EP1891198A1

EP1891198A1 - Dosing device

Info

Publication number: EP1891198A1
Application number: EP06761982A
Authority: EP
Inventors: Arnd Kessler; Ingo Hardacker; Federica Berardo
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2005-06-15
Filing date: 2006-06-08
Publication date: 2008-02-27
Anticipated expiration: 2026-06-08
Also published as: DE102005027660A1; WO2006133843A1; EP1891198B1; ES2397230T3; PL1891198T3; US20090004234A1

Abstract

Disclosed is a dosing device for metering agents in washing or cleaning processes. Said dosing device comprises a receptacle as well as a) a first active substance composition which is placed in said receptacle and contains at least one carrier material and at least one agent, and b) a second active substance composition that is arranged in said receptacle and also contains at least one carrier material and at least one agent but differs from the first active substance composition regarding at least one of the ingredients thereof. The inventive dosing device is characterized in that the carrier material in at least one active substance composition is water-insoluble while being suitable for releasing different active substances and distinguishing itself from conventional dosing devices by an improved releasing profile.

Description

metering

The present invention is in the field of metering devices for washing or cleaning-active substances, in particular the present invention relates to metering devices for the simultaneous dosage of different washing or cleaning-active substances.

In washing or cleaning processes, in addition to the active ingredients that are actually active in washing or cleaning, such as, for example, the builders, soaps or surfactants, additional additives and auxiliaries are generally used. In addition to the fragrances, the most common excipients include the corrosion inhibitors for the protection of silver or glassware, rinse aids or bleach activators in automatic dishwashing, as well as ironing aids, optical brighteners or antistatic agents in machine textile cleaning.

These additives or auxiliaries may be present as an integral part of the washing or cleaning agents used, but may also be added to these cleaning agents in the form of a special detergent or special cleaning agent. Another possibility for dosing these auxiliaries are the multidose dosing devices available on the market, for example for scenting dishwashers. These Geschirrspülmaschinendos have the task, bad odors in the dishwasher, which may result, for example, by the storage of soiled dishes, or to eliminate or reduce alkali odors after completion of the cleaning process.

These deodorants can be made up in very different ways. For the consumer, it is desirable to obtain an article for the deodorizing of dishwashers or other enclosed spaces, which has an intense product fragrance when it is provided, which not only ensures product identification, but at the same time conveys the impression of high potency and which then in the course of his Life guaranteed the most reliable release of constant fragrance quantities. Furthermore, these deodorants should also achieve their effect independently of external factors such as (air) moisture, temperature or alkalinity. A number of different deodorizers for dishwashers are described in the prior art.

A generic scent delivery system is known from WO 02/09779 A1 (Procter & Gamble). This known scent delivery system comprises a container in which a plurality of small particles loaded with fragrances are received. The container is provided with a plurality of openings whose size is dimensioned so that the small particles can not escape through the openings. On the other hand, the openings are dimensioned that an emission of the fragrances of the particles from the receiving space of the container to the outside is possible.

Deodorants for use in laundry driers are also known from the prior art.

For example, US Pat. No. 6,235,705 (Bath & Body Works Inc.) describes a scent product

Tumble dryer, which consists of perfume-containing plastic beads in a mesh bag. The

Scenting of the beads happens during their production at elevated temperature.

The present application was based on the object of providing dosing apparatus for washing or cleaning active ingredients which are suitable for the simultaneous release of different active substances and which are distinguished from conventional dosing apparatuses by an improved release profile of these active ingredients. In particular, the duration of the drug release should be extended while achieving a uniform release of the active ingredient.

To achieve this object, a metering device with two different active ingredient compositions has been provided, of which at least one has a water-insoluble carrier material.

A first subject of the present application is therefore a metering device for metering active ingredients in laundry cleaning processes, comprising a container and a) a first active ingredient composition in this container which contains at least one carrier material and at least one active substance; and b) a second active ingredient composition in said container which likewise contains at least one carrier material and at least one active substance but differs from the first active ingredient composition in regard to at least one of its ingredients, characterized in that the carrier material is water-insoluble in at least one active ingredient composition.

The metering device according to the invention is suitable for metering a multiplicity of washing or cleaning-active substances. In particular, this metering device is suitable for the separate packaging and metering of different active ingredient compositions. In a preferred embodiment, the metering device according to the invention is particularly suitable for the multiple dosing of these drug compositions.

In a preferred embodiment, the metering device according to the invention is suitable for multiple dosing of the active ingredients contained in it. In other words, the Dosing device according to the invention, these active substances preferably over a period of time, which is a multiple of the period of a washing or cleaning process. In a preferred embodiment, the dosing device according to the invention is suitable for dosing one or more active substances in 10 to 100, preferably 20 to 90 and in particular 30 to 80, cleaning cycles of a dishwasher, a textile washing machine or a textile drier.

Such a sustained release of the active ingredients can be realized, for example, by delaying the active ingredients used by appropriate preparation, in which case, in particular, the choice of the carrier material and the processing of carrier material and active ingredient for the final active ingredient composition influence the release kinetics of the active ingredient. Another way to delay or expand the release of the active ingredients based on the spatial design of the container.

In a preferred embodiment, the wall defining the container to the outside has a plurality of openings. On the one hand, these openings allow the escape of volatile active substances, such as the fragrances described below, and on the other hand permit the entry of aqueous liquors, provided that the metering devices according to the invention come into contact with such washing or cleaning liquors during their use in washing or cleaning processes.

Dosing devices, characterized in that the container has at least two separate receiving chambers, which are each filled with at least one active ingredient composition, wherein these active ingredient compositions differ at least with respect to one of their ingredients are particularly preferred according to the invention.

In a further preferred embodiment, the metering device has a fastening device.

Of course, the metering devices according to the invention may also comprise more than the two mentioned active compound preparations. Dosing devices with three, four, five or more active compound preparations which differ from one another with regard to at least one of their ingredients are preferred according to the invention.

In addition to the container described above, the metering devices according to the invention moreover comprise one or more carrier materials, of which at least one is water-insoluble. As water-insoluble carrier materials textile materials or polymers are used with particular preference. A metering device, characterized in that the container is made of a water-insoluble material, preferably of a textile material or a polymer or a polymer mixture, is preferred according to the invention.

As polymers, in particular water-insoluble polymers, synthetic polymers are preferably used. Dosing devices according to the invention, characterized in that it is at least one of the carrier materials to a polymeric material, preferably a substance from the group comprising ethylene / vinyl acetate copolymers, low or high density polyethylene (LDPE, HDPE) or mixtures thereof, polypropylene, polyethylene / Polypropylene Copolymers, Polyether / Polyamide Block Copolymers, Styrene / Butadiene (Block) Copolymers, Styrene / Isoprene (Block) Copolymers, Styrene / Ethylene / Butylene Copolymers, Acrylonitrile / Butadiene / Styrene Copolymers, Acrylonitrile / Butadiene -Copolymers, Polyetheresters,

Polyisobutene, polyisoprene, ethylene / ethyl acrylate copolymers, polyamides, polycarbonate, polyesters, polyacrylonitrile, polymethyl methacrylate, polyurethanes, polyvinyl alcohols are preferred according to the invention.

Polyethylene (PE) is a collective name for polymers belonging to the polyolefins with groups of the type CH ₂ -CH ₂ as a characteristic basic unit of the polymer chain.

Polypropylene (PP) is the name for thermoplastic polymers of propylene with the general formula - (CH ₂ -CH [CH 3]) _n -.

Polyether is a comprehensive term in the field of macromolecular chemistry for polymers whose organic repeating units are held together by ether functionalities (C-O-C). According to this definition, a large number of structurally very different polymers belong to the polyethers, eg. As the polyalkylene glycols (polyethylene glycols, polypropylene glycols and polyepichlorohydrins) as polymers of 1, 2-epoxides, epoxy resins, polytetrahydrofurans (polytetramethylene glycols), polyoxetanes, polyphenylene ethers (see polyarylethers) or polyetheretherketones (see Polyetherketone). Not to the polyethers polymers with pendant ether groups are calculated, such as. a. the cellulose ethers, starch ethers and vinyl ether polymers.

The group of polyethers also include functionalized polyethers, ie compounds having a polyether skeleton, which laterally attached to their main chains still carry other functional groups such. As carboxy, epoxy, AIIyI or amino groups, etc. are widely used block copolymers of polyethers and polyamides (so-called polyetheramides or polyether block amides, PEBA). Polyamides (PA) are polymers whose basic building blocks are held together by amide bonds (- NH-CO-). Naturally occurring polyamides are peptides, polypeptides and proteins (Ex .: protein, wool, silk). The synthetic polyamides, with a few exceptions, are thermoplastic, chain-like polymers.

In addition to the homopolyamides, some co-polyamides have gained importance. It is customary in these a qualitative and quantitative indication of the composition z. B. PA 66/6 (80:20) prepared from 1, 6-hexanediamine, adipic acid and ε-caprolactam in a molar ratio 80:80:20

Polyamides.

Because of their special properties, polyamides which contain exclusively aromatic radicals (for example those of p-phenylenediamine and terephthalic acid) are classified under the generic name.

Aramids or polyaramides summarized (Ex .: Nomex®).

The most commonly used polyamide types (especially PA 6 and PA 66) consist of unbranched chains with average molecular weights of 15,000 to 50,000 g / mol. They are partially crystalline in the solid state and have degrees of crystallization of 30-60%. An exception are polyamides of building blocks with side chains or co-polyamides of very different components, which are largely amorphous. In contrast to the generally milky-opaque, semi-crystalline polyamides these are almost crystal clear. The softening temperature of the most common homo-polyamides are between 200 and 260 ⁰ C (PA 6: 215-220 ⁰ C, PA 66: 255-260 ⁰ C).

Polyester is the collective name for polymers whose basic building blocks are held together by ester bonds (-CO-O-). According to their chemical structure, the so-called homopolyesters can be divided into two groups, the hydroxycarboxylic acid types (AB-polyester) and the dihydroxy-dicarboxylic acid types (AA-BB-polyester). The former are made of only a single monomer by z. B. polycondensation of a ω-hydroxycarboxylic acid 1 or by ring-opening polymerization of cyclic esters (lactones) 2 produced.

Branched and crosslinked polyesters are obtained in the polycondensation of trihydric or polyhydric alcohols with polyfunctional carboxylic acids. The polyesters are generally also the polycarbonates (carbonic acid polyester) counted.

AB type polyesters (I) are u. a. Polyglycolic acids, polylactic acids, polyhydroxybutyric acid [poly (3-hydroxybutyric acid), poly (ε-caprolactone) s and polyhydroxybenzoic acids.

Pure aliphatic AA-BB type polyesters (II) are polycondensates of aliphatic diols and dicarboxylic acids, which are used, inter alia, as products having terminal hydroxyl groups (as polydiols) for the preparation of polyester polyurethanes [z. B. polytetramethylene adipate]. In terms of quantity the largest technical importance have AA-BB type polyester from aliphatic Diols and aromatic dicarboxylic acids, in particular the polyalkylene terephthalates, with polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and poly (1,4-cyclohexanedimethylene terephthalate) s (PCDT) as the most important representatives. These types of polyesters can be widely varied in their properties by using other aromatic dicarboxylic acids (for example isophthalic acid) or by using diol mixtures in polycondensation and can be adapted to different fields of application.

Purely aromatic polyesters are the polyarylates to which u. a. which include poly (4-hydroxybenzoic acid). In addition to the previously mentioned saturated polyesters, it is also possible to prepare unsaturated polyesters from unsaturated dicarboxylic acids which have acquired industrial significance as polyester resins, in particular as unsaturated polyester resins (UP resins).

Polyurethanes (PU) are polymers in whose macromolecules the repeat units are linked by urethane groups -NH-CO-O-. Polyurethanes are generally obtained by polyaddition from dihydric or higher alcohols and isocyanates.

Depending on the choice and stoichiometric ratio of the starting materials so arise polyurethanes with very different mechanical properties, which are used as components of adhesives and paints (polyurethane resins), as ionomers, as a thermoplastic material for bearing parts, rollers, tires, rollers and as more or less hard elastomers in fiber form (elastofibres, short PUE for these elastane or spandex fibers) or as polyether or polyester urethane rubber (EU or AU)

Polyvinyl alcohols (PVAL, occasionally also PVOH) is the term for polymers of the general structure

in small proportions (about 2%) also structural units of the type

OHo OH OH OHo OH OH

contain. Commercially available polyvinyl alcohols are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol). The polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable. The water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The coatings of polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Polyvinyl alcohols of a certain molecular weight range are preferably used as carrier materials, wherein the water-soluble or water-dispersible container comprises a polyvinyl alcohol whose molecular weight is in the range of 10,000 to 100,000 gmol ^-1 , preferably 11,000 to 90,000 gmol ^-1 , particularly preferably 12,000 to 80,000 gmol ^"1 and in particular from 13,000 to 70,000 gmol ^{" 1} .

In a particularly preferred embodiment of the present invention, the polymeric carrier material of the particles consists at least partly of ethylene / vinyl acetate copolymer. A further preferred subject of the present application is therefore a metering device, characterized in that a polymeric carrier material contains at least 10 wt .-%, preferably at least 30 wt .-%, particularly preferably at least 70 wt .-% ethylene / vinyl acetate copolymer, preferably completely made of ethylene / vinyl acetate copolymer.

Ethylene / vinyl acetate copolymers is the name for Copoylmere of ethylene and vinyl acetate. The preparation of this polymer is basically carried out in a process similar to that of the production of low density polyethylene (LDPE). With an increasing proportion of vinyl acetate, the crystallinity of the polyethylene is interrupted and in this way the melting and softening points or the hardness of the resulting products are reduced. The vinyl acetate also makes the copolymer more polar and thus improves its adhesion to polar substrates. The ethylene / vinyl acetate copolymers described above are widely available commercially, for example under the tradename Elvax ^® (Dupont). In the present invention, particularly suitable polyvinyl alcohols are, for example Elvax ^® 265, Elvax ^® 240, Elvax ^® 205W, Elvax ^® 200W, as well as Elvax ^® 360th

Some particularly suitable copolymers and their physical properties are shown in the following table:

In the context of the present invention, in particular in the field of scenting the interiors of automatic dishwashers, dosing devices are particularly preferred in which ethylene / vinyl acetate copolymer is used as the polymeric support material and this copolymer 5 to 50 wt .-% vinyl acetate, preferably 10 to 40 wt .-% vinyl acetate and in particular 20 to 30 wt .-% vinyl acetate, each based on the total weight of the copolymer contains.

In a further preferred embodiment, at least one of the active substance compositions of the metering device contains a polyether-ester-amide polymer (PEEA- polymer) of the general formula HO [C (O) -PA-C (O) -O-PE-O] _n H. Dosing devices according to the invention, characterized in that at least one of the active ingredient compositions comprises a polyether-ester-amide polymer (PEEA polymer) of the general formula HO [C (O) -PA-C (O) -O-PE-O] _n H, in the PA for a polyamide group stands, PE is a polyether group and n is an integer, are particularly preferred.

Corresponding PEEA polymers are, for example, by copolymerization of the polyamide of a dicarboxylic acid which carries a terminal acid group and has an average molecular weight between 300 and 15,000, with a linear or branched aliphatic polyalkylene glycol, which carries a terminal Hydrxoylgruppe and has an average molecular weight between 200 and 6000 , available. The copolymerization is preferably carried out in a melt at temperatures between 100 and 400 ⁰ C.

Corresponding PEEA polymers are commercially available under the name Pebax ^® . While in principle the aforementioned PEEA polymers are suitable as an ingredient of the present invention metered drug compositions, such

Particularly preferred are active compound compositions which are capable of absorbing at least 2.3 times, preferably 5 times their own weight of fragrances. Suitable PEEA polymers are, for example, Pebax ^® 2533, Pebax ^® 3533 or Pebax ^® 4033rd

In a further preferred embodiment, at least one of the active ingredient compositions is an active ingredient-containing gel. Particular preference is given to gels comprising a) 70 to 98% by weight of at least one active ingredient, preferably of a perfume and b) 2 to 30% by weight of a polyether-ester-amide polymer (PEEA polymer) of the general formula HO [C (O) -PA-C (O) -O-PE-O] _n H wherein PA is a polyamide group, PE is a polyether group, and n is an integer.

In a further preferred embodiment, the metering device according to the invention comprises activated carbon as carrier material. Activated carbon is to be understood as meaning black, light, dry, odorless and tasteless powders or granules of minute graphite crystals and amorphous carbon with a porous structure and very large internal surfaces (preferably between 500 and 1500 m ² / g). A distinction is made between powdered activated carbon, granular activated carbon and, for example, cylindrically shaped activated carbon form. Activated carbon can contain up to 25% by weight of minerals. The activated carbon can act as a scent catcher in a particularly preferred embodiment and is thus at the same time carrier material and active ingredient.

Other suitable carrier materials are the cyclodextrins.

As an alternative or in addition to the abovementioned carrier materials, preference is furthermore given to using inorganic carrier materials. Particular preference is given to metering devices, characterized in that at least one of the carrier materials is an inorganic carrier material, preferably a silicate, phosphate or borate.

The silicates, phosphates or borates are preferably in the form of a glass, particularly preferably in the form of a water-soluble glass. Particularly preferred inorganic support materials are, for example, zeolites, preferably acid-modified zeolites.

The abovementioned carrier materials can be used alone or in combination with other carrier materials.

In the context of the present application, particular preference is given to thermoplastic carrier materials or carrier materials which plastically deform under the action of the ambient temperatures occurring during use. The plastic deformation of the carrier materials in the course of one or more applications results in a change in the carrier material surface, in particular a change in the size of the carrier material surface, which in turn advantageously affects the release profile and the release kinetics of the washing or cleaning active ingredients contained in the active ingredient compositions. Dosing devices, characterized in that at least one polymeric carrier material has a melting or softening point between 40 and 125 ° C, preferably between 60 and 100 ⁰ C, more preferably from 70 to 9O ⁰ C and in particular between 75 and 80 ⁰ C, are according to the invention prefers.

The dosing devices according to the invention are particularly suitable for the multiple dosing of the active substances contained in them. In order to ensure such a multiple dosing over a variety of washing or cleaning processes, it has proven to be advantageous to use only water-insoluble carrier materials. These water-insoluble carrier materials also simplify the production of metering devices according to the invention. Preferred metering device are therefore characterized in that all carrier materials used are water-insoluble.

In principle, the active ingredient compositions can take on any state of matter and / or three-dimensional forms that can be realized, depending on the chemical and physical properties of the carrier materials.

In a first preferred embodiment, at least one of the active ingredient compositions is present as a gel.

In a further preferred embodiment, at least one of the active ingredient compositions is present as a solid. With special preference Active ingredient compositions in the form of individual blocks comprising entire active ingredient compositions. Alternatively, the active ingredient compositions may be in particulate form, wherein the dosing device wherein the carrier material of at least one of the active ingredient compositions is in particulate form, which particles preferably have an average diameter of 0.5 to 20 mm, preferably 1 to 10 mm, and especially 3 to 6 mm, are particularly preferred.

In a further preferred embodiment, the metering device according to the invention encompasses at least two active ingredient compositions, one of which comprises a water-insoluble carrier material in particle form, this carrier material being present dispersed in a gel-like active substance preparation.

Dosing devices according to the invention which comprise at least one colored active substance composition are particularly preferred. By coloring at least one of the active ingredient compositions, optical differentiation of these compositions can be achieved and the multiple benefits of these different compositions can be illustrated in a simple manner. Furthermore, the dyes are also suitable as an indicator, in particular as a consumption indicator for the colored active ingredient compositions.

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 the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic dishes do not stain them.

When choosing the colorant, it must be remembered that the colorants have a high storage stability and insensitivity to light as well as not too strong affinity for glass, ceramic or plastic dishes. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 ^-2 to 10 ^-3 wt.% Are typically selected In the case of the pigments, which are particularly preferred but less readily water-soluble because of their brilliance, the suitable concentration of the colorant is in washing or dyeing on the other hand cleaners typically a few 10 ^-3 to ^{10 -4} wt .-%. Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.

As a further ingredient, the metering devices according to the invention comprise one or more active substances. These active ingredients are washing or cleaning active ingredients. Preferred metering devices according to the invention are characterized in that at least one of these active ingredients is selected from the group of perfumes, scent scents, dyes, glass corrosion inhibitors, silver protectants, bleach catalysts, antimicrobial agents, germicides, fungicides, washing or cleaning active polymers or surfactants.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. 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, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.

In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note" or "body note" ) and "base note" (end note or dry out). Since odor perception is also largely based on the odor intensity, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note consists for the most part of less volatile, ie adherent fragrances. For example, in the composition of perfumes, more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly. In the subsequent classification of the fragrances in "more volatile" or "adherent" fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing said. The fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

As scent catcher, for example, the known Ricenolate, especially the Zinkricenoleate be used. With particular preference be further activated carbon and / or cyclodextrins and / or zeolites, preferably acid-modified zeolites used.

Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes.

The spectrum of the invention preferred zinc salts, preferably organic acids, particularly preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 have mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C. water temperature). The first group of zinc salts includes, for example, the zinc nitrate, the zinc oleate and the zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

With particular preference is used as a glass corrosion inhibitor at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or Zinkeitrat used. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

In the context of the present invention, the content of cleaning agents to zinc salt is preferably between 0.1 to 5 wt .-%, preferably between 0.2 to 4 wt .-% and in particular between 0.4 to 3 wt .-%, or the content of zinc in oxidized form (calculated as Zn ²⁺ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight. -%, in each case based on the total weight of the glass corrosion inhibitor-containing agent.

The silver protectants used are the known substances of the prior art. In general, silver protectants selected from the group of triazoles, the Benzotriazole, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. According to the invention, preference is given to using 3-amino-5-alkyl-1, 2,4-triazoles or their physiologically tolerated salts, these substances being particularly preferably used in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 Wt .-%, particularly preferably 0.01 to 0.04 wt .-% are used. Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid. Especially effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-alkyl-3-amino-1, 2,4-triazoles and mixtures of these substances.

In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds used. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

Instead of or in addition to the silver protectants described above, for example the benzotriazoles, redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, wherein the metals preferably in one of the oxidation states II, III, IV, V or VI are present.

The metal salts or metal complexes used should be at least partially soluble in water. The counterions suitable for salt formation include all conventional mono-, di-, or tri-negatively charged inorganic anions, e.g. Oxide, sulfate, nitrate, fluoride, but also organic anions such as e.g. Stearate.

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ , and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) _{3 are used} with particular preference ,

The inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, i. completely coated with a waterproof, but easily soluble in the cleaning temperatures material to prevent their premature decomposition or oxidation during storage. Preferred coating materials, which are applied by known methods, such as Sandwik melt coating process from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids.

The metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total agent.

The bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline 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 ammine complexes can also be used as bleach catalysts.

Bleach-enhancing transition metal complexes, in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are preferred according to the invention.

Antimicrobial agents can be used 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 phenoimercuria acetate, although it is entirely possible to do without these compounds.

The group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers. "Cationic polymers" for the purposes of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride Copolymers, the quaternized polyvinyl alcohols or the polymers listed under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

For the purposes of the present invention, "amphoteric polymers" further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

Preferred washing or cleaning agents, in particular preferred automatic dishwashing agents, are characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ in which each R ¹ , R ² , R ⁴ radical ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy, C _1-30 linear or branched alkyl groups, aryl, aryl substituted C _1-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen , at least one quaternized nitrogen atom or at least one amino group having a positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one Aminogru ppe with a positive charge.

In the context of the present application, particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ³ independently of one another an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X ^" represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylene sulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula are selected from -CH _3, -CH ₂ -CH _3, - CH ₂ -CH ₂ -CH _3, -CH (CH ₃₎ -CH _3, -CH ₂ -OH , -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H.

Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer unit of the formula

H ₂ C = C H- (CH ₂ ) -N ⁺ (C H ₃ ) ₂ - (CH ₂ ) -CH = CH ₂

in the case of X ^' = chloride also referred to as DADMAC (diallyldimethylammonium chloride).

Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

R1HC = CR2-C (O) -NH- (CH ₂₎ -N ⁺ R3R4R5

X ^" in the R ¹ , R ² , R ³ , R ⁴ and R ^{5 are} independently of one another a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from CH ₃ , -CH ₂ -CH ₃ , -CH ₂ - CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ - CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _{n is} H and x is an integer between 1 and 6.

In the context of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

H ₂ C = C (CH 3) -C (O) -NH- (CH ₂ ) _X -N ⁺ (CH 3) 3

in the case of X ^" = chloride also referred to as MAPTAC (Methyacrylamidopropyl trimethylammonium chloride).

According to the invention, preference is given to using polymers which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.

Preferred usable amphoteric polymers are selected from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the

Alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the

Alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers. Also preferred are amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.

Particularly preferred amphoteric polymers are selected from the group consisting of the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyKdiallyoammonium chloride / alkyl

(meth) acrylic acid copolymers and their alkali metal and ammonium salts.

Particular preference is given to amphoteric polymers from the group of

Methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid

Copolymers, the Methacrylamidopropyltrimethylammoniumchlorid / DimethyKdiallyOammonium- chloride / acrylic acid copolymers and methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.

Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.

Particularly preferred as sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.

In the context of the present invention are as unsaturated monomer carboxylic acids of the formula

R ¹ (R ² ) C = C (R ³ ) COOH

in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the above formula are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) is preferred.

In the sulfonic acid-containing monomers are those of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

in which R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ J _n - with n = O to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ JX-SO ₃ H

HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CHz) _n - with n = O to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ J ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ J-.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.

Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds. The content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH and monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -

X-SO ₃ H. In summary, copolymers of i) unsaturated carboxylic acids of the formula R ¹ (R ² ) C =C (R ³ ) COOH in the R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, ii) sulfonic acid group-containing monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H in the R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , - OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group, which is selected from - (CH ₂ ), - with n = O to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) - ii) optionally further ionic or nonionic monomers particularly preferred.

Further particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group of acrylic acid,

Methacrylic acid and / or maleic acid ii) one or more sulfonic acid group-containing monomers of the formulas:

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CHa) -X-SO ₃ H

HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ J ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = O to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) - iii) optionally further ionogenic or non-ionogenic monomers.

The copolymers may contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) being combined with all representatives from group ii) and all representatives from group iii) can. Particularly preferred polymers have certain structural units, which are described below.

For example, copolymers which are structural units of the formula are preferred

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y is -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CHa) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. When the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred. The corresponding copolymers contain the structural units of the formula

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein O- (CH ₂ ) _n - where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NH-C (CHs) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, copolymers which are structural units of the formula

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y is -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, as preferred, as copolymers, the structural units of the formula - [CH ₂ -C (CH ₃ ) COOH] _n - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _P -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) "- with n = O to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula

- [HOOCCH-CHCOOH] _n - [CH ₂ -CHC (O) -Y-SO ₃ H] _P -

in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or aliphatic hydrocarbon radicals containing 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred. Also preferred according to the invention are copolymers which contain structural units of the formula

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] p-

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CHs) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands.

In summary, such copolymers are preferred according to the invention, the structural units of the formulas

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] p-

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p -

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p -

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CHs) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

In the case of terpolymers, particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ^'1 , preferably from 4000 to 25,000 gmol ^{' 1} and in particular from 5000 to 15,000 gmol ^'1 .

The metering devices according to the invention may contain surfactants as further active ingredient. Suitable surfactants are in principle all surfactants known to those skilled in the art from the groups of nonionic, anionic, cationic or amphoteric surfactants, but in particular the nonionic surfactants are preferred.

In a particularly preferred embodiment, the surfactants, in particular the nonionic surfactants, are present in a form chemically bound to a carrier material. In such an embodiment, the surfactant may be released in the course of the washing or cleaning processes, for example by hydrolysis or oxidative cleavage of a chemical bond. The active compounds may in principle be present in the active substance preparations in any desired amounts. However, metering devices in which the proportion by weight of the active substance (s) is 1 to 70% by weight, preferably 10 to 60% by weight, particularly preferably 20 to 50% by weight, in particular 30 to 40% by weight, are particularly preferred. in each case based on the total weight of the active ingredient composition (s).

The dosing devices according to the invention comprise at least two active ingredient compositions which differ from one another with regard to at least one of their ingredients.

In a first preferred embodiment, the two active substance compositions differ with regard to the carrier materials contained in them.

In a particularly preferred variant of this preferred embodiment of metering devices according to the invention, the two active ingredient compositions differ only in terms of the carrier materials contained, but not with regard to the active ingredients contained. By using different carrier materials for the same active ingredient, it is possible to modify the release profile for this active ingredient in an advantageous manner and thus to extend, for example, the duration of action of the metering device according to the invention.

In a further particularly preferred embodiment of the metering device according to the invention, the two active compound compositions differ both with regard to at least one of the carrier materials contained in them and with regard to at least one of the active ingredients contained in them.

Dosing devices according to the invention, characterized in that at least two active substance compositions have different carrier materials, are preferred according to the invention.

Dosing device according to one of claims 1 to 3, characterized in that all active ingredient compositions have the same carrier materials.

Particularly preferred embodiments of metering devices according to the invention having two active compound preparations of different composition are disclosed in the following table:

The different active ingredient preparations metering devices according to the invention can be present side by side, that is in direct contact with each other, in the container of the metering device. In a further preferred embodiment, however, the dosing device has at least two, preferably three or four, separate receiving chambers. Particularly preferred are those dosing devices according to the invention which have at least two separate receiving chambers, of which at least one receiving chamber at least partially surrounds at least one further receiving chamber. Dosing devices which have a first receiving chamber in the form of a trough-shaped hollow body, the trough of which is closed by a suitable closing element to form a further receiving chamber, are particularly advantageous. As closure elements are thereby used with particular preference lid or stand-alone container. The trough-shaped receiving chamber is preferably connected to the lid or the independent container by means of an adhesive, latching, plug-in or snap connection.

Particularly preferred embodiments of metering devices according to the invention having two receiving chambers are disclosed in the following table:

Further particularly preferred embodiments of metering devices according to the invention with three receiving chambers are disclosed in the following table:

The metering devices according to the invention are suitable for the metering of washing or cleaning-active substances in washing or cleaning processes. Washing or cleaning methods in which a metering device according to the invention is used for the metering of active ingredients are therefore a further subject of the present application, wherein the use of metering devices according to the invention in automatic cleaning methods is particularly preferred.

Due to the special formulation of the washing or cleaning active ingredients on special coordinated carrier materials, dosing devices according to the invention are particularly suitable for dosing washing or cleaning active ingredients washing or cleaning processes in which the metering device and the active substance compositions contained in it to temperatures between 30 and 150 ° C are heated. Method for metering active ingredients, characterized in that a metering device according to the invention is heated to temperatures between 30 and 15O ⁰ C, are therefore preferred. The metering devices according to the invention are preferably used in the interiors of buildings, vehicles or technical equipment. An inventive method, characterized in that the dosage of the active ingredients takes place indoors of buildings, vehicles or technical equipment is therefore preferred.

With particular preference, the metering devices according to the invention are used in rooms which are subject to change in humidity, that is to say in rooms with strongly fluctuating air humidity. In particular, the interiors of dishwashers, textile washing machines or textile driers are referred to as "change-over-damped spaces". characterized in that the dosage of the active ingredients takes place in interiors of textile washing machines, textile dryers or dishwashers, is therefore preferred.

Claims

claims:

A metering device for metering active ingredients in laundry cleaning processes, comprising a container and a) a first active ingredient composition in said container containing at least one carrier material and at least one active ingredient; and b) a second active ingredient composition in said container which likewise contains at least one carrier material and at least one active substance but differs from the first active ingredient composition in regard to at least one of its ingredients, characterized in that the carrier material is water-insoluble in at least one active ingredient composition.

2. Metering device according to claim 1, characterized in that the container is made of a water-insoluble material, preferably of a textile material or a polymer or a polymer mixture.

3. Dosing device according to one of claims 1 or 2, characterized in that the container has at least two separate receiving chambers, which are each filled with at least one active ingredient composition, wherein these active ingredient compositions differ in at least one of its ingredients.

4. Metering device according to one of claims 1 to 3, characterized in that at least two active ingredient compositions have different carrier materials.

5. Metering device according to one of claims 1 to 3, characterized in that all active ingredient compositions have the same carrier materials.

6. Metering device according to one of claims 1 to 5, characterized in that all carrier materials used are insoluble in water.

7. Dosing device according to one of claims 1 to 6, characterized in that the carrier material is present in at least one of the active ingredient compositions in particle form, said particles preferably having an average diameter of 0.5 to 20 mm, preferably from 1 to 10 mm and in particular of 3 to 6 mm.

8. Metering device according to one of claims 1 to 7, characterized in that it is at least one of the carrier materials to a polymeric material, preferably a substance from the group comprising ethylene / vinyl acetate copolymers, low or high density polyethylene (LDPE, HDPE or mixtures thereof, polypropylene, polyethylene / polypropylene copolymers, polyether / polyamide block copolymers, styrene / butadiene (block) copolymers, styrene / isoprene (block) copolymers, styrene / ethylene / butylene copolymers, acrylonitrile / Butadiene / styrene copolymers, acrylonitrile / butadiene copolymers, polyether esters, polyisobutene, polyisoprene, ethylene / ethyl acrylate copolymers, polyamides, polycarbonate, polyesters, polyacrylonitrile, polymethylmethacrylate, polyurethanes, polyvinyl alcohols.

9. Metering device according to one of claims 1 to 8, characterized in that a polymeric carrier material contains at least 10 wt .-%, preferably at least 30 wt .-%, particularly preferably at least 70 wt .-% ethylene / vinyl acetate copolymer, preferably completely made of ethylene / vinyl acetate copolymer.

10. Metering device according to one of claims 1 to 9, characterized in that ethylene / vinyl acetate copolymer is used as the polymeric support material and this copolymer 5 to 50 wt .-% vinyl acetate, preferably 10 to 40 wt .-% vinyl acetate and in particular 20 to Contains 30 wt .-% vinyl acetate, each based on the total weight of the copolymer.

11. Metering device according to one of claims 1 to 10, characterized in that at least one polymeric carrier material has a melting or softening point between 40 and 125 ^C C, preferably between 60 and 100 ⁰ C, more preferably from 70 to 90 ° C and in particular between 75 and 80 ⁰ C.

12. Metering device according to one of claims 1 to 1 1, characterized in that it is at least one of the carrier materials to an inorganic carrier material, preferably a silicate, phosphate or borate.

13. Dosing device according to one of claims 1 to 12, characterized in that at least one of the active ingredients is selected from the group of fragrances, scent, dyes, glass corrosion inhibitors, silver protectants, bleach catalysts, antimicrobial agents, germicides, fungicides, washing or cleaning active polymers or surfactants.

14. Dosing device according to one of claims 1 to 13, characterized in that the weight fraction of / the active ingredients 1 to 70 wt .-%, preferably 10 to 60 wt .-%, particularly preferably 20 to 50 wt .-%, in particular 30 to 40 wt .-%, each based on the total weight of the active ingredient composition (s).

15. washing or cleaning method in which a metering device according to any one of claims 1 to 14 is used for the dosage of active ingredients.

16. The method according to claim 14, characterized in that the metering device is heated to temperatures between 30 and 15O ⁰ C.

17. The method according to claim 15, characterized in that the dosage of the active ingredients in interiors of buildings, vehicles or technical equipment, preferably in interiors of textile washing machines, textile dryers or dishwashers.