 13, full a) 35 to 50 wt .-% phosphate b) 2 to 8% by weight nonionic surfactant (s) c) 4 to 16% by weight of polymer (s) d) 2 to 15% by weight of sodium percarbonate e) 1 to 6 wt .-% enzyme. Agent according to one of claims 1 to 13, full a) 15 to 45 wt .-% citrate b) 2 to 8% by weight nonionic surfactant (s) c) 4 to 16% by weight of polymer (s) d) 2 to 15% by weight of sodium percarbonate e) 1 to 6 wt .-% enzyme. Agent according to one of claims 1 to 15, characterized in that it comprises bleach-enhancing transition metal complex, especially with the central atoms Mn and Co, in an amount up to at 5% by weight, especially from 0.0025% to 1% by weight, and especially preferably from 0.01% by weight to 0.30% by weight. Composition according to claim 16, characterized in that the transition metal complex is selected from the group of the 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). Agent according to one of claims 1 to 17, characterized in that it contains up to 5% by weight, in particular 0.5 Wt .-% to 2 wt .-% phosphonate contains. Method for cleaning dishes in a dishwasher, using automatic dishwashing detergent after one of claims 1 to 18. Method according to claim 19, characterized that in the course of the cleaning process no additional Rinse aid and no additional water softener is metered into the interior of the dishwasher. Use of a machine dishwashing detergent according to one of claims 1 to 18 as a rinse aid in automatic dishwashing. Use of a machine dishwashing detergent according to any one of claims 1 to 18 as a drying accelerator in automatic dishwashing. Composition, use or method according to one of the preceding claims, characterized in that the compound of formula (I) is a polycarbonate and / or polyurethane-polyorganosiloxane compounds containing at least one structural element of the formula (II) or formula (III) : -AYA- (CO) -OZ- (CHORO) -ZO- (CO) - (II), -AYA- (CO) -O- (CHCH ₂ OH) -ZO- (CO) - (III), in which A and Y have the meanings given for formula (I) 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.