EP4244323A1 - Metal complexes-containing dishwashing detergents - Google Patents

Abstract

The invention relates to dishwashing detergents that contain a metal complex of the general formula (I), (A^q+)_p[M^s+L^m-](X^o-)_r (I) wherein q is 1 or 2 and A^q+ represents a cation, selected from alkali metal cations with q = 1, ½ alkaline earth cations with q = 2 and ammonium ions with q = 1, M^s+ represents an aluminum ion, a transition metal ion or a lanthanoid metal ion, s is a number from 1 to 5, L represents a ligand of the formula (II), in which every R¹ and R² independently of each other is selected from H, unsubstituted or substituted, linear or branched C_1-20 alkyl, unsubstituted or substituted, linear or branched C_1-20 heteroalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted, linear or branched C_2-20 alkenyl, unsubstituted or substituted, linear or branched C_2-20 heteroalkenyl and unsubstituted or substituted, linear or branched C_2-20 alkinyl, unsubstituted or substituted, linear or branched alkylaryl, unsubstituted or substituted, linear or branched alkylaryl, unsubstituted or substituted, linear or branched alkylheteroaryl, every R³ independently from each other represents CH₂COOH or CH₂COO-, n is 0 or 1, X^o- represents an anion, selected from F^-, Cl^-, Br^-, I^-, OH^-, HSO₃ ^-, SO₃ ^2-, SO₄ ^2-, HSO₄ ^-, NO₂ ^-, NO₃ ^-, PO₄ ^3-, HPO₄ ^2-, H₂PO₄ ^-, BF₄ ^-, PF₆ ^-, ClO₄ ^-, acetate, citrate, formiate, glutarate, lactate, malate, malonate, oxalate, pyruvate, tartrate, methane sulfonate, methyl sulfate, p-toluene sulfate and succinate, m is a number from 0 to 5 and o is a number from 1 to 3, and p and r independently of each other represent a number from 0 to 6, with the proviso that the sum of s and the product of p and q is equal the sum of m and the product of r and o, and with the further proviso that the charge of formula (II) resulting from the residues R¹, R² and R³ is neutral or negative.

Description

Dishwashing detergents containing metal complexes

The present invention relates to dishwashing detergents which, as a result of the content of cleaning-enhancing metal complexes, show improved cleaning performance when removing burned-on soiling, the use of these dishwashing detergents and a method for machine dishwashing using these dishwashing detergents.

The most important criterion in automatic dishwashing is the cleaning performance on a wide variety of soiling, which is often brought into the dishwasher in the form of food residues. Especially with stubborn soiling, such as those that occur when preparing protein and starchy foods at high temperatures (roasting, baking, frying, au gratin, etc.), so-called burnt-in dirt, the cleaning performance of available dishwashing detergents is still not good satisfactory. Inadequate cleaning performance leads to consumer dissatisfaction. There is therefore a general need for automatic dishwashing detergents which still have good cleaning performance even on burnt-in stains.

Surprisingly, it has now been found that the use of metal complexes with aminoamide ligands in dishwashing brings about improved cleaning performance on baked-on soiling.

One subject of the invention is a dishwashing detergent, in particular a machine dishwashing detergent, containing a metal complex of the general formula (I), (A ^< ' ⁺ ) _P [M ^{s +} L ^m ] (X ⁰ -) r (I) in which q is 1 or 2 and A ^q+ is a cation selected from alkali metal cations with q= ¹ , 1/2 alkaline earth cations with q=2 and ammonium ions with q=1, M ^s+ is an aluminum ion, a transition metal ion or a lanthanide metal ion, s is a number is from 1 to 5, L is a ligand of formula (II), wherein each R ¹ and R ² is independently selected from H, unsubstituted or substituted, linear or branched C1-20 alkyl, unsubstituted or substituted, linear or branched C1-20 heteroalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, unsubstituted or C2-20 substituted, linear or branched alkenyl, C2-20 unsubstituted or substituted, linear or branched heteroalkenyl, and C2-20 unsubstituted or substituted, linear or branched alkynyl, unsubstituted or substituted, linear or branched alkylaryl, unsubstituted or substituted, linear or branched alkylheteroaryl, each R ³ is independently CH2COOH or CH2COO-, n is 0 or 1, X ^0- is an anion selected from F-, Cb, Br , I-, OH-, HSOs', SO3 ^2- , SC ^2- , HSC ', NO2; NO3; PO4 ³ ; HPC>4 ² ', H2PO4', BF ₄ -, PFe', CIO ₄ -, acetate, citrate, formate, glutarate, lactate, malate, malonate, oxalate, pyruvate, tartrate, methanesulfonate, methyl sulfate, p-toluene sulfate and succinate, m is a number from 0 to 5 and 0 is a number from 1 to 3 and p and r are independently a number from 0 to 6 with the proviso that the sum of s and the product of p and q equals the sum of m and the product of r and 0. Substituents in the substituted variants of R ¹ and R ² mentioned are preferably -COOH, -COO-, -SH, -SO3H, -SO ₃ -, -C(O)R ⁴ , -OR ⁴ or -(NR ⁵ R ^e R ⁷ R ⁸ ) ⁺ , in which R ⁴ represents H, linear or branched C1-6 alkyl and R ⁵ to R ⁸ independently represent linear or branched C1-6 alkyl groups, with the proviso that from the radicals R ¹ , R ² and R ³ resulting charge of formula (II) is neutral or negative.

As is well known, not every number in the range defined for s is suitable for every metal, because metals in group 3 of the periodic table of the elements are usually in the +3 oxidation state, metals in group 4, group 7, group 8, group 9, group 10 and the lanthanide metals in the +2, +3 or +4 oxidation states, Group 5 metals in the +2, +3, +4 or +5 oxidation states, Group 6 metals in the +2 or +3 oxidation states, Group 11 metals in the +1, +2 or +3 oxidation state, Group 12 metals in the +1 or +2 oxidation state, and Al in the +3 oxidation state. Preferred metal ions M ^s+ are Al ³⁺ , Ti ⁴⁺ , Y ³⁺ , Zr ⁴⁺ , Ce ³⁺ , Ce ⁴⁺ , Sc ³⁺ , Yb ³⁺ and their mixtures.

Further objects of the present invention are the use of a metal complex of the formula (I) defined above or a dishwashing detergent according to the invention in a machine dishwashing process for removing soiling, in particular the use for improving the cleaning performance in an automatic dishwashing machine.

A further object of the invention is an automatic dishwashing process in which a metal complex of the formula (I) defined above or a dishwashing agent according to the invention is used, in particular for the purpose of improving the cleaning performance.

The special or preferred embodiments described above and below for the individual objects of the invention also apply to the other objects of the invention.

Ligands of the general formula II can be prepared analogously to the synthesis method published in Tetrahedron 68, 2012, 1163-1170. The detergents according to the invention contain, based on the total weight of the dishwashing detergent, preferably 0.001% by weight to 10% by weight, in particular 0.01% by weight to 3% by weight, of a metal complex of the formula (I) defined above and can in addition to the complex that is essential to the invention, other components usually contained in such agents, preferably selected from surfactants, in particular nonionic surfactants and/or anionic surfactants, builders, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, Bitter substances, antimicrobial agents and disintegration aids, especially surfactants.

The agents preferably contain at least one nonionic surfactant. All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants. Examples of suitable nonionic surfactants are alkyl glycosides of the general formula RO(G) _X , where R is a primary straight-chain or methyl-branched aliphatic radical, especially methyl-branched in the 2-position, having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol is, which is a glucose unit with 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably from 1.2 to 1.4. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamide type can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it. Other suitable surfactants are the polyhydroxy fatty acid amides known as PHFA. Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. The machine dishwashing detergents particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols. One class of nonionic surfactants that can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants is accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain. Surfactants to be used with preference come from the groups of ethoxylated primary alcohols and mixtures of these surfactants with surfactants with a more complex structure, such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants). Such (PO/EO/PO) nonionic surfactants are distinguished by good foam control. Nonionic surfactants with alternating ethylene oxide and alkylene oxide units can be preferred. Among these, surfactants with EO-AO-EO-AO blocks are preferred, in which case one to ten EO or AO groups are bonded to one another before a block of the other groups follows. Here are nonionic surfactants of the general formula R1-O-(CH ₂ -CH ₂ -O)- (CH ₂ -C HO)-(CH ₂ -CH ₂ -O)- (CH ₂ -C HO)- H

R2 R3 is preferred in which R ¹ is a straight-chain or branched, saturated or mono- or polyunsaturated Ce-24-alkyl or -alkenyl radical; each R ² or R ³ group is independently selected from -CH3, -CH2CH3, -CH2CH2-CH3, CH(CH3)2 and the indices w, x, y, z are independently integers from 1 to 6. Thus, nonionic surfactants are particularly preferred which have a Cg-is-alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units. Preferred nonionic surfactants here are those of the general formula R ¹ -CH(OH)CH2O-(AO)w-(A'O)x-(A"O)y-(A"'O)zR ² , in which R ¹ stands for a straight-chain or branched, saturated or mono- or polyunsaturated Ce-24 alkyl or alkenyl radical; R ² is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A', A" and A'" independently represent a radical from the group -CH2CH2, -CH2CH2-CH2, -CH2-CH(CH3), -CH2-CH2-CH2-CH2, -CH2-CH(CH3 )-CH2-, -CH2-CH(CH2-CH3), and w, x, y and z stand for values between 0.5 and 120, where x, y and/or z can also be 0. Preference is given in particular to those end-capped, poly(oxyalkylated) nonionic surfactants which, according to the formula R ¹ O[CH2CH2O] _X CH2CH(OH)R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic Hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, where x has values between 1 and 90, preferably values between 30 and 80 and in particular for values between 30 and 60. Surfactants of the formula R ¹ O[CH2CH(CH3)O]x[CH2CH2O]yCH2CH(OH)R ² are particularly preferred, in which R ¹ represents a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is at least 15. The group of these nonionic surfactants includes, for example, the C2-26 fatty alcohol-(PO)i-(EO) 15-40-2-hydroxyalkyl ethers, in particular the Cs-w fatty alcohol-(PO)i-(EO)22-2 -hydroxydecyl ether. Particular preference is also given to end-capped poly(oxyalkylated) nonionic surfactants of the formula R ¹ O[ ^CH2CH2O ]x[ ^CH2CH (R3)O] _y ^CH2CH (OH)R2, in which ^R1 and R2 independently represent a linear or branched , Saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ³ is independently selected from -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH3)2, but preferably represents -CH3, and x and y independently stand for values between 1 and 32, nonionic surfactants with R ³ = -CH 3 and values for x from 15 to 32 and y from 0.5 and 1.5 being very particularly preferred. Other nonionic surfactants that can preferably be used are the end-capped poly(oxyalkylated) nonionic surfactants of the formula R ¹ O[ ^CH2CH (R3)O]x[ ^CH2 ]kCH(OH)[ ^CH2 ] ^jOR2 , in which R1 and R2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ³ is H or methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x has values between 1 and 30, k and j have values between 1 and 12, preferably between 1 and 5. When the value of x is greater than or equal to 2, each R ³ in the above formula R ¹ O[CH ₂ CH(R ³ )O]x[CH 2 ]kCH(OH)[CH 2 ]jOR ² can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH3 or -CF CHs are particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15. Each R ³ can be different if x>2. This allows the alkylene oxide unit in the square brackets to be varied. For example, when x is 3, the R ³ group may be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH 3 ) moieties which may be joined in any order, e.g. (EO)(PO )(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO )(PO). The value 3 for x was selected here as an example and can certainly be larger, with the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa . Particularly preferred endcapped poly(oxyalkylated) alcohols of the above formula have values of k=1 and j=1 such that the above formula simplifies to R ¹ O[CH 2 CH(R ³ )O] _X CH 2 CH(OH)CH ² OR 2 . In the latter formula, R ¹ , R ² and R ³ are as defined above and x is a number from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Surfactants in which the radicals R ¹ and R ² has 9 to 14 carbon atoms, R ³ is H and x has values from 6 to 15. Finally, the nonionic surfactants of the general formula R ¹ --CH(OH)CH 2 O-(AO) _W --R ² , in which R ¹ is a straight-chain or branched, saturated or mono- or polyunsaturated Ce-24 -alkyl or -alkenyl; R ² represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A is a radical from the group CH2CH2, CH2CH2CH2, CH2CH(CH3), preferably CH2CH2, and w is a value between 1 and 120, preferably 10 to 80, in particular 20 to 40. The group of these nonionic surfactants includes, for example, the C4-22 fatty alcohol (EO)io-so-2-hydroxyalkyl ethers, in particular also the Cs-12 fatty alcohol (EO)22-2-hydroxydecyl ether and the C4-22 fatty alcohol -(EO)40-80-2-hydroxyalkyl ether. In various embodiments of the invention, instead of the end-capped hydroxy mixed ethers, it is also possible to use the corresponding non-end-capped hydroxy mixed ethers. These may satisfy the formulas above except that R ² is hydrogen and R ¹ , R ³ , A, A', A”, A'”, w, x, y and z are as defined above.

The agents described herein, which comprise at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, contain the surfactant in different those embodiments in an amount based on the total weight of the agent of at least 2% by weight, preferably at least 5% by weight. The absolute amounts used per application can be, for example, in the range from 0.5 g to 10 g per application, preferably in the range from 1 g to 5 g per application.

All anionic surface-active substances are suitable as anionic surfactants in dishwashing detergents. These are characterized by a water-solubilizing, anionic group such as a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium salts and the mono-, di- and trialkanolammonium salts having 2 to 4 carbon atoms in the alkanol group. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule. In various embodiments, the dishwashing detergents therefore contain at least one surfactant of the formula R ⁴ —O—(AO)n—SO 3 ^_ X ⁺ . In this formula, R ⁴ is a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C atoms are preferred. Particularly preferred radicals R ¹ are derived from Ci2-Cis-fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from Cw-C20-oxo alcohols. AO stands for an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably for an ethylene oxide moiety. The index n is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. n is very particularly preferably the numbers 2, 3, 4, 5, 6, 7 or 8. X is a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na ⁺ or K ⁺ , with Na ⁺ being extremely preferred. Further cations X ⁺ can be selected from NH4 ⁺ , % Zn ²⁺ , % Mg ²⁺ , % Ca ²⁺ , % Mn ²⁺ , and mixtures thereof. Particularly preferred anionic surfactants are selected from fatty alcohol ether sulfates of formula A-1 with k=11 to 19, n=2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na-Ci2-14 fatty alcohol ether sulfates with 2 EO (k=11-13, n=2 in formula A -1). The agents can also additionally or alternatively contain at least one surfactant of the formula R ⁵ -A-SO3' Y ⁺ (A-2). In this formula A- 2, R ⁵ is a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical and the group -A- is -O- or a chemical bond. In other words, sulfate (A = O) or sulfonate (A = chemical bond) - describe surfactants. Depending on the choice of grouping A, certain radicals R ⁵ are preferred. In the sulfate surfactants (AO), R ⁵ is preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ⁵ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C atoms are preferred. Particularly preferred radicals R ⁵ are derived from Ci2-Ci8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from Cw-C20 oxo alcohols. Y is a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na ⁺ or K ⁺ , with Na ⁺ being extremely preferred. Further cations Y+ can be selected from NH4 ⁺ , %Zn ²⁺ ,% Mg ²⁺ ,% Ca ²⁺ ,% Mn ²⁺ , and mixtures thereof. Such particularly preferred surfactants are selected from fatty alcohol sulfates of the formula with k=11 to 19. Very particularly preferred representatives are Na-Ci2-14 fatty alcohol sulfates (k=11-13). In the case of the sulfonate surfactants (A=chemical bond in formula A-2), R ⁵ preferably represents a linear or branched, unsubstituted alkylaryl radical. Here, too, X is a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na ⁺ or K ⁺ , with Na ⁺ being extremely preferred. Further cations X+ can be selected from NH ₄₊ , % Zn ²⁺ , % Mg ²⁺ , % Ca ²⁺ , % Mn ²⁺ , and mixtures ^thereof . Such surfactants can be selected from linear or branched alkyl benzene sulfonates.

Instead of the surfactants mentioned or in combination with them, cationic and/or amphoteric surfactants such as betaines or quaternary ammonium compounds can also be used. However, it is preferred that no cationic and/or amphoteric surfactants are used.

In particular, silicates, aluminum silicates (particularly zeolites), carbonates, organic di- and polycarboxylic acids and aminocarboxylic acids or their salts are builders that can be contained in the dishwashing detergent, and—where there are no ecological prejudices against their use—also phosphates. Mixtures of these substances can also be used.

For example, crystalline layered silicates of the general formula NaMSi _x O2x+i·y H2O can be used, where M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values for x is 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layered silicates of the formula NaMSi _x O2x+i·y H2O are marketed, for example, by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂ 2O45·xH2O, kenyaite), Na-SKS-2 (Na2SiuO29·xH2O, magadiite), Na-SKS-3 (Na2SisOi7 × H2O) or Na-SKS-4 (Na2Si4Og × H2O, makatite). Crystalline phyllosilicates of the formula NaMSi _x C>2x+i·y H2O, in which x is 2, are particularly suitable for the purposes of the present invention. In particular, both ß- and 5-sodium disilicates Na2Si2Ü5 ■ y H2O and above all Na-SKS-5 (a-Na2Si2Os), Na-SKS-7 (ß-Na2Si2Os, Natrosilit), Na-SKS-9 (NaHSi ₂ O ₅ ■ H2O), Na-SKS-10 (NaHSi ₂ O ₅ ■ 3 H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi2Os), but in particular Na-SKS-6 (5-Na2Si2Os) is preferred. If desired, automatic dishwashing detergents can have a weight fraction of the crystalline layered silicate of the formula NaMSi _x O2x+i·y H2O of 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0.4 to 10 % by weight, based in each case on the total weight of these agents.

Amorphous sodium silicates with an Na2O:SiO2 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 are preferably delayed in dissolution, can also be used and have secondary washing properties. The delay in dissolving compared to conventional amorphous sodium silicates can have been brought about in various ways, for example by surface treatment, compounding, compacting/densification or by overdrying. In the context of this invention, the term "amorphous" means that the silicates do not provide sharp X-ray reflections in X-ray diffraction experiments, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle exhibit, cause.

In the context of the present invention, it is preferred that these silicate(s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, are present in the agents in amounts of 1 to 40% by weight, preferably 2 to 35% by weight. -%, each based on the weight of the automatic dishwashing detergent, are included.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use is not to be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) being particularly preferred, are the most important in the detergent and dishwashing detergent industry. Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish metaphosphoric acids (HPOsjn and orthophosphoric acid H3PO4 in addition to higher molecular weight representatives. The phosphates combine several advantages: They act as Alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.Technically particularly important phosphates are pentasodium triphosphate, NasPsOw (sodium umtripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K5 3O10 (potassium tripolyphosphate) and corresponding mixed salts (sodium potassium tripolyphosphate). However, the agents are preferably phosphate-free. If, in the context of the present application, phosphates are used as active cleaning substances in automatic dishwashing detergents, preferred detergents contain this phosphate(s), preferably alkali metal phosphate(s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in Amounts from 5 to 80% by weight, preferably from 10 to 60% by weight and in particular from 18 to 45% by weight, based in each case on the weight of the machine dishwashing detergent.

The dishwashing detergents can also contain, in particular, phosphonates as a further builder. A hydroxyalkane and/or aminoalkane phosphonate is preferably used as the phosphonate compound. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkane phosphonates are ethylene diamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues. The detergents preferably contain phosphonates in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight, based in each case on the total weight of the dishwashing detergent.

Other builders are the alkali carriers. Examples of alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali metal silicates mentioned, alkali metal metasilicates and mixtures of the aforementioned substances, with preference being given to using the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, for the purposes of this invention. A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred. A builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred. Due to their low chemical compatibility with the other ingredients of machine dishwashing detergents compared to other builder substances, the optional alkali metal hydroxides are preferably used only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4 % by weight and in particular below 2% by weight, in each case based on the total weight of the machine dishwashing detergent. Agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides are particularly preferred. Particular preference is given to using carbonate(s) and/or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate, in amounts of from 2 to 50% by weight, preferably from 5 to 40% by weight. and in particular from 7.5 to 30% by weight, in each case based on the weight of the automatic dishwashing detergent. Particular preference is given to detergents which, based on the weight of the automatic dishwashing detergent, contain less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate(s ) and/or hydrogen carbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate.

Particular mention should be made of polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and the phosphonates already mentioned above as builders as organic builders. 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, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids typically also have the property of an acidifying component and are therefore also used to set a lower and milder pH in the machine dishwashing detergents. Particular mention should be made here of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these. The use of citric acid and/or citrates in these agents has proven to be particularly advantageous for the cleaning and rinsing performance of the agents described herein. Automatic dishwashing detergents are therefore preferred, characterized in that the automatic dishwashing detergent contains citric acid or a salt of citric acid. Another important class of phosphate-free builders are aminocarboxylic acids and/or their salts. Particularly preferred representatives of this class are methylglycinediacetic acid (MGDA) or its salts and glutamicdiacetic acid (GLDA) or its salts or ethylenediaminediacetic acid or its salts (EDDS). The content of these aminocarboxylic acids or their salts can be, for example, between 0.1 and 30% by weight, preferably between 1 and 25% by weight and in particular between 5 and 20% by weight. Aminocarboxylic acids and their salts can be used together with the aforementioned builders, in particular also with the phosphate-free builders.

The dishwashing detergents can also contain a sulfopolymer. The proportion by weight of the sulfopolymer in the total weight of the dishwashing detergent according to the invention is preferably from 0.1 to 20% by weight, in particular from 0.5 to 18% by weight, particularly preferably from 1.0 to 15% by weight, in particular from 4 to 14% by weight, especially from 6 to 12% by weight. The sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70% by weight, in particular 30 to 50% by weight, preferably about 35 to 40% by weight, of sulfopolymers. A copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the sulfopolymer. The copolymers can have two, three, four or more different monomer units. In addition to monomer(s) containing sulfonic acid groups, preferred copolymeric polysulfonates contain at least one monomer from the group of unsaturated carboxylic acids. The unsaturated carboxylic acid(s) used is/are particularly preferably unsaturated carboxylic acids of the formula R ¹ (R ² )C═C(R ³ )COOH, in which R ¹ bis R ³ independently represent -H, -CH3, 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, substituted with -NH2, -OH or -COOH Alkyl or alkenyl radicals 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. Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. Of course, the unsaturated dicarboxylic acids can also be used. In the case of the sulfonic acid group-containing monomers, preference is given to those of the formula R ⁵ (R ^e )C═C(R ⁷ )—X—SO 3 H in which R ⁵ to R ⁷ independently 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 -NH2, -OH or -COOH 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, and X represents an optionally present spacer group selected from -(CH2)n- with n = 0 to 4, -COO-(CH2)k - with k = 1 to 6, -C(O)-NH- C(CH ₃ ) ₂ -, -C(O)-NH-C(CH ₃ )2-CH2- and -C(O)-NH- CH(CH ₃ )-CH2-. Preferred among these monomers are those of the formulas H ₂ C=CH-X-SO ₃ H, H ₂ C=C(CH 3 )-X-SO ₃ H and HO ₃ SX-(R ^e )C=C(R ⁷ ) - X-SO3H, in which R ^e and R ⁷ are independently selected from -H, -CH3, -CH2CH3, -CH2CH2CH3 and -CH(CH ₃ )2 and X stands for an optionally present 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 -, -C(O) -NH-C(CH ₃ ) ₂ -CH2- and -C(O)-NH-CH(CH3)-CH2-. Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate , 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-soluble salts. In the polymers, some or all of the sulfonic acid groups can be present in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention. In the case of copolymers which contain only carboxylic acid group-containing monomers and sulfonic acid group-containing monomers, the monomer distribution of the copolymers preferably used is preferably 5 to 95% by weight in each case, and the proportion of the sulfonic acid group-containing monomer is particularly preferably 50 to 90% by weight. -% and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are preferably selected from those mentioned above. The molar mass of the sulfo-copolymers preferably used can be varied in order to adapt the properties of the polymers to the desired application. Preferred dishwashing detergents are characterized in that the copolymers have molar masses from 2000 g/mol to 200,000 g/mol, preferably from 4000 g/mol to 25,000 g/mol and in particular from 5000 g/mol to 15,000 g/mol.

The dishwashing detergents can also contain other polymers. The group of suitable polymers includes, in particular, the cleaning-active polymers, for example the rinse-aid polymers and/or polymers that act as softeners. Preferred polymers that can be used come from the group of alkylacrylamide/acrylic acid copolymers, alkylacrylamide/methacrylic acid copolymers, alkylacrylamide/methylmethacrylic acid copolymers, alkylacrylamide/acrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/ Methacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/methylmethacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/alkyl methacrylate/alkylaminoethyl methacrylate/alkyl methacrylate copolymers and copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated ones Carboxylic acids and optionally other ionic or non-ionic monomers. Other usable polymers come from the group of acrylamidoalkyltrialkylammonium chloride/acrylic acid copolymers and their alkali metal and ammonium salts, acrylamidoalkyltrialkylammonium chloride/methacrylic acid copolymers and their alkali metal and ammonium salts and methacroylethyl betaine/methacrylate copolymers. Usable cationic polymers come from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and methacrylic acid and their esters and amides, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, of vinylpyrrolidone-methoimidazolinium chloride copolymers, of quaternized polyvinyl alcohols or of the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

Preferably, the agents of the present invention contain at least one enzyme preparation or enzyme composition containing one or more enzymes. Suitable enzymes include, but are not limited to, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in dishwashing detergents, which are used with preference accordingly. The agents preferably contain enzymes in total amounts of 1×10 ® to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the Biuret method. Proteases are among the most technically important enzymes of all. They break down proteinaceous soiling on the items to be cleaned. Among these, in turn, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are serine proteases because of the catalytically active amino acids. They act as non-specific endopeptidases and hydrolyze any acid amide bonds that are inside peptides or proteins. Their optimum pH is usually in the clearly alkaline range. Subtilases are naturally produced by microorganisms. Among these, the subtilisins formed and secreted by Bacillus species should be mentioned in particular as the most important group within the subtilases. Examples of the subtilisin-type proteases preferably used in detergents and dishwashing detergents are the subtilisins BPN' and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, subtilisin DY and the the subtilases, but no longer the subtilisins in the narrower sense, thermitase, proteinase K and the proteases TW3 and TW7, as well as variants of the proteases mentioned, which have an altered amino acid sequence compared to the starting protease. Proteases are modified in a targeted or random manner using methods known from the prior art and are thus optimized, for example, for use in detergents and dishwashing detergents. These include point mutagenesis, deletion or insertion mutagenesis, or fusion with other proteins or protein parts. Correspondingly optimized variants are known for most of the proteases known from the prior art.

Examples of usable amylases are the α-amylases from Bacillus licheniformis, from B. amyloquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, and the further developments of the aforementioned amylases which have been improved for use in dishwashing detergents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Lipases or cutinases can also be used, in particular because of their triglyceride-splitting activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally available from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the D96L amino acid substitution.

It is also possible to use enzymes which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases and ß-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 to increase the bleaching effect. Advantageously, preferably organic, particularly preferably aromatic, compounds that interact with the enzymes are additionally added in order to increase the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons in the case of greatly differing redox potentials between the oxidizing enzymes and the soiling (mediators).

An enzyme can be protected against damage such as, for example, inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage. In the case of microbial production of the proteins and/or enzymes, inhibition of proteolysis is particularly preferred, particularly if the agents also contain proteases. Dishwashing detergents may contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.

Cleaning-active enzymes are generally not provided in the form of the pure protein, but rather in the form of stabilized preparations that can be stored and transported. These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like preparations, solutions of the enzymes, advantageously as concentrated as possible, low in water and/or mixed with stabilizers or other auxiliaries.

Alternatively, the enzymes can be encapsulated for both the solid and 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 enclosed as in a set 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. Additional active substances, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers. 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 due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.

Furthermore, it is possible to formulate two or more enzymes together, so that a single granulate has several enzyme activities. As a rule, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Preferably used enzyme preparations contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight % of the enzyme protein.

Dishwashing detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of enzyme preparations are particularly preferred.

The compositions herein may also include enzyme stabilizers. One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are often used for this purpose, including above all derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the Salts or esters of the compounds mentioned. Peptide aldehydes, ie oligopeptides with a reduced C-terminus, in particular those composed of 2 to 50 monomers, are also used for this purpose. The peptidic reversible protease inhibitors include ovomucoid and leupeptin. Specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are also suitable for this. Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanolamine and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Other enzyme stabilizers are known to those skilled in the art from the prior art.

Bleaching agents are active cleaning substances. Sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are among the compounds that serve as bleaching agents and produce H2O2 in water. Other usable bleaches are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which supply H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. All other inorganic or organic peroxy bleaches known to those skilled in the art from the prior art can also be used. The percarbonates and here in particular sodium percarbonate are particularly preferred as bleaching agents. In various embodiments, the dishwashing detergents can contain from 1% by weight to 35% by weight, preferably from 2.5% by weight to 30% by weight, particularly preferably from 3.5% by weight to 20% by weight. and in particular from 5% to 15% by weight of bleach, preferably sodium percarbonate.

In various embodiments of the invention, the machine dishwashing detergents additionally contain at least one bleach activator. Bleaching activators which can be used are compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids preferably having 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid can be used. Of all the bleach activators known to the person skilled in the art from the prior art, polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are acylated Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used. Combinations of conventional bleach activators can also be used. TAED is very particularly preferred as the bleach activator, especially in combination with a percarbonate bleach, preferably sodium percarbonate. These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2% by weight to 8% by weight and particularly preferably 2% by weight to 6 % by weight, based in each case on the total weight of the agent.

In general, the pH of the dishwashing detergent can be adjusted using customary pH regulators, with the pH being selected depending on the desired application. In various embodiments, the pH is in a range from 5.5 to 10.5, preferably from 5.5 to 9.5, more preferably from 7 to 9, in particular greater than 7, especially in the range from 7.5 to 8.5 . Acids and/or alkalis, preferably alkalis, are used as pH adjusters. Suitable acids are, in particular, organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, however, the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used. Suitable bases come from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide are preferred. However, particular preference is given to volatile alkali, for example in the form of ammonia and/or alkanolamines, which can contain up to 9 carbon atoms in the molecule. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof. To adjust and/or stabilize the pH, the agent according to the invention can also contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate 2H2O and tripotassium citrate H2O.

Glass corrosion inhibitors prevent the occurrence of cloudiness, streaks and scratches, but also iridescence on the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group consisting of magnesium and zinc salts and magnesium and zinc complexes. In the context of the present invention, the content of zinc salt in dishwashing detergents is preferably in the range from 0.1% by weight to 5% by weight, preferably from 0.2% by weight to 4% by weight % by weight and in particular from 0.4% by weight to 3% by weight, in each case based on the total weight of the agent containing glass corrosion inhibitor.

Perfume oils or fragrances which can be used in the context of the present invention are individual odorant compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance note. Perfume oils of this type can also contain natural mixtures of fragrances, such as those obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

Furthermore, preservatives can be contained in the agents. For example, preservatives from the groups of alcohols, aldehydes, antimicrobial acids and/or salts thereof, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof are suitable such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl carbamate, iodine, iodophors and peroxides . Preferred antimicrobial agents are preferably selected from the group consisting of ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-Benzyl-4-chlorophenol, 2,2'-methylene-bis(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chloro- phenyl)-N-(3,4-dichlorophenyl)-urea, N,N'-(1,10-decanediyldi-1-pyridinyl-4-ylidene)-bis-(1-octan-amine)-dihydrochloride, N, N'-bis(4-chlorophenyl)-3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide, antimicrobial quaternary surfactants, guanidines. However, particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.

In general, the machine dishwashing detergents described herein can be packaged in different ways. The agents can be presented in solid or liquid form or as a combination of solid and liquid forms. Powders, granules, extrudates, compacts, in particular tablets, are particularly suitable as solid supply forms. The liquid supply forms based on water and/or organic solvents can be thickened and in the form of gels. The agents can be packaged in the form of single-phase or multi-phase products. The individual phases of multi-phase agents can have the same or different states of aggregation.

The dishwashing detergents can be in the form of shaped bodies. In order to facilitate the disintegration of such prefabricated shaped bodies, it is possible to use disintegration aids, so-called tablet disintegrants, incorporated into these agents to shorten disintegration times. Tablet disintegrants or disintegrants are understood as meaning excipients which ensure that tablets disintegrate rapidly in water or other media and that the active ingredients are released rapidly. Disintegration aids can preferably be used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, based in each case on the total weight of the composition containing disintegration aids.

The machine dishwashing detergents described herein are preferably prepackaged to form dosing units. These dosing units preferably include the amount of cleaning-active substances required for one cleaning cycle. Preferred dosage units weigh between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g. The volume of the aforementioned dosing units and their three-dimensional shape are selected with particular preference in such a way that the prefabricated units can be dosed via the dosing chamber of a dishwasher. The volume of the dosage unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

The machine dishwashing detergents, in particular the prefabricated dosing units, particularly preferably have a water-soluble coating.

The water-soluble cover is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures. The cover can be formed from one or from two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if any, can be the same or different. Films are particularly preferred which can be glued and/or sealed to form packaging such as tubes or pillows after they have been filled with an agent.

The water-soluble packaging can have one or more compartments. The agent can be contained in one or more compartments, if any, of the water-soluble coating. The amount of agent preferably corresponds to the full or half dose required for one rinse.

It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings that contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, especially cold water solubility. Suitable water-soluble films for producing the water-soluble casing are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 g/mol to 1,000,000 g/mol, preferably from 20 000 g/mol to 500,000 g/mol, particularly preferably from 30,000 g/mol to 100,000 g/mol and in particular from 40,000 g/mol to 80,000 g/mol. Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are correspondingly produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 mole % to 100 mole %, preferably 80 mole % to 90 mole %, particularly preferably 81 mole % to 89 mole % and in particular 82 mole% to 88 mole%. A polymer containing (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid can additionally be added to a polyvinyl alcohol-containing film material suitable for producing the water-soluble covering or mixtures of the above polymers may be added. A preferred additional polymer are polylactic acids. In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers include dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred. Polyvinyl alcohol copolymers which are also preferred include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters or mixtures thereof. It can be preferred that the film material contains other additives. The film material can contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, anti-blocking agents, anti-adhesive agents or mixtures thereof. Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packages of the invention are films sold by MonoSol LLC, for example, under the designation M8630, C8400 or M8900. Other suitable films include films with the name Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

In the machine dishwashing process according to the invention, the agent according to the invention is metered into the interior of a dishwasher while a dishwashing program is running, before the start of the main wash cycle or during the course of the main wash cycle. The agent according to the invention can be dosed or introduced into the interior of the dishwasher manually, but the agent is preferably dosed into the interior of the dishwasher by means of the dosing chamber. examples

Example 1: Synthesis of a metal complex

Under an N2 atmosphere, a solution of 477 mg (0.87 mmol) anhydrous cerium (IV) ammonium nitrate in 3 ml of dry methanol was slowly added. The reaction mixture was stirred at 65°C for 48 hours, allowed to cool to room temperature and the solvent removed in vacuo. The residue was dried at 40° C. in a vacuum drying cabinet. A beige solid was obtained.

Example 2: Hydrolysis of Protein Soil

The hydrolysis of the protein soil was investigated using the degradation of bovine serum albumin (BSA). To this end, the complex prepared in Example 1 was added to an aqueous BSA solution so that the concentration of BSA was 0.02 mM and the concentration of the complex was 2 mM, and at 60°C and pH 9 (adjusted with NaOH and HCl) incubated for 24 hours. The incubated material was then examined using the known method of SDS-PAGE with regard to the intensity of the band assigned to the BSA. BSA incubated under the same conditions without the addition of a complex served as a reference. The intensity values thus obtained are relative values related to the intensity of the reference band at t=0. The values showed that the ovalbumin band decreased in the presence of the substance according to the invention from Example 1:

Claims

patent claims

1. Dishwashing detergents, in particular machine dishwashing detergents, containing a metal complex of the general formula (I),

(A ^q+ )p[M ^s+ L ^m ](X ⁰ )r (I) where q is 1 or 2 and A ^q+ is a cation selected from alkali metal cations with q=1, 1/2 alkaline earth cations with q=2 and ammonium ions with q = 1, M ^s+ is an aluminum ion, a transition metal ion or a lanthanide metal ion, s is a number from 1 to 5, L is a ligand of formula (II), wherein each R ¹ and R ² is independently selected from H, unsubstituted or substituted, linear or branched C1-20 alkyl, unsubstituted or substituted, linear or branched C1-20 heteroalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted, linear or branched C2-20 alkenyl, unsubstituted or substituted, linear or branched C2-20 heteroalkenyl and unsubstituted or substituted, linear or branched C2-20 alkynyl, unsubstituted or substituted, linear or branched alkylaryl, unsubstituted or substituted, linear or branched alkylheteroaryl, each R ³ is independently CH2COOH or CH2COO-, n is 0 or 1, X ^0- is an anion selected from F-, Cb, Br, I-, OH-, HSOs", SO3 ² ; SO4 ^2- , HSO4: NO2; NO3; PO4 ³ ; HPO4 ^2- , H2PO4', BF ₄ -, PFe', CIO4-, acetate, citrate, formate, glutarate, lactate, Ma lat, malonate, oxalate, pyruvate, tartrate, methanesulfonate, methyl sulfate, p-toluene sulfate and succinate, m is a number from 0 to 5 and 0 is a number from 1 to 3, and p and r are independently a number of 0 through 6 with the proviso that the sum of s and the product of p and q is equal to the sum of m and the product of r and 0, and with the further proviso that those of the radicals R ¹ , R ² and R ³ resulting charge of formula (II) is neutral or negative.

2. Use of a metal complex of the general formula (I), (A ^q+ ) _P [M ^s+ L ^m ](X° )r (I) in which q is 1 or 2 and A ^q+ is a cation selected from alkali metal cations with q = 1, 1/2alkaline earth cations with q = 2 and ammonium ions with q = 1, M ^s+ represents an aluminum ion, a transition metal ion or a lanthanide metal ion, s represents a number from 1 to 5, L represents a ligand of the formula (II ) stands, wherein each R ¹ and R ² is independently selected from H, unsubstituted or substituted, linear or branched C1-20 alkyl, unsubstituted or substituted, linear or branched C1-20 heteroalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted, linear or branched C2-20 alkenyl, unsubstituted or substituted, linear or branched C2-20 heteroalkenyl and unsubstituted or substituted, linear or branched C2-20 alkynyl, unsubstituted or substituted, linear or branched alkylaryl, unsubstituted or substituted, linear or branched alkylheteroaryl, each R ³ is independently CH2COOH or CH2COO-, n is 0 or 1, X ^0- is an anion selected from F', CI', Br, I', OH', HSOs', SC> 3 ² ', SC ² ', HSC', NC>2', NOs', PC ³ ', HPC ² ', H2PO4', BF ₄ ', PFe', CIO4', Acetate, Citrate, Formate, Glutarate, Lacta t, malate, malonate, oxalate, pyruvate, tartrate, methanesulfonate, methyl sulfate, p-toluene sulfate and succinate, m is a number from 0 to 5 and 0 is a number from 1 to 3, and p and r are independently one numbers from 0 to 6 with the proviso that the sum of s and the product of p and q is equal to the sum of m and the product of r and 0, and with the further proviso that the radicals formed from R ¹ , R ² and R ³ resulting charge of formula (II) is neutral or negative, or a dishwashing detergent containing such a complex, in an automatic dishwashing process for removing soils. Machine dishwashing process in which a metal complex of the general formula (I),

(A ^q+ ) _P [M ^s+ L ^m ](X° )r (I) where q is 1 or 2 and A ^q+ is a cation selected from alkali metal cations with q = ¹ , 1/2 alkaline earth cations with q = 2 and ammonium ions with q = 1, M ^s+ is an aluminum ion, a transition metal ion or a lanthanide metal ion, s is a number from 1 to 5,

L is a ligand of formula (II), wherein each R ¹ and R ² is independently selected from H, unsubstituted or substituted, linear or branched C1-20 alkyl, unsubstituted or substituted, linear or branched C1-20 heteroalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted, linear or branched C2-20 alkenyl, unsubstituted or substituted, linear or branched C2-20 heteroalkenyl and unsubstituted or substituted, linear or branched C2-20 alkynyl, unsubstituted or substituted, linear or branched alkylaryl, unsubstituted or substituted, linear or branched alkylheteroaryl, each R ³ is independently CH2COOH or CH2COO-, n is 0 or 1, X ^0- represents an anion selected from F-, Cb, Br, I-, OH-, HSOs', SO3 ² ; ^SC2 ', HSC', NO2; NO3; PC ^3- , HPC ² ', H2PO4', BF ₄ -, PFe', CIO ₄ -, acetate, citrate, formate, glutarate, lactate, malate, malonate, oxalate, pyruvate, tartrate, methanesulfonate, methyl sulfate, p-toluene sulfate and succinate, m is a number from 0 to 5 and 0 is a number from 1 to 3 and p and r are independently a number from 0 to 6 with the proviso that the sum of s and the product of p and q is equal to the sum of m and the product of r and 0, and with the further proviso that the charge of formula (II) resulting from the radicals R ¹ , R ² and R ³ is neutral or negative, or a dishwashing detergent , which ^contains a ^complex of ^{this type} , is ^used . , Ce ³⁺ , Ce ⁴⁺ , Sc ³⁺ , Yb ³⁺ and mixtures thereof Agent according to Claim 1 or 4, Use according to Claim 2 or 4, or Process according to Claim 1 or 4, characterized in that in the ligand of the general formula (II) substituents in the substituted variants of R ¹ and R ² are -COOH, -COO-, -SH, -SO3H, -SO3; -C(O)R ⁴ , -OR ⁴ or -(NR ⁵ R ^e R ⁷ R ⁸ ) ⁺ in which R ⁴ represents H, linear or branched C1-6 alkyl and R ⁵ to R ⁸ independently represent linear or branched C1-6 alkyl groups are. Agent, use or method according to one of the preceding claims, characterized in that in the ligand of the general formula (II) n is 0. Agent, use or method according to one of the preceding claims, characterized in that the agent contains 0.001% by weight to 10% by weight, in particular 0.01% by weight to 3% by weight of the metal complex of the formula (III) contains.