WO2005037974A2

WO2005037974A2 - Antimicrobial treatment for bath and toilet articles

Info

Publication number: WO2005037974A2
Application number: PCT/EP2004/010249
Authority: WO
Inventors: Hans-Jürgen Riebe; Thomas Müller-Kirschbaum
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2003-10-07
Filing date: 2004-09-14
Publication date: 2005-04-28
Also published as: WO2005037974A3; DE10346387A1

Abstract

The invention relates to an antiseptic agent, for an antimicrobial treatment of surfaces, the presence of which is marked for the user by colour, lustre, fluorescence or light fragrance, containing silver, which can be incorporated in washing and cleaning agents, textile pre-treatment or secondary treatments, which, in liquid form, is suitable for spraying by means of a spray applicator and which can be used in methods for antimicrobial treatment of surfaces and in methods for odour prevention in closed spaces.

Description

"Antimicrobial treatment of bathroom and toilet articles"

The invention relates to germicidal agents for the antimicrobial finishing of surfaces which contain silver, the antimicrobial finishing of a surface being made clear to the consumer. These agents can already be used for the factory antimicrobial finishing, for example of textiles, toilet ceramics, floor coverings or other objects in frequent contact with germs, but can also be used for the subsequent or renewed treatment of surfaces, if necessary incorporated into a washing or cleaning agent, a washing aid , a textile pre- or post-treatment agent.

There is a need to reduce the number of bacteria both in the household and in public areas, and above all in those areas in which an increased bacterial load can be expected, for example in hospitals, but also in swimming pools or public toilets, in order to avoid the formation of unsightly deposits and, if necessary, to reduce the resulting risk of illness. Furthermore, it is again desirable, in particular in public facilities exposed to high levels of germs, but also in private households, that effective protection is indicated to the consumer, so that it can be seen in the hospital, for example, which surfaces can be regarded as relatively germ-free and which ones possibly there is a risk of infection.

Antimicrobial agents have already been described many times in the prior art. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics 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 acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl butyl carbamate, iodine, iodophores, peroxo compounds, halogen compounds as well as any mixtures of the above. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenol mercuric acetate.

The use of the substances from the abovementioned groups is not always completely unproblematic, for example for reasons of cost, for reasons of processability or the stability of the compounds in the compositions, for reasons of incompatibility with other ingredients or for ecological or health reasons. Last but not least, the EU Biocides Directive means that the use of many substances is increasingly considered undesirable.

The object was therefore to provide agents which, on the surfaces treated or in contact with them, bring about a reduction in the number of bacteria without having the disadvantages mentioned, and at the same time make the antimicrobial treatment of a surface clear to the consumer.

This object is achieved with an agent which contains silver and its presence on the surface by a change in the color or in the reflection of the incident light, by a reduction in the odor nuisance or by fluorescence of the treated surface in a way which is invisible to the human eye Wavelength range that can be detected, for example, by means of UV rays, is made recognizable for the user.

This agent can be used to provide an antimicrobial surface with an effective finish, the antimicrobial active silver used having good processability and good compatibility with other ingredients, but at the same time being highly environmentally compatible and also being largely unproblematic in terms of health.

In principle, the antimicrobial properties of silver have been known since ancient times. The incorporation of nanoparticulate silver into various surfaces is carried out, for example, by the companies Nanux Co., Ltd. (Eng.Nanocomposite.net). Bio-Gate (www.bio-gate.de) or rent a Scientist (www.rent-a-scientist.com), but not the incorporation into detergents and cleaning agents, washing aids, textile pre- or post-treatment agents. Such means, however, are known from Japan, but without the consumer has the opportunity to subsequently determine the antimicrobial finish of a surface.

International patent application WO 00/78281 (Procter & Gamble) describes antimicrobial personal care products that contain nanosilver. These are hygiene products, toothbrushes, baby pacifiers and cleaning and nourishing as well as decorative cosmetic compositions such as skin creams, shampoos or mascara. Incorporation of the nanosilver into detergents and cleaning agents, washing aids, textile pretreatment or post-treatment agents is not described, nor is the antimicrobial finish displayed to the consumer.

International patent application WO 00/53413 (Icet Inc.) describes the antimicrobial treatment of plastics, in particular polyethylene terephthalate (PET), which among other things. is used in the beverage industry to manufacture bottles. Nanosilver can be used as an antimicrobial agent. Again, neither the incorporation into a detergent or cleaning agent formulation, a washing aid or a textile pre- or post-treatment agent is described, nor is the labeling of a suitably equipped plastic.

It therefore appears desirable to develop detergents and cleaning agents, auxiliary washing agents, textile pretreatment and post-treatment agents which contain the advantageous active ingredient silver, in particular nanosilver, and whose antimicrobial activity is made clear to the consumer.

Silver or silver ions have a blocking effect on thiol enzymes in microorganisms and thus have a high bactericidal and fungicidal activity. Silver is also germicidal. ' The terms "antimicrobial effect" and "antimicrobial agent" have the usual meaning in the context of the teaching according to the invention, as used, for example, by KH Wallhäußer in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene" (5th ed. - Stuttgart; New York : Thieme, 1995) is reproduced.

The agents according to the invention preferably contain the silver or the silver compound (s) in certain amounts. The silver content (Ag °) is always used as the basis for calculation in the context of the present invention. Contains an invented agent according to the invention, for example 100 mg of silver chloride per kg, its silver content is 73.53 mg per kg, expressed in% by weight, ie 0.007% by weight.

Detergents, cleaning agents or auxiliary washing agents, textile pretreatment or post-treatment agents which are in solid, liquid or flowable form, as gel, powder, granules, paste or spray and comprise an inventive germicidal agent preferably contain silver (calculated as Ag) in Amounts from 0.00005 to 5% by weight, particularly preferably from 0.0001 to 1% by weight and in particular from 0.0004 to 0.1% by weight, based on the agent.

According to the invention, silver is used either in elemental form or in the form of its compounds. Preferred germicides according to the invention contain silver in elemental form (Ag °), 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 be added to the finished solid or liquid agent, for example, and can serve as so-called "powdering agents". However, they can also be added during manufacture, for example granulated.

In a particularly preferred embodiment, the silver used is nanosilver, that is to say even more finely divided silver with particle sizes from 0.001 to 0.1 μm, preferably from 0.002 to 0.05 μm and in particular from 0.004 to 0.01 μm. The silver can also be wholly or partly in colloidal form.

Particle sizes from 0.001 to 100 μm, in particular from 0.004 to 0.1 μm, are therefore preferred.

In the case of solid agents, the processability of silver with small particle sizes can be improved by applying the silver to carrier materials. For this purpose, suitable carrier materials can be impregnated, for example, with colloidal silver solutions or mixed with finely divided silver and / or silver compounds. Of course, it is also possible to granulate the silver together with the carrier materials with the addition of suitable granulation aids. Builders, for example zeolites, are particularly suitable as carrier materials. In addition, highly porous substances such as silicas, for example pyrogenic silicas, bentonites, polymeric materials or diatomaceous earth ("diatomaceous earth") can also be used as carrier materials serve, furthermore ceramic materials capable of ion exchange, for example based on zirconium phosphate, or also glasses, especially bioactive or biocidal glasses. Nanosilver fixed on carrier materials is already commercially available, for example AlphaSan ^® (Milliken / CIariant) or AgiON ™ (AgiON Technologies).

Such composite particles made of carrier material and silver can optionally have further ingredients. For example, the use of activating noble metals such as gold or palladium, which activate the germ-reducing effect of silver in the slightest traces, has proven itself. However, other substances, for example ingredients of washing or cleaning agents, can also be applied to or incorporated into the composite particles. Here, for example, so-called small components such as dyes and fragrances, optical brighteners, polymers, etc. are suitable, provided that they are compatible with the carrier material and the silver, in particular if these small components can be used to identify treated surfaces.

The presence of the antimicrobial agent on the surface is made recognizable to the user by a change in the color or in the reflection of the incident light, by a reduction in the odor nuisance or by fluorescence of the treated surface in a wavelength range which is not visible to the human eye. In the latter case, detection is carried out by irradiation with light of the corresponding wavelength, for example with ultraviolet light. In a particularly preferred embodiment, the agent therefore contains one or more dyes, one or more metal or pearlescent agents, one or more substances which give the surface a particularly smooth, shiny appearance, or one or more substances which are in a wavelength range outside of human eyesight fluoresce, for example optical brighteners. It should be noted, however, that the dye used should only change the appearance of the treated surface to the extent necessary to distinguish treated from untreated surfaces. In a preferred embodiment, it is therefore preferably a glossy material that gives the treated surface a shimmer and / or a metallic or mother-of-pearl-like gloss, a clear lacquer, or else a substance that fluoresces in a wave range outside of human eyesight, for example, which is under a corresponding light source, for example under ultraviolet light, becomes visible. Furthermore, the dye, especially in the case of agents for surfaces which are in frequent contact with human or animal skin, should be non-toxic in the concentration used and should not be absorbed by the skin. At higher silver concentrations, the intrinsic color of the silver can also be sufficient to indicate the presence of a treated surface.

Dyes or brighteners to be used with preference are therefore selected, for example, from the group comprising effect pigments, preferably metallic effect pigments and / or pearlescent pigments. Further preferred dyes are those which are also used as optical brighteners in textile detergents, plastics, etc., for example derivatives of 4,4'-diamino-2,2'-stilbenedisulfonic acid (flavonic acid), 4,4'-distyryl -biphenylene, methylumbelliferone, coumarin, dihydroquinolinone, 1, 3-diarylpyrazoline, naphthalic imide, linked via CH = CH bonds benzoxazole, benzisoxazole and. Benzimidazole systems and heterocycle-substituted pyrene derivatives. If the consumer is to be shown the antimicrobial finish of the surface by reducing the odor nuisance, it can also be advantageous to incorporate deodorant substances. These include, for example, the cyclodextrins or the salts of abietic acid and ricinoleic acid and other higher hydroxylated fatty acids, in particular zinc ricinoleate, but also oxidation catalysts. Furthermore, the incorporation of a less volatile fragrance, which develops its fragrance over a longer period of time, in accordance with the longer-lasting antimicrobial effect, can be advantageous.

Especially when finishing hard surfaces, it may be desirable for the germicide to form a stable film or varnish on the surface. A non-continuous covering of the surface can also be desirable. Accordingly, the agent can contain one or more film-forming polymers. All polymers known from the prior art as such are suitable for this purpose, for example polyacrylates, resins, polyvinyl alcohols or polyvinyl acetals. To form a film or a lacquer layer, it may further be desirable that the agent additionally contains a crosslinking agent. Alternatively or additionally, it may also be desirable to expose the treated surface to an elevated temperature, preferably up to 200 ° C. and / or to radiation with electromagnetic waves, preferably with ultraviolet light with a wavelength of 200 to 400 nm. This procedure is particularly important when equipping factory objects with an antimicrobial protective layer is advantageous, but can also be carried out by the consumer in the household, for example by using an iron or hair dryer.

The film-forming polymers are preferably in amounts of 0 to 10% by weight, particularly preferably 0.01 to 8% by weight, in particular 0.1 to 5% by weight and very particularly preferably 0.5 to 3% by weight. %, contain.

The agents according to the invention are advantageously incorporated into detergents, cleaning agents or auxiliary washing agents, textile pretreatment or aftertreatment agents, so that the treated surface is given an antimicrobial finish in addition to cleaning.

Accordingly, the application also relates to a washing, cleaning or auxiliary washing agent, textile pretreatment or post-treatment agent which contains a germicidal, film-forming agent

All solid, liquid or flowable, gel-like, portion-packed or individually portionable, powder-like, granulated, compressed into tablets, paste-like, sprayable or in other usual dosage forms for machine or manual textile washing can be used as detergents. The cleaning agents include all agents for cleaning hard surfaces, which also occur in all of the dosage forms mentioned, manual and machine dishwashing agents, carpet cleaners, abrasive cleaners, glass cleaners, toilet fragrance cleaners, etc. For the purposes of this invention, washing aids are those agents which are added to the actual washing agent in the case of manual or machine textile washing in order to achieve a further effect, for example stain remover. Textile pre- and post-treatment agents are, on the one hand, those agents with which the item of laundry is brought into contact before the actual washing, for example for loosening stubborn soiling, on the other hand those that are desirable for the laundry in a step downstream of the actual textile washing Give properties such as a pleasant grip, freedom from creasing or low static charge. The latter means, among others, the fabric softener counted.

"Flowable" in the sense of the present application are washing, cleaning or washing aids according to the invention, textile pre-treatment or post-treatment agents, which are pourable and can have viscosities up to several 10,000 mPas. The viscosity of the agents according to the invention can be measured using customary standard methods (for example Brookfield viscometer LVT-II at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 5 to 10000 mPas. Preferred detergent and cleaning agent compositions, washing aids, textile pre- or post-treatment agents have viscosities of 10 to 8000 mPas, values between 120 to 3000 mPas being particularly preferred.

In particular, with frequent use of liquid detergents or fabric softeners and frequent washing at low temperatures, unsightly discolouration can occur in the dispenser drawer in the corresponding dosage compartments, and a deposit can also form. If, on the other hand, a detergent, auxiliary washing agent and / or a textile aftertreatment agent is used which contains a germicidal agent according to the invention, the contamination of the induction drawer is visibly counteracted.

The washing, cleaning or washing aids, textile pre-treatment or post-treatment agents can contain all the usual ingredients of washing or cleaning agents. These are described below.

Substances that also serve as ingredients in cosmetic products are referred to below in accordance with the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds have an INCI name in English, herbal ingredients are only listed according to Linne in Latin. So-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI names can be found in the "International Cosmetic Ingredient Dictionary and Handbook, Seventh Edition (1997)", published by The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101, 17th Street NW, Suite 300, Washington, DC 20036, USA, is published and contains more than 9,000 INCI names as well as references to more than 37,000 trade names and technical names including the associated distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns the ingredients one or more chemical classes, for example "Polymeric Ethers", and one or more functions (functions), for example "Surfactants - Cleansing Agents", which it again explained in more detail. This may also be referred to below.

The statement CAS means that the following sequence of numbers is a

Chemical Abstracts Service.

The washing, cleaning or washing aids according to the invention, textile pretreatment or post-treatment agents preferably contain one or more surfactant (s), anionic, nonionic, cationic and / or amphoteric surfactants being able to be used, depending on the intended use. For example, mixtures of anionic and nonionic surfactants are preferred for textile detergents. Machine dishwashing detergents preferably contain low-foaming nonionic surfactants, in particular those which are solid at room temperature, especially those with a melting point between 25 and 60 ° C. Textile aftertreatment agents such as fabric softeners, conditioning agents, etc., on the other hand, preferably also contain cationic surfactants, in particular quaternary ammonium compounds. The total surfactant content of the washing or cleaning agents according to the invention is preferably between 0.1 and 70% by weight, particularly preferably between 1 and 50% by weight, in particular between 5 and 30% by weight, based on the total agent.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated and / or propoxylated, 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 is linear or preferably in 2-position may be methyl branched or may contain linear and methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals. The surfactants can also have polyoxyethylene-polyoxypropylene block copolymer units. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C _12- ι ₄ alcohols containing 3 EO or 4 EO, _C9-11 alcohol containing 7 EO, C _13- i ₅ alcohols containing 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- i ₈ 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 ranks 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, generally C ₆ -C ₂₀ monohydroxyalkanols or alkylphenols with preferably at least 12 EO, particularly preferably at least 15 EO, in particular at least 20 EO. Furthermore, structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants can also be used. The latter are characterized by good foam control.

Further preferred nonionic surfactants are the end group-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 have 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 represents values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5, particularly preferably each for 1. 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 . If the value x ≥ 2, each R ³ in the above formula can be different. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15. If x ≥ 2, the alkylene oxide unit in the square brackets can therefore be varied so that, for example, any sequences of EO and PO are possible, for example alternately or as block polymers.

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 preferably used nonionic surfactants, which are used 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, in particular fatty acid methyl ester.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula below, 1 R I

R-CO-N- [Z] 1 in the RCO for an aliphatic acyl radical with 6 to 22 carbon atoms, R 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.

The group of polyhydroxy fatty acid amides also includes compounds of the following formula, 1 2 R -OR 1 R-CO-N- [Z] 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 group or an aryl group containing 2 to 8 carbon atoms and R ² is a linear, branched or cyclic alkyl group or an aryl group or an oxyalkyl group having 1 to 8 carbon atoms is, where C _1- alkyl or phenyl radicals are and [Z] for is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

[Z] is preferably obtained by reductive 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 converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

The content of nonionic surfactants in detergents or cleaning agents according to the invention which are suitable for textile washing is 1 to 30% by weight, preferably 2 to 25% by weight and in particular 3 to 20% by weight, in each case based on the total agent.

The washing or cleaning agents according to the invention can also contain anionic, cationic and / or amphoteric surfactants as surfactant component.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C ₉ . ₁₃ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates as obtained, for example, from C _12-18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, into consideration. Also suitable are alkanesulfonates, which are for example derived from C ₁₂ ι ₈ alkanes by sulfochlorination or sulfoxidation and 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. Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. 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.

As 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 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 and 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 moles of ethylene oxide, such as 2-methyl-branched Cg- ₁ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _12- ₈ 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 in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8- ι ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves. 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 suitable anionic surfactants are, in particular, oils. Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.

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

The anionic surfactant content of preferred textile detergents according to the invention is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20% by weight, in each case based on the total composition. Cleaning agents according to the invention for machine dishwashing are preferably free from anionic surfactants.

The agents according to the invention can contain, for example, cationic compounds of the formulas I, II or III as cationic active substances:

R ¹ IR ¹ -N < ⁺ > - (CH ₂ ) _n . -TR ² (D (CH ₂ ) _n -TR ² R ¹ IR ¹ -N «- (CH ₂ ) _n . -CH-CH ₂ (II) IR ¹ TTIIR ² R ² R ¹ R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (III) R ⁴

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each group R ^{2 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 which are formulated as fabric softeners contain cationic surfactant (s) of the formulas (I), (II) and / or (III). Preferred fabric softeners contain 0.5 to 50% by weight, preferably 1 to 45% by weight and in particular 2.5 to 40% by weight of at least one cationic surfactant, cationic surfactants of the formula (I) being preferred.

The amphoteric surfactants (amphoteric surfactants, zwitterionic surfactants) which can be used according to the invention include betaines, alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which betaines are preferred in the context of the teaching according to the invention.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁴ ) (R ⁵ ) (R ⁶ ) N ⁺ CH ₂ COO ^" , in which R ^{4 is} an alkyl radical with 8 to 25, preferably 10 to 21, carbon atoms and R, which is optionally interrupted by heteroatoms or heteroatom groups ⁵ and R ^{6 are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyldimethylcarboxymethylbetaine and Cn-C ₁₇ -alkylamidopropyldimethylcarboxymethylbetaine. The compositions contain amphoteric surfactants in amounts, based on the composition, from 0 to 20% by weight.

In the context of the present invention, preferred washing, cleaning or washing aids, textile pretreatment or post-treatment agents additionally contain one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH regulators, Fragrances, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antifog agents, anti-corrosive agents, anti-corrosive agents, anti-corrosive agents, anti-corrosive agents - and anti-slip agents as well as UV absorbers.

The builders that can be contained in the agents according to the invention are, in particular, phosphates, silicates, aluminum silicates (in particular zeolites), carbonates, Salts of organic di- and polycarboxylic acids as well as 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. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry. 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.

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. Particularly suitable are, for example, sodium dihydrogen phosphate (NaH ₂ PO ₄ ), disodium hydrogen diphosphate (Na ₂ H ₂ P ₂ O ₇ ), trisodium phosphate, tetranate 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

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, potassium polyphosphate (KPO ₃ ) _x , potassium diphosphate

(Potassium pyrophosphate), K ₄ P ₂ O ₇ , furthermore condensed phosphates and including both cyclic (sodium or potassium metaphosphates) and chain-like types (sodium or potassium polyphosphates), for example pentasodium triphosphate (sodium tripolyphosphate, Na ₅ P ₃ O ₁₀ ), melting or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x +} ι yH 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 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 provide 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, 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 (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and which has the formula nNa ₂ O ^■ (1-n) K ₂ O ^• AI 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 manufacture come. 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.

Organic cobuilders can include, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates. The polycarboxylic acids which can be used in the form of their sodium salts are particularly preferred, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Particularly preferred builders are carbonates, citrates and / or silicates, optionally in combination with phosphates. Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicates and / or metasilicates are preferably used.

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

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

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

In addition, other ingredients may be present, for example acidifying agents, chelating agents or scale-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 are the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, i. H. is at least "bidentate". In this case, normally elongated connections are closed to form rings by complex formation via an ion. The number of ligands bound depends on the coordination number of the central ion.

Common chelate complexing agents preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Also complex-forming polymers, i.e. polymers that either in the main chain itself or Functional groups which can act as ligands and react with suitable metal atoms generally to form chelate complexes can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3 -Dicarbonyl and crown ether residues with z. T. very specific activities towards ions of different metals. The base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.

All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups. Preferably, individually or in a mixture with one another, in amounts above 0.01% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight. %, each based on the weight of the agent, used:

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, isopropyl diacetic acid, and nitridodiacetic acid, nitridodiacetic acid, nitridodiacetic acid, nitridodiacetic acid, nitridodiacetic acid, , N, N-di- (β-hydroxyethyl) glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) -g! Ycin, 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 homologues with up to 8 carbon atoms as well as 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.

In the context of this patent application, polycarboxylic acids a) are understood to mean carboxylic acids - also monocarboxylic acids - in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular NTA or MGDA (methylglycine diacetate), are preferred. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.

Deposit-inhibiting polymers can also have cobuilder properties. Organic cobuilders which can be used in the dishwasher detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such polycarboxylic acids being among the polycarboxylic acids 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), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Polymeric polycarboxylates are also suitable as builders or scale inhibitors; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 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 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. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1000 to 4000 g / mol, can in turn be preferred from this group. Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, 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. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers , Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures 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, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary 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 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 can be used.

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.

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

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

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 being neutral and the tetrasodium salt being alkaline (pH 9) responding. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. 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 substances from the classes of substances mentioned, the agents according to the invention can contain further usual ingredients of detergents, dishwashing detergents or cleaning agents, bleaching agents, bleach activators, enzymes, silver protection agents, colorants and fragrances being particularly 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.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the washing and cleaning agents according to the invention. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 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 acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, 2-ethylene glycol diacetate and 2.5 5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also 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 process (bicinchoninic acid; 2,2'-bichinolyl-4,4 '-dicarboxylic acid) or the biuret method can be determined.

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 which can no longer be assigned to the subtilisins in the narrower sense and the 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 protease from Bacillus lentus DSM 5483 is derived from the BLAP ^® led off variants. 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 amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus and their further developments which are improved 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 derived variants from the α- amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948); also those belonging to the sequence space of α-amylases. 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, especially if they are intended for the treatment of textiles, can contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various performance aspects. These performance aspects include, in particular, contributions to the primary washing performance, to the secondary washing performance of the agent (anti-deposition effect or graying inhibition) and finish (tissue effect), through 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 H. insolens DSM 1800. Other possible commercial products from this company are Cellusoft ^® and Renozyme ^® . Cellulases are also 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, xanthane 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 β-glucanase from a B. alcalophilus is also suitable. The .beta.-glucanase obtained from B. subtilis is available under the name Cereflo ^® from Novozymes.

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

The enzymes used in agents according to the invention either originate from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi. The enzymes in question are advantageously purified by methods which are in themselves established, for example by means of 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 be added to the enzymes in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzyme is enclosed in a solidified gel are or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.

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

A protein and / or enzyme contained in an agent according to the invention can be protected against damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage, especially during storage. When the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Agents according to the invention can be used for this Purpose contain stabilizers; the provision of such agents is a preferred embodiment of the present invention.

A group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters. Peptide aldehydes, ie oligopeptides with a reduced C-terminus, are also suitable. Ovomucoid and leupeptin may be mentioned as peptide protease inhibitors; 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, for example, glycerol, ethylene glycol, propylene glycol or sorbitol are further frequently used enzyme stabilizers. Di-glycerol phosphate also protects against denaturation by physical influences. Calcium salts, such as calcium acetate or calcium formate, and magnesium salts are also used.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation against physical influences or pH fluctuations, among other things. 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 against 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 boric 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 machine dishwashing may contain corrosion inhibitors to protect the wash ware or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) Complexes, chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware. 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, and in powdery agents also Na ₂ SO ₄ or MgSO ₄ . The proportion of electrolytes in the agents according to the invention is usually 0.5 to 20% by weight, but can also assume values of up to 50% by weight.

In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or bases can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. Examples include hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, formic acid, acetic acid, lactic acid, malic acid, tartaric acid and, as bases, sodium hydroxide solution, potassium hydroxide solution, ammonia or amines such as monoethanolamine, but other acids and / or bases can also be present. The amount of these adjusting agents usually does not exceed 5% by weight of the total formulation.

Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials. Agents made up according to the invention as textile detergents may further contain anti-reposition agents (so-called soil repellents). Suitable antiredeposition agents are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether and the polymers known from the prior art phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention made up as textile detergents in order to to eliminate stains and yellowing of the treated textiles. These substances absorb on the fiber and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and pure with the yellow tone of the grayed or yellowed laundry White results. The presence of optical brighteners can also serve as an indicator of the antimicrobial effect. Suitable compounds originate for example from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic (flavonic), ^{4,4'-biphenylene} -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1,3-diaryl pyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems and the pyrene derivatives substituted by heterocycles. The optical brighteners are usually used in amounts between 0.05 and 0.3% by weight, based on the finished agent.

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, for example glue, gelatin, salts of ether sulfonic 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, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. 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 preferably used in amounts of 0.1 to 5% by weight, based on the composition.

The agents according to the invention can also be provided with additional benefits. For example, for agents made up according to the invention as textile detergents, there are color-transfer-inhibiting compositions, agents with "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 protection agents, color-refreshing agents etc. can be formulated. Some examples are explained below: Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can tend to wrinkle because the individual fibers are sensitive to bending, kinking, pressing and squeezing across the fiber direction, the detergents, washing aids, textile pre- and post-treatment 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.

In order to prevent undesirable changes in the agents and / or the treated textiles caused by the action of oxygen and other oxidative processes, the agents can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Increased wearing comfort can result from the additional use of antistatic agents, which can additionally be added to the detergents, washing aids or preferably textile aftertreatment agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and 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 softening effect.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example silicone derivatives can be used in the agents according to the invention. These additionally improve 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 have one to five carbon atoms and are partially or completely fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 centistokes, it being possible for the silicones to be used in amounts between 0.01 and 5% by weight, based on the total agent.

Finally, the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.

In particular, liquid, gel-like or pasty agents according to the invention can contain rheology modifiers (thickeners) to set the desired viscosity. For the purposes of the present invention, thickeners are polycarboxylates, preferably homopolymers and copolymers of acrylic acid, in particular acrylic acid copolymers, such as acrylic acid-methacrylic acid copolymers, and polysaccharides, in particular heteropolysaccharides, and other conventional polymeric thickeners. In addition, phyllosilicates and other inorganic substances known to those skilled in the art as thickeners can also be used as thickeners in the sense of this invention; Mixtures of different thickeners can also be used. However, polymers, especially polycarboxylates and / or polysaccharides, are preferably used as thickeners in cleaning agents according to the invention.

Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenan and their salts, guar, guaran, tragacant, gellan, ramsan, dextran or xanthan and their derivatives, for example propoxylated guar, and their mixtures , Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used alternatively, but preferably in addition to a polysaccharide rubber, for example a wide variety of starches Origin and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.

A preferred polymer is the microbial anionic heteropolysaccharide xanthan gum containing 10 ^6, under aerobic conditions with a molecular weight of 2-15 * produced by Xanthomonas campestris and some other species and, for example, from the company. Kelco under the trade names KeltroP and Kelzan ^® or is available from Rhodia under the trade name RhodopoP. Another preferred polysaccharide is Gellan Gum (trade name KelcogeP), also available from Kelco.

Suitable acrylic acid polymers are, for example, high molecular weight homopolymers of acrylic acid (INCI carbomer) crosslinked with a polyalkylene polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers. Such polyacrylic acids include available from BFGoodrich under the trade name CarbopoP.

However, particularly suitable polymers are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters (INCI acrylates copolymer), preferably formed with C _1-4 alkanols, to which about the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) belong and which, for example, from Rohm & Haas under the trade names Aculyn ^® and AcusoP and from Degussa (Goldschmidt) are available under the trade name Tego ^® Polymer; (ii) Crosslinked high molecular acrylic copolymers, for example the copolymers of C _{1 which are} crosslinked with an allyl ether of sucrose or pentaerythritol. ₃ o-alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably formed with C _1-4 -alkanols, esters (/ ate / C / acrylates / C 10-30 alkyl acrylate cross polymer) and the are available, for example, from BFGoodrich under the trade name CarbopoP.

Layered silicates in particular can be used as inorganic thickeners. These include, for example, the magnesium or sodium-magnesium layered silicates available from Solvay Alkali under the trade name Laponite ^® , especially the Laponite ^® RD or Laponite ^® RDS, as well as the magnesium silicates from Süd-Chemie, especially the OptigeP SH.

The thickener content is usually between 0.01 and 8% by weight, preferably between 0.1 and 6% by weight, particularly preferably between 0.5 and 3% by weight, for example between 0.5 and 1% by weight .-% or between 2 and 3 wt .-%. The viscosity of the agents according to the invention is essentially adjusted or controlled via the content of thickener, the amounts required being able to vary from thickener to thickener. The surfactant composition used also plays a role in the choice of quantity.

Liquid agents according to the invention can contain one or more water-soluble organic solvents, usually in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight, in particular 2 to 15% by weight, particularly preferably 4 to 12 % By weight, most preferably 6 to 10% by weight.

Within the framework of the teaching according to the invention, the solvent is used, in particular, as a hydrotrope, viscosity regulator and / or cold stabilizer. It has a solubilizing effect, particularly for surfactants and electrolytes, as well as perfume and dye, and thus contributes to their incorporation, prevents the formation of liquid-crystalline phases and is involved in the formation of clear products. The viscosity of the agent according to the invention decreases with increasing amount of solvent. However, too much solvent can cause an excessive drop in viscosity. Finally, the cold cloud and clear point of the agent according to the invention decrease with increasing amount of solvent.

Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C _1-20 hydrocarbons, preferably C _2- i ₅ hydrocarbons, with at least one hydroxyl group and optionally one or more ether functions COC, ie oxygen atoms interrupting the carbon atom chain.

Preferred solvents are the C _2-6 alkylene glycols and poly-C _2-3 alkylene glycol ethers, optionally etherified on one side with a C _1-6 alkanol, with an average of 1 to 9 identical or different, preferably identical, alkylene glycol groups per Molecule as well as the C _1-6 alcohols, preferably ethanol, n-propanol or / so-propanol, especially ethanol.

Exemplary solvents are the following compounds named according to INCI: Alcohol (ethanol), buteth-3, butoxydiglycol, butoxyethanol, butoxyisopropanol, butoxypropanol, n-butyl alcohol, t-butyl alcohol, butylene glycol, butyl octanol, diethylene glycol, dimethoxydiglycol , Dimethyl ether, dipropylene glycol, ethoxydiglycol, ethoxyethanol, ethyl hexanediol, glycol, hexanediol, 1, 2,6-hexanetriol, hexyl alcohol, hexylene glycol, isobutoxypropanol, isopentyl diol, isopropyl alcohol (/ so-propanol), 3-methoxybutanol , Methoxydiglycol, methoxyethanol, methoxyisopropanol,

Methoxymethylbutanol, methoxy PEG-10, methylal, methyl alcohol, methyl hexyl ether, methyl propanediol, neopentyl glycol, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-6 methyl ether, pentylene glycol, PPG-7, PPG26, PPG 400, PPG 1200, PPG-2-buteth-3, PPG-2 butyl ether, PPG-3 butyl ether, PPG-2 methyl ether, PPG-3 methyl ether, PPG-2 propyl ether, Propanediol, propyl alcohol (n-propanol), propylene glycol, propylene glycol butyl ether, propylene glycol propyl ether, tetrahydrofurfuryl alcohol, trimethylhexanol.

Particularly preferred solvents are the poly-C _2-3 -alkylene glycol ether etherified on one side with a C _1-6 alkanol with an average of 1 to 9, preferably 2 to 3, ethylene or propylene glycol groups, for example PPG-2 methyl ether (dipropylene glycol monomethyl ether).

Extremely preferred solvents are the C _2-3 alcohols ethanol, n-propanol and / or / so-propanol, in particular ethanol.

Solubilizers, for example for dyes and perfume oils, can also be present in liquid agents according to the invention. In addition to the solvents described above (especially the polyols such as ethylene glycol, 1, 2-propylene glycol, glycerol and other monohydric and polyhydric alcohols), alkanolamines and alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical can also be used as such.

To stabilize the cleaning agent according to the invention, especially with a high surfactant content, one or more dicarboxylic acids and / or their salts, alone or in a mixture, can be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, as described, for example, under the Trade name Sokalan ^® DSC is available. The use is advantageously made in amounts of 0.1 to 8% by weight, preferably 0.5 to 7% by weight, in particular 1, 3 to 6% by weight and particularly preferably 2 to 4% by weight.

A change in the dicarboxylic acid (salt) content - especially in amounts above 2% by weight - can contribute to a clear solution of the ingredients. The viscosity of the mixture can also be influenced by this agent within certain limits. This component also influences the solubility of the mixture. This component is particularly preferably used at high surfactant contents, in particular at surfactant contents above 30% by weight.

Instead of or in addition to the dicarboxylic acids and / or their salts, other organic acids or their salts, such as sodium formate, sodium acetate, sodium citrate and sodium tartrate, as well as inorganic salts such as e.g. Sodium chloride, magnesium chloride and magnesium sulfate, or also salts of the aforementioned anions with other alkali or alkaline earth metals can be used individually or in mixtures.

Abrasives can also be contained in cleaning agents according to the invention. These can be at least partially water-soluble and / or water-insoluble abrasives. The former can be, for example, alkali carbonates, bicarbonates or sulfates, the latter are preferably selected from the group comprising plastics (for example polyethylene, polypropylene and / or polystyrene), hard waxes, natural materials (for example crushed nut shells, fruit kernels or roots) , Ceramic or glass particles, inorganic substances (such as silicates) and mixtures thereof.

In addition to the components mentioned, the washing, cleaning and washing aids according to the invention, textile pretreatment and post-treatment agents can contain further auxiliaries and additives, as are customary in such agents. These include, in particular, UV stabilizers, perfumes, dyes, polymers, gloss-enhancing substances (e.g. vinegar, especially fruit vinegar), hydrotropes (e.g. cumene sulfonate, octyl sulfate, butyl glucoside, butyl glycol), cleaning enhancers, other disinfectants, preservatives and skin protection agents as described in EP-A-522506. The amount of such additives is usually not more than 12% by weight in the cleaning agent. The lower limit of use depends on the type of additive. The amount of auxiliaries is preferably between 0.01 and 7% by weight, in particular 0.1 and 4% by weight. Another object of the present invention is a process for the preparation of the washing, cleaning or washing aids according to the invention, namely a process for the production of silver-containing washing, cleaning or washing aids, which is characterized in that the solid, liquid, gel or paste-like washing, cleaning or washing aids silver in elemental and / or oxidized form, optionally on a carrier, are admixed.

As already mentioned above, the silver can be added in elemental form, it being used both in solid, preferably finely divided form, and as a solution, suspension or dispersion of silver in suitable solvents. Silver compounds as well as solutions, suspensions or dispersions of silver compounds can also be used according to the invention. Furthermore, the silver can be applied in elementary or oxidized form to carrier materials or can be embedded therein. Suitable for this are, for example, builders such as zeolites, highly porous substances such as (pyrogenic) silicas, bentonites, polymeric materials or diatomaceous earth ("diatomaceous earth"), also ceramic materials capable of ion exchange, for example based on zirconium phosphate, or glasses, especially bioactive ones or biocidal glasses.

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 °) is added to the solid or liquid washing, cleaning or washing aid, the silver particle sizes from 0.1 to 100 μm, preferably from 0.2 to 80 μm and in particular from 0.25 to 60 μm.

Even smaller particle sizes can be achieved by introducing the silver in a colloidal distribution 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 makes sense to prepare a colloidal silver solution and 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 a liquid washing, cleaning or washing aid is used in elemental (Ag °) and silver 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.

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 according to the invention, it may also be advisable to add the colloid solution directly to the agent or to produce the silver colloidally on average. A further preferred method according to the invention is therefore characterized in that the silver colloid is produced by dispersing silver in the liquid washing, cleaning or auxiliary washing agent, preferably by homogenization in a colloid mill or by arc sputtering a silver wire in the liquid washing, cleaning or auxiliary washing agent.

Alternatively or in addition to the process variants described above, silver in oxidized form can also be incorporated into the agents according to the invention. For this purpose, silver compounds, in particular silver acetate, silver bromide, silver carbonate, silver chloride, silver nitrate, silver oxide, silver phosphate, silver sulfate, silver thiosulfate, or mixtures of these can be mixed directly in solid form with the agents according to the invention. Solutions, suspensions or dispersions of the aforementioned silver salts can also 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. 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.

A further possibility for designing the method according to the invention is to enrich the liquid washing, cleaning or washing aids according to the invention with silver during their production by using silver and / or silver-containing tools, pipelines etc. Such a preferred method is characterized in that in the preparation of the solid or liquid washing, cleaning or washing aids, the agent or parts thereof are allowed to come into contact with silver or silver-containing surfaces.

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 according to the invention, it makes sense, for example, to be produced with silver or silver-containing granulating or mixing tools and / or in silver or silver-containing granulators or to be conveyed by silver or silver-containing conveying devices.

The agent according to the invention can also be suitable for spraying in liquid form, for example using a conventional trigger spray bottle or an aerosol spray can. Another object of the invention is therefore a product of a liquid agent according to the invention and a spray dispenser.

Agents according to the invention can be used for the antimicrobial finishing of surfaces, both hard surfaces, for example in the household, and soft surfaces such as textiles. Another object of the invention is accordingly the use of an agent or product according to the invention for the antimicrobial finishing of hard surfaces and the use of an agent or product according to the invention for the antimicrobial finishing of textiles. Agents and products according to the invention can also be used to control odors. Another object of the invention is therefore the use of an agent or product according to the invention for odor control.

Agents according to the invention are used to equip various surfaces. Accordingly, another subject of the invention is a method for the antimicrobial finishing of hard surfaces made of glass, ceramic, plastic, wood, cork, metal, marble, granite, terracotta, stone, such as floors, dishes, work surfaces, furniture, sanitary ware, tiles, door handles, toilet Brushes, as well as textile surfaces made of leather, synthetic and natural fibers as well as mixtures thereof, for example clothes, upholstered furniture, carpets, curtains, bed and table linen. Here, the surface to be treated is brought into contact with an agent according to the invention which, depending on the type of agent, dries directly on the surface or is washed out after silver-containing material has deposited on the surface in an amount sufficient to impart antimicrobial properties. The surface treatment agent can be incorporated into a cloth, a sponge, a brush or another auxiliary device that can be used for cleaning.

Agents according to the invention can also be used to control odors. Accordingly, yet another object of the invention is a method for controlling odors in closed rooms, an agent according to the invention being applied to a surface, for example by spraying, and drying there, with the surface being all hard surfaces, for example made of glass, ceramic, plastic, wood, cork , Metal, marble, granite, terracotta and / or stone, preferably floors, walls, crockery, furniture, bathroom ceramics, dwellings of pets or household objects, as well as textile surfaces, for example made of leather, synthetic and natural fibers and mixtures thereof, preferably clothing, upholstered furniture , Carpets, curtains, bed and table linen. In the case of textiles, the odor control can furthermore be carried out by washing the textiles in a customary manner with a detergent according to the invention or, in the case of textile washing, being brought into contact with a washing aid according to the invention, textile pretreatment or post-treatment agents.

Claims

Pate ntans sp

1. Germicidal agent for the antimicrobial treatment of surfaces, characterized in that it contains silver and its presence on the treated surface by a change in the color or in the reflection of the incident light, by a reduction in odor nuisance or by fluorescence of the treated surface in a wavelength range that is not visible to the human eye is made recognizable to the user.

2. Germicidal agent according to claim 1, characterized in that the silver is in nanoparticulate form.

3. Germicidal agent according to one of claims 1 and 2, characterized in that the silver in amounts of 0.00005 to 5 wt .-%, preferably 0.0001 to 1 wt .-%, particularly preferably 0.0004 to 0, 1 wt .-%, based on the agent, is included.

4. Germicidal agent according to one of the preceding claims, characterized in that the silver has an average particle size of 0.001 to 100 microns, preferably from 0.004 to 0.1 microns.

5. Germicidal agent according to one of the preceding claims, characterized in that the silver is present in elemental and / or oxidized form, optionally also fixed on a carrier.

6. Germicidal agent according to one of the preceding claims, characterized in that its presence on the surface is preferably made visible by the coloring of the surface, in particular by a metallic or pearlescent shimmer, by gloss or by fluorescence, for example in the ultraviolet wavelength range.

7. Germicidal agent according to one of the preceding claims, characterized in that it contains one or more dyes and / or one or more optical brighteners and / or a means for producing a gloss.

8. Germicidal agent according to one of the preceding claims, characterized in that its presence on the surface is indicated by a reduction in odor nuisance.

9. Germicidal agent according to claim 8, characterized in that it comprises deodorant substances selected from the group comprising cyclodextrins, the salts of abietic acid, ricinoleic acid and other higher hydroxylated fatty acids, and / or oxidation catalysts.

10. Germicidal agent according to one of the preceding claims, characterized in that it forms a stable film or a lacquer layer after application to the surface.

11. Germicidal agent according to one of the preceding claims, characterized in that it contains one or more film-forming polymers in amounts of 0.01 to 10 wt .-%, preferably 0.1 to 5 wt .-%, particularly preferably 0.5 to 3 wt .-%, wherein the film-forming polymers are preferably selected from the group comprising polyacrylates, polyvinyl alcohols, polyvinyl acetals and mixtures thereof.

12. Germicidal agent according to one of the preceding claims, characterized in that it is incorporated into a detergent, a washing aid, a textile pre- or post-treatment agent and / or a cleaning agent for hard surfaces.

13. washing or cleaning agents, washing aids, textile pre- or after-treatment agents, containing a germicidal agent according to any one of claims 1 to 11, characterized in that it contains at least one surfactant.

14. washing or cleaning agents, washing aids, textile pre- or post-treatment agents containing a germicidal agent according to any one of claims 1 to 11, characterized in that it contains one or more anionic and / or nonionic and / or cationic and / or amphoteric surfactants Contains amounts from 0.1 to 60% by weight, preferably from 1 to 50% by weight, in particular from 5 to 30% by weight.

15. washing or cleaning agents, washing aids, textile pre- or post-treatment agents containing a germicidal agent according to one of claims 1 to 11, characterized in that it contains one or more further ingredients, preferably selected from the group comprising builders ("builder") , Bleaching agents, bleach activators, thickeners, enzymes, electrolytes, non-aqueous solvents, pH regulators, polymers and mixtures thereof.

16. washing or cleaning agents, washing aids, textile pre- or post-treatment agents containing a germicidal agent according to one of claims 1 to 11, characterized in that it contains further auxiliaries and additives, preferably selected from the group comprising fragrances, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, additional preservative / disinfectant, Vergrauungsinhibi- factors, shrink preventatives, anticrease agents, soil repellents, Farbübertragungsinhibi- factors, skin protective agents, antimicrobial active ingredients, germicides, fungicides, antioxidants, corrosion inhibitors, pearlescent agents, antistatic agents , Ironing aids, phobing and impregnating agents, swelling and anti-slip agents as well as UV absorbers.

17. Germicidal agent according to one of claims 1 to 12 or washing or cleaning agents, washing aids, textile pre- or after-treatment agent according to one of claims 13 to 16, characterized in that it is pressed in solid form, into tablets, as powder, granules, can be used in liquid, diluted or undiluted form, as a gel or paste.

18. Germicidal agent according to one of claims 1 to 12 or detergents or cleaning agents, washing aids, textile pretreatment or aftertreatment agent according to one of claims 13 to 16, characterized in that it also thanks to its antimicrobial effect for odor control and / or for avoiding the Development of bad smells can be used.

19. Product from a liquid agent according to one of the preceding claims and a spray dispenser.

20. A process for the preparation of silver-containing detergents, cleaning agents or auxiliary washing agents, textile pretreatment or aftertreatment agents, characterized in that the solid, liquid, gel- or paste-like washing, cleaning or washing aid is silver in elemental and / or oxidized form, optionally on a carrier.

21. Use of an agent according to one of claims 1 to 18 or a product according to claim 19 for the antimicrobial finishing of hard surfaces.

22. Use of an agent according to one of claims 1 to 18 or a product according to claim 19 for the antimicrobial finishing of textiles.

23. Use of an agent according to any one of claims 1 to 18 or a product according to claim 19 for odor control.

24. Process for the antimicrobial finishing of hard surfaces made of glass, ceramic, plastic, wood, cork, metal, marble, granite, terracotta, stone, such as floors, dishes, work surfaces, furniture, sanitary ceramics, tiles, door handles, toilet brushes and textiles Surfaces made of leather, synthetic and natural fibers and mixtures thereof, for example clothing, upholstered furniture, carpets, curtains, bed and table linen, characterized in that the surface to be treated is brought into contact with an agent according to one of Claims 1 to 18 and then dries on the surface.

25. The method according to claim 24, characterized in that the means for surface treatment is incorporated in a cloth, a sponge, a brush or other auxiliary means that can be used for cleaning.

26. A method for controlling odors in closed rooms, characterized in that an agent according to one of claims 1 to 18, optionally by spraying with a product according to claim 19, is applied to a surface and dries there, with all hard surfaces, for example, as the surface made of glass, ceramic, plastic, wood, cork, metal, marble, granite, terracotta and / or stone, preferably floors, walls, dishes, furniture, bathroom ceramics, dwellings of pets or household objects, as well as textile surfaces, for example made of leather, synthetic and natural fibers and mixtures thereof, preferably clothing, upholstered furniture, carpets, curtains, bed and table linen.

27. A method for odor control on textiles, characterized in that the textiles are washed with a detergent and / or a washing aid, textile pretreatment agent or textile post-treatment agent according to one of claims 13 to 18.