EP0872543A2 - Corrosion-inhibiting cleaning composition - Google Patents

Abstract

In a detergent containing builder, bleach, bleach activator and a corrosion inhibitor for metals, the inhibitor comprises either (A) metal triazole complex (I), obtained by reacting a triazole of formula (II) or a triazole (IIIA) or bis-triazole (IIIB) of formula (III) with (b) salt(s) of manganese (Mn), cobalt (Co), zinc (Zn), iron (Fe), molybdenum (Mo), tungsten (W) and/or copper (Cu) and/or (B) (IIB) of formula (II) or a mixture of 2 or more components (A) and/or (B); in which R<1> = 1-4 substituents selected from hydrogen (H) and linear and branched 1-10C alkyl groups; in (IIIA), R<2>, R<3> = H, 1-20C alkyl or 2-20C alkenyl; or one of R<2>, R<3> = NHR<4>; R<4> = H or 1-10C alkyl; in (IIIB), 2 R<2> and R<3> groups of 2 different molecules = 1-10C alkylene and the other R<2>, R<3> groups = as in (IIIA).

Description

The invention relates to detergents, in particular machine detergents, containing a Corrosion protection agents for metals, especially for silver. As an anti-corrosion agent special triazole derivatives or complexes of di-, tri- or tetravalent metal salts with triazoles or mixtures of two or more of the components mentioned.

Metal objects, especially those made of silver, usually show on the long standing Air a significantly increasing discoloration, which is commonly used in common usage "Tarnishing" (corrosion) is called. As a rule, this "tarnishing" leads to the formation of darker, brownish, bluish or possibly blue-black spots. reason for that is usually the particular sensitivity of the metal surface to oxygen as well sulfur-containing, especially sulfidic gases, such as those found in the ambient air.

Corrosion is particularly noticeable when cleaning metal objects, especially when cleaning machine cleaning in dishwashers. Come as metal objects in the sense of the invention all commercially or privately used metal objects in question, such as those in industry, Research and technology as well as in the private sector can be found. The metal objects show in usually contamination that should be removed by the cleaning process, for example fat or protein or carbohydrate pollution. Especially Dinnerware and cutlery and kitchen utensils used in food preparation (where the latter three groups of items are below for the sake of simplicity Collective term "tableware") are exposed to such soiling.

The problem arises in particular in the case of so-called silverware that it is included in the As a rule, food residues containing sulfide groups are contaminated, and on the other hand cleaning usually together with other dishes, which usually also contain leftovers is dirty. Such soiling will occur in the course of the cleaning process regularly in the cleaning liquid (wash liquor), usually an aqueous one Solution and / or suspension of the detergent, distributed and therefore occur intensely with the Silverware surface in contact. In particular, food residues such as mustard, peas or egg bring sulfide groups Connections in the aqueous solution or dispersion of the cleaning liquid (washing liquor) a, both the food residues and other sulfur-containing compounds such as Mercaptoamino acids are a major cause of silver tarnishing. This Tarnishing is mainly due to the formation of colored silver complex compounds.

When mechanically cleaning silver objects, they are usually worn in the Compared to hand cleaning processes much higher temperatures and the longer contact times of the silver with the wash liquor to tarnish the surface. Because of the intense Cleaning process in the dishwasher also completes the silver surface degreased and therefore more sensitive to corrosion.

When using active chlorine-containing cleaners, tarnishing can be caused by sulfur-containing ones Compounds are largely prevented because these compounds in chlorine-containing cleaners are oxidatively converted to sulfones or sulfates, which do not contribute to corrosion of the Afford silver surface.

However, the problem of silver corrosion became acute again as an alternative to that Active chlorine compounds so-called active oxygen compounds, for example sodium perborate or sodium percarbonate, were used to remove bleachable stains, For example, tea stains / tea deposits, coffee residues, vegetable dyes, lipstick residues and the like serve.

"Active chlorine" and "active oxygen" are those in the sense of the present invention Proportions of chlorine or oxygen from the compounds containing active chlorine and active oxygen understood that are available for bleaching or for oxidation. Methods for determining the Active chlorine or active oxygen content is known to the person skilled in the art; Based on DIN 38409.

Such active oxygen compounds are usually used together with bleach activators used especially in so-called low-alkaline machine dishwashing detergents. Under In this text, "lower alkaline" detergents with pH values of less than about 10.8, for example about 8 to about 10.8, preferably with a pH of about 9 to about 10.5 Understood

Detergents generally consist of the functional building blocks and the bleaching system (Bleach plus bleach activator) and optionally other additives, for example Enzymes, wetting agents (surfactants) and / or fragrances.

Metal surfaces, especially silver surfaces, react to low-alkaline, active chlorine-free Detergents are generally more sensitive than those containing active chlorine. During the cleaning process the active oxygen-containing detergents set what is actually bleaching when cleaning Agent (active oxygen) free. The bleaching effect of the active oxygen-containing cleaners is due to Bleach activators accelerated so that a good bleaching effect is achieved even at low temperatures becomes. In the presence of these bleach activators, the reactive intermediate usually forms Peracetic acid. Under these changed cleaning conditions, silver surfaces appear not only sulfidic, but also by the oxidizing attack of the intermediates Peroxides or the active oxygen preferably oxidic coatings. Can under high salt load additional chloride deposits are formed. The tarnishing of the silver is also reinforced by higher residual water hardness during the cleaning cycle.

For this reason, the problem of corrosion of silver surfaces has mainly with the introduction Active oxygen-containing detergents instead of active chlorine-containing detergents have increased in importance.

Avoiding such corrosion of the silver surface by so-called silver protection agents known from numerous publications.

Thus, from "Soap & Chemical Spec.", 46, Issue 4 (1970), page 33, are machine-applicable Dishwashing detergent containing pentasodium triphosphate, sodium metasilicate, alkali carbonate and alkali perborate. They are usually used with pH values from 10.0 to 10.4 are free of activators.

DE-B 12 79 877 describes a method for mechanical dishwashing, the Detergent used per compounds and activators for these per compounds - including fatty acid Manganese salts - in the form of separate granules. As per connections organic peracids or their salts are also suitable. An addition from Anti-corrosion agents are recommended, but these anti-corrosion agents are not specified be designated.

DE-B 13 02 394 describes machine dishwashing detergents which also May contain alkali metal salts and a bleach activator. They also contain Enzymes and therefore only a pH value instead of the usually strongly alkaline pH value from 7-9.

From GB-A 1 131 738 alkaline dishwashing detergents are known which act as a corrosion inhibitor for Silver contain benzotriazoles.

US-A 3,549,539 describes strongly alkaline, machine-applicable dishwashing detergents described as an oxidizing agent i.a. Contain perborate with an organic bleach activator can. As a preventive agent, additives are used also of benzotriazole and also iron (III) chloride recommended.

From DE-B 16 95 219 it is known that acylated organic substances as activators for Per compounds can be used wherever peroxy compounds are used, e.g. in the Passivation of aluminum or other light metal surfaces. PH values of preferably called 7 to 11.5.

In EP-B 0 135 226 and EP-B 0 135 227 weakly alkaline, mechanically applicable Dishwashing detergent containing peroxy compounds and activators described as Silver protection agents etc. May contain benzotriazoles and fatty acids.

EP-B 0 145 090 protects alkaline structures, which can also be used for machine dishwashing Detergent, the peroxy compounds and as an activator for this one in aqueous solution Manganese (II) ion-providing compound and sodium metasilicate and their aqueous solutions have a pH of 9.5 to 13. You can still use surface active compounds and contain additional known organic peroxide activators. The bleaching effect of the peroxy compounds tar stains are enhanced there by the addition of manganese (II) salt activators.

Finally, it is known from DE-A 41 28 672 that peroxy compounds by addition known organic bleach activators are activated in strong alkaline detergents Prevent tarnishing of silver parts.

DE-A 43 15 397 describes the use of redox compounds, for example manganese sulfate, Catechol, gallic acid or hydroquinone, as a corrosion protection agent for silver surfaces known. DE-A1 43 25 922 also relates to the prevention of corrosion on silver surfaces. For this purpose, the corresponding detergents are metal salts and metal complexes of Ti, Zr, Hf, V, Co and Ce added.

A disadvantage has an effect on all triazole-containing detergents known from the prior art, that it can come in connection with active oxygen to the oxidation of the triazole compounds. The in Derivatives resulting from such an oxidation often have an unpleasant, sometimes annoying smell.

The object of the invention is therefore to provide a detergent with an anti-corrosion agent place that shows a good corrosion-inhibiting effect without the occurrence of unpleasant odors.

A) ein Metall-Triazol-Komplex herstellbar durch Umsetzung

a) eines Triazols der allgemeinen Formel I

worin R¹ für ein, zwei, drei oder vier Substituenten, die unabhängig voneinander Wasserstoff oder ein oder mehrere lineare und/oder verzweigte Alkylreste mit 1 bis 10 C-Atomen sein können, steht,
oder

b) eines Triazols der allgemeinen Formel II

worin R² und R³ unabhängig voneinander für Wasserstoff, C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl oder einer der Reste R² oder R³ für NHR⁴, wobei R⁴ Wasserstoff oder C₁-C₁₀-Alkyl bedeutet, stehen, oder jeweils zwei der Reste R² und R³ von zwei Triazolmolekülen gemeinsam für C₁-C₁₀-Alkylen stehen,
oder eines Gemischs aus zwei oder mehr Triazolen der allgemeinen Formeln I und/oder II, mit

c) einem Metallsalz oder einem Gemisch aus zwei oder mehr Metallsalzen, ausgewählt aus der Gruppe der Salze von Mn, Co, Zn, Fe, Mo, W oder Cu

oder

B) ein Triazol der allgemeinen Formel II, worin jeweils zwei der Reste R² und R³ von zwei Triazolmolekülen gemeinsam für C₁-C₁₀-Alkylen stehen und die verbleibenden Reste unabhängig voneinander für Wasserstoff, C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl oder für NHR⁴ stehen, wobei R⁴ Wasserstoff oder C₁-C₁₀-Alkyl bedeutet,
oder ein Gemisch aus zwei oder mehr der Komponenten A) und/oder B) enthalten ist.

The invention relates to a dishwashing detergent, at least containing scaffold, bleach, bleach activator and an anticorrosive for metals, being either an anticorrosive

A) a metal-triazole complex can be prepared by reaction

a) a triazole of the general formula I.

in which R ^{1 represents} one, two, three or four substituents which, independently of one another, can be hydrogen or one or more linear and / or branched alkyl radicals having 1 to 10 C atoms,
or

b) a triazole of the general formula II

wherein R ² and R ^{3 are} independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl or one of the radicals R ² or R ³ for NHR ⁴ , where R ^{4 is} hydrogen or C ₁ -C ₁₀ - Is alkyl, or two of the radicals R ² and R ³ of two triazole molecules together represent C ₁ -C ₁₀ alkylene,
or a mixture of two or more triazoles of the general formulas I and / or II, with

c) a metal salt or a mixture of two or more metal salts selected from the group of the salts of Mn, Co, Zn, Fe, Mo, W or Cu

or

B) a triazole of the general formula II, in which two of the radicals R ² and R ³ of two triazole molecules together represent C ₁ -C ₁₀ -alkylene and the remaining radicals independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ alkenyl or NHR ⁴ , where R ^{4 is} hydrogen or C ₁ -C ₁₀ alkyl,
or a mixture of two or more of components A) and / or B) is contained.

For the purposes of the present invention, “dishwashing agents” include solid and liquid Compounds understood to remove unwanted stains from hard Surfaces are used. The detergents are usually in the liquid during the rinsing process Condition used, with solid detergent in a suitable solvent, preferably before use be dissolved or dispersed in water. It is particularly preferred to use the detergent use as a dilute aqueous solution and / or dispersion.

The detergent according to the invention contains at least one water-soluble framework substance. As In principle, scaffolding substance comes with all scaffolding substances usually used in detergents in question, e.g. polymeric alkali phosphates, which can be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples include: tetrasodium diphosphate, Disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate as well as the corresponding potassium salts or mixtures of sodium hexametaphosphate and the corresponding Potassium salts or mixtures of sodium and potassium salts. The framework substance is usually in an amount of up to about 60% by weight, preferably up to about 35% by weight based on the total detergent, preferably the detergents according to the invention however free of phosphates. Other possible water-soluble framework substances are e.g. organic polymers of native or synthetic origin, especially polycarboxylates, which act as so-called co-builders, especially in hard water regions. Be considered for example polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the Alkali, preferably the sodium salts of these polycarboxylates. Commercial products are e.g. Sokalan® CP5 and PA30 from BASF Alcosperse® 175 or 177 from Alco, LMW® 45N and SPO2 N from Norsohaas. The native polymers include, for example, oxidized Starch (as described in German patent application DE-A 42 28 786) and polyamino acids, such as polyglutamic acid or polyaspartic acid, as made by Cygnus or SRCHEM are available.

Other possible builder substances are naturally occurring hydroxycarboxylic acids, such as mono- and Dihydroxysuccinic acid, á-hydroxypropionic acid and gluconic acid. Preferred The builders are the salts, especially the alkali salts, the citric acid, in particular Sodium citrate.

Anhydrous trisodium citrate or preferably trisodium citrate dihydrate is used as sodium citrate Consideration. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. In Depending on the pH ultimately set in the agents according to the invention, the acids on which the citrate is based.

The framework substances also include the alkali silicates, the alkali carbonates and Alkali hydrogen carbonates.

As alkali silicates, which mainly inhibit the corrosion of aluminum, onglaze decorations and Glasses are used, preferably anhydrous sodium or potassium disilicate, in which the ratio of alkali oxide to silicon dioxide is approximately 1: 2. The amount of alkali silicates in the total washing-up liquid is expediently about 0-10, preferably about 0-4% by weight.

Alkali carbonates which can preferably be used are water-free compounds, but also those containing water of crystallization, and naturally occurring forms, for example Trona (Na ₂ CO ₃ x NaHCO ₃ , from Solvay). Sodium carbonate and trona are preferred, the amount of the former being generally up to about 20% by weight, preferably about 7-12% by weight, the amount of the latter being up to about 40% by weight, preferably about 14-24 wt .-%, each based on the total detergent.

Are significantly higher levels of alkali carbonate or disilicate, such as 10 or 5% by weight used, the pH of the 1% -gen cleaner formulation rises above the desired weak alkaline range from 8 to 10.8, preferably about 9 to 9.5. In this case, a Substitution of sodium bicarbonate against citric acid in amounts of up to about 15% by weight, preferably up to about 8% by weight.

Furthermore, alkali hydrogen carbonate, which is generally used in the sodium form, can be used as Use the scaffold in the detergents according to the invention. The alkali hydrogen carbonate, especially sodium bicarbonate, should preferably be in a coarse, compact form with a Grain size in the main fraction between about 0.4 and about 1.0 mm can be used. The amount of the alkali metal bicarbonate on the detergent according to the invention is about 5 to about 50% by weight, preferably about 25 to about 40% by weight.

The detergents according to the invention have a pH of about 1% aqueous solution 7.5 to about 12, preferably about 8 to about 10.8 and particularly preferably about 9 to about 10.5. Preferred bleaches are oxygen-based bleaches, although they are these are primarily sodium perborate mono- and tetrahydrate or percarbonate salts. The use of percarbonate salts is advantageous because they are particularly beneficial for the Corrosion behavior of the detergent on glasses. The bleach is oxygen based therefore preferably a percarbonate salt, especially sodium percarbonate.

It is particularly preferred if the detergent according to the invention is used at least as a bleach Contains sodium perborate or sodium percarbonate or a mixture thereof.

Since the bleaches containing active oxygen generally only increase the active oxygen when they are high Release temperatures, and the bleaching agent only reaches its full temperature at elevated temperatures So-called bleach activators can have an effect on the detergent according to the invention added. These bleach activators lead to an accelerated release of the active oxygen from the active oxygen-containing salt even at lower temperatures, such as at automatic cleaning of dishes, for example silverware, in conventional dishwashers to rule. As a rule, these are temperatures of approximately 50 ° C. and more, preferably approximately 60 ° C. As Bleach activators are used e.g. PAG (pentaacetylglucose), DADHT (1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine) and ISA (isatoic anhydride), but preferably N, N, N ', N'-tetraacetylethylene diamine (TAED). In addition, the addition of small amounts of known bleach stabilizers, for example of phosphonates, borates or metaborates and metasilicates and of Magnesium salts such as magnesium sulfate may be useful. The proportion of bleach in the total detergent is a total of about 5-20% by weight, preferably about 5-15% by weight, based on the total mean. Sodium perborate is used in particular in amounts of up to approximately 15% by weight, preferably used in amounts of about 5 to about 10% by weight, sodium percarbonate in Amounts up to about 20% by weight, preferably in amounts from about 5 to about 12% by weight. The amount the bleach activator on the detergent according to the invention is about 1 to about 10% by weight, preferably about 2 to about 6% by weight, all the data in% by weight referring to the total Obtain detergent.

It is particularly preferred if the detergent according to the invention is a bleach activator N, N, N ', N'-tetraacetylethylenediamine (TAED) contains.

A) einen Metall-Triazol-Komplex erhältlich aus der Umsetzung von

a) einem Triazol der allgemeinen Formel I

worin R¹ für Wasserstoff oder jeweils für einen oder mehrere, voneinander unabhängige, lineare oder verzweigte Alkylreste mit 1 bis 10 C-Atomen steht,
oder

b) einem Triazol der allgemeinen Formel II

worin R² und R³ unabhängig voneinander für Wasserstoff, C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl steht, oder einer der Reste R² oder R³ für NHR⁴, wobei R⁴ Wasserstoff oder C₁-C₁₀-Alkyl bedeutet, stehen, oder jeweils zwei der Reste R² und R³ von zwei verschiedenen Molekülen gemeinsam für C₁-C₁₀-Alkylen stehen,
oder einem Gemisch aus zwei oder mehr Triazolen der allgemeinen Formeln I und/oder II, und

c) einem Metallsalz oder einem Gemisch aus zwei oder mehr Metallsalzen, ausgewählt aus der Gruppe der Salze von Mn, Co, Zn, Fe oder Cu.

Als Komponente a) können 1,2,3-Benzotriazole eingesetzt werden, deren Benzolkern entweder unsubstituiert ist, d.h. R¹ in Formel I steht für vier Wasserstoffatome, oder die einen, zwei, drei oder vier Alkylsubstituenten am Benzolkern aufweisen. Bei den Substituenten am Benzolkern handelt es sich um lineare und/oder verzweigte Alkylgruppen. Die Alkylgruppen weisen 1 bis etwa 10 C-Atome auf. Erfindungsgemäß bevorzugt als Komponente a) ist das unsubstituierte Benzotriazol, d.h. eine Verbindung der Formel I, in der R¹ für vier Wasserstoffatome steht.Als Komponente b) werden 1,2,4-Triazole der allgemeinen Formel II eingesetzt. Insbesondere steht dabei einer der Reste R² oder R³ für NHR⁴, wobei R⁴ Wasserstoff oder C₁-C₁₀-Alkyl bedeutet, während der verbleibende Rest für C₁-C₂₀-Alkyl steht. Besonders bevorzugt ist es, wenn R² für C₅-C₉-Alkyl, insbesondere für einen Heptyl- oder Nonylrest, und R³ für NH₂ steht.Besonders bevorzugt sind als Komponente a) das Benzotriazol und als Komponenten b) das 3-Amino-5-heptyl- und das 3-Amino-5-nonyl-1,2,4-triazol.Weiterhin können jeweils zwei der Reste R² und R³ von zwei verschiedenen Molekülen gemeinsam für C₁-C₁₀-Alkylen stehen, wodurch ein "verbrücktes" 1,2,4-Triazol entsteht. Unter einem verbrückten 1,2,4-Triazol ist daher erfindungsgemäß ein Molekül zu verstehen, das zwei 1,2,4-Triazolringe aufweist, die über eine bis zu 10 CH₂-Gruppen aufweisende Alkylkette verbunden sind. Vorzugsweise weist die Alkylkette im verbrückten Triazol eine, zwei, drei, vier oder fünf CH₂-Gruppen auf. Bevorzugt ist es, wenn zwei der Reste R² oder R³ aus zwei Triazolmolekülen gemeinsam für C₃-C₅-Alkylen stehen.Beispiele für die letztgenannten Verbindungen der Komponente b) sind 1,3-Bis[3-(5-amino-1,2,4-triazolyl)]-propan, 1,4-Bis[3-(5-amino-1,2,4-triazolyl)]-butan, 1,5-Bis[3-(5-amino-1,2,4-triazolyl)]-pentan, 1,6-Bis[3-(5-amino-1,2-4-triazolyl)]-hexan oder 1,7-Bis[3-(5-amino-1,2,4-triazolyl)]-heptan. Besonders bevorzugt ist hieraus das 1,4-Bis[3-(5-amino-1,2,4-triazolyl)]-butan.Um zur als Komponente A) bezeichneten Verbindung zu gelangen, werden die unter a) und b) beschriebenen Triazole mit einem Metallsalz, wie es als Komponente c) beschrieben ist, zu einem Komplex umgesetzt. Als Komponente c) wird wenigstens ein Salz eines Metalls ausgewählt aus der Gruppe Mn, Co, Zn, Fe, Mo, W oder Cu eingesetzt. Die Metalle können dabei in beliebigen Oxidationsstufen (außer Oxidationsstufe I) vorkommen, bevorzugt ist jedoch jeweils die Oxidationsstufe II, III oder IV, insofern das jeweilige Metall zur Bildung einer solchen Oxidationsstufe in der Lage ist. Fehlt die Fähigkeit zur Bildung höherer Oxidationsstufen, so ist die zweiwertige oder (wenn möglich) dreiwertige Oxidationsstufe im jeweiligen Metallsalz bevorzugt.Als Gegenionen in den Metallsalzen sind alle Gegenionen denkbar, die bei geeigneter Reaktionsführung mit den Triazolen der Komponenten a) oder b) oder Gemischen aus zwei oder mehr davon mindestens einen Komplex bilden. Die Metalle werden jedoch bevorzugt in Form ihrer Halogenide, Sulfate, Hydroxide, Acetate, Benzoate oder Citrate eingesetzt, wobei derzeit der Einsatz der Acetate bevorzugt ist.Unter den Metallsalzen besonders bevorzugt sind die Mangansalze und Gemische aus zwei oder mehr Mangansalzen, insbesondere bevorzugt sind die Acetate des Mangans in den Oxidationsstufen II, III oder IV.Verfahren zur Herstellung der jeweiligen Komplexe sind dem Fachmann bekannt. Besonders gut zur Herstellung der im erfindungsgemäßen Spülmittel einsetzbaren Komplexe geeignet sind die Verfahren, wie sie in Gmelin Handbook of Inorg. Chemistry, Mn, D4 (1985) und von R. N. B. Sahai et al. in Indian J. Chem., 14A, 05 (1976) beschrieben sind.Bevorzugt werden die unter A) eingesetzten Komplexe hergestellt, indem das in der Regel deprotonierte Triazol a) oder b) in heißer methanolischer Lösung mit dem Metallsalz bei einem pH-Wert von etwa 7 bis 8 umgesetzt wird. Das molare Verhältnis von Ligand zu Metallsalz beträgt dabei in der Regel etwa zwischen 1:1,5 und 1:5, bevorzugt etwa 1:2 bis 1:4.Ein Verhältnis von Ligand zu Metallsalz von etwa 1:4 bei der Herstellung der Komponente A) führt in der Regel zu einkernigen Komplexen, d.h. zu Komplexen, die lediglich ein Metallatom pro Molekül aufweisen.In einer alternativen Darstellungsform für die Komponente A) werden Ligand und Metallsalz in heißer, ethanolischer Lösung in einem 1:2 Verhältnis umgesetzt. Hierbei entstehen mehrkernige Komplexe, die mehr als ein Metallatom pro Molekül aufweisen,Beide beschriebenen Darstellungsformen führen zu Metall-Triazol-Komplexen, die in den erfindungsgemäßen Spülmitteln einsetzbar sind.Alternativ oder zusätzlich zur Komponente A) kann als Korrosionsschutzmittel im erfindungsgemäßen Spülmittel

B) ein Triazol der allgemeinen Formel II, worin jeweils zwei der Reste R² und R³ von zwei verschiedenen Molekülen gemeinsam für C₁-C₁₀-Alkylen stehen und die verbleibenden Reste unabhängig voneinander für Wasserstoff, C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl oder für NHR⁴ stehen, wobei R⁴ Wasserstoff oder C₁-C₁₀-Alkyl bedeutet,
eingesetzt werden.

The detergent according to the invention contains as a corrosion protection agent for metals

A) a metal-triazole complex obtainable from the reaction of

a) a triazole of the general formula I.

in which R ^{1 represents} hydrogen or in each case one or more, independently of one another, linear or branched alkyl radicals having 1 to 10 C atoms,
or

b) a triazole of the general formula II

wherein R ² and R ^{3 are} independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, or one of the radicals R ² or R ^{3 is} NHR ⁴ , where R ^{4 is} hydrogen or C ₁ -C _{10 represents} alkyl, or two of the radicals R ² and R ³ of two different molecules together represent C ₁ -C ₁₀ alkylene,
or a mixture of two or more triazoles of the general formulas I and / or II, and

c) a metal salt or a mixture of two or more metal salts selected from the group of the salts of Mn, Co, Zn, Fe or Cu.

As component a), 1,2,3-benzotriazoles can be used, the benzene nucleus of which is either unsubstituted, ie R ¹ in formula I represents four hydrogen atoms, or which have one, two, three or four alkyl substituents on the benzene nucleus. The substituents on the benzene nucleus are linear and / or branched alkyl groups. The alkyl groups have 1 to about 10 carbon atoms. According to the invention, preferred as component a) is the unsubstituted benzotriazole, ie a compound of the formula I in which R ^{1 represents} four hydrogen atoms. 1,2,4-triazoles of the general formula II are used as component b). In particular, one of the radicals R ² or R ^{3 is} NHR ⁴ , where R ^{4 is} hydrogen or C ₁ -C ₁₀ alkyl, while the remaining radical is C ₁ -C ₂₀ alkyl. It is particularly preferred if R ^{2 is} C ₅ -C ₉ alkyl, in particular a heptyl or nonyl radical, and R ^{3 is} NH _2. Particular preference is given to component a) as benzotriazole and as component b) as 3- Amino-5-heptyl- and 3-amino-5-nonyl-1,2,4-triazole. Furthermore, two of the radicals R ² and R ³ of two different molecules can together represent C ₁ -C ₁₀ alkylene, creating a "bridged" 1,2,4-triazole. A bridged 1,2,4-triazole is therefore to be understood according to the invention as a molecule which has two 1,2,4-triazole rings which are connected via an alkyl chain having up to 10 CH ₂ groups. The alkyl chain in the bridged triazole preferably has one, two, three, four or five CH ₂ groups. It is preferred if two of the radicals R ² or R ³ from two triazole molecules together represent C ₃ -C ₅ alkylene. Examples of the latter compounds of component b) are 1,3-bis [3- (5-amino- 1,2,4-triazolyl)] propane, 1,4-bis [3- (5-amino-1,2,4-triazolyl)] butane, 1,5-bis [3- (5-amino- 1,2,4-triazolyl)] - pentane, 1,6-bis [3- (5-amino-1,2-4-triazolyl)] - hexane or 1,7-bis [3- (5-amino- 1,2,4-triazolyl)] heptane. From this, the 1,4-bis [3- (5-amino-1,2,4-triazolyl)] butane is particularly preferred. To get to the compound referred to as component A), those described under a) and b) are described Triazoles with a metal salt, as described as component c), converted into a complex. At least one salt of a metal selected from the group Mn, Co, Zn, Fe, Mo, W or Cu is used as component c). The metals can occur in any oxidation state (except for oxidation state I), but preference is given to oxidation state II, III or IV, inasmuch as the respective metal is capable of forming such an oxidation state. If the ability to form higher oxidation levels is lacking, then the divalent or (if possible) trivalent oxidation level in the respective metal salt is preferred. As counter ions in the metal salts, all counter ions are conceivable which, if the reaction is carried out appropriately with the triazoles of components a) or b) or mixtures form at least one complex from two or more of them. However, the metals are preferably used in the form of their halides, sulfates, hydroxides, acetates, benzoates or citrates, with the use of the acetates currently being preferred. Among the metal salts, the manganese salts and mixtures of two or more manganese salts are particularly preferred, and those are particularly preferred Acetates of manganese in oxidation states II, III or IV. Processes for the preparation of the respective complexes are known to the person skilled in the art. The processes as described in Gmelin Handbook of Inorg are particularly well suited for the preparation of the complexes which can be used in the detergent according to the invention. Chemistry, Mn, D4 (1985) and by RNB Sahai et al. in Indian J. Chem., 14A, 05 (1976) . The complexes used under A) are preferably prepared by the generally deprotonated triazole a) or b) in hot methanolic solution with the metal salt at a pH from about 7 to 8 is implemented. The molar ratio of ligand to metal salt is generally about 1: 1.5 to 1: 5, preferably about 1: 2 to 1: 4. A ratio of ligand to metal salt of about 1: 4 in the preparation of the component A) usually leads to mononuclear complexes, ie to complexes that have only one metal atom per molecule. In an alternative representation for component A), ligand and metal salt are reacted in hot, ethanolic solution in a 1: 2 ratio. This gives rise to multinuclear complexes which have more than one metal atom per molecule. Both of the described forms lead to metal-triazole complexes which can be used in the detergents according to the invention. Alternatively or in addition to component A), it can be used as a corrosion inhibitor in the detergent according to the invention

B) a triazole of the general formula II, in which in each case two of the radicals R ² and R ³ of two different molecules together represent C ₁ -C ₁₀ -alkylene and the remaining radicals independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ alkenyl or NHR ⁴ , where R ^{4 is} hydrogen or C ₁ -C ₁₀ alkyl,
be used.

Mixtures of two or more triazoles of the general formula II in the detergents according to the invention are used.

The triazole which can be used as component B) likewise shows a good corrosion protection effect for metal surfaces, in particular for silver. R ³ is preferably C ₂ -C ₆ alkylene, C ₄ alkylene being preferred.

Examples of compounds of component B) are 1,3-bis [3- (5-amino-1,2,4-triazolyl)] propane, 1,4-bis [3- (5-amino-1,2, 4-triazoyl)] - butane, 1,5-bis [3- (5-amino-1,2,4-triazolyl)] pentane, 1,6-bis [3- (5-amino-1,2-4-triazolyl)] hexane or 1,7-bis [3- (5-amino-1,2,4-triazolyl)] heptane. Is particularly preferred from this the 1,4-bis [3- (5-amino-1,2,4-triazoyl)] butane.

The detergent according to the invention contains a metal-triazole complex A) or a mixture of several metal-triazole complexes A) or a bridged triazole B) or a mixture of several bridged triazoles B) or a mixture of A) and B) in an amount of about 0.001 up to 5% by weight, preferably in an amount of about 0.005 to 2.5% by weight, particularly preferably in in an amount of about 0.01 to 2% by weight and in particular in an amount of about 0.03 to 1.5 % By weight, based on the total detergent.

• nichtionische Tenside
• Enzyme
• Entschäumer
• Duftstoffe.

In addition to at least one compound selected from the group of the framework substances already described, bleaching agents, bleach activators and the corrosion inhibitor for metals, the dishwashing detergent according to the invention optionally also comprises at least one of the following substances:

• nonionic surfactants
• Enzymes
• Defoamer
• Fragrances.

The nonionic surfactants can be used in the dishwashing detergent, for example, as wetting agents, granulation aids or for better detachment of fatty substances such as food residues. They are generally used in an amount of up to about 4% by weight, preferably about 1 to about 2% by weight, based on the total detergent. Extremely low-foam connections are usually used. These preferably include the C ₁₂ -C ₁₈ alkyl polyethylene glycol polypropylene glycol ethers, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. However, other nonionic surfactants known to be low-foaming can also be used, such as, for example, C ₁₂ -C ₁₈ -alkylpolyethylene glycol-polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, end-capped alkylpolyethylene glycol mixed ethers and the foaming but extremely advantageous for ecological reasons C ₈ -C ₁₄ alkyl polyglycosides with a degree of polymerization of about 1-4 (APG®225 and APG®600 from Henkel) and / or C ₁₂ -C ₁₄ alkyl polyethylene glycols with 3-8 ethylene oxide units in the molecule. The nonionic surfactants can be used individually or as a mixture of two or more of the nonionic surfactants listed in the detergent according to the invention.

It turned out to be advantageous to use the non-ionic surfactants in bleached quality use, otherwise the detergent may have a dark color.

Also suitable for use in the detergents according to the invention are surfactants from the family of the glucamides, for example alkyl-N-methyl-glucamides, the term alkyl referring to fatty alcohol residues with a chain length of the alkyl residue of 6 to 14 carbon atoms. It may be advantageous if the surfactants described are not used in pure form, but rather as a mixture, for example the combination of alkyl polyglycoside with fatty alcohol ethoxylates or glucamides with alkyl polyglycosides and further binary or, if appropriate, ternary or quaternary or higher combinations of the nonionic surfactants disclosed here. Particularly low-foam surfactant combinations result from mixtures of C ₆ -C ₁₄ -alkyl polyglycosides with C ₈ -alkyl-N-methyl-glucamides.

If the detergents foam too much during use, they can still contain up to about 6% by weight, preferably about 0.5 to about 5% by weight, based on the detergent, of a defoamer, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized Silicic acid, paraffin oil / Guerbet alcohols, paraffins, hydrophobicized silicic acid, bisstearic acid amides and other defoamers known to those skilled in the art can be added. Are also suitable Mixtures of two or more of the defoamers mentioned.

For better detachment of protein or starchy soiling, such as food residues usually enzymes, such as proteases, amylases, lipases and cellulases, for example proteases, such as BLAP®150 from Henkel, Optimase®-M-440, Optimase®-M-330, Opticlean®-M-375, Opticlean®-M-250 from Solvay Enzymes; Maxacal® CX 450.000, Maxapem® from Ibis, Savinase® 4.0 T, 6.0 T, 8.0 T from Novo; or Esperase® T from Ibis; and amylases, such as Termamyl® 60 T, 90 T from Novo; Amylase-LT® from Solvay Enzymes; or Maxamyl® P 5000, CXT 5000 or CXT 2900 from Ibis; Lipases such as Lipolase® 30 T from Novo or cellulases such as Celluzym® 0.7 T from Novo Nordisk. The enzymes are made up either individually or as a mixture two or more of the enzymes mentioned. As a rule, their respective share is on total detergent at about 0.2 to about 5 wt .-%, preferably at 0.5 to about 1.5 wt .-%.

If necessary, the detergent according to the invention can also improve fragrances to improve the smell contain.

The detergents according to the invention can be present as solid or liquid detergents, preferably However, powdery, granular or tablet-like preparations are used, which are in Compact in the usual way, for example by mixing, granulating, rolling and / or by Spray drying,

To produce the detergent according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range from 800 to 900 g / l in a first stage of the process, the framework substance or a mixture of two or more Framework substances with at least a proportion of liquid mixture components, such as water or non-ionic surfactants, mixed with increasing the bulk density of this premix, and Subsequently - if necessary after an intermediate drying - the other components of the detergent, including, for example, the anti-corrosion agent for metals, with the resultant Premix combined. Here, too, is caused by a possible alkali carbonate content Alkalinity of the product strongly influenced in the direction of higher pH values, therefore the Intermediate drying should be carried out so that the alkali bicarbonate decomposes into alkali carbonate is as low as possible. Low drying temperatures don't just work for that Sodium bicarbonate fall counter, but increase the solubility of the granulated detergent the application. It is therefore advantageous when drying a supply air temperature that on the one hand Avoidance of bicarbonate decay should be as low as possible and, on the other hand, as high as necessary to obtain a product with good storage properties. Is preferred at Drying a supply air temperature of approx. 80 ° C. The granules themselves shouldn't be over temperatures be heated to about 60 ° C.

In the first stage of the mixing process, the framework substance or the mixture of two or more builders generally in admixture with at least one other component of the Dishwasher detergent with the liquid components. Consider here, for example a preliminary stage in which the framework substance mixed with perborate with the liquid nonionic Surfactants and / or a solution of the fragrances, if such are desired, are applied and is intimately mixed. The remaining components and the total mixture are then added worked through and homogenized in a mixing device. The shared use additional amounts of liquid, in particular the use of additional water, is in here usually not required. The resulting mixture of substances then lies as free-flowing, not dusting powder of the desired high bulk density.

The pre-granules are then with the missing components of the invention Detergent, including, for example, the anti-corrosion agent for metals, for the finished product mixed. The mixing time is in all cases shown here, both in the preliminary stage of compacting mixture under the influence of liquid components as well as in the following Final mixing with the other components, in the range of a few minutes, for example in Range from 1 to 5 minutes.

In a special embodiment, it can be used in the production of fine granules be expedient, a further by powdering the surface of the granules formed To achieve stabilization of the granulate and leveling of the surface. Are suitable for this especially small proportions of water glass powder or powdered alkali carbonate.

To produce detergents in tablet form according to the invention, the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture is pressed by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 × 10 ⁵ Pa to 1500 × 10 ⁵ Pa . In this way, unbreakable tablets are obtained which, under application conditions, dissolve sufficiently quickly and generally have a flexural strength of more than 150 N. A tablet produced in this way preferably has a weight of approximately 15 g to approximately 50 g, in particular approximately 20 g to approximately 30 g, the diameter of the tablet being about 35 mm to about 40 mm.

The detergents according to the invention can be used as dishwashing detergents, preferably as machine detergents Dishwashing detergent can be used for dishwashers. In the dishwasher can be both domestic dishwashers as well as commercial ones, as a rule larger dishwashers. The addition of the detergent according to the invention is usually done by hand or by means of suitable dosing devices. The application concentrations in the usually aqueous rinsing solution or rinsing dispersion (rinsing liquor) is about 2 to about 8 g detergent per liter of cleaning liquor, preferably about 3 to about 5 g / l.

The cleaning of the parts to be cleaned is generally carried out sequentially. That is, on one The cleaning cycle is followed by an intermediate rinse cycle with clear water, with the cleaning-rinsing sequence can be repeated several times in succession. If necessary, and when using the The detergent according to the invention is preferred as the dishwashing detergent, follows the last cleaning-rinsing sequence a rinse cycle with a common rinse aid. After drying the cleaned parts are usually not only clean and hygienic, parts with a silver surface in particular remain brightly shiny.

a) ein Triazol der allgemeinen Formel I

worin R¹ für Wasserstoff oder jeweils für einen oder mehrere, voneinander unabhängige, lineare oder verzweigte Alkylreste mit 1 bis 10 C-Atomen steht,
oder

b) ein Triazol der allgemeinen Formel II

worin R² und R³ unabhängig voneinander für Wasserstoff, C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl steht, oder einer der Reste R² oder R³ für NHR⁴, wobei R⁴ Wasserstoff oder C₁-C₁₀-Alkyl bedeutet, stehen, oder zwei der Reste R² und R³ von zwei verschiedenen Molekülen gemeinsam für C₁-C₁₀-Alkylen stehen und die verbleibenden Reste die oben angegebene Bedeutung haben,
oder ein Gemisch aus zwei oder mehr Triazolen der allgemeinen Formeln I und/oder II,
und

c) ein Metallsalz oder ein Gemisch aus zwei oder mehr Metallsalzen, ausgewählt aus der Gruppe der Salze von Mn, Co, Zn, Fe, Mo, W oder Cu,
miteinander umgesetzt werden,
als Korrosionsschutzmittel in Spülmitteln, insbesondere in maschinellen Spülmitteln und besonders bevorzugt in maschinellen Geschirrspülmitteln.

The invention thus relates to the use of a metal-triazole complex which can be prepared by

a) a triazole of the general formula I.

in which R ^{1 represents} hydrogen or in each case one or more, independently of one another, linear or branched alkyl radicals having 1 to 10 C atoms,
or

b) a triazole of the general formula II

wherein R ² and R ^{3 are} independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, or one of the radicals R ² or R ^{3 is} NHR ⁴ , where R ^{4 is} hydrogen or C ₁ -C _{10 represents} alkyl, or two of the radicals R ² and R ³ of two different molecules together represent C ₁ -C ₁₀ alkylene and the remaining radicals have the meaning given above,
or a mixture of two or more triazoles of the general formulas I and / or II,
and

c) a metal salt or a mixture of two or more metal salts selected from the group of the salts of Mn, Co, Zn, Fe, Mo, W or Cu,
implemented with each other
as an anti-corrosion agent in detergents, in particular in machine detergents and particularly preferably in machine dishwashing detergents.

The invention furthermore relates to the use of a triazole of the general formula II, in which in each case two of the radicals R ² and R ³ of two different molecules together represent C ₁ -C ₁₀ alkylene and the remaining radicals independently of one another are hydrogen, C ₁ - C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl or NHR ⁴ , where R ^{4 is} hydrogen or C ₁ -C ₁₀ alkyl, as corrosion inhibitor in detergents, in particular in machine detergents and particularly preferably in machine dishwashing detergents.

The invention also relates to the use of a detergent according to the invention as automatic dishwashing detergent and the use of a detergent according to the invention for Cleaning of objects.

• 20 - 60, vorzugsweise etwa 30 bis 50 Gew.-% Gerüstsubstanzen, hierunter insbesondere etwa
  • 20 bis 60, vorzugsweise etwa 30 bis 50 Gew.-% Pentanatriumtriphosphat oder
  • 20 - 60, vorzugsweise etwa 30 bis 50 Gew.-% Citrat bzw. Salze der Hydroxycarbonsäuren oder
  • 20 - 60, vorzugsweise etwa 30 bis 50 Gew.-% Citrat bzw. Salze der Hydroxycarbonsäuren und Pentanatriumtriphosphat mit einem beliebigen Mischungsverhältnis zwischen Citrat, gegebenenfalls weiteren Hydroxycarbonsäuren und Pentanatriumtriphosphat, und zusätzlich
• 0 - 15, vorzugsweise etwa 0 bis 8 Gew.-% Citronensäure,
• 0 - 12, vorzugsweise etwa 3 bis 8 Gew.-% Polymer (native oder synthetische Basis)
• 0 - 20, vorzugsweise etwa 7 bis 12 Gew.-% Natriumcarbonat, bzw. 0-40, vorzugsweise 14 bis 24 Gew.-% Trona,
• 0 - 10, vorzugsweise etwa 0 bis 4 Gew.-% Natriumsilikat,
• 5 - 50, vorzugsweise etwa 25 bis 40 Gew.-% Natriumhydrogencarbonat,
• 5 - 20, vorzugsweise etwa 5 bis 15 Gew.-% Bleichmittel, insbesondere
  • 0 - 15, vorzugsweise etwa 5 bis 10 Gew.-% Natriumperborat und
  • 0 - 20, vorzugsweise etwa 5 bis 12 Gew.-% Natriumpercarbonat, wobei entweder Perborat oder Percarbonat anwesend sein muß,
• 1 - 10, vorzugsweise etwa 2 bis 6 Gew.-% Bleichaktivator,
• 0 - 4, vorzugsweise etwa 1 bis 2 Gew.-% eines nichtionischen Tensids
• < 5, vorzugsweise 0,5 bis 1,5 Gew.-% Amylase,
• < 5, vorzugsweise 0,5 bis 1,5 Gew.-% Protease,
• < 5, vorzugsweise 0,5 bis 1,5 Gew.-% Lipase,
• < 5, vorzugsweise 0,5 bis 1,5 Gew.-% Cellulase,
• 0,001 bis 5, vorzugsweise 0,005 bis 2,5 Gew.-% mindestens eines Metall-Triazol-Komplexes wie unter A) definiert oder eines Triazols wie unter B) definiert, oder eines Gemischs aus A) und/oder B).

The invention also relates to a washing-up liquid which, for example

• 20-60, preferably about 30 to 50% by weight of builder substances, including in particular about
  • 20 to 60, preferably about 30 to 50 wt .-% pentasodium triphosphate or
  • 20-60, preferably about 30 to 50 wt .-% citrate or salts of the hydroxycarboxylic acids or
  • 20-60, preferably about 30 to 50% by weight of citrate or salts of the hydroxycarboxylic acids and pentasodium triphosphate with any mixing ratio between citrate, optionally further hydroxycarboxylic acids and pentasodium triphosphate, and additionally
• 0-15, preferably about 0 to 8% by weight of citric acid,
• 0 - 12, preferably about 3 to 8 wt .-% polymer (native or synthetic basis)
• 0-20, preferably about 7 to 12% by weight sodium carbonate, or 0-40, preferably 14 to 24% by weight trona,
• 0-10, preferably about 0 to 4% by weight sodium silicate,
• 5-50, preferably about 25 to 40% by weight sodium hydrogen carbonate,
• 5 - 20, preferably about 5 to 15 wt .-% bleach, in particular
  • 0-15, preferably about 5 to 10 wt .-% sodium perborate and
  • 0-20, preferably about 5 to 12% by weight sodium percarbonate, with either perborate or percarbonate being present,
• 1-10, preferably about 2 to 6% by weight of bleach activator,
• 0-4, preferably about 1 to 2 wt .-% of a nonionic surfactant
• <5, preferably 0.5 to 1.5% by weight of amylase,
• <5, preferably 0.5 to 1.5% by weight of protease,
• <5, preferably 0.5 to 1.5% by weight lipase,
• <5, preferably 0.5 to 1.5% by weight of cellulase,
• 0.001 to 5, preferably 0.005 to 2.5% by weight of at least one metal-triazole complex as defined under A) or a triazole as defined under B), or a mixture of A) and / or B).

The invention is explained in more detail below by examples.

Examples: Recipe:

To a detergent containing 10% by weight sodium percarbonate, 4% by weight TAED, 56% by weight Trisodium citrate dihydrate, 36.1% by weight sodium bicarbonate, 6.1% by weight sodium carbonate, anhydrous, and 1.8% by weight of a mixture of nonionic surfactants from APG 225 and Dehydol®LS2 (1: 1, from Henkel), are the amounts of metal-triazole complexes given in Table 1 given.

The metal-triazole complexes were prepared by two different methods. With method 1) triazole and metal salt were used in a molar ratio of 1: 4, which is preferable leads to mononuclear complexes, in process 2) triazole and metal salt were in a ratio of 1: 2 used, which leads to preferably multinuclear complexes

Example for procedure 1):

0.08 mol of manganese acetate tetrahydrate was dissolved in 500 ml of hot methanol with stirring. Of the the resulting white precipitate was filtered off. In portions into the clear filtrate 0.32 mol of benzotriazole entered. The pH of the solution was adjusted to 7.5 and the solution then heated to 50-60 ° C with stirring for 1 h. The resulting precipitate was filtered off, washed with methanol and air-dried. Yield: 21 g of light brown product.

The silver protection effect was checked by putting 500 ml of tap water (16 ° d) in the beaker submitted and heated to 35 ° C with stirring in the thermostat. After adding 2.5 g of the o.g. A silver spoon was dipped into the beaker, the contents of the beaker were opened Heated to 65 ° C (duration of heating: 20 ± 1 min) and up to a total test duration of Leave at this temperature for 30 min. The test spoon was after the treatment with demineralized water rinsed and visually inspected.

0 = keine Veränderung (Löffel einwandfrei)

1 = völlig mattierte (kaum verfärbte) Oberfläche

2 = teilweise fleckenartige (Schwarz-)färbung

3 = mäßige flächendeckende Färbung

4 = ganzflächige Dunkel-/Violettfärbung

Metall-Triazol-Komplex Dosierung in % 0,001 0,01 0,05 0,1 0,25 0,5 1 [Mn(C₆H₄H₃)CH₃COO)]_n Verfahren 2) 4 0-1 0 0 0 0 0 Mn(III)-benzotriazol-acetat Verfahren 2) 3 Mangan(II)-benzotriazol-acetat Verfahren 1) 0-1 Mangan(III)-benzotriazol-acetat Verfahren 1) 0 0 Vergleichsbeispiel: Mangansulfat 4 4 3 The test spoon was then evaluated according to the following scheme:

0 = no change (spoon perfect)

1 = completely matt (hardly discolored) surface

2 = partially spotty (black) coloring

3 = moderate full color

4 = all over dark / violet color

Metal triazole complex Dosage in% 0.001 0.01 0.05 0.1 0.25 0.5 1 [Mn (C ₆ H ₄ H ₃ ) CH ₃ COO)] _n method 2) 4th 0-1 0 0 0 0 0 Mn (III) benzotriazole acetate process 2) 3rd Manganese (II) benzotriazole acetate process 1) 0-1 Manganese (III) benzotriazole acetate process 1) 0 0 Comparative example: Manganese sulfate 4th 4th 3rd

Claims (14)

Dishwashing detergent, at least containing builders, bleach, bleach activator and an anticorrosive for metals, characterized in that either as an anticorrosive A) a metal-triazole complex can be prepared by reaction a) a triazole of the general formula I.

in which R ^{1 represents} one, two, three or four substituents which, independently of one another, can be hydrogen or one or more linear and / or branched alkyl radicals having 1 to 10 C atoms,
or b) a triazole of the general formula II

wherein R ² and R ^{3 are} independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl or one of the radicals R ² or R ³ for NHR ⁴ , where R ^{4 is} hydrogen or C ₁ -C ₁₀ - Is alkyl, or two of the radicals R ² and R ³ of two different molecules together represent C ₁ -C ₁₀ alkylene,
or a mixture of two or more triazoles of the general formulas I and / or II,
With c) a metal salt or a mixture of two or more metal salts selected from the group of the salts of Mn, Co, Zn, Fe, Mo, W or Cu
or B) a triazole of the general formula II, in which two of the radicals R ² and R ³ of two triazole molecules together represent C ₁ -C ₁₀ -alkylene and the remaining radicals independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ alkenyl or NHR ₄ , where R ^{4 is} hydrogen or C ₁ -C ₁₀ alkyl,
or a mixture of two or more of components A) and / or B) is contained. Flushing agent according to claim 1, characterized in that R ^{1 represents} four hydrogen atoms. Detergent according to claim 1 or 2, characterized in that R ^{2 is} C ₅ -C ₉ alkyl and R ^{3 is} NH ₂ . Detergent according to one of the preceding claims, characterized in that two of the radicals R ² or R ³ from two triazole molecules together represent C ₃ -C ₅ alkylene. Detergent according to one of the preceding claims, characterized in that as Metal salt a manganese salt or a mixture of two or more manganese salts used becomes. Detergent according to one of the preceding claims, characterized in that it is used as Bleach contains at least sodium perborate or sodium percarbonate or a mixture thereof. Detergent according to one of the preceding claims, characterized in that it is used as Bleach activator contains N, N, N ', N'-tetraacetylethylene diamine (TAED). Detergent according to one of the preceding claims, characterized in that it is approximately 1% aqueous solution has a pH of about 7.5 to about 12, preferably about 8 to has about 10.8. Detergent according to one of the preceding claims, characterized in that it also contains at least one of the following substances: nonionic surfactants Enzymes Defoamer Fragrances. Detergent according to one of the preceding claims, characterized in that it is approximately 20-60, preferably about 30 to 50% by weight of builder substances, in particular about 20 to 60, preferably about 30 to 50 wt .-% pentasodium triphosphate or 20-60, preferably about 30 to 50 wt .-% citrate or salts of the hydroxycarboxylic acids or 20-60, preferably about 30 to 50% by weight of citrate or salts of the hydroxycarboxylic acids and pentasodium triphosphate with any mixing ratio between citrate, optionally further hydroxycarboxylic acids and pentasodium triphosphate, 0-15, preferably about 0 to 8% by weight of citric acid, 0 - 12, preferably about 3 to 8 wt .-% polymer (native or synthetic basis) 0-20, preferably about 7 to 12% by weight of soda, or 0-40, preferably 14 to 24% by weight of trona, 0-10, preferably about 0 to 4% by weight sodium silicate, 5-50, preferably about 25 to 40% by weight sodium hydrogen carbonate, 5-20, preferably about 5 to 10 wt .-% bleach, in particular 0-15, preferably about 5 to 10 wt .-% sodium perborate and 0-20, preferably about 5 to 10% by weight of sodium percarbonate, with either perborate or percarbonate being present, 1-10, preferably about 2 to 6% by weight of bleach activator, 0-4, preferably about 1 to 2 wt .-% of a nonionic surfactant <5, preferably 0.5 to 1.5% by weight of amylase, <5, preferably 0.5 to 1.5% by weight of protease, <5, preferably 0.5 to 1.5% by weight lipase, <5, preferably 0.5 to 1.5% by weight of cellulase, 0.001 to 5, preferably 0.005 to 2.5% by weight of at least one metal-triazole complex as defined in Claim 1 under A) or of a triazole as defined in Claim 1 under B),
or a mixture of A) and / or B)
contains. Use of a metal-triazole complex, producible by a) a triazole of the general formula I.

wherein R ^{1 represents} hydrogen or in each case one or more, independently of one another, linear or branched alkyl radicals having 1 to 10 carbon atoms, or b) a triazole of the general formula II

wherein R ² and R ^{3 are} independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, or one of the radicals R ² or R ^{3 is} NHR ⁴ , where R ^{4 is} hydrogen or C ₁ -C _{10 represents} alkyl, or two of the radicals R ² and R ³ of two different molecules together represent C ₁ -C ₁₀ alkylene and the remaining radicals independently of one another are hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl or NHR ⁴ , where R ^{4 is} hydrogen or C ₁ -C ₁₀ alkyl, or a mixture of two or more triazoles of the general formulas I and / or II,
and c) a metal salt or a mixture of two or more metal salts selected from the group of the salts of Mn, Co, Zn, Fe, Mo, W or Cu,
implemented with each other
as an anti-corrosion agent in detergents, in particular in machine detergents and particularly preferably in machine dishwashing detergents. Use of a triazole of the general formula II, in which two of the radicals R ² and R ³ of two triazole molecules together represent C ₁ -C ₁₀ alkylene and the remaining radicals independently of one another are hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl or NHR ⁴ , where R ^{4 is} hydrogen or C ₁ -C ₁₀ alkyl, as a corrosion inhibitor in detergents, in particular in machine detergents and particularly preferably in machine dishwashing detergents. Use of a detergent according to claims 1 to 9 as an automatic dishwashing detergent. Use of a detergent according to claims 1 to 9 for cleaning objects.