DE10312617A1 - Germ-reducing detergent or cleaning agent and process for its production - Google Patents

Abstract

To provide detergents or cleaning agents or auxiliary washing agents which bring about a reduction in the number of germs on the surfaces treated or come into contact with them and advantages in terms of cost, processability, stability and applicability even on surfaces which are directly in contact with skin or mucous membranes Coming into contact, causing, containing silver in elemental and / or oxidized form, preferably finely divided and in particular colloidal.

Description

The present invention relates to Washing, cleaning or washing aids, which reduce germs Have effects, i.e. the number of germs on those treated with them or reduce surfaces that have come into contact. In the group the detergents particularly include universal detergents, Color detergent, special detergent for colorful and / or delicate laundry and Detergent for special Applications such as curtain detergent in solid or liquid form. Detergents are particularly those for manual or machine dishwashing, detergents for hard surfaces in the household such as floor cleaning agents, window cleaners and others Cleaning or wiping agents in solid or liquid form. Means for washing are especially fabric softeners, Means of strengthening, separate bleach, water softener or other washing additives in solid or liquid Shape.

For washing or cleaning processes in sensitive Areas, for example in hospitals or facilities that are exposed to a high bacterial load (e.g. public Toilets) but also in the household there is a need for one counteract excessive contamination of textiles and / or surfaces, to avoid illness or unsightly appearance.

For this purpose, the state of the art describe various antimicrobial agents. differs depending on the antimicrobial spectrum and mechanism of action between bacteriostats and bactericides, fungistats and fungicides etc. Suitable antimicrobial agents are preferably selected from the groups of alcohols, amines. Aldehydes, antimicrobial acids or their Salts, carboxylic acid esters, acid amides, Phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, Oxygen, nitrogen acetate and formals, benzamidines, isothiazolines, Phthalimide derivatives, pyridine derivatives, antimicrobial surfactants Compounds, guanidines, antimicrobial amphoteric compounds, Quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl carbamate, Iodine, iodophores, peroxo compounds, halogen compounds and any Mixtures of the foregoing. Important substances from these groups are for example benzalkonium chlorides, alkylarylsulfonates, halophenols and phenol mercuric acetate.

The use of substances from the above Groups is for cost reasons, for reasons of Processability or the stability of the compounds in the media, for reasons of intolerance with other ingredients or from ecological or health establish not always completely unproblematic. It was therefore the task of washing or cleaning agents or Provide washing aids based on those treated with them or surfaces that have come into contact with a reduction in Cause bacterial count and advantages in terms of costs, processability, of stability and the applicability also to surfaces that are directly with skin or Mucous membranes in contact come, effect.

It has now been found that silver as an inexpensive, easy to process, well tolerated and ecological and germ reduction agent that is largely harmless to health be incorporated into washing or cleaning agents or washing aids can.

The invention relates to a first embodiment a washing, cleaning or washing aid containing silver in elementary and / or oxidized form.

Silver or silver ions practice one blocking effect on thiol enzymes in microorganisms from and have a high bactericidal and fungicidal effect. Furthermore silver kills germs. The terms antimicrobial effect and antimicrobial agent have the customary meaning in the context of the teaching according to the invention, for example by K. H. Wallhäußer in "Practice of Sterilization, Disinfection - preservation : Germ Identification - Industrial Hygiene "(5th ed. - Stuttgart ; New York Thieme, 1995) is reproduced.

The washing, cleaning or washing aids according to the invention preferably contain the silver or the silver compounds) in certain amounts. The silver (Ag ⁰ ) content is always used as the basis for calculation in the context of the present invention. If an agent according to the invention contains, for example, 100 mg of silver chloride per kg, its silver content is 73.53 mg per kg.

Washing, cleaning or Washing aids that are in solid form and silver (calculated as Ag) in amounts from 0.1 to 1000 mg / kg, preferably from 1 to 500 mg / kg, particularly preferably from 2 to 250 mg / kg, further preferred from 3 to 150 mg / kg and in particular from 4 to 100 mg / kg, are preferred according to the invention.

In the case of liquid or flowable agents according to the invention, the amounts of silver are preferably based on the volume and not on the mass. “Flowable” in the sense of the present application are agents according to the invention which are pourable and can have viscosities of up to several 10,000 mPas. The viscosity of the agents according to the invention can be determined using customary standard methods (for example Brookfield viscometer LVT-II at 20 rpm and 20 ° C, spindle 3) are measured and is preferably in the range from 500 to 10000 mPas. Preferred detergent compositions have viscosities of 1000 to 8000 mPas, values between 1300 to 5000 mPas being particularly preferred. Preferred washing, cleaning or washing aids according to the invention, which are in liquid form, contain silver (calculated as Ag) in amounts of 0.1 to 200 mg / l, preferably 1 to 100 mg / l, particularly preferably 2 to 75 mg / l, more preferably from 3 to 50 mg / l and in particular from 4 to 10 mg / l.

A particularly preferred washing, Cleaning or washing aids is characterized in that it is as Ready-made fabric softener which contains 0.5 to 50% by weight of cationic surfactant (s).

Such fabric softeners according to the invention have the advantage that the Items of laundry in one final Treatment course of the washing machine with the germ-reducing silver in touch come, whereby the number of germs on the surface of the laundry is reduced again. About that in addition, the agent itself has a germ-reducing effect and prevents it this way the contamination of the fabric softener dosing compartment, which is often unsightly black discoloration and deposit formation expresses the displease excited at the consumer.

The other ingredients of fabric softener according to the invention described below.

According to the invention, silver is used either in elemental form or in the form of its compounds. Preferred washing, cleaning or washing aids according to the invention contain silver in elemental form (Ag ⁰ ), the silver having particle sizes from 0.1 to 100 μm, preferably from 0.2 to 80 μm and in particular from 0.25 to 60 μm , Such silver dusts can, for example, be added to the finished solid or liquid agent and can serve as so-called “powdering agents”. However, they can also be added during manufacture, for example granulated.

Even finer particle sizes of silver can be achieved by using them in colloidal form. Here, washing, cleaning or washing aids according to the invention are preferred which contain silver in elemental (Ag ⁰ ) and colloidal form, the silver particle sizes from 0.001 to 0.1 μm, preferably from 0.002 to 0.05 μm and in particular from 0.005 to 0.01 μm. Such silver colloids can either be prepared separately and added to liquid agents according to the invention or applied to solid agents according to the invention. However, it is also possible to generate the silver colloid directly in liquid agents according to the invention, details of which will be given later.

Of course, it is also possible according to the invention to add silver to the washing, cleaning or washing aids in oxidized form, ie in the form of silver compounds. Washing, cleaning or washing aids according to the invention which contain silver in oxidized form (Ag ⁺ ) are preferred here, the silver salts silver acetate, silver bromide, silver carbonate, silver chloride, silver nitrate, silver oxide, silver phosphate, silver sulfate, silver thiosulfate, or mixtures thereof being preferred ,

With fixed funds, the processability of dusty silver compounds or silver with small particle sizes be improved that one the silver or the silver compounds) on carrier materials. For this can be suitable support materials for example with solutions or suspensions or dispersions of silver compounds and / or colloidal silver solutions waterproof or mixed with finely divided silver and / or silver compounds become. Of course is it also possible the finely divided silver compounds and / or the silver together with the carrier materials granulate with the addition of suitable granulation aids. As carrier materials are builders in particular (Description see below). In addition, highly porous materials can also be used like silicas, for example pyrogenic silicas, Bentonites, polymeric materials or diatomaceous earth ("diatomaceous earth") as carrier materials serve.

Accordingly, washing, cleaning or washing aids are preferred in which the silver or the silver compounds) on substrates, preferably builders, angry.

The composite particles made of carrier material and Silver or silver compound can optionally have other ingredients. Has proven itself for example the use of activating precious metals such as gold or palladium, which has the slightest trace of the germ-reducing Activate the effect of the silver. But also other substances, for example Ingredients of detergents or cleaning agents can the composite particles are applied or incorporated into them. So-called small components such as Dyes and fragrances, optical brighteners, polymers, etc., if them with the backing material and compatible with silver are.

The washing, cleaning or Washing aids can all usual Contain ingredients of washing or cleaning agents. This are described below.

The washing or cleaning agents according to the invention preferably contain surfactant (s), it being possible to use anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants in textile detergents, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants. The total surfactant content of the washing or cleaning agent according to the invention tel is preferably below 30% by weight, based on the total agent.

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 residue 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 _{12-1 4} 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 can be used 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, in particular Fatty acid methyl ester.

Also non-ionic surfactants of the type the amine oxides, 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 not more than that of the ethoxylated fatty alcohols, in particular not more than half from that.

In particular with cleaning agents according to the invention for the machine dishwashing it is preferred that they contain a nonionic surfactant that has a melting point above Has room temperature. Nonionic surfactants to be used with preference have melting points above 25 ° C, particularly preferably to be used nonionic surfactants have melting points between 25 and 60 ° C, in particular between 26.6 and 43.3 ° C.

Suitable nonionic surfactants, the 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. Become highly viscous nonionic surfactants used at room temperature, it is preferred that these a viscosity above 20 Pas, preferably above 35 Pas and in particular have above 40 Pas. Also nonionic surfactants, which are waxy at room temperature Have consistency are preferred.

Preferred than at room temperature fixed nonionic surfactants come from the groups of alkoxylated Nonionic surfactants, especially ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control out.

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

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.

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. 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 preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molmas se such non-ionic surfactants.

Other nonionic surfactants to be used with particular preference with melting points above room temperature contain 40 to 70% 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 trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

Another preferred surfactant can be represented by the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ] describe 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 can be used 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 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15.

Another class of preferred nonionic Surfactants, either as the sole nonionic surfactant or can be used 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, in particular Fatty acid methyl ester.

Also non-ionic surfactants of the type the amine oxides, 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 not more than that of the ethoxylated fatty alcohols, in particular not more than half from that.

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 below,

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 odercyclischen 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 propxylierte Derivate dieses Restes.To the group of polyhydroxy fatty acid amides include compounds of the formula below,

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 is 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 propylated, derivatives of this rest.

[Z] is preferably by reductive Obtaining amination of a sugar, for example glucose, fructose, Maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds can then be reacted with fatty acid methyl ester in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

The content more preferred for textile washing washing machine according to the invention or detergent on nonionic surfactants is 5 to 20 % By weight, preferably 7 to 15% by weight and in particular 9 to 14% by weight, each based on the total mean.

In automatic dishwashing detergents are preferably low-foaming non-ionic surfactants used.

In conjunction with the surfactants mentioned can also anionic, cationic and / or amphoteric surfactants are used, these because of their foaming behavior in automatic dishwashing detergents are of minor importance and mostly only in quantities below 10% by weight, mostly even below 5% by weight, for example from 0.01 to 2.5% by weight, based in each case on the agent become. In contrast, these surfactants are of significantly greater importance in detergents. The washing or Detergents can thus also anionic, cationic and / or as a surfactant component contain amphoteric surfactants.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.The agents according to the invention can contain, for example, cationic compounds of the formulas I, II or III as cationic active substances:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In particular, agents according to the invention, the as a fabric softener are formulated, contain cationic (s) surfactants) of the formulas (I), (II) and / or (III). Preferred fabric softeners contain 0.5 to 50% by weight, preferably at least 1 to 45% by weight and in particular 2.5 to 40% by weight a cationic surfactant, where cationic surfactants of the formula (I) are preferred.

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 a terminal 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. Likewise, the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters hydrogenated coconut, palm kernel or tallow fatty acids.

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 in the manufacture 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 glycerin be preserved. Preferred sulfonated fatty acid glycerol esters are included 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.

As alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty 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, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar 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 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 radicals 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, the fatty alcohol residues of which 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.

Other anionic surfactants especially soaps. Saturated and unsaturated Fatty acid soaps, like the salts of lauric acid, myristic, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid as well especially from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.

The anionic surfactants including soaps can in the form of their sodium, potassium or ammonium salts as well as soluble Salts of organic bases, such as mono-, di- or triethanolamine, are present. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

The content of preferred textile detergents according to the invention of anionic surfactants 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 up to 20% by weight, each based on the total mean. Cleaning agents according to the invention for the machine Wash the dishes are preferably free of anionic surfactants.

Within the scope of the present invention also contain preferred agents one or more substances from the group of builders, bleaching agents, bleach activators, Enzymes, electrolytes, non-aqueous solvents, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, Dyes, hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, run-in preventers, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, Swelling and sliding resistant agents as well as UV absorbers.

As builders in the agents according to the invention may be included are in particular phosphates, silicates, aluminum silicates (in particular Zeolites), carbonates, salts of organic di- and polycarboxylic acids as well To name mixtures of these substances.

The use of the generally known phosphates as builder substances is possible according to the invention, provided that such use in detergents should not be avoided for ecological reasons. Detergents for automatic dishwashing are usually phosphate-based and preferably contain 30 to 70% by weight, particularly preferably 35 to 65% by weight and in particular 45 to 60% by weight of phosphate (s), in each case based on the total agent. Among the large number of commercially available phosphates, the alkali metal phosphates have particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the detergent industry.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish 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 fabrics and also contribute to cleaning performance. Sodium dihydrogen phosphate, NaH ₂ PO ₄ , disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ , trisodium phosphate, tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , tertiary sodium phosphate, Na ₃ PO ₄ , sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below), potassium dihydrogen phosphate (KH ₂ PO ₄ ), dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , potassium polyphosphate (KPO ₃ ) _x , potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ .

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. In 100 g of water about 17 g of the salt of water free of crystal water dissolve at room temperature, about 20 g at 60 ° and about 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

According to the invention, these are accurate such as sodium tripolyphosphate, potassium tripolyphosphate or mixtures usable from these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and are potassium tripolyphosphate and sodium potassium tripolyphosphate usable according to the invention.

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. 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 be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. 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. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. 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, ze are also suitable olith X and mixtures of A, X and / or P. Commercially available and preferably used in the context of the present invention is, for example, also a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which of is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and through the formula nNa 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. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. 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.

Other important builders are in particular the carbonates, citrates and silicates. To be favoured Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate Builder from the class of disilicate and / or metasilicate used.

Alkali carriers can be present as further constituents his. As an alkali carrier apply alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the aforementioned substances, wherein for the purposes of this invention preferably the alkali carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate can be used.

A builder system is particularly preferred a mixture of tripolyphosphate and sodium carbonate.

It is also particularly preferred a builder system containing a mixture of tripolyphosphate and Sodium carbonate and sodium disilicate.

In addition, other ingredients be present, with washing, rinsing or Cleaning agents are preferred which additionally contain one or more substances from the group of acidifying agents, chelating agents or of the deposit-inhibiting polymers.

Both inorganic acids and organic acids are suitable as acidifiers, provided that these are compatible with the other ingredients. The solid mono-, oligo- and polycarboxylic acids can be used in particular for reasons of consumer protection and handling safety. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. The anhydrides of these acids can also be used as acidifying agents, maleic anhydride and succinic anhydride in particular being commercially available. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

Another possible group of ingredients represent the chelating agents. Chelating agents are Substances that form cyclic compounds with metal ions, where a single ligand has more than one coordination site on a central atom busy, d. H. is at least "bidentate". In this case are usually elongated connections by complex formation over a Ion closed to rings. The number of ligands bound depends on the coordination number of the central ion.

Common and in the context of Preferred chelate complex images are present invention polyoxycarboxylic, Polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Also complex-forming polymers, i.e. polymers that are either in the Main chain itself or sideways contribute to this functional groups that can act as ligands and with suitable metal atoms, usually with the formation of chelate complexes react, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can from only one macromolecule originate or belong to different polymer chains. The latter leads to Cross-linking of the material, unless the complex-forming polymers already before covalent bonds were cross-linked.

Complexing groups (ligands) more common complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, Guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cycl.) Polyamino, mercapto, 1,3-dicarbonyl and crown ether residues with z. T. very specific activities across from Ions of different metals. Many base polymers are also commercially available important complex-forming polymers are polystyrene, polyacrylates, Polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethylene imines. Even natural Polymers such as cellulose, starch or chitin are complex-forming polymers. In addition, this provided with further ligand functionalities by polymer-analogous conversions become.

• (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• (iii) geminalen Diphosphonsäuren,
• (iv) Aminophosphonsäuren,
• (v) Phosphonopolycarbonsäuren,
• (vi) Cyclodextrine

in Mengen oberhalb von 0,1 Gew.-%, vorzugsweise oberhalb von 0,5 Gew.-%, besonders bevorzugt oberhalb von 1 Gew.-% und insbesondere oberhalb von 2,5 Gew.-%, jeweils bezogen auf das Gewicht des Mittels, enthalten.Are particularly preferred in the context of Present invention washing or cleaning agents containing one or more chelating agents from the groups of

• (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• (ii) nitrogen-containing mono- or polycarboxylic acids,
• (iii) geminal diphosphonic acids,
• (iv) aminophosphonic acids,
• (v) phosphonopolycarboxylic acids,
• (vi) cyclodextrins

in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the By means of, included.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
• b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-asparaginsäure oder Nitrilotriessigsäure (NTA),
• c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppenhaltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,
• d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),
• e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie
• f) Cyclodextrine.

All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups. The following are preferably used individually or in a mixture:

• a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,
• b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di- (β-hydroxyethyl) 1,2-glycine Dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA),
• c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues with up to 8 carbon atoms, and derivatives thereof containing hydroxyl or amino groups, and 1-aminoethane-1,1-diphosphonic acid, their higher homologs with up to 8 carbon atoms and derivatives thereof containing hydroxyl or amino groups,
• d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid),
• e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and
• f) cyclodextrins.

As polycarboxylic acids a) in the context of this Patent application for carboxylic acids -also monocarboxylic acids- understood, in which the sum of carboxyl and those contained in the molecule Hydroxyl groups is at least 5. Complexing agent from the Group of nitrogen-containing polycarboxylic acids, especially EDTA prefers. With those required according to the invention these are alkaline pH values of the treatment solutions. complexing agents at least partially as anions. It is immaterial whether it is in the form of acids or introduced in the form of salts. In case of use as salts are alkali, ammonium or alkylammonium salts, in particular Sodium salts, preferred.

Deposit-inhibiting polymers can also in the agents according to the invention be included. These substances that are chemically different could be come, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, with polymers with Molar masses below 15,000 daltons are preferred.

Deposit-inhibiting polymers can also have cobuilder properties exhibit. As organic cobuilders in the machine according to the invention dishwashing detergents in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are as follows described.

Usable organic builders are for example the polycarboxylic acids which can be used in the form of their sodium salts, where under polycarboxylic acids such carboxylic acids can be understood that carry more than one acid function. For example these are citric acid, Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), unless such use for ecological reasons objectionable, and mixtures of these. Preferred salts are the salts of polycarboxylic acids like 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 In addition to their builder effect, they typically also have the property an acidifying component and thus also serve to set a lower and milder one pH of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

As a builder or base inhibitor polymeric polycarboxylates are also suitable, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight from 500 to 70000 g / mol.

In the context 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), a UV detector being used. The measurement was carried out against an external polyacrylic acid re-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 500 to 20,000 g / mol exhibit. Because of their superior solubility can from this group, in turn, the short-chain polyacrylates, the molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1000 to 4000 g / mol, may be preferred.

Are particularly preferred in the agents according to the invention both polyacrylates and copolymers of unsaturated Carboxylic acids, Containing sulfonic acid Monomers and optionally other ionic or nonionic monomers used. Those containing sulfonic acid groups Copolymers are described in detail below.

Copolymers are also suitable Polycarboxylates, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been particularly suitable Maleic acid proven the 50 to 90 wt .-% acrylic acid and 50 to 10% by weight of maleic acid contain. Your 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 either used as a powder or as an aqueous solution become. The content of the agents in (co) polymeric polycarboxylates is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

Are also particularly preferred biodegradable polymers from more than two different monomer units, for example those which are salts of acrylic acid and monomers the maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Acrylic acid salts and 2-alkylallylsulfonic acid as well as sugar derivatives. Other preferred copolymers are those that preferably contain acrolein and acrylic acid / acrylic acid salts as monomers or acrolein and vinyl acetate.

Are also preferred as others Builder substances polymeric aminodicarboxylic acids, their salts or their precursors to call. Polyaspartic acids or theirs are particularly preferred Salts and derivatives which, in addition to cobuilder properties, also have a have a bleach-stabilizing effect.

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The Hydrolysis can be carried out according to the usual for example acid or enzyme-catalyzed processes. Preferably acts hydrolysis products with average molecular weights in the range of 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, preferably DE a common one Measure of the reducing Effect of a polysaccharide compared to dextrose, which a DE of 100 has. Both maltodextrins can be used with a DE between 3 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. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Also oxydisuccinates and other derivatives of Disuccinates, preferably ethylenediamine disuccinate, are others suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferred in the form its sodium or magnesium salts used. Also preferred in this context are also glycerol disuccinates and glycerol trisuccinates. Suitable amounts are those containing zeolite and / or silicate Formulations at 3 to 15% by weight.

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. 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 reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). The preferred aminoalkane phosphonates are ethylenedia mintetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition to the fabrics from the mentioned substance classes the agents according to the invention further usual ingredients of washing, rinsing or detergents, in particular bleach, Bleach activators, enzymes, silver preservatives, colors and fragrances are important. These substances are described below.

Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

To when washing at temperatures of 60 ° C and among them to achieve an improved bleaching effect, bleach activators can in washing according to the invention and cleaning agents can be incorporated. As bleach activators can Compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result can be used. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Prefers are multiply acylated alkylenediamines, especially 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 Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional Bleach activators or in their place can also be so-called bleach catalysts be incorporated. 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 tripod ligands containing nitrogen and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

Agents according to the invention can contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all the enzymes established in the prior art for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Agents ^according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5 percent by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and that which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. The variants listed under the name BLAP ^{® are} derived from the protease from Bacillus lentus DSM 5483. Other proteases that can be used come from various Bacillus sp. and B. gibsonii.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, which is sold under the trade name Protosol ^® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ^® by Wuxi Snyder Bioproducts Ltd., China, and in the trade name Proleather ^® and Protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of usable according to the invention Amylases are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus as well as their further developments for use in detergents and cleaning agents. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

Furthermore are for this Purpose of the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948); furthermore the that the sequence space of α-amylases belong. Fusion products of the molecules mentioned can also be used.

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae. Another commercial product is the Amylase-LT ^® .

Agents according to the invention can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^® , Lipolase ^® Ultra, LipoPrime ^® , Lipozyme ^® and Lipex ^® . Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. Lipase ^® , Lipase AP ^® , Lipase M-AP ^® and Lipase AML ^® available. For example, the Genencor company can use the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention, also the product Lumafast ^® from Genencor.

Agents according to the invention can, especially if they for the Treatment of textiles are thought to contain cellulases, each by purpose as pure enzymes, as enzyme preparations or in the form of Mixtures in which the individual components are advantageously complement in terms of their various performance aspects. To count these performance aspects especially contributions for primary washing performance, for secondary washing performance of the agent (anti-redeposition effect or graying inhibition) and finish (tissue effect), up to the exertion of a "stone washed" effect.

A useful fungal, endoglucanase (EG) -rich cellulase preparation or its further developments are offered by the Novozymes company under the trade name Celluzyme ^® . The products Endolase ^® and Carezyme ^® , also available from Novozymes, are based on the 50 kD-EG and the 43 kD-EG from N. insolens DSM 1800. Other possible commercial products from this company are Cellusoft ^® and Renozyme ^® . Cellulases can also be used; for example the 20 kD EG from Melanocarpus, which is available from AB Enzymes, Finland, under the trade names Ecostone ^® and Biotouch ^® . Other commercial products from AB Enzymes are Econase ^® and Ecopulp ^® . Other suitable cellulases from Bacillus sp. CBS 670.93 and CBS 669.93, the ones from Bacillus sp. CBS is available from Genencor under the trade name Puradax® ^® 670.93. Other commercial products from Genencor are "Genencor detergent cellulase L" and IndiAge ^® Neutra.

Agents according to the invention can contain further enzymes, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, United States. A B. alcalophilus β-glucanase is also suitable. The obtained from B. subtilis β-glucanase is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, washing and cleaning agents according to the invention can contain oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain. Suitable commercial products are Denilite ^® 1 and 2 from Novozymes. Advantageously, organic, particularly preferably aromatic, interact with the enzymes Compounds added to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) when the redox potentials between the oxidizing enzymes and the soiling differ greatly.

The agents according to the invention the enzymes used are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or according to known biotechnological processes produced by suitable microorganisms, such as transgenic Expression hosts of the genera Bacillus or filamentous fungi.

Purification of the concerned Enzymes are conveniently made by themselves established processes, for example via precipitation, sedimentation, concentration, Filtration of the liquid Phases, microfiltration, ultrafiltration, exposure to chemicals, Deodorization or suitable combinations of these steps.

Agents according to the invention can Enzymes are added in any form established according to the prior art become. This includes for example by granulation, extrusion or lyophilization obtained solid preparations or, especially with liquid or gel-shaped Means, solutions the enzymes, advantageously as concentrated as possible, low in water and / or mixed with stabilizers.

Alternatively, the enzymes can be used for both the solid for as well the liquid Dosage form are encapsulated, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural polymer or in the form of capsules, for example those in which the enzymes as in enclosed in a solidified or in the core-shell type, in which an enzyme-containing core with a water, air and / or Chemical-impermeable Protective layer covered is. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or Dyes are applied. Such capsules are after known methods, for example by shaking or Roll granulation or applied in fluid-bed processes. advantageously, are such granules, for example by applying polymeric Film former, low in dust and stable in storage due to the coating.

It is also possible to have two or assemble several enzymes so that a single Granulate multiple enzyme activities having.

One in an agent according to the invention contained protein and / or enzyme can be particularly during the Storage against damage such as inactivation, denaturation or decay, for example through physical influences, Oxidation or proteolytic cleavage are protected. With microbial Obtaining the proteins and / or enzymes is an inhibition of Proteolysis is particularly preferred, especially if the agents Proteases included. Agents according to the invention can stabilizers for this purpose contain; the provision of such means is preferred embodiment of the present invention.

A group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, Borax, boric acids, Boronic acids or whose salts or esters are used, including mainly derivatives with aromatic groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters. Also peptide aldehydes, ie oligopeptides with reduced C-terminus are suitable. As peptide protease inhibitors are mention ovomucoid and leupeptin among others; an additional Option is the formation of fusion proteins from proteases and peptide inhibitors.

Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders can additionally stabilize an enzyme contained.

Lower aliphatic alcohols but above all polyols, such as glycerol, ethylene glycol, Propylene glycol or sorbitol are other frequently used enzyme stabilizers. Di-glycerol phosphate also protects against denaturation by physical influences. Calcium salts are also used, such as calcium acetate or calcium formate, and magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, among other things, against physical influences or pH fluctuations. Polymers containing polyamine-N-oxide act simultaneously as enzyme stabilizers and as color transfer inhibitors. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkyl polyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds fulfill a double function as soil release agents and as enzyme stabilizers.

Reducing agents and antioxidants increase the stability of the enzymes oxidative decay. Sulfur-containing reducing agents are also known. Other examples are sodium sulfite and reducing sugars.

Combinations of stabilizers are preferably used, for example made of polyols, boric acid and / or borax, the combination of boron acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is increased by the combination with boric acid and / or boric acid derivatives and polyols and is further enhanced by the additional use of divalent cations, such as calcium ions.

Cleaning agents according to the invention for the machine Wash the dishes can to protect the dishes or the machine contain corrosion inhibitors, especially Silver protective agents in the field of automatic dishwashing have special meaning. The known substances can be used the state of the art. In general, silver protection agents in particular selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. To be used particularly preferably are benzotriazole and / or alkylaminotriazole. One finds in cleaner formulations about that out often Active chlorine-containing agents that clearly corrode the silver surface can reduce. In chlorine-free cleaners are especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, z. 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 common Use. The transition metal salts which are selected are preferred here 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 for prevention corrosion on the wash ware be used.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl ₂ in the agents according to the invention is preferred. The proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.

The pH of the agents according to the invention in the desired Bringing range, the use of pH adjusting agents can be indicated his. All of them can be used here known acids or lyes, provided that their use does not result from application technology or ecological establish or for reasons of consumer protection. Usually exceeds the amount of these adjusting agents is not 5% by weight of the total formulation.

As foam inhibitors used in the agents according to the invention can be used come for example soaps, paraffins or silicone oils, which may be considered on substrates may be upset. For inventive as a textile detergent Assembled suitable anti-redeposition agents, which are also available as should be called repellents, for example, are nonionic Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30 wt .-% and of hydroxypropyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether and the polymers of phthalic saunas and / or known from the prior art terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and Terephthalic acid polymers.

Optical brighteners (so-called "whiteners") can according to the invention as a textile detergent added preparations according to the invention to prevent graying and yellowing of the treated textiles to eliminate. These substances absorb on the fiber and cause a brightening and feigned Bleaching effect by converting invisible ultraviolet radiation into visible longer-wave Convert light, being the ultraviolet absorbed from sunlight Light as a slightly bluish Fluorescence is emitted and with the yellow tone of the grayed or yellowed laundry pure white results. Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2'-stilbene disulfonic acids (flavonic acids), 4,4'-distyrylbiphenylene, Methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid, Benzoxazole, benzisoxazole and benzimidazole systems as well as by Heterocycle-substituted pyne derivatives. The optical brighteners are common in amounts between 0.05 and 0.3% by weight, based on the finished product Means used.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatin, salts of ethensulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Before However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are added in amounts of 0.1 to 5% by weight, based on the composition, used. The compositions according to the invention can - also be equipped with additional benefits. For example, for agents made up according to the invention as textile detergents, there are color-transfer-inhibiting compositions, agents with an “anti-gray formula”, agents with ironing relief, agents with special fragrance release, agents with improved dirt release or prevention of re-soiling, antibacterial agents, UV protective agents, color-refreshing agents etc. Some examples are explained below:
Since textile fabrics, in particular made from rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending and kinking. If pressing and squeezing across the grain are sensitive, the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

To unwanted, due to exposure to oxygen and other oxidative processes caused changes in the agents and / or To prevent the treated textiles, the agents can have antioxidants contain. This class of compounds includes, for example, substituted ones Phenols, hydroquinones, pyrocatechols and aromatic amines as well organic sulfides, polysulfides, dithiocarbamates, phosphites and Phosphonates.

An increased wearing comfort can the additional Use of antstatics result, the agents according to the invention additionally enclosed become. Antistatic agents increase the surface conductivity and enable thus an improved drainage formed charges. External antistatic agents are usually substances with at least one hydrophilic molecular ligand and give on the surfaces a more or less hygroscopic film. These are mostly surface-active Antistatic agents can be broken down into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphoric (phosphoric acid esters) and divide sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for Textiles or as an additive to detergents, with an additional Finishing effect is achieved.

To improve water absorption, the Rewettability of the treated textiles and for relief of ironing of the treated textiles can in the agents according to the invention for example silicone derivatives are used. Improve this additionally the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups one to five Have carbon atoms and are partially or completely fluorinated. preferred Silicones are polydimethylsiloxanes, which may be derivatized could be and then are amino-functional or quaternized or Si-OH-, Si-H- and / or have Si-Cl bonds. The viscosities of the preferred silicones are at 25 ° C in the range between 100 and 100,000 centistokes, with the silicones in amounts between 0.2 and 5% by weight, based on the total agent can be used.

Finally, the agents according to the invention also contain UV absorbers that attach to the treated textiles and lightfastness of the fibers improve. Connections that you want Have properties are, for example, those due to non-radiation Deactivating active compounds and derivatives of benzophenone with substituents in the 2- and / or 4-position. Furthermore, too substituted benzotriazoles, in the 3-position phenyl substituted acrylates (Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanic suitable.

Another object of the present invention is a process for producing the washing, Cleaning or washing aids, namely a process for Production of silver-containing detergents, cleaning agents or auxiliary washing agents, which is characterized in that the solid or liquid washing, Cleaning or washing aids silver in elementary and / or admixed oxidized form.

As already mentioned above, the silver can be added in elemental form, being both in solid, preferably finely divided form is used as also as a solution, Suspension or dispersion of silver in suitable solvents. Also silver compounds and solutions, Suspensions or dispersions of silver compounds can be used according to the invention.

One way of producing the washing, cleaning or washing aids according to the invention is to add silver to the finished solid or liquid agent. This is done as already described above, preferably in finely divided form. Preferred processes according to the invention are therefore characterized in that silver elemental form (Ag ⁰ ) is added to the solid or liquid washing, cleaning or washing aid, the silver particle sizes from 0.1 to 100 microns, preferably from 0.2 to 80 microns and in particular from 0.25 to 60 μm.

Even smaller particle sizes can be rea lize by introducing the silver colloidal distributed into the washing, cleaning or washing aids according to the invention. For incorporation into solid washing, cleaning or washing aids according to the invention, it is advisable to prepare a colloidal silver solution and to either impregnate the solid agent and / or constituents thereof and / or suitable carrier materials with the colloid solution. Processes according to the invention are preferred here, in which silver is added to a liquid washing, cleaning or washing aid in elemental (Ag ⁰ ) and colloidal form, the silver particle sizes from 0.001 to 0.1 μm, preferably from 0.002 to 0.05 μm and in particular from 0.005 to 0.01 μm.

Colloidal silver solutions with particle sizes around 7.5 nm can be produced, for example, using the Argentox ^® process, in which silver salts are reduced in the presence of protective colloids (e.g. starch, dextrin, etc.). Alternatively, silver can be ground to a colloid solution in a suitable mill (colloid mill). Arc sputtering of silver (silver wires) in water or other liquids can also be used to produce colloidal silver solutions. The colloidal silver solutions obtained can be added directly to liquid washing, cleaning or washing aids according to the invention or applied to solid agents and / or constituents thereof and / or suitable carrier materials.

In particular for liquid washing, Cleaning or washing aids can also offer that colloid solution to be added directly to the medium or the silver to collide in the medium to create. Another preferred method according to the invention is therefore characterized in that the silver colloid by dispersion of silver in the liquid Washing, cleaning or washing aids is produced, preferably by homogenization in a colloid mill or by sputtering an arc Silver wire in liquid washing, Cleaning or washing aids.

Alternatively or in addition to The process variants described above can also be silver be incorporated into the agents according to the invention in oxidized form. You can do this Silver compounds, especially silver acetate, silver bromide, silver carbonate, Silver chloride, silver nitrate, silver oxide, silver phosphate, silver sulfate, Silver thiosulfate, or mixtures of these directly in solid form the agents according to the invention be added. Solutions too Suspensions or dispersions of the aforementioned silver salts liquid washing, Add cleaning or washing aids directly or to solid agents according to the invention and / or components thereof and / or suitable carrier materials muster.

Another possibility for the production of silver solutions is the Katadyn ^® -Ag ⁺ process, in which silver ions are added electrolytically to water or an aqueous solution.

Another possibility, the inventive method It is to design the liquid washing, cleaning or to enrich washing aids with silver during their manufacture, that he Silver and / or silver-containing tools, pipes, etc. are used. Such a preferred method is characterized in that the production of solid or liquid washing, cleaning or washing aids the agent or parts thereof in contact with silver or silver-containing surfaces lets kick.

Liquid washing, cleaning or washing aids according to the invention can be mixed, for example, with silver or silver-containing stirring tools and / or in silver or silver-containing kettles or conveyed through silver or silver-containing pipelines. So-called Katadyn ^® filters, in which silver is embedded in sintered diatomaceous earth (diatomaceous earth), can also be used by passing water used to produce liquid agents through these filters.

For solid washing, Cleaning or washing aids are available, for example on, with silver or silver-containing granulating or mixing tools and / or produced in silver or silver-containing granulators to be or through silver or silver-containing conveyors promoted to become.

Claims (13)

Containing washing, cleaning or washing aids Silver in elemental and / or oxidized form. Washing, cleaning or washing aids according to claim 1, characterized in that it is in solid form and silver (calculated as Ag) in quantities from 0.1 to 1000 mg / kg, preferably from 1 to 500 mg / kg, particularly preferably from 2 to 250 mg / kg, more preferably from 3 to 150 mg / kg and in particular from 4 to 100 mg / kg. Washing, cleaning or washing aids according to claim 1, characterized in that it in liquid Form is present and silver (calculated as Ag) in amounts from 0.1 to 200 mg / l, preferably from 1 to 100 mg / l, particularly preferably from 2 to 75 mg / l, more preferably from 3 to 50 mg / l and in particular from 4 to 10 mg / l. Washing, cleaning or washing aids according to claim 3, characterized in that it is considered softener is made up, the 0.5 to 50 wt .-% cationic (s) surfactants) contains. Washing, cleaning or washing aid according to one of claims 1 to 4, characterized is characterized in that it contains silver in elemental form (Ag ⁰ ), the silver having particle sizes from 0.1 to 100 μm, preferably from 0.2 to 80 μm and in particular from 0.25 to 60 μm. Detergent, cleaning agent or auxiliary washing agent according to one of Claims 1 to 5, characterized in that it contains silver in elemental (Ag ⁰ ) and colloidal form, the silver having particle sizes from 0.001 to 0.1 μm, preferably from 0.002 to 0, 05 μm and in particular from 0.005 to 0.01 μm. Washing, cleaning or washing aids according to one of claims 1 to 6, characterized in that it contains silver in oxidized form (Ag ⁺ ), the silver salts silver acetate, silver bromide, silver carbonate, silver chloride, silver nitrate, silver oxide, silver phosphate, silver sulfate, silver thiosulfate , or mixtures of these are preferred. Washing, cleaning or washing aids after one of claims 1 to 7, characterized in that the silver or the silver compounds) on substrates, preferably builders, angry. Process for the production of silver-containing washing, Cleaning or washing aids, characterized in that the solid or liquid washing, Cleaning or washing aids silver in elementary and / or admixed oxidized form. Process according to Claim 9, characterized in that silver elemental form (Ag ⁰ ) is added to the solid or liquid washing, cleaning or washing aid, the silver having particle sizes from 0.1 to 100 µm, preferably from 0.2 to 80 µm and in particular from 0.25 to 60 μm. Process according to Claim 9, characterized in that silver is added to a liquid washing, cleaning or washing aid in elemental (Ag ⁰ ) and colloidal form, the silver having particle sizes from 0.001 to 0.1 μm, preferably from 0.002 to 0.05 μm and in particular from 0.005 to 0.01 μm. A method according to claim 11, characterized in that this Silver colloid by dispersing silver in the liquid washing, Cleaning or washing aids is generated, preferably by Homogenization in a colloid mill or by arc sputtering of a silver wire in the liquid Washing, cleaning or washing aids. A method according to claim 9, characterized in that he in the manufacture of solid or liquid washing, cleaning or washing aid the agent or parts thereof in contact with silver or silver-containing surfaces can occur.