EP1195429A1 - Automatic dishwashing process and automatic dishwashing compositions having improved anti-corrosion characteristics - Google Patents

Abstract

In washing dishes in a domestic dishwashing machine, using a detergent containing corrosion inhibitor(s) (I) and surfactant(s) (II), (I) is released into the washing solution before (II). Independent claims are also included for: (a) a machine dish-washing process, which involves: (i) contacting the dishes with an aqueous washing solution containing (I) and free from (II); (ii) contacting them with an aqueous washing solution containing (II); and (iii) optionally rinsing and drying; (b) the use of aqueous solutions containing (I) but no (II) for machine dish-washing; and (c) various machine dish-washing detergents.

Description

The present invention relates to agents for the mechanical cleaning of metallic surfaces as well as the use of these agents in household dishwashers and a cleaning process using these means.

Detergent compositions for cleaning soiled dishes in dishwashers are widely described in the prior art. A disadvantage that these funds often have is however the cleaning performance on metal surfaces, for example tarnished silver surfaces. Since machine dishwashing detergent both with regard to the substrates to be treated as well as a variety of requirements with regard to the contamination that occurs certain task fields are not to the complete satisfaction of the user solved. In the case of cleaning metallic, especially silver or silver-plated Surfaces are therefore mostly satisfied with the addition of corrosion inhibitors, which is another Prevent tarnishing, but tarnished silver surfaces cannot clean.

Special cleaning agents are available for cleaning silver, some of which can also be used in dishwashers. Based on the well-known method of placing the silver objects on aluminum foil and covering them with an electrolyte solution, US Pat. No. 3,701,736 (Colgate) suggests automatic dishwashing detergent (MGSM) which contains builder salts and at least 3.25% by weight aluminum in the form of the contain pure metal or aluminum alloys.

A similar product for non-machine cleaning is described in EP 039 193 (Crown & And-rews).

A newer approach to silver cleaning in dishwashers can be found in WO98 / 51769 (Procter & Gamble). According to the teaching of this document, silver cleaning agents should be used which contain alkaline electrolyte, metal and at least 1% by weight of builder and nonionic surfactant. The metal must have a more negative standard potential than silver. The agents can also be incorporated as a component in conventional MGSM. A mechanical silver cleaning process is also claimed in this document.
The proposed solutions of the prior art have the disadvantage that they can only be used as pure cleaning agents for metallic objects (hereinafter referred to as silver cleaning agents for short). However, since the consumer rarely provides an entire dishwasher filling only from metallic surfaces, the machine either has to run partially loaded, or one accepts poor cleaning performance on other objects, such as baking dishes, plates, tea cups, etc.

The object of the present invention was to provide a cleaning agent which on the one hand, metallic objects well lined up and also good on tarnished surfaces Has cleaning performance, but on the other hand also a "full" cleaning agent for the normal mixed load condition of the dishwasher. In other words, one should Detergents for household dishwashers are provided, which improve the cleaning performance achieved conventional means and improved the performance on metallic surfaces, so that comparable results are achieved with special cleaners. For cost reasons, these should Results can be achieved with the same or reduced use of corrosion inhibitors.

It has now been found that the timing of the release of individual ingredients is crucial Influence the performance of the product. It is important that existing Corrosion inhibitors (hereinafter also referred to as "silver protection agents") in as few surfactants as possible Solutions are used. Contain automatic dishwashing detergents, so these should only be released into the application fleet after the corrosion inhibitors. there the positive effects are more pronounced, the lower the surfactant the fleet is exposed to Silver protection is. Agents according to the invention can therefore either be low in surfactants or completely Formulate free of surfactants, or have packaging measures to ensure controlled release of the individual connection classes.

In a first embodiment, the present invention relates to a method for the mechanical cleaning of dishes in a domestic dishwasher using a detergent composition which contains anticorrosive agents and surfactant (s), the anticorrosive agent (s) being released before the surfactant (s) into the application liquor ,
This embodiment takes into account that surfactants are part of most automatic dishwashing detergents and that their use can be desired for a variety of reasons. Corresponding agents according to the invention (see below) contain representatives of both classes of substances (corrosion inhibitors and surfactants) and have suitable measures for realizing the above-mentioned release sequence.

a) Kontaktieren des Geschirrs mit einer wäßrigen Anwendungsflotte, welche Korrosionsschutzmittel enthält und frei von Tensid(en) ist;

b) Kontaktieren des Geschirrs mit einer wäßrigen Anwendungsflotte, welche Tensid(e) enthält;

c) optionales Klarspülen und Trocknen des Geschirrs,

gekennzeichnet ist.The cleaning method according to the invention comprises the release of corrosion inhibitor into a surfactant-free environment and the subsequent release of surfactant (s) into the application liquor. In a further embodiment, the present invention therefore relates to a method for the mechanical cleaning of dishes in a domestic dishwasher, which comprises the steps

a) contacting the dishes with an aqueous application liquor which contains anticorrosive agents and is free from surfactant (s);

b) contacting the dishes with an aqueous application liquor which contains surfactant (s);

c) optional rinsing and drying of the dishes,

is marked.

The aqueous application liquor for step a) of the cleaning process according to the invention is required in the household dishwasher by adding water to the Interior in which there is a detergent composition in addition to the dirty dishes which contains anti-corrosion agents. Contains this detergent composition in addition to the anti-corrosion agent (s) as ingredient (s) surfactant (s), so these Protected against early release by suitable measures to create a surfactant-free application fleet to ensure for step a). The concentration of the anti-corrosion agent (s) in The application fleet depends on the one hand on the amount of water that goes into the dishwasher flows, on the other hand according to the amount of detergent composition and the concentration the anti-corrosion agents herein. In cleaning methods preferred according to the invention the concentration of the corrosion protection agent (s) in the application liquor is 0.0001 to 1 g / l, preferably 0.001 to 0.5 g / l, particularly preferably 0.002 to 0.25 g / l and in particular 0.005 up to 0.1 g / l.

In the cleaning process according to the invention, all known from the prior art can Corrosion inhibitors are used, with silver protection agents in particular Machine dishwashing have a special meaning. They can be used known substances of the prior art. In general, silver protection agents in particular selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. invention Processes in which the application liquor contains one or more anti-corrosion agents Group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and which contains transition metal salts or complexes, with benzotriazoles and / or alkylaminotriazoles are preferred are therefore preferred embodiments of the present invention.

In addition, active chlorine-containing agents that corrode are often found in detergent formulations significantly reduce the silver surface. Chlorine-free cleaners are special Organic and redox-active compounds containing oxygen and nitrogen, such as divalent and trivalent Phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic Compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Prefers are the transition metal salts selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the Cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion be used on the wash ware.

in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten, gegebenenfalls durch Hydroxy- oder Alkoxylgruppen substituierten Alkylrest mit 1 bis 15 C-Atomen oder eine gegebenenfalls durch Hydroxy-, primäre, sekundäre, tertiäre Aminogruppen, Alkoxy- Alkylthio- oder Thiolgruppen substituierte Aryl-, Furyl-, Tetrahydrofuryl, Thienyl-, Pyridyl-, Pyrrolidinyl-, 5-Oxo-2-pyrrolidinyl-, Pyrryl-, Imidazolyl-, Pyrimidylgruppe steht, sind daher ebenfalls besonders bevorzugt.Among the corrosion inhibitors from the groups of benzotriazoles or alkylaminotriazoles which are preferably used in the process according to the invention, 1,2,4-triazoles substituted in the 5-position are again particularly preferred. Processes according to the invention which are characterized in that the application liquor substituted in the 5-position 3-amino-1,2,4-triazoles of the formula (I) or their mixtures and / or their salts, preferably with hydrochloric acid, sulfuric acid, phosphoric acid, Contains carbonic acid, sulfurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid or mixtures thereof

in the R for a linear or branched, saturated or unsaturated, optionally substituted by hydroxyl or alkoxyl groups, alkyl radical having 1 to 15 carbon atoms or an aryl optionally substituted by hydroxyl, primary, secondary, tertiary amino groups, alkoxy, alkylthio or thiol groups -, furyl, tetrahydrofuryl, thienyl, pyridyl, pyrrolidinyl, 5-oxo-2-pyrrolidinyl, pyrryl, imidazolyl, pyrimidyl group are therefore also particularly preferred.

In particularly preferred cleaning processes according to the invention, those substituted in the 5-position are 3-amino-1,2,4-triazoles selected from the group of 5-propyl, butyl, pentyl, heptyl, -Octyl-, -Nonyl-, -Decyl-, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-acid alkyl-, -Phenyl-, -p-tolyl-, - (4-tert.butylphenyl) -, - (4-methoxyphenyl) -, - (2-, -3-, -4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2- furyl) -, - (5-Oxo-2-pyrrolidinyl) -3-amino-1,2,4-triazoles.

5-Pentyl-, 5-heptyl-, 5-nonyl-, 5-undecyl-, 5-isononyl-, 5-versatic-10-acid-alkyl-3-amino-1,2,4-triazoles are very particularly effective as well as mixtures of these substances.

As already mentioned, preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, Carbonic acid, sulphurous acid, organic carboxylic acids such as vinegar, glycol, citric, Succinic acid. In dishwashing detergents, the alkylamino-1,2,4-triazoles or their physiological compatible salts usually in a concentration of 0.001 to 10 wt .-%, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04% by weight, in each case based on the means used. Under normal household conditions, these quantities lead to the above concentrations mentioned in the application fleet.

In addition to the anti-corrosion agent (s), the application liquor can be used in the first step of the The cleaning method according to the invention naturally also contains other ingredients of cleaning agents included, wherein surfactant (s) are not present according to the invention in this step. In particular, further possible ingredients of the application liquor in the first process step are Builders, cobuilders, complexing agents, bleaches, bleach activators, enzymes, dyes, To name fragrances etc. In particularly preferred cleaning processes according to the invention contains the application liquor in step a) in addition to the corrosion inhibitor (s) builders and / or cobuilders, polymers and / or complexing agents. It is also preferred if the Application liquor in step a) is free of bleaching agents and bleach activators.

In the second step of the cleaning process according to the invention, the crockery parts are also contacted a cleaning agent containing surfactant, which of course contains other ingredients from Cleaning agents, such as bleaches, bleach activators, builders, enzymes, fragrances, Dyes, etc., may contain.

The surfactant component, which is in the second step in the application liquor, come Anionic, nonionic, cationic and / or amphoteric surfactants into consideration, with nonionic Surfactants are preferred because of their foaming power.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol can be obtained. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, Palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated Erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut-, Palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferred nonionic surfactants, either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably no longer than that of ethoxylated fatty alcohols, especially not more than half of them.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (II),

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (III)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds can be reacted with fatty acid methyl esters in The presence of an alkoxide as a catalyst is converted into the desired polyhydroxy fatty acid amides become.

Low-foaming nonionic surfactants are used as preferred surfactants. The application liquor in step b) of the cleaning process according to the invention particularly preferably contains nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Cleaning processes according to the invention in which the application liquor is particularly preferred in step b) contains a nonionic surfactant which has a melting point above room temperature having. Accordingly, preferred cleaning methods are characterized in that the Application liquor in step b) nonionic surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C included.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.
Preferred nonionic surfactants to be used at room temperature originate from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the is nonionic surfactant with a melting point above room temperature an ethoxylated nonionic surfactant resulting from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 moles, particularly preferably at least 15 moles, in particular at least 20 moles Ethylene oxide per mole of alcohol or alkylphenol has emerged.

A particularly preferred nonionic surfactant which is solid at room temperature is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide , Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, the application liquors in step b) is particularly preferred inventive cleaning method ethoxylated (s) nonionic surfactant (s), which / from C _6-20 monohydroxyalkanols or C _{6- 20} -alkylphenols or C _16-20 fatty alcohols and more than 12 mole , preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the Molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Surfactants. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules is preferred more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70 % By weight of the total molecular weight of such nonionic surfactants. Preferred cleaning methods are characterized in that the application liquor in step b) ethoxylated and propoxylated nonionic surfactants contain, in which the propylene oxide units in the molecule up to 25 wt .-%, preferred up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.

Other nonionic surfactants to be used with particular preference with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with and containing trimethylolpropane 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.

Examples of nonionic surfactants that can be used with particular preference are available under the name Poly Tergent® SLF-18 from Olin Chemicals.

A further preferred cleaning method according to the invention is characterized in that the application liquor nonionic 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 ] contains, in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1, 5 and y represents a value of at least 15.

Further 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 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if x ≥ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if 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 can be joined together 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 chosen here by way of example and may well be larger, the range of variation 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, so that the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for 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 represents} H and x assumes values from 6 to 15.

If the latter statements are summarized, cleaning processes according to the invention are preferred in which the application liquor of step b) 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 contains 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, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² in which x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

Instead of the surfactants mentioned or in combination with them, cationic and / or amphoteric surfactants are used. In summary, cleaning methods according to the invention preferred, in which the application liquor in step b) surfactant (s), preferably nonionic (s) Surfactant (s) and in particular nonionic surfactant (s) from the group of the alkoxylated Contain alcohols.

The other ingredients of cleaning agents that are part of the cleaning fleet in Step a) and step b) of the method according to the invention can be further described below in the description of agents according to the invention.

Another object of the present invention is the use of surfactant-free aqueous Corrosion protection solutions for machine washing of dishes.

As already mentioned above, the cleaning method according to the invention can be used, among other things by performing specially made cleaning agents in a household dishwasher brings in and runs a cleaning program. In the simplest case, the Cleaning according to the invention dispenses with surfactants as intentionally added ingredients in the agents, thereby achieving essentially surfactant-free application liquors and the inventive ones Benefits are used.

"Substantially free from surfactants" means that the agents are free from intentionally added surfactants are. Contamination of raw materials or manufacturing equipment can, however, result in small quantities of surfactants in agents that release them into the application liquor when used. A previous level can also result in a residual content with cleaning agents containing surfactants Stick surfactants to the crockery baskets or the spray arms of the dishwasher the application fleet of a subsequent cleaning process according to the invention is slight contaminated with surfactants.

Another object of the present invention is therefore a dishwasher detergent, containing builders, corrosion inhibitors and possibly other ingredients of cleaning agents, which - based on its weight - contains a maximum of 0.5% by weight of surfactant (s).

The residual content of surfactants on average can - as already mentioned - through contaminated manufacturing equipment or by raw materials that contain small amounts of surfactants. So be some raw materials are granulated or coated with the addition of small amounts of surfactant, resulting in a The product is exposed to tensides. In preferred embodiments of this part of the present However, one pays particular attention to the invention when selecting the raw materials and the manufacturing apparatus lowest possible contamination, so that agents according to the invention are preferred, the maximum 0.25% by weight, preferably at most 0.1% by weight, particularly preferably at most 0.05% by weight and in particular contain a maximum of 0.01% by weight (in each case based on the weight of the composition) of surfactants. Agents according to the invention which are free from surfactant (s) are particularly preferred.

Another possibility, cleaning method according to the invention by adding a single To enable means in the dishwasher is to assemble the means in such a way that the corrosion inhibitors are released into the application liquor before the surfactants in the application medium are released. This can be caused by a delay in the dissolution of the surfactants or by accelerating the release of the corrosion inhibitors, a combination of which both options is possible. Therefore, both automatic dishwashing detergents are the Builders, corrosion inhibitors, surfactants and possibly other ingredients of cleaning agents included and are characterized in that they the surfactant (s) in dissolving Contain form, as well as machine dishwashing detergent, containing builders, corrosion inhibitors, Surfactants and possibly other ingredients of cleaning agents that contain the corrosion inhibitor (s) in accelerated form, other items of present invention.

A delay in the dissolution of surfactants can be achieved, for example, by coating surfactant compounds, by compounding alone or by embedding in dissolution-delayed matrices respectively. A release acceleration of corrosion inhibitors takes place, for example, by assembly with disintegration aids, shower systems, dissolving accelerators (easily soluble Substances) etc. The physical packaging can also accelerate or slow down the solution act, for example by a dishwasher detergent body, which surfactant (s) contains and is coated or "powdered" on its surface with corrosion inhibitor (s) dissolve before the molded body goes into solution. Also multi-phase moldings, in which whole Phases are delayed in release (for example due to ingredients, high pressure and thus high compression with poor solubility, through coating etc.), while others accelerate dissolution are (for example, by using disintegration aids, by low Pressing pressure and thus low compression with better solubility, etc.) are used to carry out the Teaching according to the invention can be easily produced.

The corrosion inhibitors are preferably released and can have their effect via a unfold for a certain period of time before surfactants enter the fleet. Another subject of The present invention is therefore a machine dishwashing detergent containing builders, Corrosion inhibitors, surfactants and possibly other ingredients of cleaning agents, which is characterized in that the surfactant (s) wholly or partially with a coating material coated or compounded or so physically made up that they are in the cleaning liquor after a period t1 of 10 s to 5 min. at most 10% and after t1 plus 1 minute up to 30 min. is at least 90% released, while the corrosion inhibitor (s) are so is compounded or physically assembled, that these are in the cleaning liquor a period t1 from 10 s to 5 min. is / are released to at least 90%.

These agents according to the invention lead to the desired application fleets for implementation of the cleaning method according to the invention in household dishwashers. The surfactant or the surfactants are / are preferably in a period t1 of 10 s to 5 min. and especially preferably from 1 min. up to 5 min. at most 10% and preferably after t1 plus 5 min. to 15 minute and particularly preferably from t1 plus 7 min. up to 10 min. released at least 90%. On this way the surfactants only reach the application liquor later, while the corrosion inhibitors are already in the application fleet. The time t1 can be the start of the wash cycle be in the case of specially made-up agents (for example in the case of coated moldings) t1 can also mean the time of dissolution of the assembly (here: coating). It is crucial that there is a fixed time "starting point" from which to start First dissolve the corrosion inhibitors and then the surfactants in the application liquor. The the exact location of this point in time t1 in the washing program is not important.

In order to adjust the release of the surfactants to the period defined according to the invention, it has these agents (or compounds containing them) with coating materials proved to be suitable provided that dissolve in the cleaning fleet with a defined kinetics. Are preferred as Enveloping materials fatty alcohols or fatty acids, which may be mixed with other enveloping substances can be mixed. A mixture of fatty alcohols and aluminum stearate is an example called. Other envelope materials known from the prior art are as follows summarized in key words: magnesium sulfate and sodium hexaphosphate, dihydrogen phosphate or pyrophosphates, phosphonic acids, sodium metaborate and silicate, water glass and sodium polyphosphate, Sodium sulfate and silicate, or sodium bicarbonate, borax and magnesium sulfate, Boric acid, but also some organic components such as fat derivatives, paraffins and waxes (Melting temperature of the compounds between 25 and 90 ° C), polyethylene glycols and fatty acid esters of which with a molecular weight of 300 to 1,700, combinations with magnesium oxide, Vinyl chloride-ethylene copolymer emulsions or vinyl chloride-ethylene methacrylate copolymer emulsions. Polycarboxylates or other water-soluble polymers.

The coating materials can be applied from the melt or from solutions or dispersions, the solvent or emulsifier being removed by evaporation. Application as a fine powder, for example by electrostatic techniques, is also possible, although this method leads to irregular and poorly adhering coatings. The coating materials can be applied to particles in agitators, mixers and granulators. However, it is preferred to apply the coating materials in a fluidized bed, it being possible for the particles to be sized at the same time. If the coating materials lead to sticky products under certain circumstances, it can make sense to apply fine particles to the coated particles ("powdering"). All fine-particle substances can be used as powdering agents, although other detergent components such as builder substances can also be used. Zeolites, silicates, polymeric polycarboxylates, carbonates, citrates, starch, cellulose derivatives etc. are preferably used as additional powdering agents. Part of an existing buffer system can also be used for powdering.
The coating materials for particles containing surfactants are used in such amounts that an optimal interaction of the individual components and thus an exactly controlled release is made possible. Depending on the period within which the release is to be largely suppressed and depending on the size of the coated particles, the amount of coating material will be measured. Preferred embodiments use less than 20% by weight of shell material, based on the amount of the coated particles, in particular less than 10% by weight of shell material is preferred.

In addition to the material ("chemical") packaging of the surfactants described above Setting the defined release within a certain period of time can also "physical" assembly can be made. Combinations are of course also possible from material and procedural measures for the setting according to the invention the time of release.

A preferred "physical" way to delay the release of surfactants is to use them in compared to the other ingredients of poorly soluble form. For example can be achieved by varying the particle size of surfactant-containing particles, since Dissolve finely divided detergent ingredients faster due to the larger surface.

The combination of differently densified ingredients is also preferred Way to realize different solubilities. For example, powdered ingredients with more compressed, for example extruded, and thus more slowly soluble Surfactant particles can be combined.

In the context of the present invention, the "physical release delay" is particularly preferred to be realized within a molded body. For this purpose, detergent tablets can be produced are made up of several phases, one phase being less compressed as a different phase. The more easily compressed phase disintegrates faster in the cleaning process previously compressed premix, which increases solubility compared to a harder compressed phase is increased. According to the invention, particular preference is given to two-layer tablets in which one layer is softer pressed than the other, the harder pressed layer containing the surfactant (s) contains. Alternatively, the retardation of a phase can also have a lower content a de-integration aid contained in it can be achieved.

In addition to the two-layer tablet, there is also a system of two separate tablets with different ones Decay time, e.g. can be packed in a common bag. The retardation one of these tablets can be made in the same way as above of the two-layer tablet.

The agents according to the invention generally contain one or more builders, in particular Zeolites, silicates, carbonates, organic cobuilders and - where no ecological prejudices against their use persists - including the phosphates. The latter are particularly in detergent tablets for machine dishwashing preferred builders. The following The builders mentioned are also suitable as alkalizing agents.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can have been brought about in various ways, for example by surface treatment, compounding, compacting / compaction, by overdrying or by coating. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na ₂ O (1-n) K ₂ O Al ₂ O ₃ (2 - 2.5) SiO ₂ (3.5 - 5.5) H ₂ O can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons. Among the large number of commercially available phosphates, the alkali metal phosphates are among particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) of greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These can be made just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures these two are used; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

Polycarboxylates in particular can be used as organic cobuilders in the agents according to the invention / Polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, others organic cobuilders (see below) and phosphonates are used. These substance classes are described below.

Usable organic builders are, for example, those that can be used in the form of their sodium salts Polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have more than one acid function. For example, these are citric acid, adipic acid, Succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use from ecological Reasons is not objectionable, as well as mixtures of these. Preferred salts are the salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids and mixtures of these.

The acids themselves can also be used. The acids have a builder effect typically also the property of an acidifying component and are therefore also used for Setting a lower and milder pH value for detergents or cleaning agents. In particular are citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 have up to 20,000 g / mol. Because of their superior solubility, this group can again the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As particularly suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and contain 50 to 10% by weight of maleic acid. Their relative molecular mass, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol, and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution become. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 up to 20% by weight, in particular 3 to 10% by weight.

To improve the water solubility, the polymers can also allylsulfonic acids, such as Allyloxybenzenesulfonic acid and methallylsulfonic acid, contained as a monomer.

Also particularly preferred are biodegradable polymers made from more than two different ones Monomer units, for example those which are salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid as monomers and the 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymers are those which preferably use acrolein and acrylic acid / acrylic acid salts as monomers or acrolein and vinyl acetate.

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives.

Other suitable builder substances are polyacetals, which are obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, can be obtained. Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes be performed. They are preferably hydrolysis products with medium molecular weights in the range from 400 to 500000 g / mol. Here is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, are preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is. Both maltodextrins with a DE between 3 can be used and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. An oxidized oligosaccharide, e.g. B. a product oxidized at C _{6 of} the saccharide ring.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferred used in the form of its sodium or magnesium salts. Are further preferred in this Connection also glycerol disuccinate and glycerol trisuccinate. Suitable quantities in formulations containing zeolite and / or silicate are 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt is alkaline (pH 9). Preferred aminoalkane phosphonates are Ethylene diamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in shape the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta and Octa sodium salt of DTPMP, used. As a builder, the class of phosphonates preferably HEDP used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the agent also bleach contain, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can can be used as a cobuilder.

The amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%, each based on the entire agent according to the invention.

In a possible embodiment of the present invention, the invention contain Agents organic and / or in particular inorganic bleaching agents.

Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. Other useful bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate peroxypyrophosphate, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoxyacidoxy (PAP), )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxydalsoxyperiperyldoxybutyldiacyldiperbutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacid-diperoxybiperyl-doxy-oxy-oxy-doxy-oxy-oxy-oxyacetate, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

The bleaching agent content of the agents can be 1 to 40% by weight and in particular 10 to 20% by weight. amount, advantageously using percarbonate or perborate mono- or tetrahydrate becomes.

To improve the bleaching effect when cleaning at temperatures of 60 ° C and below reach, bleach activators can be incorporated. As bleach activators, compounds those under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 up to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result, are used.

Substances containing O- and / or N-acyl groups of the number of carbon atoms mentioned and / or are suitable optionally substituted benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and Mannitol or their in European patent application EP 0 525 239 (Ausimont SPA) described mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-Benzoylcaprolactam resulting from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626 (all Procter & Gamble), WO 95/14759 (Warwick) and WO 95/17498 (Procter & Gamble) are known. The from the international patent application Acyl lactams described in WO 95/14075 (Degussa) are also preferably used. The combinations known from German patent application DE 44 43 177 (Henkel) conventional bleach activators can be used. Such bleach activators are contained in amounts of 0.5 wt .-% to 15 wt .-%, based on the total agent.

In addition to the conventional bleach activators or in their place, so-called Bleach catalysts can be included. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes are as Bleaching catalysts are suitable, preference being given to using compounds which are used in the DE 197 09 284 A1 are described.

The cleaning agent according to the invention can be further conventional ingredients, in particular enzymes, Sequestering agents, electrolytes, and other auxiliary substances, such as foam regulators, additional Contain bleach activators, colors and fragrances.

Enzymes in the agents according to the invention include in particular those from the classes of Hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases carry for the removal of stains such as stains containing protein, fat or starch. to Bleach can also be used with oxidoreductases. Bacterial strains are particularly suitable or mushrooms such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and their genetically modified variants obtained enzymatic active ingredients. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic acting enzymes or from protease, amylase and lipase or lipolytically acting enzymes or protease, lipase or lipolytic enzymes, but especially protease and / or mixtures containing lipase or mixtures with lipolytically active enzymes of particular importance Interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. To The suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and Pectinases.

The enzymes can be adsorbed on carriers or embedded in enveloping substances around them protect against premature decomposition. The percentage of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight be. Agents preferred in the context of the present invention are characterized in that that they contain protease and / or amylase.

Dyes and fragrances can be added to the automatic dishwashing detergents according to the invention to improve the aesthetic impression of the resulting products and the Consumers in addition to performance a visually and sensory "typical and distinctive" To provide product. As perfume oils or fragrances, individual fragrance compounds, e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohol type and hydrocarbons are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example Benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, among the Ketones e.g. the Jonone, α-isomethylionon and methylcedryl ketone, to the alcohols anethole, Citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly include the terpenes like limes and pinene. However, mixtures are preferred different fragrances are used, which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures such as those from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the cleaning agents according to the invention can also be advantageous to apply the fragrances on carriers.

In order to improve the aesthetic impression of the agents according to the invention, it (or parts of which) are dyed with suitable dyes. Preferred dyes, the selection of which Specialist poses no difficulty, has a high storage stability and insensitivity compared to the other ingredients of the agents and against light and no pronounced Substantivity towards the substrates to be treated with the agents such as glass, ceramic or Plastic dishes so as not to stain them.

The agents according to the invention can be provided in all known forms of offer, in particular powdered cleaners and detergent tablets being of particular importance. If detergent tablets are produced, they can contain disintegration aids, so-called tablet disintegrants, in order to facilitate the disintegration of highly compressed moldings and to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184), tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.

These substances, which are also called "explosives" due to their effect, enlarge their volume when water enters, the volume on the one hand increasing (swelling) and on the other a pressure can also be generated via the release of gases, which the tablet in lets smaller particles disintegrate. Well-known disintegration aids are, for example, carbonate / citric acid systems, other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the weight of the tablet. If only the basic tablet contains disintegration aids, the information given relates only to the weight of the basic tablet.
Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight .-% contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be compressed. Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above-mentioned coarser disintegration aids based on cellulose which are described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from the company Rettenmaier.

As a further disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is made by partial Hydrolysis of celluloses obtained under conditions that only the amorphous areas (approx. Attack 30% of the total cellulose mass) of the celluloses and completely dissolve the crystalline ones Leave areas (approx. 70%) undamaged. A subsequent disaggregation of the The hydrolysis of the microfine celluloses produces the microcrystalline celluloses, the primary particle sizes of about 5 µm and for example to granules with a medium Particle size of 200 microns can be compacted.

Preferred detergent tablets in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 % By weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight.

Shaped detergent tablets according to the invention can also be a gas-evolving Shower system included. The gas-developing shower system can consist of a single substance exist, which releases a gas on contact with water. Among these connections is particular to name the magnesium peroxide, which releases oxygen when in contact with water. Usually however, the gas-releasing bubble system itself consists of at least two components, that react with each other to form gas. While here a variety of systems is conceivable and executable, which will release nitrogen, oxygen or hydrogen, for example the bubble system used in the detergent tablets according to the invention Choose both from an economic and an ecological point of view to let. Preferred shower systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable from the alkali metal salts to release carbon dioxide in aqueous solution.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are out Cost reasons clearly preferred over the other salts. Needless to say the pure alkali metal carbonates or bicarbonates concerned are not used; rather, mixtures of different carbonates and hydrogen carbonates may be preferred.

In preferred shaped detergent bodies, 2 to 20% by weight, preferably, are used as the shower system 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight of one Acidifying agent, based in each case on the entire molded body.

As acidifying agents that release carbon dioxide from the alkali salts in aqueous solution for example boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, organic acidifying agents are preferred used, the citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. From this group, tartaric acid, succinic acid, malonic acid, adipic acid, Maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. Commercially available and as an acidifier in Sokalan® DCS (trademark from BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).

In the context of the present invention, preference is given to detergent tablets in which Acidifying agent in the effervescent system a substance from the group of organic di-, tri- and oligocarboxylic acids or mixtures of these are used.

Regardless of the form of the agents according to the invention, agents are preferred in which the corrosion inhibitor content of the agents is 0.001 to 10% by weight, preferably 0.0025 to 2 % By weight and in particular 0.01 to 0.04% by weight, in each case based on the total cleaning agent, is.

Claims (13)

Process for the automatic cleaning of dishes in a domestic dishwasher using a detergent composition which contains anticorrosive agents and surfactant (s), characterized in that the anticorrosive agent (s) are released into the application liquor before the surfactant (s). Method for the automatic cleaning of dishes in a domestic dishwasher, characterized by the steps a) contacting the dishes with an aqueous application liquor which contains anti-corrosion agents and is free from surfactant (s); b) contacting the dishes with an aqueous application liquor which contains surfactant (s); c) optional rinsing and drying of the dishes. Method according to one of claims 1 or 2, characterized in that the concentration of the corrosion protection agent (s) in the application liquor 0.0001 to 1 g / l, preferably 0.001 to 0.5 g / l, particularly preferably 0.002 to 0, 25 g / l and in particular 0.005 to 0.1 g / l. Process according to one of claims 1 to 3, characterized in that the application liquor contains one or more corrosion protection agents from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, benzotriazoles and / or alkylaminotriazoles are preferred. Method according to one of claims 1 to 4, characterized in that the application liquor substituted in the 5-position 3-amino-1,2,4-triazoles of the formula (I) or their mixtures and / or their salts, preferably with hydrochloric acid, sulfuric acid , Phosphoric acid, carbonic acid, sulfurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid or mixtures thereof

in the R for a linear or branched, saturated or unsaturated, optionally substituted by hydroxyl or alkoxyl groups, alkyl radical having 1 to 15 carbon atoms or an aryl optionally substituted by hydroxyl, primary, secondary, tertiary amino groups, alkoxy, alkylthio or thiol groups -, Furyl, tetrahydrofuryl, thienyl, pyridyl, pyrrolidinyl, 5-oxo-2-pyrrolidinyl, pyrryl, imidazolyl, pyrimidyl group. A method according to claim 5, characterized in that the 3-amino-1,2,4-triazoles substituted in the 5-position are selected from the group of 5-propyl, butyl, pentyl, heptyl, Octyl-, -Nonyl-, -Decyl-, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-acid alkyl -, - Phenyl-, -p-Tolyl-, - (4-tert.butylphenyl) - , - (4-methoxyphenyl) -, - (2-, -3-, -4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5-oxo -2-pyrrolidinyl) -3-amino-1,2,4-triazoles. Use of surfactant-free aqueous solutions of anti-corrosion agents for mechanical Cleaning of dishes. Automatic dishwashing detergent, containing builders, corrosion inhibitors and optionally further ingredients of cleaning agents, characterized in that it contains - based on its weight - a maximum of 0.5% by weight of surfactant (s). Agent according to claim 8, characterized in that it is free from surfactant (s). Automatic dishwashing detergent, containing builders, corrosion inhibitors, surfactants and, if appropriate, further ingredients of cleaning agents, characterized in that it contains the surfactant (s) in a solution-delayed form. Automatic dishwashing detergent, containing builders, corrosion inhibitors, surfactants and optionally other ingredients of cleaning agents, characterized in that it contains the corrosion inhibitor (s) in solution-accelerated form. Automatic dishwashing detergent, containing builders, corrosion inhibitors, surfactants and possibly further ingredients of cleaning agents, characterized in that the surfactant (s) is coated in whole or in part with a coating material or is compounded or physically made up so that this (s) in the cleaning liquor after a period t1 of 10 s to 5 min. at most 10% and after t1 plus 1 min. up to 30 min. is released to at least 90% while the corrosion inhibitor (s) are compounded or physically assembled so that they are in the cleaning liquor after a period t1 of 10 s to 5 min. is / are released to at least 90%. Agent according to one of claims 8 to 13, characterized in that the corrosion inhibitor content of the agent is 0.001 to 10% by weight, preferably 0.0025 to 2% by weight and in particular 0.01 to 0.04% by weight , each based on the total detergent.