EP1891198B1 - Dosing device - Google Patents

Description

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 off WO 02/09779 A1 (Procter & Gamble) known. 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 tumble driers are also known from the prior art.

That's how it describes U.S. Patent 6,235,705 (Bath & Body Works Inc.) a tumble-scent product consisting of perfume-containing plastic beads in a mesh bag. The scenting of the beads happens during their production at elevated temperature.

EP 0 287 132 describes a product comprising a water-permeable, water-insoluble substrate coated with a soil release polymer and having a pouch containing a water-soluble detergent composition.

EP 0 145 438 describes a water-insoluble substrate containing different agglomerates stuck to the surface of the substrate.

The present application was based on the object of providing metering devices for washing or cleaning active ingredients which are suitable for the simultaneous release of different active substances and which are distinguished from conventional metering devices by an improved release profile of these active substances. In particular, the duration of the drug release should be prolonged and at the same time a uniform release of the active substance should be achieved.

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.

1. a) eine erste in diesem Behälter befindliche Wirkstoffzusammensetzung, die mindestens ein Trägermaterial und mindestens einen Wirkstoff enthält ; sowie
2. b) eine zweite in diesem Behälter befindliche, Wirkstoffzusammensetzung, die ebenfalls mindestens ein Trägermaterial und mindestens einen Wirkstoff enthält, sich jedoch hinsichtlich mindestens einer ihrer Inhaltsstoffe ausgewählt aus Trägermaterialien und/oder Wirkstoffen von der ersten Wirkstoffzusammensetzung unterscheidet,

wobei das Trägermaterial in mindestens einer Wirkstoffzusammensetzung wasserunlöslich ist, es sich bei mindestens einem der Trägermaterialien um ein polymeres Material handelt, welches mindestens 10 Gew.-% EthylenNinylacetat-Copolymer enthält, und mindestens einer der Wirkstoffe ausgewählt ist aus der Gruppe der Duftfänger, Farbstoffe, Glaskorrosionsinhibitoren, Silberschutzmittel, Bleichkatalysatoren, wasch- oder reinigungsaktiven Polymeren oder Tenside.A first subject of the present application is therefore a metering device for metering active ingredients in laundry cleaning processes, comprising a container and

1. a) a first active ingredient composition contained in this container and containing at least one carrier material and at least one active ingredient; such as
2. b) a second active substance composition located in this container, which likewise contains at least one carrier material and at least one active substance, but with respect to at least one of its ingredients selected from carrier materials and / or active ingredients, differs from the first active ingredient composition,

wherein the carrier material is water-insoluble in at least one active ingredient composition, at least one of the carrier materials is a is polymeric material containing at least 10 wt .-% ethylene vinyl acetate copolymer, and at least one of the active ingredients is selected from the group of scent scavengers, dyes, glass corrosion inhibitors, silver protectants, bleach catalysts, washing or cleaning active polymers or surfactants.

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.

According to the invention, at least one of the carrier materials is a polymeric carrier material which comprises at least 10% by weight, preferably at least 30% by weight, particularly preferably at least 70% by weight, of ethylene / vinyl acetate copolymer, preferably entirely of ethylene / vinyl acetate. Copolymer is produced.

Ethylene / vinyl acetate copolymers is the name given to copolyamers of ethylene and vinyl acetate. The preparation of this polymer is basically carried out in a process similar to that used to produce 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: product name % By weight of vinyl acetate (based on the total weight) melting point Elvax ^® 40W 40 47 ° C Elvax ^® 150 33 63 ° C Elvax ^® 265 28 75 ° C Elvax ^® 240 28 74 ° C Elvax ^® 205 W 28 72 ° C Elvax ^® 200 W 28 71 ° C Elvax ^® 360 25 78 ° C Elvax ^® 460 18 88 ° C Elvax ^® 660 12 96 ° C Elvax ^® 760 9 100 ° C

In the context of the present invention, metering devices are particularly preferred in which ethylene / vinyl acetate copolymer is used as the polymeric carrier material and this copolymer contains 5 to 50% by weight of vinyl acetate, preferably 10 to 40% by weight of vinyl acetate and in particular 20 to 30% by weight. % Vinyl acetate, based in each case on the total weight of the copolymer.

As other polymers, in particular water-insoluble polymers, synthetic polymers are preferably used. Dosing devices according to the invention, characterized in that at least one of the support materials is a substance from the group comprising 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. For example, 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, allyl or amino groups, etc. Versatile it is possible to use 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) for from 1,6-hexanediamine, adipic acid and ε-caprolactam in a molar ratio 80:80:20 prepared 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 (in particular 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 ° C (PA 6: 215-220 ° C, PA 66: 255-260 ° 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 w-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) include 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, the u. a. as hydroxy terminated products (as polydiols) for the preparation of polyester polyurethanes [e.g. B. polytetramethylene adipate]. The most technically significant in terms of quantity are AA-BB type polyesters of 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 (elastofasem, short PUE for these elastane or spandex fibers) or as polyether or polyester urethane rubber (EU or AU)

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten.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

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 highly 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 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 ° C.

Corresponding PEEA polymers are commercially available under the name Pebax ^® . While, in principle, the abovementioned PEEA polymers are suitable as constituents of the active ingredient compositions metered in accordance with the invention, those active compound compositions which are capable of absorbing at least 2.3 times, preferably 5 times their own weight, fragrances are particularly preferred. Suitable PEEA polymers are, for example, Pebax ^® 2533, Pebax ^® 3533 or Pebax ^® 4033rd

1. a) 70 bis 98 Gew.-% mindestens eines Wirkstoffes, vorzugsweise eines Duftstoffs und
2. b) 2 bis 30 Gew.-% eines Polyether-Ester-Amid Polymers (PEEA-Polymer) der allgemeinen Formel HO[C(O)-PA-C(O)-O-PE-O]_nH, in der PA für eine Polyamidgruppe steht, PE für eine Polyethergruppe steht und n für eine ganze Zahl steht.

In a further preferred embodiment, at least one of the active ingredient compositions is an active ingredient-containing gel. Especially preferred are gels comprising

1. a) 70 to 98 wt .-% of at least one active ingredient, preferably a perfume and
2. b) 2 to 30 wt .-% of 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 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 has an advantageous effect on the release profile and the release kinetics of the washing or cleaning active ingredients contained in the active substance 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 ° C, more preferably from 70 to 90 ° C and in particular between 75 and 80 ° 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. This water-insoluble. Support 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, these particles preferably have an average diameter of 0.5 to 20 mm, preferably 1 to 10 mm and especially of 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 to 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 % by weight are typically selected. By contrast, in the case of the particularly preferred, but less readily water-soluble, pigment dyes due to their brilliance, the suitable concentration of the colorant in detergents or cleaners is typically about 10 ^-3 to 10 ^-4 % by weight.

Colorants are preferred which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable are, for example, anionic colorants, e.g. anionic nitrosofarads.

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. Dosing devices according to the invention are characterized in that at least one of these active substances is selected from the group of scent scavengers, dyes, glass corrosion inhibitors, silver protectants, bleach catalysts, 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, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

With particular preference, the glass corrosion inhibitor used is 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 zinc citrate. 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, see above in 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 from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, 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 bacteriostats and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric 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" in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers come from the groups of 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 dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified 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 Aminogr uppe with a positive charge is.

bei der R¹ und R⁴ unabhängig voneinander für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen steht; R² und R³ unabhängig voneinander für eine Alkyl-, Hydroxyalkyl-, oder Aminoalkylgruppe stehen, in denen der Alkylrest linear oder verzweigt ist und zwischen 1 und 6 Kohlenstoffatomen aufweist, wobei es sich vorzugsweise um eine Methylgruppe handelt; x und y unabhängig voneinander für ganze Zahlen zwischen 1 und 3 stehen. X^- repräsentiert ein Gegenion, vorzugsweise ein Gegenion aus der Gruppe Chlorid, Bromid, Iodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen.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, xylenesulfonate, 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 = CH- (CH ₂ ) -N ⁺ (CH ₃ ) ₂ - (CH ₂ ) -CH = CH ₂ X ^-

in the case of X ^- = chloride, they are also referred to as DADMAC (diallyldimethylammonium chloride).

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

R ¹ HC = CR ² -C (O) -NH- (CH ₂ ) _x -N ⁺ R ³ R ⁴ R ⁵ X ^- ,

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another are 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 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 X ^-

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 employable amphoteric polymers are 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 / alkylaminoethylmethacrylate / alkylmethacrylate 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 / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid Copolymers and their alkali metal and ammonium salts.

Particular preference is given to amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali 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 ) _n - with n = 0 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 ) -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 ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 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 ) -.

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.

• i) ungesättigten Carbonsäuren der Formel R¹(R²)C=C(R³)COOH in der R¹ bis R³ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• ii) Sulfonsäuregruppen-haltigen Monomeren der Formel R⁵(R⁶)C=C(R⁷)-X-SO₃H in der R⁵ bis R⁷ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k-mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃).
• ii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren besonders bevorzugt.

In summary, copolymers are made 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, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above, or -COOH or -COOR ⁴ , where 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 with 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 in which R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group which is selected from - (CH ₂ ) _n - where n = 0 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 ionogenic or nonionic monomers are particularly preferred.

• i) einer oder mehreren ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln:
  
          H₂C=CH-X-SO₃H
  
          H₂C=C(CH₃)-X-SO₃H
  
          HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H ,
  
  in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃).
• iii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren.

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 (CH ₃ ) -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 ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 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 nonionic 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 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 (CH ₃ ) 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 - with n = 0 to 4, for -O- (C ₆ H ₄₎ -for -NH-C (CH ₃ ) 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 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 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] _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 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 (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] _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 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 (CH ₃ ) 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 (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. in that 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 voflneutralisierten sulfonsäuregruppenhaltigen copolymers is inventively preferred.

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. Active ingredient preparation 1 Active ingredient preparation 2 support material active substance support material active substance Organic polymer Perfume 1 Organic carrier odor trap PEEA polymer Perfume 1 Organic carrier odor trap Organic polymer Perfume 1 Organic polymer Glass corrosion inhibitor PEEA polymer Perfume 1 Organic polymer Glass corrosion inhibitor Organic polymer Perfume 1 Inorganic carrier Glass corrosion inhibitor Organic polymer Perfume 1 Water-soluble glass Glass corrosion inhibitor Organic polymer Perfume 1 Organic polymer oxidation catalysts PEEA polymer Perfume 1 Organic polymer oxidation catalysts Organic polymer Perfume 1 Inorganic carrier oxidation catalysts Organic polymer Perfume 1 Water-soluble glass oxidation catalysts Organic polymer Perfume 1 Organic polymer surfactant PEEA polymer Perfume 1 Organic polymer surfactant Organic polymer Perfume 1 Inorganic carrier surfactant Organic polymer Perfume 1 Water-soluble glass surfactant Organic polymer Perfume 1 Organic polymer sulfopolymer PEEA polymer Perfume 1 Organic polymer sulfopolymer Organic polymer Perfume 1 Inorganic carrier sulfopolymer Organic polymer Perfume 1 Water-soluble glass sulfopolymer

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. PEEA polymer Perfume 1 Organic polymer oxidation catalysts Organic polymer Perfume 1 Inorganic carrier oxidation catalysts Organic polymer Perfume 1 Water-soluble glass oxidation catalysts Organic polymer Perfume 1 Organic polymer surfactant PEEA polymer Perfume 1 Organic polymer surfactant Organic polymer Perfume 1 Inorganic carrier surfactant Organic polymer Perfume 1 Water-soluble glass surfactant Organic polymer Perfume 1 Organic polymer sulfopolymer PEEA polymer Perfume 1 Organic polymer sulfopolymer Organic polymer Perfume 1 Inorganic carrier sulfopolymer Organic polymer Perfume 1 Water-soluble glass sulfopolymer

Further particularly preferred embodiments of metering devices according to the invention with three receiving chambers are disclosed in the following table: Receiving chamber 1 Receiving chamber 2 Receiving chamber 3 Carrier material al active substance support material active substance support material active substance Organic polymer Perfume 1 Organic polymer Perfume 2 Organic or inorganic carrier fragrance catcher PEEA polymer Perfume 1 PEEA polymer Perfume 2 Organic carrier fragrance catcher Organic polymer Perfume 1 Organic polymer Glass corrosion inhibitor Organic polymer surfactant PEEA polymer Perfume 1 Organic polymer Glass corrosion inhibitor Organic polymer surfactant Organic polymer Perfume 1 Inorganic carrier Glass corrosion inhibitor Organic polymer surfactant PEEA polymer Perfume 1 Inorganic carrier Glass corrosion inhibitor Organic polymer surfactant Organic polymer Perfume 1 Water-soluble glass Glass corrosion inhibitor Organic polymer surfactant PEEA polymer Perfume 1 Water-soluble glass Glass corrosion inhibitor Organic polymer surfactant Organic polymer Perfume 1 Organic polymer Glass corrosion inhibitor Organic polymer sulfopolymer PEEA polymer Perfume 1 Organic polymer Glass corrosion inhibitor Organic polymer sulfopolymer Organic polymer Perfume 1 Inorganic carrier Glass corrosion inhibitor Organic polymer sulfopolymer PEEA polymer Perfume 1 Inorganic carrier Glass corrosion inhibitor Organic polymer sulfopolymer Organic polymer Perfume 1 Water-soluble glass Glass corrosion inhibitor Organic polymer sulfopolymer PEEA polymer Perfume 1 Water-soluble glass Glass corrosion inhibitor Organic polymer sulfopolymer Organic polymer Perfume 1 Organic polymer oxidation catalysts Organic polymer surfactant PEEA polymer Perfume 1 Organic polymer oxidation catalysts Organic polymer surfactant Organic polymer Perfume 1 Inorganic carrier oxidation catalysts Organic polymer surfactant PEEA polymer Perfume 1 Inorganic carrier oxidation catalysts Organic polymer surfactant organic perfume water-soluble oxidation catalysts organic surfactant polymer 1 Glass polymer PEEA polymer Perfume 1 Water-soluble glass oxidation catalysts Organic polymer surfactant Organic polymer Perfume 1 Organic polymer oxidation catalysts Organic polymer sulfopolymer PEEA polymer Perfume 1 Organic polymer oxidation catalysts Organic polymer sulfopolymer Organic polymer Perfume 1 Inorganic carrier oxidation catalysts Organic polymer sulfopolymer PEEA polymer Perfume 1 Inorganic carrier oxidation catalysts Organic polymer sulfopolymer Organic polymer Perfume 1 Water-soluble glass oxidation catalysts Organic polymer sulfopolymer PEEA polymer Perfume 1 Water-soluble glass oxidation catalysts Organic polymer sulfopolymer Organic polymer Perfume 1 Organic polymer surfactant Organic polymer sulfopolymer PEEA polymer Perfume 1 Organic polymer surfactant Organic polymer sulfopolymer Organic polymer Perfume 1 Inorganic carrier surfactant Organic polymer sulfopolymer PEEA polymer Perfume 1 Inorganic carrier surfactant Organic polymer sulfopolymer Organic polymer Perfume 1 Water-soluble glass surfactant Organic polymer sulfopolymer PEEA polymer Perfume 1 Water-soluble glass surfactant Organic polymer sulfopolymer Organic polymer Perfume 1 Organic polymer sulfopolymer Organic polymer disinfectant PEEA polymer Perfume 1 Organic polymer sulfopolymer Organic polymer disinfectant Organic polymer Perfume 1 Inorganic carrier sulfopolymer Inorganic carrier disinfectant Organic polymer Perfume 1 Water-soluble glass sulfopolymer Water-soluble glass disinfectant

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 150 ° 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 "alternating wet rooms". An inventive method, characterized in that the dosage of the active ingredients in interior spaces of textile washing machines, textile driers or dishwashers, is therefore preferred.

Claims (16)

1. A dispensing device for dispensing active ingredients in washing or cleaning methods comprising a container and

   a) a first active ingredient composition located in said container, which composition contains at least one carrier material and at least one active ingredient; together with

   b) a second active ingredient composition located in said container, which composition likewise contains at least one carrier material and at least one active ingredient but differs from the first active ingredient composition with regard to at least one of the ingredients thereof selected from carrier materials and/or active ingredients,

   wherein the carrier material in at least one active ingredient composition is water-insoluble, at least one of the carrier materials is a polymeric material which contains at least 10 wt.% ethylene/vinyl acetate copolymer, and at least one of the active ingredients is selected from the group of odour scavengers, glass corrosion inhibitors, silver protection agents, bleach catalysts, polymers with a washing or cleaning action or surfactants.
2. A dispensing device according to claim 1, characterised in that the container is manufactured from a water-insoluble material, preferably from a textile material or a polymer or a polymer blend.
3. A dispensing device according to either one of claims 1 or 2, characterised in that the container comprises at least two compartments which are separate from one another and are in each case filled with at least one active ingredient composition, wherein said active ingredient compositions differ at least with regard to one of the ingredients thereof.
4. A dispensing device according to any one of claims 1 to 3, characterised in that at least two active ingredient compositions comprise different carrier materials.
5. A dispensing device according to any one of claims 1 to 3, characterised in that all the active ingredient compositions comprise the same carrier materials.
6. A dispensing device according to any one of claims 1 to 5, characterised in that all the carrier materials used are water-insoluble.
7. A dispensing device according to any one of claims 1 to 6, characterised in that, in at least one of the active ingredient compositions, the carrier material is in particulate form, wherein said particles preferably have an average diameter of 0.5 to 20 mm, more preferably of 1 to 10 mm and in particular of 3 to 6 mm.
8. A dispensing device according to any one of claims 1 to 7, characterised in that at least one of the carrier materials is a polymeric material from the group comprising 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, polymethyl methacrylate, polyurethanes, polyvinyl alcohols.
9. A dispensing device according to any one of claims 1 to 8, characterised in that the polymeric carrier material contains at least 30 wt.%, particularly preferably at least 70 wt.% ethylene/vinyl acetate copolymer and is preferably completely produced from ethylene/vinyl acetate copolymer.
10. A dispensing device according to any one of claims 1 to 9, characterised in that the ethylene/vinyl acetate copolymer contains 5 to 50 wt.% vinyl acetate, preferably 10 to 40 wt.% vinyl acetate and in particular 20 to 30 wt.% vinyl acetate, in each case relative to the total weight of the copolymer.
11. A dispensing device according to any one of claims 1 to 10, characterised in that at least one polymeric carrier material has a melting or softening point between 40 and 125°C, preferably between 60 and 100°C, particularly preferably of 70 to 90°C and in particular between 75 and 80°C.
12. A dispensing device according to any one of claims 1 to 11, characterised in that at least one of the carrier materials is an inorganic carrier material, preferably a silicate, phosphate or borate.
13. A dispensing device according to any one of claims 1 to 12, characterised in that the proportion by weight of the active ingredient(s) amounts to 1 to 70 wt.%, preferably 10 to 60 wt.%, particularly preferably 20 to 50 wt.%, in particular 30 to 40 wt.%, in each case relative to the total weight of the active ingredient composition(s).
14. A washing or cleaning method in which a dispensing device according to any one of claims 1 to 13 is used for dispensing active ingredients.
15. A method according to claim 14, characterised in that the dispensing device is heated to temperatures of between 30 and 150°C.
16. A method according to claim 14, characterised in that the active ingredients are dispensed into the interiors of buildings, vehicles or industrial appliances, preferably into the interiors of textile washing machines, textile dryers or dishwashing machines.