DE102017212348A1 - Use of a cleaning agent containing aminocarboxylic acids and sulfopolymers for the inhibition of deposits - Google Patents

Abstract

The present invention relates to the use of at least one copolymer as defined herein and at least one aminocarboxylic acid in a hard surface cleaner to prevent or reduce scale formation on surfaces, especially metal surfaces.

Description

The present invention relates to the use of at least one copolymer as defined herein and at least one aminocarboxylic acid in a hard surface cleaner to prevent or reduce scale formation on surfaces, especially metal surfaces.

The most important criteria in automatic dishwashing are the cleaning performance on a wide variety of stains which are introduced into the dishwasher in the form of food residues and the avoidance of deposits on the items to be washed. In this respect, there is generally a need for dishwashing detergents with increased cleaning performance and improved inhibition of coating. In addition, a general trend for reasons of environmental protection in machine dishwashing to dispense with phosphates is observed. The problem thus arises of providing phosphate-free automatic dishwashing detergents without adversely affecting the cleaning performance and the inhibition of coating.

The object of the present invention was therefore to provide a, preferably phosphate-free, machine dishwasher detergent which has improved coating inhibition.

It has now been found that the use of certain copolymers in combination with builders from the class of aminocarboxylic acids in automatic dishwasher detergents surprisingly leads to improved deposit inhibition on surfaces, in particular metallic surfaces.

1. a) mindestens einem Copolymer enthaltend mindestens ein Sulfonsäuregruppen-haltiges Monomer und mindestens ein Monomer aus der Gruppe der α,β ethylenisch ungesättigten Carbonsäuren; und
2. b) mindestens einer Aminocarbonsäure oder einem Salz davon, insbesondere Methylglycindiessigsäure oder deren Salzen;

in einem Reinigungsmittel für harte Oberflächen, vorzugsweise einem maschinellen Geschirrspülmittel, zur Vermeidung oder Reduzierung von Belagsbildung auf einer Oberfläche, vorzugsweise einer Metalloberfläche.A first object of the present invention is therefore the use of

1. a) at least one copolymer containing at least one sulfonic acid-containing monomer and at least one monomer selected from the group of α, β-ethylenically unsaturated carboxylic acids; and
2. b) at least one aminocarboxylic acid or a salt thereof, in particular methylglycinediacetic acid or salts thereof;

in a hard surface cleaner, preferably a machine dishwashing detergent, to prevent or reduce deposit formation on a surface, preferably a metal surface.

For the purposes of the invention, metal surfaces are in particular those surfaces which are made of metal or coated with metal.

The surface is in particular the surface of the washed dishes and the use is made to prevent the formation of deposits on dishes during its cleaning in an automatic dishwasher. In particular, the surface is the metallic surface (or metal surface) of the washed dishes as well as the surfaces in the dishwasher itself made of metal. This also includes the interior, in particular the inner walls of the dishwasher, which are made of metal or coated with metal. In particular, the use according to the invention for avoiding the formation of deposits on dishes takes place during its cleaning in an automatic dishwashing machine.

These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Further, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular that the invention is not limited to these examples. Numeric ranges indicated in the format "from x to y" include the above values. If multiple preferred numeric ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints are also captured.

"At least one" as used herein means 1 or more, i. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to an ingredient, the indication refers to the type of ingredient, not the absolute number of molecules. Thus, "at least one copolymer" means, for example, at least one type of copolymer, i. that is, one kind of copolymer or a mixture of several different copolymers may be meant. The term, together with weights, refers to all compounds of the type indicated which are included in the composition / mixture, i. that the composition does not contain any further compounds of this type beyond the stated amount of the corresponding compounds.

When referring to molecular weights herein, these references always refer to the number average molecular weight M _n , unless explicitly stated otherwise. The number average molecular weight can be determined, for example, by means of gel permeation chromatography (GPC) according to DIN 55672-1: 2007-08 using THF as the eluent. The mass average molecular weight M _w can also be determined by GPC, as described for M _n .

All percentages taken in connection with the compositions described herein, unless explicitly stated otherwise, are% by weight, based on the particular mixture / composition, of "about", "about" or "about" used herein interchangeably and in connection with a numerical value mean the corresponding value ± 10%, preferably ± 5%.

The agents described herein are hard surface cleaners, especially dishwashing detergents, more preferably automatic dishwashing detergents. Each embodiment described herein for detergents in general is thus also applicable to dishwashing detergents, and in particular automatic dishwashing detergents, and vice versa.

In the context of the present invention are fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms. In particular, the oxo alcohols obtainable, for example, according to the R _OELEN's oxo-alcohols or their derivatives can also be used accordingly.

Whenever alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.

The copolymers used according to the invention may have two, three, four or more different monomer units. Preferred copolymers contain, in addition to sulfonic acid-containing monomer (s), at least one monomer from the group of unsaturated carboxylic acids.

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

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid (methylmaleic acid), methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. Very particular preference is given to acrylic acid.

In the sulfonic acid-containing monomers are those of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H in which R ⁵ to R ⁷ are each 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 ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - , -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

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

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.

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

The monomer distribution of the copolymers preferably used in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably the proportion of the sulfonic acid group-containing monomer is from 50 to 90% by weight. and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.

In various embodiments, in addition to the above-described carboxylic acid group-containing monomers and sulfonic acid group-containing monomers, the copolymers may contain other monomers, particularly unsaturated carboxylic acid ester group-containing monomers. In such terpolymers, the carboxylic acid ester group-containing monomers are, for example, those of the formula R ¹ (R ² ) C =C (R ³ ) COOR ⁴ , in which R ¹ to R ^{3 are} as defined above and R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acid esters are alkyl esters of monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, sorbic acid, cinnamic acid or mixtures thereof. Very particular preference is given to C _1-8 -alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate. Very particular preference is given to ethyl acrylate.

The molecular weight of the copolymers used can be varied in order to adapt the properties of the polymers to the desired use. Preferred agents are characterized in that the copolymers have molar masses M _{n of} from 2000 to 200,000 g / mol, preferably from 4000 to 25,000 g / mol and in particular from 5000 to 15,000 g / mol.

The copolymers may each be used in amounts of 0.5 to 20% by weight, preferably 1 to 18% by weight, more preferably 2 to 15% by weight, most preferably 2 to 12% by weight, based on the Total weight of the agent are used. Absolute amounts are typically in the range of 0.1 to 4 g / job, preferably in the range of 0.2 to 3.0 g / job.

The aminocarboxylic acids used according to the invention are in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), aspartic diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS), ethylenediamine disuccinate (EDDS), glutamine-N, N-diacetic acid (also known as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA), methylglycinediacetic acid (MGDA) and derivatives thereof and mixtures thereof. Particularly preferred are GLDA and MGDA and their salts, more preferably MGDA and its salts.

Particularly preferred is the use of MGDA or GLDA, in particular MGDA, as granules or Kompaktat. Particularly advantageous are those MGDA granules which contain as little water as possible and / or have a lower hygroscopicity (water absorption at 25 ° C., normal pressure) compared to the non-granulated powder.

The at least one aminocarboxylic acid, which is preferably MGDA or which comprises MGDA, is preferably used in an amount of 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 5 to 25% by weight. -%, most preferably 5 to 20 wt .-%, based on the total weight of the agent used. Absolute amounts are typically in the range of 0.1 to 8 g / job, preferably in the range of 0.2 to 5.0 g / job.

The mass ratio of the at least one copolymer and the at least one aminocarboxylic acid is preferably in the range of 4: 1 to 1: 4, more preferably 3: 1 to 1: 3, still more preferably 2.5: 1 to 1: 2.5 more preferably 2: 1 to 1: 2, for example 1.8: 1 to 1: 1.8, in particular about 1: 1, for example 1.2: 1 to 1: 1.2.

Surprisingly, the copolymer / builder combinations used in accordance with the invention, as defined above, exhibit the property of improving the performance of dishwashing agents in terms of scale inhibition, and therefore result in improved cleaning performance, i. reduced coverings on the items to be washed, in particular metallic Spülgutoberflächen.

In this case, the improvement of the scale inhibition is generally to be understood as meaning that with the use according to the invention less deposits on the items to be washed remain in an automatic dishwashing machine in comparison with the use of dishwashing agents which do not contain the combinations used according to the invention.

The cleaning agents may further contain other polymers. The group of suitable polymers includes, in particular, homopolymers of α, β-ethylenically unsaturated carboxylic acids and the cleaning-active amphoteric, zwitterionic or cationic polymers, for example the rinse aid polymers and / or polymers which act as softeners.

The homopolymers of α, β-ethylenically unsaturated carboxylic acids used according to the invention are in particular those homopolymers in which the carboxylic acids described above in the context of the copolymers are used as the unsaturated carboxylic acid (s). Particularly preferred unsaturated carboxylic acids are also acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid (methylmaleic acid), methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof , Very particular preference is given to acrylic acid. In various embodiments of the invention, the homopolymer is therefore a polyacrylic acid.

Also in said homopolymers, the carboxylic acid groups may be wholly or partially in neutralized form, i. in that the acidic carbon atom of the carboxylic acid group in some or all of the carboxylic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or completely neutralized polymers is preferred according to the invention.

The molecular weight of the homopolymers used can be varied in order to adapt the properties of the polymers to the desired end use. Preferred cleaning agents are characterized in that the homopolymers, in particular the polyacrylic acids, have molar masses M _{n of} from 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1100 to 10 000 g / mol, and more preferably from 1200 to 5000 g / mol, may again be preferred from this group.

Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth ) -acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Further 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 methacroylethylbetaine / methacrylate copolymers.

Useful cationic polymers come from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the 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 methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

• - die Verkapselung der Polymere mittels wasserlöslicher oder wasserdispergierbarer Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• - die Verkapselung der Polymere mittels wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30°C;
• - die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder (Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the abovementioned amphoteric, zwitterionic or cationic polymers are present in prefabricated form. For the preparation of the polymers is suitable inter alia

• the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• - The encapsulation of the polymers by means of water-insoluble, fusible coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;
• - The cogranulation of the polymers with inert support materials, preferably with support materials from the group of washing or cleaning-active substances, particularly preferably from the group of builders (builders) or cobuilders.

The compositions contain the aforementioned homopolymers, cationic and / or amphoteric polymers, preferably in amounts between 0.01 and 10 wt .-%, each based on the total weight of the composition. In the context of the present application, however, preference is given to those agents in which the proportion by weight of the homopolymers, cationic and / or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0 , 01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the composition.

In various embodiments of the invention, the agent may further contain at least one bleaching agent and optionally at least one bleach catalyst.

The bleach catalysts preferably used in the present invention include, but are not limited to, the group of bleach-enhancing transition metal salts and transition metal complexes, preferably Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the agents which are macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (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 ).

Means comprising 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-TACN) or 1,2,4, 7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN) are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.

The abovementioned bleach-enhancing transition metal complexes, in particular having the central atoms Mn and Co, are preferably used in an amount of up to 1% by weight, in particular from 0.001% by weight to 0.1% by weight and more preferably of 0.01% by weight. % to 0.05 wt .-%, each based on the Total weight of the bleach catalyst-containing agents used. In special cases, however, more bleach catalyst can be used.

The bleaching agents which can be used according to the invention are washing or cleaning-active substances. 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. Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. It is also possible to use all other inorganic or organic peroxy bleaches known to the person skilled in the art.

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

Preferably, the bleaching agent is in an amount of 1-35 wt%, and more preferably 2-30 wt%, 3.5-25 wt%, 4-20 wt%, and most preferably 5 -15% by weight in the composition, in each case based on the total weight of the composition. Preferred agents are further characterized in that the agent, based in each case on the total weight of the composition, 2 to 20 wt .-%, preferably 3 to 18 wt .-% and in particular 4 to 15 wt .-% sodium percarbonate.

Particularly preferred embodiments of the invention agents are characterized in that the bleach catalyst is 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 -TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN), and / or the hydrogen peroxide source is sodium percarbonate, sodium perborate tetrahydrate or sodium perborate monohydrate, or a combination thereof. Most preferably, the bleach catalyst is a complex of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), in particular [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ , or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN) or a mixture thereof, and the hydrogen peroxide source sodium percarbonate. In the said combinations, the bleach catalyst and the hydrogen peroxide source are preferably present in the amounts stated above.

In various embodiments of the invention, the agents additionally contain at least one bleach activator. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Of all the bleach activators known to the person skilled in the 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. Very particular preference is TAED. Combinations of conventional bleach activators can also be used. These bleach activators 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 more preferably from 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.

The agents used according to the invention preferably comprise at least one further constituent, in particular at least two further constituents selected from the group consisting of other builders, surfactants, enzymes, corrosion inhibitors and glass corrosion inhibitors, disintegration aids, fragrances and perfume carriers which differ from the aminocarboxylic acids.

The following describes possible ingredients which can be used advantageously in the compositions used according to the invention.

The use of further builder substances (builders) such as silicates, aluminum silicates (in particular zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builder substances, may be advantageous.

In a preferred embodiment, the use of phosphates (including polyphosphates) is largely or completely omitted. The agent in this embodiment preferably contains less than 5% by weight, more preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s). Most preferably, in this embodiment, the agent is completely phosphate-free, i. the agents contain less than 0.1% by weight of phosphate (s).

The builders include in particular carbonates, citrates, phosphonates, organic builders and silicates. The proportion by weight of the total builders including the aminocarboxylic acids in the total weight of the composition used according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight.

Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which have more than one, especially two to eight, acid functions, preferably two to six, in particular two, three, four or five acid functions carry throughout the molecule. Preferred polycarboxylic acids are thus dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids. The polycarboxylic acids may carry further functional groups, such as hydroxyl or amino groups. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid) and derivatives thereof and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid and mixtures thereof.

Also suitable as organic builders are polymeric polycarboxylates (organic polymers having a multiplicity of (in particular greater than 10) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins.

In addition to their builder effect, the free acids also typically have the property of an acidifying component and can thus, if desired, also serve to set a lower pH. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Particularly preferred cleaning agents used according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, contain one or more salts of citric acid, ie citrates, as one of their essential builders. These are preferably in a proportion of 2 to 40 wt .-%, in particular from 5 to 30 wt .-%, particularly from 7 to 28 wt .-%, particularly preferably 10 to 25 wt .-%, most preferably 15 to Contain 20 wt .-%, each based on the total weight of the composition.

Also particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate (soda), in amounts of 2 to 50 wt .-%, preferably from 4 to 40 wt. -% and in particular from 10 to 30 wt .-%, most preferably 10 to 24 wt .-%, each based on the weight of the composition.

Particularly preferred cleaning agents used according to the invention, in particular dishwashing detergents, preferably automatic dishwasher detergents, are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates and citrates, the weight fraction of these builders, based on the total weight of the detergent, being preferred 5 to 70 wt .-%, preferably 15 to 60% by weight and in particular 20 to 50 wt .-% is. The combination of two or more builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of cleaning agents used according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents. In addition to the builders mentioned here, one or more other builders may additionally be present.

Preferred cleaning agents, in particular dishwashing agents, preferably automatic dishwasher detergents, are characterized by a builder combination of citrate and carbonate and / or bicarbonate.

In a very particularly preferred embodiment according to the invention, a mixture of carbonate and citrate is used in the composition, the amount of carbonate preferably being from 5 to 40% by weight, in particular from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight .-% and the amount of citrate preferably from 5 to 35 wt .-%, in particular 10 to 25 wt .-%, most preferably 15 to 20 wt .-%, each based on the total amount of the cleaning agent is, wherein the Total amount of these two builders preferably 20 to 65 wt .-%, in particular 25 to 60 wt .-%, preferably 30 to 50 wt .-%, is. In addition, one or more further builders may additionally be included.

The detergents used according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, may, as far as is not excluded by the legislator in the individual countries, contain as further builders in particular phosphonates. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the hydroxyalkane phosphonates, the 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates, in particular HEDP, are preferably used in compositions according to the invention in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight, very particularly preferably from 2.5 to 7.5% by weight .-%, each based on the total weight of the composition.

Particularly preferred is the combined use of citrate, (hydrogen) carbonate and phosphonate (in addition to the aminocarboxylic acids used in the invention). These can be used in the above quantities. In particular, in this combination amounts of, in each case based on the total weight of the composition, 10 to 25 wt .-% citrate, 10 to 30 wt .-% carbonate (or bicarbonate), and 2.5 to 7.5 wt .-% Phosphonate used. A particularly preferred combination is therefore, for example, citrate, (hydrogen) carbonate and MGDA and optionally phosphonate.

The combination of at least three, in particular at least four, builders from the above-mentioned group has proven to be advantageous for the cleaning and rinsing performance of cleaning agents used according to the invention, in particular dishwashing detergents, preferably automatic dishwasher detergents. In addition, other builders may be included.

As organic builders, polymeric polycarboxylates are furthermore suitable; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol. Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

The content of the cleaning agents, in particular dishwashing agents, preferably automatic dishwashing agents, of (homo) polymeric polycarboxylates is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight.

Detergents used in accordance with the invention, in particular dishwashing agents, preferably automatic dishwashing detergents, may furthermore comprise, as builder, crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values for x being 2, 3 or 4, and y being 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. The preferred amount of silicate, in particular the above-described sodium disilicate, is from 0 to 35% by weight, in particular from 2 to 25% by weight, preferably from 5 to 20% by weight, based on the total weight of the cleaning agent. In special administration forms, for example washing or cleaning agent tablets, the amount of sodium disilicate is 5 to 10, in particular 5 to 9,% by weight.

In preferred cleaning agents, in particular certain dishwashing agents, preferably automatic dishwashing detergents, the content of silicates, based on the total weight of the detergent, is limited to amounts below 15% by weight, preferably below 10% by weight.

In addition to the aforementioned builders, the agents may further contain alkali metal hydroxides. These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, more preferably between 0.1 and 5% by weight and in particular between 0.5 and 5% by weight , in each case based on the total weight of the detergent used. Alternative detergents used according to the invention are free of alkali metal hydroxides.

The agents used according to the invention may contain surfactants, the nonionic, the anionic, the cationic, the zwitterionic and the amphoteric surfactants being counted among the group of surfactants.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

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 alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

However, low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. With particular preference, the agents contain nonionic surfactants from the group of alkoxylated alcohols.

A class of useful nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Preferably used surfactants come from the groups of ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are characterized by good foam control.

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder-Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.Suitable nonionic surfactants are those which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

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

Of these, particular preference is given to nonionic surfactants which have a C _9-15 -alkyl radical containing 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.

• - R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder-Alkenylrest steht;
• - R² für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• - A, A', A" und A'" unabhängig voneinander für einen Rest aus der Gruppe -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, - CH₂-CH(CH₂-CH₃) stehen,
• - w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.

Preferred nonionic surfactants here are those of the general formula R ^{1 is} -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A '''O) _z -R ² ,
in the

• - R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 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 -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 are 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, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms and 90, preferably for values between 10 and 80 and in particular for values between 20 and 60. Especially preferred are surfactants of the above formula in which R ^{1 is} C ₇ to C ₁₃ , x is an integer from 16 to 28 and R ^{2 is} C ₈ to C ₁₂ .

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

The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ - (EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2 -hydroxydecylether. Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1 such that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH ) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is Numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 have} 9 to 14 carbon atoms, R ^{3 is} H and x values of 6 until 15.

• - R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder-Alkenylrest steht;
• - R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• - A für einen Rest aus der Gruppe CH₂CH₂, CH₂CH₂CH₂, CH₂CH(CH₃), vorzugsweise für CH₂CH₂ steht, und
• - w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht

Finally, the nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w- R ^{2 have} proved to be particularly effective, in which

• - R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 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 ), preferably CH ₂ CH ₂ , and
• w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40

The group of these nonionic surfactants include, for example, the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ethers and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether.

In various embodiments of the invention, instead of the above-defined end-capped hydroxy mixed ethers, it is also possible to use the corresponding non-end-capped hydroxy mixed ethers. These may satisfy the above formulas, but R ² is hydrogen and R ¹ , R ³ , A, A ', A ", A"', w, x, y and z are as defined above.

The compositions described herein, which comprise at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, contain the surfactant in various embodiments in an amount based on the total weight of the composition of at least 2 wt.%, Preferably at least 5 wt. %. For example, the amounts used per application may be in the range of 0.5-10 g / job, preferably in the range of 0.5-5 g / job.

Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred ,

Suitable anionic surfactants in the compositions are all anionic surfactants. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium as well as mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

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

The amounts given above for the described surfactants and builders usually refer to the amounts that are used when the particular surfactant or the respective builders used alone, unless explicitly stated otherwise. It is therefore natural that when using multiple surfactants or builders, the quantities are adjusted accordingly.

Preferably, the agents 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 basically of natural origin; starting from the natural ones Molecules are available for use in cleaning agents improved variants, which are preferably used accordingly. Detergents used according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Proteases are among the most technically important enzymes of all. For detergents and cleaners, they are the longest established and contained in virtually all modern, powerful detergents and cleaners enzymes. They cause the degradation of protein-containing stains on the items to be cleaned. Of these, in turn, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are due to the catalytically active amino acids serine proteases. They act as nonspecific endopeptidases and hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range. An overview of this family is provided, for example, by the article "Subtilases: Subtilisin-like Proteases" by R. Siezen, pages 75-95 in "Subtilisin enzymes", edited by R. Bott and C. Betzel, New York, 1996. Subtilases are naturally occurring formed by microorganisms. Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.

Examples of the subtilisin-type proteases preferably used in detergents and cleaners 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 not the subtilisins in the narrower sense attributable enzyme thermitase, proteinase K and the proteases TW3 and TW7, as well as variants of said proteases, which have a relation to the parent protease modified amino acid sequence. Proteases are selectively or randomly modified by methods known from the prior art and thus optimized, for example, for use in detergents and cleaners. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. Thus, correspondingly optimized variants are known for most proteases known from the prior art.

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

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L, T213R and / or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.

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

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations. Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

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

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.

Particular preference is given to 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.

The compositions described 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 frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned. Also, peptide aldehydes, that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose. Among the peptidic reversible protease inhibitors include ovomucoid and leupeptin. Also, specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Other enzyme stabilizers are known to those skilled in the art.

In general, the pH of the agent can be adjusted by means of customary pH regulators, the pH value being selected depending on the desired application. In various embodiments, the pH is in a range of 5.5 to 10.5, preferably 5.5 to 9.5, more preferably 7 to 9, especially greater than 7, especially in the range 7.5 to 8.5 , The pH adjusting agents are acids and / or alkalis, preferably alkalis. 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, it is also possible to use the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof. Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred. However, particularly preferred is volatile alkali, for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule. The alkanolamine here 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 used according to the invention may also contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents). Particularly preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate.2H ₂ O and tripotassium citrate H ₂ O.

Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes. In the context of the present invention, the content of zinc salt in the compositions is preferably between 0.1 and 5 wt.%, Preferably between 0.2 and 4 wt.% And in particular between 0.4 and 3 wt the content of zinc in oxidized form (calculated as Zn ²⁺ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight .-%, each based on the total weight of the glass corrosion inhibitor-containing agent. Additionally or alternatively to the abovementioned salts (in particular the zinc salts), polyethyleneimines, such as are obtainable, for example, under the name Lupasol® (BASF), may preferably be present in an amount of from 0 to 5% by weight, in particular from 0.01 to 2% by weight. %, are used as glass corrosion inhibitors.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

Furthermore, preservatives may be included in the compositions. Suitable examples are preservatives from the groups of alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof 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, iodophores and peroxides. Preferred antimicrobial agents are preferably selected from the group comprising 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'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4- Chlorophenyl) -3,12-diimino-2,4,11,13-tetraazatetradecandiimidamide, antimicrobial quaternary surface active compounds, 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 formulation of cleaning agents described herein, in particular automatic dishwashing agents, can take place in different ways. The agents may be in solid or liquid form as well as in a combination of solid and liquid forms. Powder, granules, extrudates, compacts, in particular tablets, are particularly suitable as firm supply forms. The liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels. The agents can be formulated in the form of single-phase or multi-phase products. The individual phases of multiphase agents may have the same or different states of matter.

A phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous. A phase differs from another phase by various features, such as ingredients, physical properties, appearance, etc. Preferably, different phases can be visually distinguished. Thus, for the consumer, the at least one first phase is clearly distinguishable from the at least one second phase. If the cleaning agent used according to the invention has more than one first phase, then these can likewise be distinguished from one another by the naked eye, because they differ, for example, in color. The same applies if two or more second phases are present. Also in this case, a visual differentiation of the phases, for example due to a color or transparency difference is possible. Phases in the sense of the present invention are thus self-contained Areas that can be visually distinguished from the consumer by the naked eye. The individual phases may have different properties in use, such as the rate at which the phase dissolves in water and thus the rate and order of release of the ingredients contained in the respective phase.

The phases are typically spatially separated. This can be done in various embodiments such that when one or both of the phases are liquid phases, the liquid phase is separate from the other phase in a separate, sealed area, for example the chamber of a pouch. Such Konfektionsformen are known in the art. For solid agents, i. Means in which both phases are solids, the two phases are also made up spatially separated from each other, for example in the form of a multi-chamber pouches, each of the phases is present in a separate chamber. Alternatively, in the case of compacted agents, such as tabs or tablets, in particular multi-phase tabs as known in the art, the two phases may be arranged directly adjacent to each other spatially in such a way that the phases are formulated separately and contact each other, but can not mix.

The cleaning agents, in particular dishwashing agents, can be present as shaped bodies. In order to facilitate the disintegration of such prefabricated shaped bodies, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times. By tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients. Desintegration aids may preferably be used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.

The automatic dishwashing agents described herein are preferably prefabricated into dosage units. These metering units preferably comprise the amount of cleaning-active substances necessary for a cleaning cycle. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g. The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

The automatic dishwashing agents, in particular the prefabricated metering units, have a water-soluble coating, with particular preference.

The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.

The water soluble package may have one or more chambers. The agent may be contained in one or more chambers, if any, of the water soluble envelope. The amount of agent preferably corresponds to the full or half dose needed for a rinse.

It is preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.

Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 5,000 to 1,000,000 gmol ^-1 , preferably 20,000 to 500,000 gmol ^-1 , more preferably 30,000 to 100,000 gmol ^-1 and especially from 40,000 to 80,000 gmol ^-1 .

The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers corresponding to be prepared 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 makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

In addition, a polymer selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above may be additionally used in a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating Be added polymers. A preferred additional polymer is polylactic acids.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.

It may be preferred that the film material contains further additives. The film material may 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, antiblocking agents, anti-sticking agents or mixtures thereof.

Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

According to a preferred embodiment, the multi-phase dishwashing detergent is closely enveloped by a water-soluble film

The water-soluble film, which is preferably used in the narrow envelope, particularly preferably comprises polyvinyl alcohol, as described above, wherein as starting thickness preferably a thickness of 10 .mu.m to 100 .mu.m, in particular from 12 .mu.m to 60 .mu.m, particularly preferably from 15 .mu.m to 50 μm, especially from 20 microns to 40 microns, in particular from 22 microns to 35 microns is used.

In the case of a tight enclosure, a disposable portion of the detergent is wrapped in each case. It is important for the coated detergent portion that the wrapper rests close to its surface at each point of the tablets. Ideally, the envelope is even under tension, which is not absolutely necessary. This dense covering of the envelope is conducive to disintegration: upon first contact with water, the envelope will pass a small amount of water at some point, and at first it does not need to dissolve at all. At this point, the disintegrant contained in the tablet begins to swell. As a result, the wrapper suddenly ruptures as a result of the volume increase of the tablet and releases the tablet. If the wrapper is not tight, the mechanism described here will not work as the tablet can swell without bursting the wrapper. In this case, the use of a swellable disintegrating agent is superior to a gas-developing system, since its explosive effect in each case leads to a rupture of the casing. In a gas-evolving system, the explosive effect may "fizzle out" of the enclosure by leakage of the gas from a leak.

Preferred cleaning agent disposable portions are characterized in that the distance between the disposable portion and water-soluble coating over the entire surface is 0.1 to 1000 μm, preferably 0.5 to 500 μm, particularly preferably 1 to 250 μm and in particular 2.5 to 100 μm ,

In a preferred embodiment, the foil wrapper is first loosely wrapped around a detergent feed portion and sealed and then shrunk onto it so that there is close contact between the foil wrapper and the detergent concentrate. Accordingly, are Detergent disposable portions used in the invention characterized in that the envelope is a shrunk onto this film packaging.

For example, this wrapping can be carried out by placing a water-soluble lower film on a conveyor chain or a mold (s) tool, then one or more detergent portion (s) are placed on the lower film; then a water-soluble upper film is placed on the detergent portion (s) on the lower film and this is then fixed on the lower film including the detergent portion (s),

Alternatively, this step can also be done by a single-stranded film, which is then placed around the disposable portions as a tube. This is followed by sealing and optional cutting of the films. Subsequently, then the shrinking of the film by the use of hot air or infrared radiation, optionally with pressing done.

Such water-soluble coatings are also in the patent applications WO 2004/031338 A such as WO 2003/099985 A , the disclosure of which is hereby incorporated by reference, already described.

Exemplary formulations of the agents include, in particular, phosphate-free dishwashing detergents. An exemplary formulation is the following (phosphate-free, solid dishwashing detergent formulation (tab), data indicating active ingredient in% by weight based on the total weight of the formulation). TABLE 1 raw material Amount (wt%) g / job based on the application amount of a single serving (in particular a tablet of 20 g) Na citrate 15.00 to 20.00 3.00-4.00 Phosphonate (eg HEDP) 0.00-7.50; preferably 2.5 to 7.5 0.0-1.50; preferably 0.50-1.50 MGDA 0.50 to 25.00 0.01 -5.00 Silicate (Na disilicate) 5.00 to 35.00 1,00 - 7,00 soda 12.50 to 25.00 2.50 to 5.00 Na Percarbonate 10.00 to 15.00 2.00-3.00 bleach catalyst 0.02-0.50 0.003 - 0.100 TAED 2.00-3.00 0.40 - 0.60 nonionic surfactant 2.50 to 10.00 0.50 to 2.00 Cationic copolymer 0.25-0.75 0.05-0.15 PVP (cross-linked) 0.00 to 1.50 0.00 to 0.30 Sulfonic acid containing polymer 0.5 to 10.00 0.01 -4.00 Polyacrylathomopolymer 0,5 -10,00 1.00-2.00 protease 1.50 to 5.00 0.30-1.00 amylase 0.50 to 3.00 0.10-0.60 Silver protection (eg benzotriazole) 0.00 to 0.50 0.00-0.10 Perfume 0.05-0.15 0.01 -0.03 dye solution 0.00-1.00 0.00-0.20 Zn acetate 0.10-0.30 0.02 -0.06 Na sulfate 0.00 to 25.00 0.00 to 5.00 water 0.00 to 1.50 0.00 to 0.30 pH adjusting agent (citric acid) 1.00-1.50 0.20 - 0.30 processing aids 0.00 to 5.00 0.00-1.00

In the uses according to the invention, the agent can be metered into the interior of a dishwasher during the passage of a dishwashing program before the start of the main wash cycle or during the main wash cycle. The metering or the entry of the agent into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher.

The coating inhibition, i. the avoidance or reduction of the formation of deposits on the items to be washed, such as dishes or cutlery, during dishwashing, can be observed on all surfaces, but is particularly pronounced on metallic surfaces. In particularly preferred embodiments, the use is therefore directed to the surface inhibition on metallic surfaces, such as stainless steel surfaces, such as occur for example in pots or cutlery. The use preferably takes place in the context of dishwashing, in particular automatic dishwashing.

Another object of the invention is the use of the means described above, in particular dishwashing detergent, more preferably the automatic dishwashing detergent, to prevent or reduce the formation of deposits on the inner surfaces of the dishwasher. Although the agent can also be applied in concentrated form on the inner surfaces, in particular the walls of the dishwasher. Prevention or reduction of deposit formation preferably takes place on the inner surfaces of the dishwasher, in particular on the inner walls of the dishwasher, during the execution of a dishwashing program or cleaning program. Most preferably, the avoidance or reduction of deposit formation on the inner surfaces of the dishwasher, in particular the metallic inner surfaces, in particular on the inner walls of the dishwasher takes place during a dishwashing cycle in the presence of items to be washed. With regard to the composition of the means, the one described above applies.

Examples

Example 1: Pad inhibition

TABLE 2 Formulations Active substance in% by weight based on the total weight of the formulation: V1 V2 E1 E2 Citrate dihydrate 25 25 25 25 MGDA (trisodium salt) 20 13 7 Sulfonic acid group-containing copolymer * 20 7 13 Soda heavy 6 6 6 6 bicarbonate 29 29 29 29 percarbonate 12 12 12 12 TAED 3 3 3 3 Amylase preparation (tq) 1 1 1 1 Protease preparation (tq) 1 1 1 1 nonionic surfactant 2 2 2 2 Perfume 0.6 0.6 0.6 0.6 Mn TACN 0,015 0,015 0,015 0,015 * Copolymer (AMPS and acrylic acid containing)

The deposit inhibition was determined in a Miele GSL 2 dishwasher in the 65 ° C program (R65 ° / 10 '/ KI65). Water hardness 21 ° dH. For this purpose, 20 g of the above formulations (Table 2, as a tablet) were used. In each case 30 rinsing cycles were carried out. After completion of all rinse cycles, the dishes were visually scanned in a black room with normalized illumination on a 1-10 scale. The higher the value, the better the coating inhibition. It can be seen that the formulations according to the invention, which contain copolymer and MGDA, show better deposit inhibition, in particular on metal, compared to the comparison formulations which contain only one of the two constituents in each case (Table 3).

The results show that all formulations used according to the invention show a better deposit inhibition on metal than the comparative formulations V1 and V2. Table 3: Pad inhibition Cutlery WMF Knife Solid Cutlery BSF knife Melody V1 only MGDA 4.0 4.0 V2 only copolymer 5,7 5,7 E1 MGDA: Copolymer 13: 7 7.3 7.0 E2 MGDA: Copolymer 7:13 7.7 7.5

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2004/031338 A [0141]
• WO 2003/099985 A [0141]

Claims (9)

use of a) at least one copolymer containing at least one sulfonic acid-containing monomer and at least one monomer selected from the group of α, β-ethylenically unsaturated carboxylic acids; and b) at least one aminocarboxylic acid or a salt thereof, in particular methylglycinediacetic acid or salts thereof; in a hard surface cleaner, preferably a machine dishwashing detergent, to prevent or reduce deposit formation on a surface, preferably a metal surface. Use after Claim 1 , characterized in that the at least one copolymer is a copolymer of (i) at least one monomer from the group of α, β-ethylenically unsaturated carboxylic acids of the formula R ¹ (R ² ) C =C (R ³ ) COOH, where R ¹ to R ^{3 is,} independently of one another, -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, in particular acrylic acid; and (ii) at least one sulfonic acid group-containing monomer of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H, where R ⁵ to R ⁷ 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 or -COOH or -COOR ⁴ wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO - (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and - C (O) -NH-CH (CH ₃ ) -CH ₂ -, preferably at least one monomer of the formula H ₂ C =CH-X-SO ₃ H, H ₂ C =C (CH ₃ ) -X-SO ₃ H or HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H where R ⁶ and R ^{7 are} independently others are selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -, more preferably a monomer selected from the group consisting of 1-acrylamido-1-propanesulfonic acid, 2-acrylamido 2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy- 3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, and sulfomethylmethacrylamide, most preferably 2-acrylamido-2-methyl-1-propanesulfonic acid; and (iii) optionally at least one α, β-ethylenically unsaturated carboxylic acid ester group-containing monomer of the formula R ¹ (R ² ) C =C (R ³ ) COOR ⁴ , wherein R ¹ to R ^{3 are} as defined above and R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, in particular an alkyl acrylate, particularly preferably ethyl acrylate. Use after Claim 1 or Claim 2 , characterized in that the at least one aminocarboxylic acid is methylglycine acetic acid or a salt thereof. Use according to one of Claims 1 to 3 , characterized in that the at least one copolymer has a molecular weight M _n of 2000 to 200,000 g / mol, preferably from 4000 to 25,000 g / mol and in particular from 5000 to 15,000 g / mol. Use according to one of Claims 1 to 4 , characterized in that a) the at least one copolymer in an amount of 0.5 to 20 wt .-%, preferably 1 to 18 wt .-%, more preferably 2 to 15 wt .-%, most preferably 2 to 12 Wt .-%, based on the total weight of the composition in this is included; and / or b) the at least one aminocarboxylic acid in an amount of 0.5 to 40 wt .-%, preferably 1 to 30 wt .-%, more preferably 5 to 25 wt .-%, most preferably 5 to 20 wt. -%, based on the total weight of the agent in this is included; and / or c) the mass ratio of the at least one copolymer and the at least one aminocarboxylic acid 4: 1 to 1: 4, preferably 3: 1 to 1: 3, more preferably 2.5: 1 to 1: 2.5, in particular 2: 1 to 1: 2. Use according to one of Claims 1 to 5 , characterized in that the cleaning agent further comprises at least one bleaching agent and optionally at least one bleach catalyst, the latter being preferably selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably complexes of manganese in the oxidation state II, III, IV or IV, which comprises a or more macrocyclic ligand (s) having the donor functions N, NR, PR, O and / or S, most preferably the macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (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), most preferably the ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN). Use after Claim 6 characterized in that (1) the bleach catalyst is contained in an amount of 0.001 to 0.1% by weight, preferably 0.01 to 0.05% by weight, based on the total weight of the composition; and / or (2) the at least one bleaching agent is selected from the group consisting of sodium percarbonate, sodium perborate tetrahydrate, sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates, perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid, diperdodecanedioic acid, diacyl peroxides, alkyl peroxyacids and aryl peroxyacids, preferably sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate, more preferably, sodium percarbonate; and / or (3) the at least one bleaching agent in an amount of 1-35 wt.%, and more preferably 2-30 wt.%, 3.5-25 wt.%, of 4-20 wt. % and more preferably from 5-15% by weight is contained in the composition, in each case based on the total weight of the composition. Use according to one of Claims 1 to 7 characterized in that (1) the automatic dishwashing detergent is in solid form; and / or (2) the automatic dishwashing detergent is in preportioned form; and / or (3) the automatic dishwashing detergent has a plurality of spatially separate compositions of which at least one composition is solid and / or a composition is liquid; and / or (4) the automatic dishwashing agent contains at least one bleach activator; and / or (5) the automatic dishwashing agent contains at least one further constituent, preferably at least two further constituents selected from the group consisting of other builders, surfactants, enzymes, corrosion inhibitors, glass corrosion inhibitors, disintegration aids, fragrances and perfume carriers which differ from aminocarboxylic acids. Use according to one of Claims 1 to 8th for avoiding or reducing deposit formation on the inner surfaces of the dishwasher, preferably during the execution of a dishwashing program, in particular in the presence of items to be washed.