WO2007009618A1

WO2007009618A1 - Alkali metal halogenides as tracers

Info

Publication number: WO2007009618A1
Application number: PCT/EP2006/006668
Authority: WO
Inventors: Thomas Holderbaum; Werner Pichler; Lars Kucka
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2005-07-16
Filing date: 2006-07-07
Publication date: 2007-01-25
Also published as: DE102005033347A1

Abstract

The invention relates to different types of agents, such as cosmetic agents or washing and cleaning agents which contain an alkali metal halogenide in a defined concentration of below 0.9 wt.%.This fulfils the function of a tracer. Said invention also relates to the use of an alkali metal halogenide as a tracer in said type of agents and raw substances. Lithium salts and lithium chloride are particularly suitable in addition to alkali metal halogenides.

Description

Alkali metal halides as tracers

The present application relates to various types of agents such as cosmetics or detergents containing an alkali metal halide in a defined concentration below 0.9% by weight. This application further relates to the use of an alkali metal halide as a tracer in such agents or raw materials.

Tracers are chemical compounds that can also be detected in very small quantities in combination with other substances. For example, in hydrology and hydrogeology, for exploring flow paths and flow rates of surface and groundwater flows, for example, dyes, fluorescent dyes or chlorides are used (see below).

It is known from WO 94/04741 A1 to use a reducing sugar as tracer in order to set the concentration of the detergent in the liquor constant in a washing process.

In the publication by Combes, Ye, and Zwick, Monsan: "Effects of salts on enzyme stability" in Annais of the New York Academy of Sciences (1988), 542 (Enzyme Eng.9), 7-10; ISSN 0077-8923 describes LiCl, NaCl and potassium chloride (KCl) as enzyme stabilizers.

DE 69704224 T2 discloses special cosmetic surfactant compositions with acrylamide as thickener and an electrolyte content of up to 20% by weight. These may be, inter alia, alkali metal salts. The obtained total compositions have desirable biophysical properties (flow behavior, foaming, etc.) in the context in question. An additional effect of the salts is not discussed.

German Patent Application DE 10234256 A1 discloses a cosmetic and / or dermatological dosage form ("substrate"), which in turn contains a preparation containing 3 to 65% by weight of one or more inorganic salts revealed Dosage forms serve to supply the skin with these salts in a suitable form. The intended effect is the physiological action of the salts.

The patent EP 132126 B1 discloses medical and especially cosmetic preparations to treat the skin with various lithium salts. These are contained in the respective preparations up to 10 wt .-%. The intended effect is the physiological action of the lithium salts for the treatment of skin diseases.

The shampoo disclosed in US 4834901 contains up to 5% by weight of a salt. This is a lodate. As a further ingredient also 1 wt .-% LiCl is disclosed, which fulfills a thickening function and serves to obtain the iodate in solution.

Patent EP 319536 B1, which is in the field of textile technology, discloses chitosan preparations for finishing textiles, which are sprayed onto the material, for example. These preparations may also contain surfactants and / or 0.1% by weight of lithium chloride as further ingredients. These serve to influence the physical properties of the spray, in particular to ensure a certain moisture content (as "wetting agent").

U.S. Patent 5,826,507, which is in the printing field, discloses that lithium chloride is suitable as a tracer for a particular problem. Because there are certain printing press rolls with a fountain solution (fountain solution) and other rollers wetted with the ink; Both liquids are then applied to the paper to be printed. At the same time, the paper has a certain moisture content, which is decisive for the print quality. In order to be able to determine in this finely coordinated process how much swelling solution is applied to the paper, US 5826507 discloses the addition of a tracer to the swelling solution, the concentration of which can be determined comparatively easily and accurately and thus indirectly provides information about the moisture content of the paper. Possible tracers are isotopes, organic compounds and metal salts; Among the latter are also called lithium salts.

The application US 2003/0100121 A1 is in the field of cell biology and deals with the problem of the activity of membrane-bound sodium channels determine the intracellular concentrations of suitable ions within the framework of a specific experimental procedure. For this purpose, indicators (tracers) of sodium, lithium or rubidium ions are used, which can be detected by special detection methods.

The application JP 51111388 A proposes to add the water-soluble lithium chloride as tracer in the monitoring of water flows and water cycles instead of the otherwise customary, analytically difficult or complex chemicals.

Based on this, the application JP 2004004045 A discloses lithium-complexing compounds with the aid of which the lithium concentration can be determined electrochemically or optically.

In the publication "How dense is our sewer system?" By J. Rieckermann in EAWG news, vol. 57 (9) (2003), p. 29-31, it is described that for the inspection of sewers the exfiltration of leaky pipelines and the infiltration As a possible, relatively easily detectable compounds for this purpose, among other sodium and lithium chloride are disclosed.

This related art of using alkali metal halides can be summarized in that alkali metal halides are common components of various chemical preparations such as cosmetics, pharmaceuticals and textile finishes. They fulfill various functions due to their chemical reactivity. Furthermore, these salts, including lithium chloride, are established in special technical applications as so-called tracers in order to facilitate the analysis of actually interesting components, such as in printing technology and in the monitoring of substance flows, for example in water cycles or wastewater. The specific lithium-ion analysis as an integral part of such approaches is the subject of further developments.

The use of alkali metal halides as tracers in detergents or cleaners, cosmetics or pharmaceutical preparations, in particular for the determination of the content of a particular raw material such as especially an enzyme or Such agents with a small but well-defined content of alkali metal halides, however, can not be gathered from the prior art.

It is an object of the present invention to establish in a very wide variety of types of agents, such as those for the treatment of all types of surfaces, in particular detergents or cleaners or cosmetic preparations, a detection method which is comparatively simple to carry out, with the aid of which certain raw materials contained can be checked with regard to their concentration. In particular, this approach should allow quality control of the funds concerned during the manufacturing process. Of particular interest was the facilitation of enzyme analysis, as it is relatively expensive on the enzyme activity and enzymes are important ingredients of all types of agents.

This object is achieved by means selected from pharmaceutical agents, personal care products, shampoos, hair care products, hair dyes, oral, dental or denture care products, cosmetics, detergents, cleaning agents, rinse aids, hand detergents, hand dishwashing detergents, machine dishwashing detergents, bleaching agents, disinfectants or agents for Treatment of filter media, textiles, furs, paper, hides or leather, containing an alkali metal halide in a defined concentration below 0.9 wt .-%.

Ingredients whose presence or concentration can be detected by the use of an alkali metal halide according to the invention as a tracer are basically all compounds that are chemically compatible with the tracer. Conversely, the alkali metal halide selected as the tracer must be so inert to the other ingredients that there are no chemical reactions between the two components which alter their respective concentrations and / or chemical properties. Even against external influences, the tracer should be largely inert, that is, it should remain virtually unchanged over the period of observation to ensure reliable measurement.

Furthermore, it should be a compound that does not occur in the funds to be doped or - compared to the amount of added tracer - occurs only in extremely small amounts that do not affect the measurement. For safety's sake, the should Initial concentration of this compound determined and subtracted from the respective measured values.

For the purposes of the present application, "defined concentration" means that the tracer is added to the agents concerned in a quantity weighed per unit volume or weight by the user of the invention, not including the occurrence of the tracer compound as an impurity, accidental admixture or This must be taken into account in the measurements taken (see above).

The tracer dosage is conveniently proportional to the originally weighed amount of the interesting and more complicated to detect in comparison to the tracer ingredient, so that in the course of further processing such as mixing with other ingredients a precise and inexpensive quality control of the ingredient on the analysis of the tracer instead of the of the ingredient itself.

By way of example, processing processes but also transport and storage can be monitored, in the course of which, for example, demixing processes take place.

Preferably, this is a detergent, a cleaning agent, a rinse aid, a hand wash, a hand dishwashing detergent or a machine dishwashing detergent.

Preferred embodiments are characterized in that the alkali metal halide is contained in a concentration of 1 to 500 ppm, preferably 10 to 250 ppm, particularly preferably 50 to 150 ppm.

Furthermore, the object is achieved by a raw material for an agent which is selected from pharmaceutical agents, personal care products, shampoos, hair care products, hair dyes, oral, dental or denture care products, cosmetics, detergents, cleaning agents, rinse aids, hand detergents, hand dishwashing detergents, machine dishwashing detergents, bleaching agents , Disinfectants or agents for the treatment of filter media, textiles, furs, paper, skins or leather, wherein the Raw material is an alkali metal halide in a defined concentration below 0.9 wt .-%. contains.

Because of the detection of the alkali metal halide can be during the further production process, the concentration of the relevant raw material component, as well - with a known relation of the raw material to the overall recipe - that follow the overall formulation.

Preferably, such a raw material is characterized by being an enzyme preparation, more preferably an enzyme granule.

Preferred embodiments of the raw material are characterized in that the alkali metal halide is contained in a concentration of 20 to 9,000 ppm, preferably from 200 to 5,000 ppm, particularly preferably 1,000 to 3,000 ppm.

In preferred embodiments, the agent or the raw material is characterized in that the alkali metal halide is selected from potassium chloride, potassium bromide, potassium iodide, potassium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium fluoride, lithium bromide, lithium fluoride, lithium nitride halides, rubidium chloride, rubidium fluoride, rubidium zinc bromide, Rubidium silver iodide, cesium chloride, cesium iodide, cesium fluoride, preferably lithium bromide, lithium fluoride or lithium nitride halides, more preferably lithium chloride.

In further preferred embodiments, the agent or the raw material is characterized in that the alkali metal halide is contained in a defined size ratio to an ingredient of a washing or cleaning agent, preferably to an enzyme, in particular to an amylase, a cellulase, a lipase, an oxidoreductase, a hemicellulase or a protease, more preferably an α-amylase and / or a subtilisin protease.

Preferred are those which are naturally produced by Bacillus species or which are derived from them by well-known biotechnological methods. Of particular importance are the α-amylases of Termamyl ^® - type (originally obtained from Bacillus licheniformis) and from the Bacillus Ientus- alkaline protease (BLAP) -derived subtilisins. They will be described in more detail below.

In the case of enzymes, there are in principle two calculation possibilities, namely the relation of the tracer concentration to that of the enzyme substance or to that of the enzyme activity. Since normally the enzyme is of interest not because of its material characteristics but because of its reactivity, the content of the tracer is conveniently weighed in a fixed relation to the enzyme activity. It should be noted, however, that enzyme activities decrease during processing or storage, for example, when exposed to moisture. This could be set up before establishing a production process once a corresponding activity curve. If an enzyme activity in a given process decreases by 10% in one hour, for example, an unchanged tracer concentration after 2 h corresponds to only 81% of the activity concerned.

In an advantageous embodiment, the agent according to the invention or the raw material according to the invention, characterized in that the tracer is detectable by atomic absorption spectrometry (AAS).

Devices suitable for detection are, for example, the atomic absorption spectrometers from AnalytikJena AG, which are listed on the Internet at the URL http://www.analytik-jena.de/d/bu/as/aas/aas.html (last) on 13.07.2005) are listed. Chemical compounds which are particularly suitable for determining the content of lithium chloride and can be read out electrochemically or optically are disclosed, for example, in the application JP 2004004045 A.

Further preferred embodiments are characterized in that the agent or the raw material is in solid form.

The object is achieved in the same way by the use of an alkali metal halide as a tracer in an agent which is selected from pharmaceutical agents, personal care products, shampoos, hair care products, hair dyes, oral, dental or denture care products, cosmetics, detergents, cleaning agents, Rinse-off preparations, hand washing agents, hand dishwashing detergents, dishwasher detergents, bleaching agents, disinfectants or agents for the treatment of filter media, textiles, furs, paper, skins or leather. Preferably, the agent to be determined is a detergent, a detergent, a rinse aid, a hand wash, a hand dishwashing detergent, or a machine dishwashing detergent.

Preferred such uses are characterized in that the alkali metal halide is used in a defined concentration below 0.9 wt .-%, preferably in a concentration of 1 to 500 ppm, more preferably from 10 to 250 ppm, particularly preferably 50 to 150 ppm, based on the agent.

Another object of the present invention is the use of an alkali metal halide as a tracer in a raw material for an agent which is selected from pharmaceutical agents, personal care products, shampoos, hair care products, hair dyes, oral, dental or denture care products, cosmetics, detergents, cleaning agents , Rinse aids, hand washing agents, hand dishwashing detergents, machine dishwashing detergents, bleaching agents, disinfectants or agents for the treatment of filter media, textiles, furs, paper, skins or leather.

Preferably, the raw material is an enzyme preparation, more preferably an enzyme granule.

Preferred such uses are characterized in that the alkali metal halide is used in a defined concentration below 0.9 wt .-%, preferably in a concentration of 20 to 9,000 ppm, more preferably from 200 to 5,000 ppm, particularly preferably 1,000 to 3,000 ppm, based on the raw material.

Preferably, the alkali metal halide is selected from potassium chloride, potassium bromide, potassium iodide, potassium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium fluoride, lithium bromide, lithium fluoride, lithium nitride halides, rubidium chloride, rubidium fluoride, rubidium zinc bromide, rubidium silver iodide, cesium chloride, cesium iodide, cesium fluoride, preferably lithium bromide, lithium fluoride or lithium nitride halides, more preferably lithium chloride.

In preferred embodiments, the use is directed to the detection of an ingredient of a washing or cleaning agent, preferably an enzyme, in particular an amylase, a cellulase, a lipase, an oxidoreductase, a hemicellulase or a protease, particularly preferably an α-amylase and / or a subtilisin protease.

The tracer dosage, if the concentration of an enzyme is to be detected, preferably in proportion to the enzyme activity, so that a precise and inexpensive quality control can be carried out.

In preferred embodiments, the use according to the invention is characterized in that the detection of the tracer takes place by means of atomic absorption spectrometry (AAS).

In preferred embodiments, the use according to the invention is characterized in that the agent or the raw material is in solid form.

The washing or bleaching agent to be determined according to the invention as tracer by means of an alkali metal halide is preferably in solid form, preferably as a free-flowing powder having a bulk density of 300 g / l to 1,200 g / l, in particular 500 g / l to 900 g / l , Alternatively, it may also be in the form of a pasty or liquid detergent, in particular in the form of a non-aqueous liquid detergent or a non-aqueous paste or in the form of an aqueous liquid detergent or a water-containing paste.

Due to their great technical importance, the various aspects and other ingredients according to the invention will now be described in detail in accordance with the invention by the above-described tracer washing and cleaning agent to be examined in addition to the above-described particularly preferred embodiments.

Here, a distinction is made according to the laundry between textiles and solid surfaces. The conditions to be selected for this purpose, in particular via the other ingredients, such as temperature, pH, ionic strength, redox ratios or mechanical influences, should be optimized for the respective cleaning problem. So are usual temperatures for detergents and cleaners in the range of 10 ⁰ C for manual agents above 40 ⁰ C and 60 ⁰ C up to 95 ° for mechanical means or in technical applications. Since modern washing and rinsing If the temperature is usually steplessly adjustable, all intermediate temperatures are also included. Preferably, the ingredients of the respective agents are coordinated. Synergies in terms of cleaning performance are preferred.

The tracer which can be used according to the invention can be used both in compositions according to the invention for large consumers or technical users and in products for the private consumer, with all types of detergents established in the prior art also representing embodiments of the present invention. These include, for example, concentrates and undiluted agents; for use on a commercial scale, in the washing machine or in hand washing or cleaning. These include, for example, detergents for textiles, carpets, or natural fibers, for which according to the present invention the term laundry detergent is used. These include, for example, dishwashing detergents for dishwashers or manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather; for such according to the present invention, the term cleaning agent is used.

Embodiments of the present invention relate to all established and / or all suitable dosage forms. These include, for example, solid, powdery, liquid, gelatinous or pasty agents, optionally also of several phases, compressed or uncompressed; further include, for example: extrudates, granules, tablets or pouches, packed both in large containers and in portions. However, solid agents are preferred according to the invention.

The tracer which can be used according to the invention is combined in inventive compositions with, for example, one or more of the following ingredients: nonionic, anionic and / or cationic surfactants, (optionally further) bleaching agents, bleach activators, bleach catalysts, builders and / or cobuilders, solvents, thickeners, sequestering agents, electrolytes , optical brighteners, grayness inhibitors, corrosion inhibitors, in particular silver protectants, soil release agents, color transfer (or transfer) inhibitors, foam inhibitors, abrasives, dyes, perfumes, antimicrobial agents, UV protectants, enzymes such as proteases, amylases, lipases, Cellulases, hemicellulases or oxidases, stabilizers, in particular other enzyme stabilizers, and other components known in the art.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position , or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C ₁₃ . ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -i ₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci _2- i ₄ -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred nonionic surfactants 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 having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable Alkypolyglycoside meet the general formula RO (G) _Z , in which R is a linear or branched, especially in the 2-position methy I branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G the symbol is that which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of glycosylation z is between 1, 0 and 4.0, preferably between 1, 0 and 2.0 and in particular between 1, 1 and 1, 4. Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The proportion of these nonionic surfactants is preferably not higher than that of the ethoxylated fatty alcohols, especially not more than half of them.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula (II)

R1

I

R-CO-N- [Z] (II)

in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 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 formula (III)

R ¹ -OR ²

I R-CO-N- [Z] (III)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 Carbon atoms, wherein C _1-4 alkyl or phenyl radicals are preferred and [Z] 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 reducing sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Suitable surfactants of the sulfonate type are preferably C ₉ - _I3 - alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C ₂ .i ₈ mono- olefins with a terminal or internal double bond, by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelsäurehalbester C ₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C ₁₀ -C ₂ o oxo and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.

Also, the sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight or branched C _7-2 i alcohols, such as 2-methyl-branched C _9-11 alcohols having an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ -i ₈ fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of up to 5% by weight, usually from 1 to 5% by weight.

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

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.

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

The surfactants may be present in the cleaning or washing agents according to the invention overall in an amount of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight, based on the finished composition ,

Inventive agents may contain bleaching agents. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as persulfates or persulfuric acid. Also useful is the urea peroxohydrate percarbamide, which can be described by the formula H ₂ N-CO-NH ₂ H ₂ O ₂ . In particular, when using the means for cleaning hard surfaces, for example in automatic dishwashing, they may, if desired, also contain bleaching agents from the group of organic bleaches, although their use is also possible in principle for laundry detergents. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid (Phthalimidoperoxyhexansäure, PAP), o- Carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonylamidoperoperuccinates, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1, 4- diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used.

The content of bleaching agent content may be from 1 to 40% by weight and in particular from 10 to 20% by weight, with perborate monohydrate or percarbonate being advantageously used. A synergistic use of amylase with percarbonate or of Amylase with percarboxylic acid is disclosed in applications WO 99/63036 and WO 99/63037, respectively.

In order to achieve an improved bleaching effect during washing at temperatures of 60 ^° C. and below, and in particular during the laundry pretreatment, the agents may also contain bleach activators. As bleach activators, it is possible to use 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. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular 1, 3,4,6 Tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI) ₁ acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids, such as triethyl-O-acetylcitrate (TEOC), Carboxylic acid anhydrides, in particular phthalic anhydride, isoic anhydride and / or succinic anhydride, carboxamides, such as N-methyldiacetamide, glycolide, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, isopropenyl acetate, 2,5-diacetoxy-2,5-dihydrofuran and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their in the European Patentanmeldu ng EP 0 525 239 described mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetyl (PAG) ₁ Pentaacetylfructose, tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine or gluconolactone, triazole or triazole derivatives and / or particulate caprolactams and / or caprolactam derivatives preferred N-acylated lactams, for example N-benzoyl-caprolactam and N-acetyl-caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. Likewise, nitrile derivatives such as cyanopyridines, nitrile quats, for example N-alkylammonium acetonitriles, and / or cyanamide derivatives can be used. Preferred bleach activators are sodium 4- (octanoyloxy) benzenesulfonate, n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), undecenoyloxybenzenesulfonate (UDOBS) ₁ sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzenesulfonate (OBS 12), as well as N-methylmorpholinum acetonitrile (MMA). Such bleach activators can be used in the customary amount range of from 0.01 to 20% by weight, preferably in amounts of from 0.1 to 15% by weight, in particular from 1% to 10% by weight, based on the total composition, be included.

In addition to or in place of the conventional bleach activators, so-called bleach catalysts may also be included. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salene complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes are also suitable as bleach catalysts, wherein such compounds are preferably used, which are described in DE 197 09 284 A1. According to WO 99/63038 also acetonitrile derivatives and according to WO 99/63041 bleach-activating transition metal complex compounds in combination with amylases can develop a bleach-activating effect.

Inventive agents usually contain one or more builders, in particular zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological reasons against their use - also the phosphates. The latter are particularly preferred builders to be used in automatic dishwashing detergents.

To mention here are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + I.} yH ₂ O, where M is sodium or hydrogen, x is a number from 1, 6 to 4, preferably 1.9 to 4.0, and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European Patent Application EP 0 164 514. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both SS and δ-sodium Na ₂ Si ₂ O ₅ ^ H ₂ O preferred. Such compounds are commercially available, for example, under the name ^SKS® (from Clariant). For example, SKS-6 ^{® is} predominantly a δ-sodium disilicate with the formula Na ₂ Si ₂ O ₅ .yH ₂ O; in the case of SKS-7 ^{® it is} predominantly the β-sodium disilicate. By reaction with acids (for example citric acid or carbonic acid), the δ-kanemite NaHSi ₂ O ₅ .yH ₂ O, commercially available under the names of SKS-9 ^® and SKS-10 ^® (Clariant). It may also be advantageous to use chemical modifications of these phyllosilicates. For example, the alkalinity of the layered silicates can be suitably influenced. Phyllosilicates doped with phosphate or with carbonate have altered crystal morphologies in comparison with the δ-sodium disilicate, dissolve more rapidly and show an increased calcium binding capacity in comparison to δ-nathium disilicate. Thus, phyllosilicates of the general empirical formula x Na ₂ O • y SiO ₂ • z P ₂ O ₅ , in which the ratio x to y is a number 0.35 to 0.6, the ratio x to z a number from 1, 75 to 1200 and the ratio y to z correspond to a number from 4 to 2800, can be used advantageously. The solubility of the layered silicates can also be increased by using particularly finely divided layered silicates. Also compounds from the crystalline layer silicates with other ingredients can be used. In particular, compounds with cellulose derivatives which have advantages in the disintegrating effect and are used in particular in detergent tablets, and compounds with polycarboxylates, for example citric acid, or polymeric polycarboxylates, for example copolymers of acrylic acid, may be mentioned.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification 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 do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates. An optionally usable, finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P zeolite MAP ^® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ O ^• (1-n) K ₂ O ^• Al ₂ O ₃ '(2 - 2.5) SiO ₂ ^■ (3.5-5.5) H ₂ O

can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of greatest importance in the washing and cleaning agent industry.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ J _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives Advantages in itself: They act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1, 91, ³ , melting point 60 °) and as a monohydrate (density 2.04, ^"3. ) Both salts are white, very soluble in water powders, which on heating lose the water of crystallization and at 200 ⁰ C in the weak acid diphosphate (disodium hydrogen, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) J and is readily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 like ^"3 , water loss at 95 °), 7 moles (density 1, 68 like ^{" 3} , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 ^"3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and goes on stronger heating in the diphosphate Na ₄ P ₂ O _7. Disodium hydrogen phosphate is by neutralization of phosphoric acid with sodium carbonate solution under Use of phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals containing as dodecahydrate a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅₎ a melting point of 10O ⁰ C and in anhydrous form (corresponding to 39-40% P ₂ O ₅₎ like to have a density of 2.536 ^{'. 3} trisodium phosphate is readily soluble in water with an alkaline reaction and is prepared by evaporating a solution of exactly 1 Triphosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 ^'3 , has a melting point of 1340 ° and is alkaline in water Reaction slightly soluble, for example, when heating Thomas slag with coal and potassium sulphate Despite the higher price, in the detergent industry, the more soluble, therefore highly effective, potassium phosphates often preferred over corresponding sodium compounds.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 ^'3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1, 815-1, 836 like ^"3 , melting point 94 ° with loss of water.) Both substances are colorless crystals soluble in water with alkaline reaction. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° C or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33% ^'3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ gives rise to higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates, and chain-type, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 10O g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° about 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH ^■ * Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O These can be used analogously to sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; It is also possible to use mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate.

As organic cobuilders, it is possible in particular to use in the detergents and cleaners according to the invention polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals, optionally oxidized dextrins, further organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use can not be avoided 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 thereof.

The acids themselves can also be used. In addition to their builder effect, they also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents, unless the pH resulting from the mixture of the other components is desired. In particular, system and non-polluting acids such as citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof are mentioned here. But also mineral acids, in particular sulfuric acid or bases, in particular ammonium or alkali hydroxides can serve as pH regulators. Such regulators are contained in the agents according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight. Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses 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 with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, may again be preferred from this group.

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 from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 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 the (co) polymeric polycarboxylates may be from 0.5 to 20% by weight, in particular from 1 to 10% by weight.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer. Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

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

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives.

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

Further 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. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500 000 g / mol. In this case, 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 action of a polysaccharide in comparison to dextrose, which is a DE of 100 has. Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also yellow dextrins and white dextrins with relatively high molecular weights in the range from 2 000 to 30 000 g / mol are useful.

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. Especially preferred Organic builders for agents according to the invention are oxidized starches or their derivatives from the applications EP 472 042, WO 97/25399, and EP 755 944.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, ^{N'-disuccinate} (EDDS) is preferably in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations between 3 and 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present 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 substance class 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 co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). As Aminoalkanphosphonate preferably Ethylenendiamintetrarnethylenphosphonat (EDTMP), Diethylentriaminpentamethylen- phosphonate (DTPMP) and their higher homologues in question. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

Moreover, all compounds capable of forming complexes with alkaline earth ions can be used as co-builders. Builder substances may optionally be present in the agents relevant to the invention in amounts of up to 90% by weight. They are preferably contained in amounts of up to 75% by weight. Inventive detergents have builder contents of, in particular, from 5% by weight to 50% by weight. In inventively relevant agents for the cleaning of hard surfaces, in particular for the automated cleaning of dishes, the content of builder substances is in particular 5 wt .-% to 88 wt .-%, wherein preferably no water-insoluble builder materials are used in such agents. In a preferred embodiment of invention-relevant means for the particular machine cleaning of dishes are 20 wt .-% to 40 wt .-% of water-soluble organic builder, in particular alkali, 5 wt .-% to 15 wt .-% alkali carbonate and 20 wt .-% bis 40 wt .-% Alkalidisilikat included.

Solvents that can be used in the liquid to gelatinous compositions of detergents and cleaners, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible in the specified concentration range with water. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol propyl ether,

Ethylene glycol mono-n-butyl ether, diethylene glycol, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl, or ethyl ether, di-isopropylene glycol monomethyl, or ethyl ether, methoxy, ethoxy or Butoxytriglykol , 1-Butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.

Solvents can be used in the liquid-to-gel detergents and cleaners according to the invention in amounts of between 0.1 and 20% by weight, but preferably below 15% by weight and in particular below 10% by weight.

To adjust the viscosity, compositions according to the invention may be admixed with one or more thickeners or thickening systems. These high-molecular substances, which are also called swelling agents, usually absorb the liquids and swell up to finally pass into viscous true or colloidal solutions. Suitable thickeners are inorganic or polymeric organic compounds. The inorganic thickeners include, for example, polysilicic acids, clay minerals such as montmorillonites, zeolites, silicic acids and bentonites. The organic thickeners are derived from the groups of natural polymers, modified natural polymers and fully synthetic polymers. Such naturally derived polymers include, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar gum, locust bean gum, starch, dextrins, gelatin and casein. Modified natural products, which are used as thickeners, come mainly from the group of modified starches and celluloses. By way of example, carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and core flour ethers may be mentioned here. Fully synthetic thickeners are polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.

The thickeners may be present in an amount of up to 5% by weight, preferably from 0.05 to 2% by weight, and more preferably from 0.1 to 1.5% by weight, based on the finished composition ,

The washing or cleaning agent relevant to the invention may optionally comprise, as further customary ingredients, sequestering agent, electrolyte and other auxiliaries.

Inventive textile laundry detergents can contain as optical brighteners derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or similarly constructed compounds which replace the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Further, brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the aforementioned optical brightener can be used.

Graying inhibitors have the task of removing the dirt removed from the textile fiber to keep suspended in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions ,

To effect silver corrosion protection, silver corrosion inhibitors can be used in dishwashing detergents that are relevant to the invention. Such are known in the art, for example benzotriazoles, iron (III) chloride or CoSO ₄ . For common use with enzymes are manganese, titanium, zirconium, hafnium, vanadium, cobalt or cerium salts and / or complexes in which the said metals in one of the oxidation states II, III, IV, V or VI present, particularly suitable silver corrosion inhibitors. Examples of such compounds are MnSO ₄ , V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , Co (NO ₃ ) ₂ , Co (NO ₃ ) ₃ , and the like mixtures.

"Soil-release" or "soil repellents" are mostly polymers which impart soil repellency when used in a laundry detergent detergent and / or aid in the soil release performance of the other detergent ingredients. A similar effect can also be observed in their use in hard surface cleaners.

Particularly effective and long-known soil release agents are copolyesters with dicarboxylic acid, alkylene glycol and polyalkylene glycol units. Examples of these are copolymers or copolymers of polyethylene terephthalate and polyoxyethylene glycol. Among them are acidic agents which include, inter alia, a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol. Polymers of ethylene terephthalate and polyethylene oxide terephthalate and their use in detergents are advantageously used. Furthermore, agents according to the invention may contain a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. Also known are methyl or ethyl group end-capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such soil release polymer. Further embodiments are characterized by a polyester which, in addition to oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and also glycerol units; Polyesters which contain, in addition to oxyethylene groups and terephthalic acid units, 1, 2-propylene, 1, 2-butylene and / or 3-methoxy-1, 2-propylene groups and also glycerol units and end-capped with C ₁ - to C ₄ -alkyl groups are; at least partially by C ^ -alkyl or acyl radicals end-capped polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units; sulfoethyl end-capped terephthalate-containing soil release polyesters; Soil-release polyesters prepared by sulfonation of unsaturated end groups with terephthalate, alkylene glycol and poly-C _2-4 glycol units; or acid, aromatic soil release polymers. Further, non-polymeric soil repellent agents are useful for multi-functional cotton materials: a first entity, which may be cationic, for example, is capable of adsorption to the cotton surface by electrostatic interaction, and a second entity which is hydrophobic; is responsible for the retention of the drug at the water / cotton interface.

Polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole are particularly suitable for use in color-relevant inhibitors of relevance to the invention in laundry detergents.

When used in automated cleaning processes, it may be advantageous to add foam inhibitors to the compositions. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci ₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally signed silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with signed silica or bistearylethylenediamide. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes. Preferably, the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, to a granular, water-soluble, or dispersible carrier substance bound. In particular, mixtures of paraffins and bistearylethylenediamides are preferred.

In addition, an inventive cleaning agent for hard surfaces may contain abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and glass microspheres and mixtures thereof. Abrasive substances are preferably not more than 20% by weight, in particular from 5% by weight to 15% by weight, in the cleaning agents according to the invention.

Dyes and fragrances are added to detergents and cleaners in order to improve the aesthetic appearance of the products and to provide the consumer with a visually and sensory "typical and unmistakable" product in addition to the washing and cleaning performance. As perfume oils or fragrances, individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones, for example, the ionone, α-lsomethylionon and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, for example, pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood. Usually, the content of detergents and cleaners to dyes is less than 0.01 wt .-%, while perfumes can account for up to 2 wt .-% of the total formulation. The fragrances can be incorporated directly into the detergents and cleaners, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the items to be cleaned and provide a slower fragrance release for long-lasting fragrance, especially of treated textiles. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients. A further preferred carrier for fragrances is the described zeolite X, which can also absorb fragrances instead of or in mixture with surfactants. Preference is therefore given to washing and cleaning agents containing the described zeolite X and fragrances, which are preferably at least partially absorbed on the zeolite.

Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers so as not to stain them.

Detergents or cleaners may contain antimicrobial agents to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate. The terms antimicrobial action and antimicrobial active ingredient have the usual meaning within the scope of the teaching according to the invention, it being possible in principle to use all the substances described having antimicrobial activity. Suitable antimicrobial agents are preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic 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-propyl-butyl-carbamate, iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of the foregoing , The antimicrobial agent may be selected from: ethanol, n-propanol, i-propanol, 1, 3-butanediol, phenoxyethanol, 1, 2-propylene glycol, glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine acetonitrile (MMA) ₁ 2-benzyl-4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (dichlosan), 2, 4,4'-trichloro-2 ^I -hydroxydiphenylether (triclosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) -hamstoff, N, N '- (1, 10- decane-diyldi 1-pyridinyl-4-ylidene) bis- (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3,12-diimino-2,4,11,13-tetraaza tetradecandiimidamide, glucoprotamines, antimicrobial quaternary compounds, guanidines including the bi- and polyguanidines such as 1,6-bis (2-ethylhexyl-biguanido-hexane) dihydrochloride, 1,6-di- (N ₁ , N _T '-phenyldiguanido-Ns.Ns'J-hexane-tetrahydrochloride, 1, 6-di- (N ₁₁ N ₁ ' - phenyl-N ^ Num ethyldiguanido-Ns.Ns'J-hexane dihydrochloride, 1,6-di- (N ₁ , N 2 -o-chloro-phenyl-diguanido-N ₅ , N ₅ ') -hexane-dihydrochloride, 1,6-di- ( N _{1 l} N ₁ '-2,6-dichlorophenyldiguanido-N ₅ , N ₅ ') hexane dihydrochloride, 1,6-di- [N ₁ , N ₁ '-beta (p-methoxyphenyl) diguanido-N ₅ , N ₅ '] - hexane dihydrochloride, 1,6-di- (N ₁ , NV-alpha-methyl-.beta.-phenyldiguanido-Ns.Ns'J-hexane dihydrochloride, 1,6-di- ( N _1, N _T '-p-nitrophenyldiguanido-Ns.Ns ^ hexane dihydrochloride, omegaiomega-di ^ Ni.N _T' -phenyldiguanido-Ns.Ns'J-di-n-propyl ether dihydrochloride, omega: omega'- Di- (N ₁ , N ₁ '-p-chlorophenyldiguanido-N ₅ , N ₅ ') -di-n-propyl ether tetrahydrochloride, 1,6-di- (N ₁ , N 2 -2,4-dichlorophenyldiguanido -N ₅ , N ₅ ') hexane-tetrahydrochloride, 1,6-di- (N ₁ , N 1 -p -methylphenyl-diguanido- N ₅ , N ₅ ') -hexane dihydrochloride, 1,6-di- (N ₁ , N, -2,4,5-trichlorophenyldiguanido-N _5> N ₅ ') hexane-tetrahydrochloride, 1,6-di- [N ₁ , N 1 -alkyl-p-chlorophenyl) -ethyldiguanido-N ₅ , N ₅ '] hexane dihydrochloride, omega: omega-di- (N ₁ , N _{1 '} p-chlorophenyldiguanido-N ₅ , N ₅ ') m-xylenedihydrochloride, 1, 12-di (N ₁ , N _1, p -chlorophenyldiguanido-N ₅ , N ₅ ') dodecane dihydrochloride, 1 , 10-di- (N ₁ , N 1 -phenyl-diguanido- N ₅ , N ₅ ') -decane-tetrahydrochloride, 1, 12-di- (N ₁ , N 1 -phenyl-diguanido- N ₅₁ N ₅ ') dodecane-tetrahydro-chloride , 1, 6-di- (N ₁ , N 1 -o-chlorophenyl-diguanido- N ₅₁ N ₅ ') hexane-dihydrochloride, 1,6-di- (N ₁ , N ₂ -o-chlorophenyl-diguanido- N ₅₁ N ₅ ' ) hexane tetrahydrochloride, ethylene bis (1-tolyl biguanide), ethylene bis (p-tolyl biguanide), ethylene bis (3,5-dimethylphenyl biguanide), ethylene bis (p-tert-amylphenyl biguanide) Ethylene bis (nonylphenylbiguanide), ethylene bis (phenylbiguanide), ethylene bis (N-butylphenylbiguanide), ethylene bis (2,5-diethoxyphenylbiguanide), ethylene bis (2,4-dimethylphenyl biguanide), Ethylene bis (o-diphenylbiguanide), ethylene bis (mixed amyl naphthyl biguanide), N-butyl ethylene bis (phenylbiguanide), trimethylene bis (o-tolyl biguanide), N-butyl trimethyl bis (phenyl biguanide) and the corresponding salts such as acetates, gluconates, hydrochlorides, Hydrobromides, citrates, bisulfites, fluorides, polymaleates, N-cocoalkyl sarcosinates, phosphites, hypophosphites, perfluorooctanoates, silicates, sorbates, salicylates, maleates, tartrates, fumarates, ethylenediaminetetraacetates, iminodiacetates, cinnamates, thiocyanates, arginates, pyromellitates, tetracarboxybutyrates, benzoates, glutarates, Monofluorophosphates, perfluoropropionates and any mixtures thereof. Also suitable are halogenated xylene and cresol derivatives, such as p-chlorometacresol or p-chloro-meta-xylene, and natural antimicrobial agents of plant origin (for example, from spices or herbs), animal and microbial origin. Preferably, antimicrobial surface active quaternary compounds, a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial agent of animal origin from the group, comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface active quaternary compound with an ammonium, sulfonium, phosphonium, iodonium - or Arsoniumgruppe, peroxo compounds and chlorine compounds are used. Also substances of microbial origin, so-called bacteriocins, can be used.

The quaternary ammonium compounds (QAV) suitable as antimicrobial agents have the general formula (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) N ⁺ X ^" , in which R ¹ to R ^{4 are} identical or different C _r C ₂₂ Alkyl radicals, C ₇ -C ₂₈ -Aralkylreste or heterocyclic radicals, wherein two or in the case of an aromatic inclusion as in pyridine even three radicals together with the nitrogen atom, the heterocycle, for example a pyridinium or imidazolinium compound, form, and X ^~ For optimal antimicrobial activity, at least one of the radicals preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QACs can be prepared by reacting tertiary amines with alkylating agents, such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide. The alkylation of tertiary amines with a long alkyl radical and two methyl groups succeeds particularly easily, the quaternization of tertiary amines with two long radicals and a methyl group can with the aid of methyl chloride under mild conditions are carried out. Amines having three long alkyl radicals or hydroxy-substituted alkyl radicals are less reactive and are preferably quaternized with dimethyl sulfate.

Suitable QACs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyl-dimethyl-C 12 -alkylammonium chloride, CAS No. 58390- 78-6), benzoxonium chloride (benzyldodecyl bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium bromide, CAS No. 57-09-0), benzetonium chloride ( N, N-dimethyl-N- [2- [2- [p- (1, 1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzyl ammonium chloride, CAS No. 121-540), Dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldi-methylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammoniumchloric, 1-cetylpyridiniumchloride ( CAS No. 123-03-5) and thiazoline iodide (CAS No. 15764-48-1) and mixtures thereof. Particularly preferred QACs are the benzalkonium chlorides having C ₈ -C ₁₈ -alkyl radicals, in particular C ₁₂ -C ₄ -alkyl-benzyl-dimethyl-ammonium chloride.

Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ^® ex Lonza, Marquat® ^® ex Mason, Variquat ^® ex Witco / Sherex and Hyamine ^® ex Lonza and as Bardac ^® ex Lonza. Other commercially obtainable antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide and Dowicil ^® ^® ex Dow, benzethonium chloride such as Hyamine ^® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ^® 1ox ex Rohm & Haas, cetylpyridinium chloride such as Cepacol ex Merrell Labs ,

The antimicrobial agents are used in amounts of 0.0001 wt .-% to 1 wt .-%, preferably from 0.001 wt .-% to 0.8 wt .-%, particularly preferably from 0.005 wt .-% to 0.3 wt .-% and in particular from 0.01 to 0.2 wt .-% used.

The agents may contain UV absorbers (UV absorbers), which are applied to the treated textiles and improve the light resistance of the fibers and / or the light resistance of other formulation ingredients. Under UV absorber are organic substances (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, for example, to give off heat. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are 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 urocanic acid. The biphenyl and especially stilbene derivatives such as for example, are commercially available as Tinosorb ^® FD or Tinosorb ^® FR ex Ciba. UV-B absorbers which may be mentioned are: 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, for example 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably 4-

(Dimethylamino) benzoic acid 2-ethylhexyl ester, 4- (dimethylamino) benzoic acid 2-octyl ester and 4- (dimethylamino) benzoic acid amyl ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester

(Octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzaldehyde acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives such as 2 _{L of} 4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine and octyl triazone; Dioctyl butamido triazone (Uvasorb® HEB); Propan-1, 3-diones, such as 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1, 3-dione, or ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.

As a typical UV-A filter, in particular derivatives of benzoylmethane come into question, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane 1, 3-dione and enamine compounds, as described in DE 19712033 A1 (BASF). Of course, the UV-A and UV-B filters can also be used in mixtures. In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments may also be surface-treated, that is to say hydrophilized or hydrophobicized. Typical examples are coated titanium dioxides, for example titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck; preferred hydrophilic coating agents are silicones and particularly preferably trialkoxyoctylsilanes or simethicones.) Micronized zinc oxide is preferably used the review by P. Finkel in SÖFW Journal, Volume 122 (1996), p 543.

The UV absorbents are usually used in amounts of from 0.01% by weight to 5% by weight, preferably from 0.03% by weight to 1% by weight.

In order to increase the washing or cleaning performance, agents which are relevant to the invention may additionally contain enzymes, it being possible in principle to use all enzymes established for this purpose in the prior art. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Relevant invention means preferably comprise enzymes in total amounts of 1 x 10 ^"-6 to 5 weight percent based on active protein. The protein concentration can be known by using methods, for example the BCA Method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method (AG Gornall, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 ).

Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvserd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. Of the protease from Bacillus lentus DSM 5483 (WO 91/02792 A1) the listed under the name BLAP ^® variants, particularly in WO 92/21760 A1, WO 95/23221 A1, WO 02/088340 A2 and WO 03 derive, / 038082 A2. Other useful proteases from various Bacillus sp. and B. gibsonii are apparent from the patent applications WO 03/054185 A1, WO 03/056017 A2, WO 03/055974 A2 and WO 03/054184 A1.

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, Purafect ^® Prime and Properase.RTM ^® from Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ^® and protease P ^® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and sold under the name proteinase K-16 from Kao Corp., Tokyo, Japan, available enzymes.

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

Furthermore, for this purpose, the α-amylase from Bacillus sp. Disclosed in the application WO 02/10356 A2. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) described in the application WO 02/44350 A2. Furthermore, the amylolytic enzymes belonging to the sequence space of α-amylases defined in the application WO 03/002711 A2 and those described in the application WO 03/054177 A2 can be used. Likewise, fusion products of the molecules mentioned can be used, for example those from application DE 10138753 A1.

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae. Further suitable commercial products are for example the Amylase-LT ^® or Stainzyme® ^® and Stainzyme® ^® Ultra, also the latter by the company. Novozymes.

Agents of the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to produce in situ peracids from suitable precursors in addition to the present invention. 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 for example marketed 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® are} available. From the company Genencor are For example, the lipases, or cutinases can be used whose Ausgangsenzyme 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.

Depending on the purpose, agents of relevance to the invention may contain cellulases, in particular if they are intended for the treatment of textiles, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously supplement each other in terms of their various performance aspects. These performance aspects include, in particular, contributions to the primary washing performance, the secondary washing performance of the composition (anti-redeposition effect or graying inhibition) and softening (fabric effect), up to the exercise of a "stone washed" effect.

A useful fungal, endoglucanase (EG) -rich cellulase preparation, or its further developments are offered by Novozymes under the trade name Celluzyme ^®. The products Endolase® ^® and Carezyme ^® available also from Novozymes based on the 50 kD EG and 43 kD EG applicable from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® ^® and Renozyme ^®. The latter is based on the application WO 96/29397 A1. Performance-enhanced cellulase variants are disclosed, for example, in the application WO 98/12307 A1. Likewise, the cellulases disclosed in the application WO 97/14804 A1 can be used; For example, it revealed 20 kD EG Melanocarpus, available from AB Enzymes, Finland, under the trade names Ecostone® ^® and Biotouch ^®. Further commercial products from AB Enzymes are Econase® ^® and ECOPULP ^®. Other suitable cellulases from Bacillus sp. CBS 670.93 and CBS 669.93 are disclosed in WO 96/34092 A2, wherein those derived from Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax ^{® is} available. Further commercial products of the company Genencor are "Genencor detergent cellulase L" and lndiAge ^® Neutra. Compositions of relevance to the invention may contain other enzymes, in particular to remove certain problem soils, which are grouped under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 L from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, USA , A suitable β-glucanase from a B. alcalophilus is disclosed, for example, in the application WO 99/06573 A1. The .beta.-glucanase obtained from B. subtilis is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect fiction, detergent and cleaning agents oxidoreductases, such as oxidases, oxy genases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases ) contain. Suitable commercial products Denilite® ^® 1 and 2 from Novozymes should be mentioned. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

The enzymes used in invention-relevant agents are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.

The cleaning of the enzymes in question is conveniently carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps. For the purposes of the invention, the enzymes can be added in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.

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

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

A protein and / or enzyme contained in an agent relevant to the invention can be protected, especially during storage, against damage such as, for example, inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Preferred agents relevant to the invention contain stabilizers for this purpose.

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

Other enzyme stabilizers are aminoalcohols, such as up to Ci _2, such as succinic acid, other dicarboxylic acids or salts of said acids, mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Certain organic acids used as builders are capable, as disclosed in WO 97/18287, of additionally stabilizing a contained enzyme.

Lower aliphatic alcohols, but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers. Di-glycerol phosphate also protects against denaturation due to physical influences. Likewise, calcium and / or magnesium salts are used, such as calcium acetate or calcium formate.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polyamine N-oxide containing polymers act simultaneously as enzyme stabilizers and as dye transfer inhibitors. Other polymeric stabilizers are linear C ₈ -C ₁₈ polyoxyalkylenes. Also, alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and, preferably, are capable of additionally increasing their performance. Crosslinked N-containing compounds preferably perform a dual function as soil release agents and as enzyme stabilizers. Hydrophobic, nonionic polymer stabilizes in particular an optionally contained cellulase.

Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation; For example, sulfur-containing reducing agents are familiar. Other examples are sodium sulfite and reducing sugars. Particular preference is given to using combinatons of stabilizers, for example 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 favorably enhanced by the combination with boric acid and / or boric acid derivatives and polyols, and still further by the additional action of divalent cations, such as calcium ions.

In a preferred embodiment, agents relevant to the invention are characterized in that they consist of more than one phase, for example in order to release the active substances contained in time or space separately from one another. These may be phases in different, but in particular phases in the same physical states.

Inventive agents, which are composed of more than one solid component, can be prepared in a simple manner by mixing together various solid components, in particular powders, granules or extrudates with different ingredients and / or different release behavior in total loose form. The preparation of solidifying agents which are relevant to the invention from one or more phases can be carried out in a known manner, for example by spray drying or granulation, the enzymes and any further thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later. For the preparation of agents of relevance to the invention having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process known from European Patent EP 0 486 592 and having an extrusion step is preferred. Another preferred preparation by means of a granulation process is described in the European patent EP 0 642 576.

Proteins can be used for solid agents, for example in dried, granulated, encapsulated or encapsulated and additionally dried form. They may be added separately, ie as a separate phase, or with other ingredients together in the same phase, with or without compaction. If microencapsulated enzymes are to be processed in solid form, the water can also be used with the Known prior art methods are removed from the resulting from the workup aqueous solutions, such as spray drying, centrifuging or by re-solubilization. The particles obtained in this way usually have a particle size between 50 and 200 microns.

The encapsulated form lends itself, as discussed above, also to protecting the enzymes from other ingredients, such as bleaches, or to allow for controlled release. Depending on the size of these capsules, a distinction is made to MiIIi-, micro- and nanocapsules, with microcapsules for enzymes being particularly preferred. Such capsules are disclosed, for example, with the patent applications WO 97/24177 and DE 199 18 267. Another possible encapsulation method is that the enzymes suitable for use in detergents or cleaning agents, starting from a mixture of the enzyme solution with a solution or suspension of starch or a starch derivative, are encapsulated in starch or the starch derivative. Such an encapsulation process is described in the German application DE 199 56 382.

There may also be at least two solid phases connected to each other. Thus, there is a possibility to provide a solid means according to the invention in which compression or compacting into tablets. Such tablets may be monophase or polyphase. Thus, this dosage form also offers the possibility to present a solid agent according to the invention with two solid phases. For the production of compositions according to the invention in tablet form, which may be single-phase or multiphase, monochromatic or multicolored and / or consist of a plurality of layers, preferably all constituents - optionally one layer at a time - are mixed together in a mixer and the mixture is mixed by means of conventional tablet presses, For example, eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN / cm ² , preferably at 60 to 70 kN / cm ² . Particularly in the case of multilayer tablets, it may be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN / cm ² , in particular at 10 to 15 kN / cm ² . Preferably, a tablet produced in this way has a weight of from 10 g to 50 g, in particular from 15 g to 40 g. The spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. It is particularly advantageous if in multiphase means at least one of the phases contains an amylase-sensitive material, in particular starch, or is at least partially surrounded or coated by it. In this way, this phase is mechanically stabilized and / or protected against external influences and simultaneously attacked by an effective in the wash liquor amylase, so that the release of the ingredients is facilitated.

Also preferred inventive agents are characterized in that they are present in total liquid, gel or pasty. The proteins contained, preferably a protein which can be used according to the invention, are preferably obtained from a state-of-the-art protein recovery and preparation in concentrated aqueous or non-aqueous solution, for example in liquid form, for example as solution, suspension or emulsion, but also in gel form or encapsulated or added as a dried powder. Such inventive washing or cleaning agents in the form of solutions in conventional solvents are usually prepared by simply mixing the ingredients that can be added in bulk or as a solution in an automatic mixer.

One embodiment of the present invention relates to those liquid, gelatinous or pasty compositions to which a protein essential to the invention and / or one of the other proteins contained and / or one of the other ingredients contained has been encapsulated, preferably added in the form of microcapsules. Particularly preferred are those with capsules of amylase sensitive material. Such co-use of amylase-sensitive materials and an amylolytic enzyme in a detergent may exhibit synergistic effects, such as the starch-cleaving enzyme assisting cleavage of the microcapsules, thus controlling the release process of the encapsulated ingredients so that their release will not occur during the time Storage and / or not at the beginning of the cleaning process, but only at a certain time takes place. On this mechanism, complex detergent and cleaner systems can be based on a wide variety of ingredients and various capsule types, which are particularly preferred embodiments of the present invention. A comparable effect is given when the ingredients of the detergent or cleaner are distributed over at least two different phases, for example two or more solid, interconnected phases of a tablet detergent or detergent, or different granules within the same powdered agent. Two or more phase cleaners are state of the art for use in both automatic dishwashers and detergents. The activity of an amylolytic enzyme in an earlier activated phase is a prerequisite for the activation of a later phase when it is surrounded by an amylase-sensitive envelope or coating or the amylase-sensitive material is an integral part of the solid phase, in its partial or complete Hydrolysis disintegrates the relevant phase.

The ingredients of detergents and cleaners are suitably able to assist one another in their performance. Thus, it is also known from the application WO 98/45396 that polymers which can be used simultaneously as co-builders, such as, for example, alkyl-poly-glycosides, can stabilize and increase the activity and the stability of enzymes contained. Thus, it is preferred if the agent according to the invention modified by one of the other ingredients listed above, in particular stabilized and / or increased in its contribution to the washing or cleaning performance of the agent.

The inventively relevant pharmaceutical compositions, hair washing and / or hair care products and foam baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat compositions, stick preparations, powders or ointments comprising alkali metal halides according to the invention as tracers , as adjuvants and additives mild surfactants, oil body, emulsifiers, superfatting agents, pearlescent, consistency, thickeners, polymers, silicone compounds, fats, waxes, stabilizers, biogenic agents, deodorants, antiperspirants, antidandruff agents, film formers, swelling agents, UV light protection factors , Antioxidants, hydrotropes, preservatives, insect repellents, self-tanning, solubilizers, perfume oils, dyes and the like.

Typical examples of suitable mild, ie particularly skin-friendly, surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, Fatty acid glutamates, α-olefinsulfonates, ether carboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamido betaines and / or protein fatty acid condensates, the latter preferably based on wheat proteins.

Examples of oil bodies are Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear C ₆ -C ₂₂ fatty alcohols, esters of branched C ₆ -C ₃ carboxylic acids with linear C ₆ -C ₂₂ -fatty alcohols, such as myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, myristyl, Myristylbehenat, Myristylerucat, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, stearyl oleate , stearyl behenate, Stearylerucat, isostearyl, isostearyl palmitate, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, Oleylbehenat, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl, Behenylisostearat, behenyl oleate, behenyl behenate, Behenyleruca t, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. In addition, esters of linear C ₆ -C ₂₂ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, in particular dioctyl malates, esters of linear and / or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -C ₁₀ fatty acids, liquid mono- / di- / triglyceride mixtures based on C ₆ -C ₈ fatty acids, esters of C ₆ -C ₂₂ -fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C ₂ -C ₂ -dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable Oils, branched primary alcohols, substituted cyclohexanes, linear and branched C ₆ -C ₂₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acids acid with linear and / or branched C ₆ -C ₂₂ -alcohols (for example Finsolv® TN), linear or branched, symmetrical or unsymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, ring-opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons, such as, for example, squalane, squalene or dialkylcyclohexanes into consideration. Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

(1) addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms, to alkylphenols having 8 to 15 carbon atoms in the Alkyl group and alkylamines having 8 to 22 carbon atoms in the alkyl radical;

(2) C _{_2/18} fatty acid monoesters and diesters of addition products of 1 to 30 mol ethylene oxide onto glycerol;

(3) glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;

(4) alkyl and / or alkenyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs;

(5) addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

(6) polyol and especially polyglycerol esters;

(7) addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

(8) partial esters based on linear, branched, unsaturated or saturated C _{_6/22} fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, butyl glucoside, lauryl glucoside ) as well as polyglucosides (for example cellulose);

(9) mono-, di- and trialkyl phosphates and also mono-, di- and / or Th-PEG-alkyl phosphates and their salts;

(10) wool wax alcohols;

(11) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

(12) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE 1165574 PS and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol,

(13) Polyalkylene glycols as well

(14) Glycerol carbonate. The addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products. These are mixtures of homologs whose mean Alkoxylierungsgrad the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out corresponds. ₁₂ C _/ i ₈ fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are known from DE 2024051 as refatting agents for cosmetic preparations.

Alkyl and / or alkenyl mono- and oligoglycosides, their preparation and their use are known in the art. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. With regard to the glycoside radical, both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of preferably approximately 8 are suitable. The degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.

Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearates (Dehymuls® PGPH), polyglycerol-3-diisostearates (Lameform® TGI), polyglyceryl-4 isostearates (Isolan® Gl 34), polyglyceryl-3 oleates, diisostearoyl polyglyceryl-3 diisostearates (Isolan ® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL), Polyglyceryl -3 distearates (Cremophor® GS 32) and polyglyceryl polyricinoleates (Admul® WOL 1403) polyglyceryl dimerate isostearates and mixtures thereof.

Furthermore, zwitterionic surfactants can be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3 -hydroxyethylimidazolines each having 8 to 18 C atoms in the alkyl or acyl group and the Kokosacylaminoethylhydroxyethyl- carboxymethylglycinat. Particularly preferred is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine. Also suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are understood to mean those surface-active compounds which, apart from a Cβπβ-alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidoproylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _{12 /} ie acylsarcosine. In addition to the ampholytic, quaternary emulsifiers are also suitable, with those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

As superfatting agents, substances such as lanolin and lecithin as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used, the latter also serving as foam stabilizers.

Suitable pearlescing waxes are, for example: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polybasic, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof. As consistency factors are primarily fatty alcohols or hydroxy fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms and in addition partial glycerides, fatty acids or hydroxy fatty acids into consideration. Preference is given to a combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates.

Suitable thickening agents are, for example, Aerosil types (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, furthermore higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, (for example Carbopole® from Goodrich or Synthalene® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid reglycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with narrow homolog distribution or alkyl oligoglucosides and electrolytes such as common salt and ammonium chloride.

Suitable cationic polymers include, for example, cationic cellulose derivatives, such as a quaternized hydroxyethylcellulose available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such as Luviquat® (US Pat. BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides, such as Lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®LJGrünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides as described, for example, in FR 2252840 A and their crosslinked water-soluble polymers, cationic chitin derivatives ate such as, for example, quaternized chitosan, optionally microcrystalline dispersed, condensation products of dihaloalkylene, such as dibromobutane with bis-dialkylamines, such as bis-dimethylamino-1, 3-propane, cationic guar gum, such as Jaguar® CBS, Jaguar® C 17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers such as Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol. Examples of anionic, zwitterionic, amphoteric and nonionic polymers are vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers,

Methyl vinyl ether / maleic anhydride copolymers and their esters, uncrosslinked and polyols crosslinked polyacrylic acids, acrylamidopropyltrimethylammonium chloride / acrylate copolymers, octylacrylamide / methyl methacrylate / tert.butylaminoethyl methacrylate / 2-

Hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methacrylate / vinylcaprolactam terpolymers and optionally derivatized cellulose ethers and silicones in question.

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds which may be both liquid and resin-form at room temperature. Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units and hydrogenated silicates. A detailed overview of suitable volatile silicones can also be found in Todd et al. in Cosm.Toil. 91, 27 (1976).

Typical examples of fats are glycerides, as waxes include natural waxes, such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax) , Rump fat, ceresin, ozokerite (groundwax), petrolatum, paraffin waxes, microwaxes; chemically modified waxes (hard waxes) such as montan ester waxes, sasol waxes, hydrogenated jojoba waxes and synthetic waxes such as polyalkylene waxes and polyethylene glycol waxes in question.

As stabilizers metal salts of fatty acids, such as magnesium, aluminum and / or zinc stearate or ricinoleate can be used.

Biogenic active ingredients are, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes. Cosmetic deodorants (deodorants) counteract, cover or eliminate body odors. Body odors are caused by the action of skin bacteria on apocrine sweat, forming unpleasant-smelling degradation products. Accordingly, deodorants contain active ingredients which act as anti-sprouting agents, enzyme inhibitors, odor absorbers or odor maskers.

As germ-inhibiting agents, which may optionally be added to the cosmetics according to the invention, in principle all substances active against gram-positive bacteria are suitable, for example 4-hydroxybenzoic acid and its salts and esters, N- (4-chlorophenyl) -N ^' - (3,4 dichlorophenyl) urea, ^{2,4,4'-trichloro-2} ^'- hydroxydiphenyl ether (triclosan), 4-chloro-3,5-dimethylphenol, ^2,2' -methylene-bis (6-bromo-4-chlorophenol), 3 Methyl 4- (1-methylethyl) phenol, 2-benzyl-4-chlorophenol, 3- (4-chlorophenoxy) -1,2-propanediol, 3-iodo-2-propynyl butyl carbamate, chlorhexidine, 3,4,4 ^' - trichlorocarbanilide (TTC), antibacterial fragrances, menthol, mint oil, phenoxyethanol, glycerol monolaurate (GML), diglycerol monocaprinate (DMC), salicylic acid N-alkylamides such as salicylic acid-n-octylamide or salicylic acid-n-decylamide.

Enzyme inhibitors can also be added to the cosmetics relevant to the invention. For example, esterase inhibitors may be suitable enzyme inhibitors. These are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and in particular triethyl citrate (Hydagen® CAT, Henkel KGaA, Dusseldorf / FRG). The substances inhibit the enzyme activity and thereby reduce odors. Further substances which are suitable as esterase inhibitors are sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, Adipic acid monoethyl ester, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or diethyl tartrate, and zinc glycinate.

Suitable odor absorbers are substances that absorb and largely retain odor-forming compounds. They lower the partial pressure of the individual Components and thus also reduce their propagation speed. It is important that perfumes must remain unimpaired. Odor absorbers have no activity against bacteria. They contain, for example, as the main constituent of a complex zinc salt of ricinoleic acid or special, largely odorless fragrances, which are known in the art as "fixatives", such as extracts of Labdanum or Styrax or certain Abietinsäurederivate. Odor maskers are fragrances or perfume oils which, in addition to their function as odor maskers, give the deodorants their respective scent. Examples of perfume oils are mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peel, roots, woods, herbs and grasses, needles and twigs, as well as resins and balsams. Furthermore, animal raw materials come into question, such as civet and Castoreum. Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons.

Antiperspirants (Antiperspirants) reduce the formation of sweat by influencing the activity of the eccrine sweat glands and thus counteract underarm wetness and body odor. Aqueous or anhydrous formulations of antiperspirants typically contain the following ingredients:

(a) astringent agents,

(b) oil components,

(c) nonionic emulsifiers,

(d) coemulsifiers,

(e) bodybuilder,

(f) adjuvants such as thickeners or complexing agents and / or

(g) nonaqueous solvents such as ethanol, propylene glycol and / or glycerin.

Salts of aluminum, zirconium or zinc are especially suitable as astringent antiperspirant active ingredients. Such suitable antiperspirant active ingredients are, for example, aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complex compounds, for example with propylene glycol-1,2. Aluminiumhydroxyallantoinat,

Aluminum chloride tartrate, aluminum-zirconium trichlorohydrate, aluminum-zirconium-tetra- chlorohydrate, aluminum zirconium pentachlorohydrate and their complex compounds for example with amino acids such as glycine.

In addition, antiperspirants may contain customary oil-soluble and water-soluble adjuvants in smaller amounts. Such oil-soluble auxiliaries may be, for example:

• anti-inflammatory, skin-protecting or fragrant essential oils,

• synthetic skin-protecting agents and / or

• oil-soluble perfume oils.

Typical water-soluble additives are, for example, preservatives, water-soluble perfumes, pH adjusters, for example buffer mixtures, water-soluble thickeners, for example water-soluble natural or synthetic polymers such as xanthan gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high molecular weight polyethylene oxides.

Climbazole, octopirox and zinc pyrethion can be used as anti-dandruff agents.

Typical film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or salts thereof and similar compounds.

Suitable swelling agents for aqueous phases are montmorillonites, clay minerals, pemulen and alkyl-modified carbopol types (Goodrich). Further suitable polymers or swelling agents can be reviewed by R. Lochhead in Cosm.Toil. 108, 95 (1993).

Examples of UV sun protection factors are the classes of compounds already listed above, in particular those listed as UV-B and UV filters. In addition to the two groups of primary light stabilizers mentioned above, secondary sunscreens of the antioxidant type can also be used in cosmetic products, interrupting the photochemical reaction chain which is triggered when UV radiation penetrates into the skin. Typical examples thereof are amino acids (for example glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (for example urocanic acid) and derivatives thereof, peptides such as D, L-carnosine, D-camosine, L-carnosine and their derivatives (cf. Example anserine), carotenoids, carotenes (for example α-carotene, β-carotene, lycopene) and derivatives thereof, chlorogenic acid and its derivatives, lipoic acid and its derivatives (for example dihydrolipoic acid), rothioglucose, propylthiouracil and other thiols (for example Thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and also sulfoximine compounds (for example buthionine sulfoximines, homocysteinsulfoximine, Buti oninsulfone, penta, hexa, heptathionine sulfoximine) in very low tolerated dosages (for example pmol to μmol / kg), furthermore (metal) chelators (for example α-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (cf. Citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (for example γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (for example ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (for example vitamin E acetate), vitamin A and derivatives (vitamin A palmitate), and benzylic resin, benzylic acid, rutinic acid and their derivatives, α-glycosylrutin, ferulic acid, furfurylideneglucitol, carnosine, butylhydroxytoluene,

Butylhydroxyanisole, nordihydroguaiakolic acid, nordihydroguiaretic acid,

Trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and its derivatives (for example ZnO, ZnSO ₄ ) selenium and its derivatives (for example selenium methionine), stilbenes and their derivatives (for example stilbene oxide, trans Stilbene oxide) and the inventively suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of said active substances. To improve the flow behavior, it is also possible to use hydrotropes, such as, for example, ethanol, isopropyl alcohol, or polyols. Polyols contemplated herein preferably have from 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols may contain other functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

• glycerin;

Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and polyethylene glycols having an average molecular weight of 100 to 1,000 daltons;

Technical Oligoglyceringemische with an intrinsic degree of condensation of 1, 5 to 10 such as technical Diglyceringemische with a diglycerol content of 40 to 50 wt .-%;

Methyolverbindungen, in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;

Lower alkyl glucosides, especially those having 1 to 8 carbons in the alkyl radical, such as, for example, methyl and butyl glucoside;

Sugar alcohols having 5 to 12 carbon atoms, such as sorbitol or mannitol,

• sugars with 5 to 12 carbon atoms, such as glucose or sucrose;

• amino sugars, such as glucamine;

• Dialcoholamines, such as diethanolamine or 2-amino-1,3-propanediol.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the other classes of substances listed in Appendix 6, Part A and B of the Cosmetics Regulation. Insect repellents are N.N-diethyl-m-toluamide, 1, 2-pentanediol or ethyl Butylacetylaminopropionate in question, suitable as a self-tanner dihydroxyacetone.

As perfume oils may be mentioned: mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (macis, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, Thyme), needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Furthermore, animal raw materials come into question, such as civet and Castoreum. Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons.

Dyes which may be used are those which are suitable and approved for cosmetic purposes. These dyes are usually used in concentrations of 0.001 to 0.1 wt .-%, based on the total mixture.

The total amount of auxiliaries and additives may be 1 to 50, preferably 5 to 40% by weight, based on the average. The preparation of the agent can be done by conventional cold or hot processes; It is preferable to work according to the phase inversion temperature method.

To prepare the hair dye according to the invention preferably oxidation dye precursors and oxidases are incorporated into a suitable aqueous carrier with the exclusion of atmospheric oxygen. Such carriers are, for example, thickened aqueous solutions, creams (emulsions), gels or surfactant-containing foaming preparations, for example shampoos or foam aerosols or other preparations which are suitable for use on the hair.

In principle, anhydrous powders are also suitable as carriers; in this case, the oxidation colorants are dissolved or dispersed in water immediately before use. As carrier components are preferred

Wetting and emulsifying agent

thickener

Reducing agents (antioxidants) Hair care additives

Fragrances and

Solvent such as water, glycols or lower alcohols

used. Suitable wetting and emulsifying agents are, for example, anionic, zwitterionic, ampholytic and nonionic surfactants. Also cationic surfactants can be used to achieve certain effects.

Suitable thickeners are the water-soluble high molecular weight polysaccharide derivatives or polypeptides, for example cellulose or starch ethers, gelatin, vegetable gums, biopolymers (xanthan gum) or water-soluble synthetic polymers such as, for example, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene oxides, polyacrylamides, polyurethanes, polyacrylates and other.

Furthermore, surfactant-containing preparations can also be thickened by solubilization or emulsification of polar lipids. Such lipids are for example fatty alcohols having 12-18 C-atoms, (free) fatty acids having 12-18 C-atoms, fatty acid partial glycerides, sorbitan fatty acid esters, fatty acid alkanolamides, low ethoxylated fatty acids or fatty alcohols, lecithins, sterols. Finally, one can produce gel-like carrier based on aqueous soap gels, for example of ammonium oleate.

Reducing agents (antioxidants) added to the carrier to prevent premature oxidative development of the dye before application to the hair are, for example, sodium sulfite or sodium ascorbate.

Hair care additives can be, for example, fats, oils or waxes in emulsified form, structuring additives such as glucose or pyridoxine, corrosive components such as water-soluble proteins, protein degradation products, amino acids, water-soluble cationic polymers, silicones, vitamins, panthenol or plant extracts.

Finally, perfumes and solvents such as glycols such as 1,2-propylene glycols, glycerol, glycol ethers such as butyl glycol, ethyl diglycol or lower monohydric alcohols such as ethanol or isopropanol may be included.

In addition, other adjuvants may be included to improve the stability and performance characteristics of the oxidation dyes, for example, chelating agents such as EDTA, NTA or organophosphonates, swelling and penetrating agents such as urea, guanidine, bicarbonates, buffer salts such as Ammonium chloride, ammonium citrate, ammonium sulfate or alkanolammonium salts and optionally propellants.

The invention-relevant agents for oral, dental or dental prosthesis care, in particular prosthesis cleaner, preferably contain oxidases for bleaching or disinfection.

In partial dentures or dentures, both the presentation as Gebißreinigungstabletten, as well as mouthwash or mouthwash or toothpaste is suitable.

The oral, dental and / or dental prosthesis care agents relevant to the invention can be present, for example, as a mouthwash, gel, liquid toothbrush lotion, stiff toothpaste, denture cleaner or denture adhesive cream.

For this purpose, it is necessary to incorporate the active ingredients in a suitable carrier.

For example, pulverulent preparations or aqueous-alcoholic solutions which serve as mouthwashes 0 to 15% by weight of ethanol, 1 to 1.5% by weight of aroma oils and 0.01 to 0.5% by weight of sweeteners can also be used as carriers or as mouthwash concentrates 15 to 60 wt .-% ethanol, 0.05 to 5 wt .-% flavor oils, 0.1 to 3 wt .-% sweeteners and optionally other excipients may be included and diluted with water before use. The concentration of the components must be so high that, after dilution, the specified lower concentration limits are not undershot during use.

However, gels and more or less flowable pastes, which are expressed from flexible plastic containers or tubes and applied to the teeth with the aid of a toothbrush, can also serve as the carrier. Such products contain higher levels of humectants and binders or consistency regulators and polishing components. In addition, aromatic oils, sweeteners and water are also contained in these preparations.

Glycerol, sorbitol, xylitol, propylene glycols, polyethyleneglycols or mixtures of these polyols, in particular those, can be used as humectants Polyethenylenglycole be used with molecular weights of 200 to 800 (from 400 - 2000). Preferably, sorbitol is contained as humectant in an amount of 25-40 wt .-%.

As anticalculus agents and as demineralization inhibitors, condensed phosphates may be present in the form of their alkali metal salts, preferably in the form of their sodium or potassium salts. The aqueous solutions of these phosphates react alkaline due to hydrolytic effects. By addition of acid, the pH of the oral, dental and / or dental prosthesis care agents according to the invention is adjusted to the preferred values of 7.5-9. It is also possible to use mixtures of different condensed phosphates or else hydrated salts of the condensed phosphates. The specified amounts of 2-12% by weight, however, refer to the anhydrous salts. Preferably, the condensed phosphate is a sodium or potassium tripolyphosphate in an amount of 5-10% by weight of the composition.

A preferred active ingredient is a caries-inhibiting fluorine compound, preferably from the group of fluorides or monofluorophosphates in an amount of 0.1 to 0.5 wt .-% fluorine. Suitable fluorine compounds are, for example, sodium monofluorophosphate (Na ₂ PO ₃ F), potassium monofluorophosphate, sodium or potassium fluoride, tin fluoride or the fluoride of an organic amino compound.

Suitable binders and consistency regulators are, for example, natural and synthetic water-soluble polymers such as carrageenan, tragacanth, guar, starch and their nonionic derivatives such as hydroxypropyl guar, hydroxyethyl starch, cellulose ethers such as hydroxyethyl cellulose or methylhydroxypropyl cellulose. Also, agar-agar, xanthan gum, pectins, water-soluble carboxyvinyl polymers (for example Carbopol ^® types), polyvinyl alcohol, polyvinyl pyrrolidone, high molecular weight polyethylene glycols (molecular weight 10 ³ to 10 ⁶ D). Further substances which are suitable for viscosity control are phyllosilicates such as montmorillonite clays, colloidal thickening silicas, for example airgel silicic acid or fumed silicas.

As polishing components, all polishers known for this purpose, but preferably precipitates and gel silicas, aluminum hydroxide, aluminum silicate, aluminum oxide, Are, for example, polymethacrylate, used alumina trihydrate, insoluble sodium metaphosphate, calcium pyrophosphate, calcium hydrogen phosphate, dicalcium phosphate, chalk, hydroxyapatite, hydrotalcites, talc, magnesium aluminum silicate (Veegum ^®), calcium sulfate, magnesium carbonate, magnesium oxide, sodium aluminum silicates, for example Zeolite A or organic polymers. The polishing agents are preferably used in smaller amounts of, for example, 1-10% by weight.

The tooth and / or oral hygiene products relevant to the invention can be improved in their organoleptic properties by adding aroma oils and sweeteners. Aromatic oils are all natural and synthetic flavors which are customary for oral, dental and / or dental care products. Natural flavors can be used both in the form of the essential oils isolated from the drugs and the individual components isolated from them. At least one aromatic oil from the group of peppermint oil, spearmint oil, aniseed oil, caraway oil, eucalyptus oil, fennel oil, cinnamon oil, geranium oil, sage oil, thyme oil, marjoram oil, basil oil, citrus oil, Gaultheria oil or one or more synthetically produced components of these oils isolated therefrom should preferably be present. The most important components of the oils mentioned are, for example, menthol, carvone, anethole, cineol, eugenol, cinnamaldehyde, geraniol, citronellol, linalool, salvos, thymol, terpinene, terpinol, methylchavicol and methyl salicylate. Other suitable flavors are, for example, menthyl acetate, vanillin, ionone, linalyl acetate, rhodinol and piperitone. Suitable sweeteners are either natural sugars such as sucrose, maltose, lactose and fructose or synthetic sweeteners such as saccharin sodium salt, sodium cyclamate or aspartame. _;

As surfactants in particular alkyl and / or alkenyl (oligo) glycosides are used, their preparation and use as surfactants are known. With respect to the glycoside, it is true that both monoglycosides (x = 1) in which a pentose or hexose is glycosidically bonded to a primary alcohol having 4 to 16 carbon atoms, as well as oligomeric glycosides having a degree of oligomerization x to 10 are suitable. The degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.

As alkyl and / or alkenyl (oligo) glycoside, an alkyl and / or alkenyl (oligo) glucoside of the formula RO (C ₆ H ₁₀ O) _x -H in which R is an alkyl radical and is preferably suitable or alkenyl group having 8 to 14 carbon atoms and x has an average value of 1 to 4. Especially preferred are alkyl oligoglucosides based on hydrogenated C ₁₂ yi ₄ cocoalcohol having a DP of 1 to 3. The alkyl and / or alkenyl glycoside surfactant can be used very sparingly, already amounts of 0.005 to 1 wt .-% sufficient are.

In addition to the alkyl glucoside surfactants mentioned, other nonionic, ampholytic and cationic surfactants may also be present in cosmetic products, such as, for example: fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, monoglyceride ether sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, ether carboxylic acids, fatty acid glucamides , Alkylamido betaine and / or protein fatty acid condensates, the latter preferably based on wheat proteins. In particular, to solubilize the usually water-insoluble aroma oils, a non-ionic solubilizer from the group of surface-active compounds may be required. Particularly suitable for this purpose are, for example, ethoxylated fatty acid glycerides, ethoxylated fatty acid sorbitan partial esters or fatty acid partial esters of glycerol or sorbitan ethoxylates. Solubilizers from the group of ethoxylated Fettsäureglyceride include especially addition products of 20 to 60 moles of ethylene oxide with mono- and diglycerides of linear fatty acids having 12 to 18 carbon atoms or triglycerides of hydroxy fatty acids such as oxystearic acid or ricinoleic acid. Further suitable solubilizers are ethoxylated fatty acid sorbitan partial esters; these are preferably addition products of 20 to 60 moles of ethylene oxide with sorbitan monoesters and sorbitan diesters of fatty acids with 12 to 18 carbon atoms. Also suitable solubilizers are fatty acid partial esters of glycerol or sorbitan ethoxylates; these are preferably mono- and diesters of C ₁₂ -C ₁₈ fatty acids and addition products of from 20 to 60 mol ethylene oxide with 1 mol glycerol or with 1 mol sorbitol.

The oral, dental and / or dental prosthesis care agents which are relevant to the invention preferably comprise addition products of 20 to 60 mol of ethylene oxide to hardened or unhardened castor oil (that is to say oxystearic acid or ricinoleic acid triglyceride), to glycerol mono- and / or as solubilizers for optionally contained aroma oils. or distearate or sorbitan mono- and / or distearate.

Other common additives for oral, dental and / or denture care medium are, for example

Pigments, for example titanium dioxide, and / or dyes pH adjusting agents and buffer substances such as sodium bicarbonate,

Sodium citrate, sodium benzoate, citric acid, phosphoric acid or acid salts, for

Example NaH ₂ PO ₄ wound-healing and anti-inflammatory substances such as allantoin,

Urea, panthenol, azulene or chamomile extract further anticalculus substances such as organophosphonates, for example Hydroxyethandiphosphonate or Azacycloheptandiphosphonat

Preservatives such as sorbic acid salts, p-hydroxybenzoic acid

Ester.

Plaque inhibitors such as hexachlorophene, chlorhexidine, hexetidine,

Triclosan, bromochlorophene, phenylsalicylic acid ester.

In a particular embodiment, the composition is a mouthwash, a mouthwash, a denture cleanser or a denture adhesive.

For prosthesis cleaners according to the invention, in particular prosthesis cleansing tablets and powders, in addition to the already mentioned ingredients for oral, dental and / or dental prosthesis care, per-compounds such as, for example, peroxoborate, peroxomonosulfate or percarbonate are additionally suitable. They have the advantage that, in addition to the bleaching effect, they simultaneously have a deodorizing and / or disinfecting effect. The use of such per-compounds in denture cleaners is between 0.01 and 10 wt .-%, in particular between 0.5 and 5 wt .-%.

As further cosmetic ingredients, enzymes such as proteases and carbohydrase are also suitable for the degradation of proteins and carbohydrates. The pH can be between pH 4 and pH 12, in particular between pH 5 and pH 11.

The prosthesis cleansing tablets additionally require further auxiliaries, such as, for example, agents which give rise to a bubbling effect, for example CO ₂ releasing substances such as sodium bicarbonate, fillers, for example sodium sulfate or dextrose, lubricants, for example magnesium stearate, flow regulators, for example colloidal silica and granulating agents, such as the already mentioned high molecular weight polyethylene glycols or polyvinylpyrrolidone. Denture adhesives can be offered as powders, creams, foils or liquids and support the adhesion of the prostheses.

As active ingredients natural and synthetic swelling substances are suitable. In addition to alginates, vegetable gums such as gum arabic, tragacanth and karaya gum as well as natural rubber are to be regarded as natural bulking agents. In particular, alginates and synthetic bulking agents such as sodium carboxymethyl cellulose, high molecular weight ethylene oxide copolymers, salts of poly (vinyl ether-co-maleic acid) and polyacrylamides.

As adjuvants for pasty and liquid products are particularly hydrophobic bases, in particular hydrocarbons, such as white Vaseline (DAB) or paraffin oil.

Claims

claims

1. Agents selected from pharmaceuticals, body care products, shampoos, hair care products, hair dyes, oral, dental or denture care products, cosmetics, detergents, cleaning agents, rinse aids, hand detergents, hand dishwashing detergents, machine dishwashing detergents, bleaching agents, disinfectants or agents for the treatment of filter media, textiles , Furs, paper, skins or leather containing an alkali metal halide in a defined concentration below 0.9% by weight.

A composition according to claim 1, which is a detergent, a detergent, a rinse aid, a hand wash, a hand dishwashing detergent or a machine dishwashing detergent.

3. Composition according to claim 1 or 2, characterized in that the alkali metal halide in a concentration of 1 to 500 ppm, preferably 10 to 250 ppm, more preferably 50 to 150 ppm is included.

4. Raw material for an agent which is selected from pharmaceutical agents, personal care products, shampoos, hair care products, hair dyes, oral, dental or denture care products, cosmetics, detergents, cleaning agents, rinse aids, hand detergents, hand dishwashing detergents, machine dishwashing detergents, bleaching agents, disinfectants or agents for Treatment of filter media, textiles, furs, paper, hides or leather, wherein the raw material is an alkali metal halide in a defined concentration below 0.9 wt .-%. contains.

5. Raw material according to claim 4, characterized in that it is an enzyme preparation, particularly preferably an enzyme granules.

6. Raw material according to claim 4 or 5, characterized in that the alkali metal halide in a concentration of 20 to 9,000 ppm, preferably from 200 to 5,000 ppm, more preferably 1,000 to 3,000 ppm is included.

7. A composition or a raw material according to any one of claims 1 to 6, characterized in that the alkali metal halide is selected from potassium chloride, potassium bromide, potassium iodide, potassium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium fluoride, lithium bromide, lithium fluoride, lithium nitride halides, Rubidium chloride, rubidium fluoride, rubidium zinc bromide, rubidium silver iodide, cesium chloride, cesium iodide, cesium fluoride, preferably lithium bromide, lithium fluoride or lithium nitride halides, more preferably lithium chloride.

8. A composition or a raw material according to any one of claims 1 to 7, wherein the alkali metal halide is contained in a defined size ratio to an ingredient of a washing or cleaning agent, preferably to an enzyme, in particular to an amylase, a cellulase, a lipase, an oxidoreductase, a hemicellulase or a protease, more preferably an α-amylase and / or a subtilisin protease.

9. agent or raw material according to any one of claims 1 to 8, characterized in that the tracer is detectable by atomic absorption spectrometry.

10. A composition or raw material according to any one of claims 1 to 9, characterized in that the agent or the raw material is in solid form.

11. Use of an alkali metal halide as tracer in an agent selected from pharmaceuticals, personal care products, shampoos, hair care products, hair dyes, oral, dental or denture care preparations, cosmetics, detergents, cleaners, rinse aids, hand detergents, hand dishwashing detergents, machine dishwashing detergents, bleaching agents, Disinfectants or agents for the treatment of filter media, textiles, furs, paper, hides or leather or as a tracer in a raw material for such an agent.