DE10237066A1 - System for deodorizing and fragrancing spaces, especially washing machines, dryers or dishwashers, comprises a container and particles comprising a fragrance and a polymer carrier with a defined melting or softening point - Google Patents

Abstract

Fragrance-emitting system for deodorizing and fragrancing spaces comprises a container and particles comprising a fragrance and a polymer carrier with a melting or softening point of 30-150degreesC. An Independent claim is also included for deodorizing and fragrancing spaces by introducing the system into the space and heating it to 30-150degreesC.

Description

The present invention resides the field of systems for deodorization and scenting of interiors. In particular This invention relates to fragrance delivery systems used for scenting of the interiors of technical devices such as textile washing machines, dryers or dishwashers are suitable.

In rooms without sufficient fresh air supply occur frequently unpleasant smells on. This also applies, for example, to the interiors of dishwashers if the dishes to be cleaned there are very dirty is and / or about a longer one Period before the rinsing process remains in the dishwasher. About such smells in the case of dishwashers, so-called dishwasher endos are to be eliminated offered. These deodorants can can be assembled in very different ways. For the consumer is it desirable an article on the deodorization of dishwashers or other interiors receive an intense product fragrance when it is provided which not only ensures product identification, but at the same time gives the impression of high potency and which one then in the course of its lifespan the most reliable release possible Guaranteed amounts of fragrance. Furthermore, these deodorants should also work independently of external factors such as (air) humidity, temperature or alkalinity. A range of different deodorants for dishwashers are described in the prior art.

Articles containing fragrance made from ethylene / vinyl acetate copolymer are described in international application WO 91/00744 (Delphic Manor Pty. Ltd.). It is injection molded Plastic plates that are hung in the dishwasher can. Since the fragrance is mixed with the plastic before injection molding, will this during exposed to high thermal processing. A leads to such thermal stress partial loss of fragrance due to evaporation or thermal decomposition. Such plastic plates also show no about their service life constant release profile for the contained Fragrances.

Subject of the international application WO 85/00981 (Slagmulder et al) is a method for impregnation of plastic particles with fragrances at low temperatures. The particles can including in dishwashers can be used for deodorization. These particles are said to be between ten and twenty washes be durable.

Deodorants for use too in tumble dryers can be found in the state of the art.

For example, U.S. Patent 6,235,705 describes (Bath & Body Works Inc.) a product for scenting in a tumble dryer, which is made of fragrance Plastic beads in a mesh bag. The fragrance of the pearls happens during their manufacture at increased Temperature.

Object of the present invention it was now to provide a means for deodorising rooms, in particular dishwasher interiors, which about has an optimized fragrance release profile. Such an optimized Fragrance release profile is characterized by an increased fragrance release Start of use (product identification, proof of potency) and a subsequent reduced but constant fragrance. The middle should also be effective for a long time and its effectiveness through external Factors like temperature, humidity or alkalinity are not affected become.

It has been found that the aforementioned Tasks are solved by fragrance delivery systems, which certain polymeric carrier materials exhibit. A first subject of the present application is therefore a fragrance delivery system comprising a container and particles for deodorization and scenting rooms, which at least one polymeric carrier material and at least contain a fragrance, characterized in that the polymer support material has a melting or softening point between 30 and 150 ° C.

The improved fragrance release of fragrance delivery systems according to the invention is based on a change the relationship from surface to the internal volume of the particles contained in the fragrance delivery system. These particles are in a brand new, unused system as singular Particles with large particle surface in front. However, the composition of the particles is chosen so that at a thermal stress of these particles the polymeric carrier material of these particles superficial softens or melts and individual particles together with reduction of the total surface stick together. The height the melting or softening point of the polymeric carrier materials is accordingly by the area of use of agents according to the invention certainly. So kick during machine dishwashing, especially in the rinse cycle, for example highs between 65 and 75 ° C on. Serve agents of the invention Scenting of rooms in buildings or vehicles, for example as an attachment for heaters, they are there maximum temperatures reached usually in the range of 70 to 90 ° C. In any case, the Melting or softening points of the particles above those at their Transport and storage usual Ambient temperature and below the decomposition temperatures of the contained fragrances lie.

Another preferred subject of the present application is therefore a fragrance delivery system, characterized in that the polymeric carrier material has a melting or softening point between 40 and 125 ° C, preferably between 60 and 100 ° C, particularly preferably from 70 to 90 ° C and in particular between 75 and 80 ° C.

As a polymeric carrier material for those containing fragrances Particles are generally suitable for all polymers or polymer mixtures, which meet the above criteria regarding melting or softening temperature. in the Preferred fragrance delivery systems are within the scope of the present application characterized in that the polymeric carrier material at least one substance from the group comprising ethylene / vinyl acetate copolymers, polyethylene low or high density (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, polyester, polyacrylonitrile, polymethyl methacrylate, polyurethanes, Contains polyvinyl alcohols.

Polyethylene (PE) is a collective name for polymers belonging to the polyolefins with groupings of the type CH ₂ -CH ₂ as a characteristic basic unit of the polymer chain. Polyethylenes are generally produced by polymerizing ethylene using two fundamentally different methods, the high pressure u. the low pressure process. The resulting products are accordingly often referred to as high-pressure polyethylenes or low-pressure polyethylenes; they differ mainly in their degree of branching and, related to this, in their degree of crystallinity and density. Both processes can be carried out as solution polymerization, emulsion polymerization or gas phase polymerization.

The high-pressure process produces branched polyethylenes with low density (approx. 0.915-0.935 g / cm ³ ) and degrees of crystallinity of approx. 40-50%, which are referred to as LDPE types (low density polyethylene). Products with higher molecular weight and. resulting improved strength u. Stretchability has the short name HMW-LDPE (HMW = high molecular weight). By copolymerizing ethylene with longer-chain olefins, especially with butene and the like. Octene, the pronounced degree of branching of the polyethylenes produced in the high-pressure process can be reduced; the copolymers have the code LLD-PE (linear low density polyethylene).

The macromolecules of polyethylenes from low pressure processes are largely linear and unbranched. These polyethylenes, abbreviations HDPE (from E high density polyethylene) have degrees of crystallinity of 60-80% u. a density of approximately 0.94-0.965 g / cm3. They are called high or ultra high molecular weight products (about 200,000-5 000,000 g / mol or 3,000,000-6 000 000 g / mol) under the short name HD-HMW-PE or UHMW-HD-PE offered. Also medium density products (MDPE) from mixtures of Low and high density polyethylenes are commercially available. Linear P. with densities <0.918 g / cm3 (VLD-PE, from E very low density polyethylene) only gain slowly market importance.

Polyethylenes are very low Water vapor permeability, the diffusion of gases as well as aromas and. ethereal substances through polyethylene is relatively high. The mechanical properties are heavily dependent of molecular size and structure the polyethylene. In general, the degree of crystallinity increases. Density of polyethylene with decreasing degree of branching and with shortening of the side chains. The shear modulus, hardness, yield strength and so on increase with density. Melting range; it decrease from shock resistance, transparency, swellability u. Solubility. At the same density, the tensile strength decreases with increasing molar mass. Elongation, shock resistance, impact resistance u. Creep strength to. Depending on the method of polymerization, you can use products with paraffin wax-like Properties (MR around 2000) and Products with the highest toughness (MR over 1 million) receive.

Processing of polyethylene types can after all for Thermoplastics usual Methods are done.

Polypropylene (PP) is the name for thermoplastic polymers of propylene with the general formula: - (CH ₂ -CH [CH3]) _n -

Basis for the production of polypropylene was the development of the process for stereospecific polymerization of propylene in the gas phase or in suspension by Natta. This is using Ziegler-Natta catalysts, but increasingly also initiated by metallocene catalysts and either leads to highly crystalline isotactic or less crystalline syndiotactic or to amorphous atactic polypropylenes.

Polypropylene is characterized by high hardness, resilience, rigidity and heat resistance. Short-term heating of objects made of polypropylene is even possible up to 140 ° C. At tempera At temperatures below 0 ° C, the polypropylenes become brittle, but this can be shifted to much lower temperature ranges by copolymerizing propylene with ethylene (EPM, EPDM). Gen. the impact strength of P. can be improved by modification with elastomers. As with all polyolefins, the chemical resistance is good. The mechanical properties of P. can be improved by reinforcing with talc, chalk, wood flour or glass fibers. P. are oxidation and u to an even greater extent than PE. sensitive to light, which is why the addition of stabilizers (antioxidants, light stabilizers, UV absorbers) is necessary.

Polyether is one in the field spanning macromolecular chemistry Term for Polymers, whose organic repeating units by ether functionalities (C-O-C) be held together. According to this definition one belongs Numerous structurally very different polymers to the polyethers, z. B. the polyalkylene glycols (polyethylene glycols, polypropylene glycols u. Polyepichlorohydrins) as polymers of 1,2-epoxides, epoxy resins, Polytetrahydrofurans (polytetramethylene glycols), polyoxetanes, polyphenylene ethers (see polyaryl ether) or polyether ether ketone (see polyether ketone). Polymers with pendant ether groups are not counted among the polyethers, like u. a. the cellulose ethers, starch ethers u. Vinyl ether polymers.

The group of polyethers continues to count also functionalized polyethers, i.e. H. Compounds with a polyether backbone that other functional ones attached to the side of their main chains Groups wear such. B. carboxy, epoxy, allyl or amino groups etc. Block copolymers of polyethers can be used in many ways and polyamides (so-called polyether amides or polyether block amides, PEBA).

Polymers are called polyamides (PA) referred to, whose basic building blocks held together by amide bonds (-NH-CO-) become. Naturally Occurring polyamides are peptides, polypeptides and the like. Proteins (ex .: Protein, Wool, silk). The synthetic polyamides are, with a few exceptions thermoplastic, chain-shaped Polymers, some of which are large technical significance as synthetic fibers u. Have obtained materials. After the chemical structure, the so-called homo-polyamides divide into two groups, the aminocarboxylic acid types (AS) and the diamine dicarboxylic acid types (AA-SS; A denotes amino groups and S carboxy groups). The former are made from only a single monomer by e.g. B. polycondensation a ☐-aminocarboxylic acid 1 (polyamino acids) or by ring opening Polymerization of cyclic amides (lactams) 2 prepared.

In addition to the homopolyamides, too some co-polyamides became important. This is usually a qualitative one u. quantitative indication of the composition z. B. PA 66/6 (80:20) for out 1,6-hexanediamine, adipic acid u. Molecular ratio of e-caprolactam 80:80:20 produced polyamides.

Because of their special properties, P. which are exclusively aromatic. Contain residues (e.g. those from p-phenylenediamine and terephthalic acid), under the generic name. Aramids or polyaramides combined (example: Nomex ^® ).

The most common types of polyamide (especially PA 6 and PA 66) consist of unbranched chains with medium Molar masses from 15,000 to 50,000 g / mol. They are in a solid state semi-crystalline and have degrees of crystallization of 30–60%. A Polyamides from building blocks with side chains or co-polyamides are an exception from very different components that are largely amorphous. In contrast to the generally milky-opaque, partially crystalline Polyamides are almost crystal clear. The softening temperature of the common Homo-polyamides are between 200 u. 260 ° C (PA 6: 215-220 ° C, PA 66: 255-260 ° C).

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

Branched and cross-linked polyester in the polycondensation of trihydric or polyhydric alcohols with polyfunctional carboxylic acids receive. In general, polycarbonates also become polyesters (Carbonated polyester) expected.

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

Purely aliphatic AA-BB type polyesters (II) are polycondensates made from aliphatic diols and dicarboxylic acids, which are used, inter alia, as products with terminal hydroxyl groups (as polydiols) for the production of polyester polyurethanes [e.g. B. Polytetramethylene adipate. In terms of quantity, AA-BB type polyesters made 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) e (PCDT) are the most important representatives. These types of P. can vary widely in their properties by using other aromatic dicarboxylic acids (e.g. isophthalic acid) or by using diol mixtures in the polycondensation and different uses areas to be adapted.

They are purely aromatic polyesters Polyarylates to which u. a. which include poly (4-hydroxybenzoic acid). In addition to the previously mentioned saturated Unsaturated polyesters can also be made from unsaturated polyesters dicarboxylic acids produce that as polyester resins, especially as unsaturated polyester resins (UP resins), have gained technical importance.

Polyesters are usually thermoplastics. Own products based on aromatic dicarboxylic acids pronounced material character. The purely aromatic polyarylates are characterized by high thermal stability.

Polymers are called polyurethanes (PUR) referred to in their macromolecules the repeating units by urethane groups -NH-CO-O- connected are.

Polyurethanes are generally by polyaddition from di- or higher-quality alcohols and isocyanates receive.

Depending on your choice and stoichiometric relationship The raw materials are made of very different polyurethanes mechanical properties as components of adhesives and varnishes (P. resins), as ionomers, as thermoplastic material for bearing parts, Rollers, tires, rollers are used and more or less hard elastomers in fiber form (elastofibers, short PUE for this Elastane or spandex fibers) or as polyether or polyester urethane rubber (EU or AU)

Polyurethane foams are created during polyaddition, if water u./od. carboxylic acids are present, because they react with the isocyanates with elimination of foaming and foaming carbon dioxide. With polyalkylene glycol ethers as diols u. Water as a reaction component leads to flexible polyurethane foams with Polyols and the like CFC propellants (esp. R 11) give rigid polyurethane foams and structural or integral foams. Additional auxiliary substances are here z. B. catalysts, emulsifiers, foam stabilizers (esp. Polysiloxane-polyether copolymers), Pigments, aging u. Flame retardants. To manufacture from also complicated shaped objects The so-called polyurethane foam was used in the 1970s RIM technology developed (reaction injection molding). The RIM process based on rapid dosing u. Mixing the components, injection of the reactive Mixture in the form u. rapid curing; the cycle time is only a few Minutes. Using RIM technology u. a. Car body parts, shoe soles, window profiles and television housings produced.

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

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

which in small proportions (approx. 2%) also structural units of the type

contain.

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

Polyvinyl alcohols are dependent on Degree of hydrolysis soluble in water and a few strongly polar organic solvents (Formamide, dimethylformamide, dimethyl sulfoxide); from (chlorinated) They do not attack hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be achieved by post-treatment with aldehydes (acetalization) Complexing with Ni or Cu salts or by treatment with dichromates, boric acid or reduce borax. The coatings are made of polyvinyl alcohol largely impenetrable for Gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but let water vapor pass through.

Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the containers, it being preferred according to the invention that the water-soluble or water-dispersible container comprises a polyvinyl alcohol, the molecular weight of which is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 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 in part of ethylene / vinyl acetate copolymer. Another before The subject of the present application is therefore a fragrance delivery system, characterized in that the polymeric carrier material contains at least 10% by weight, preferably at least 30% by weight, particularly preferably at least 70% by weight, of ethylene / vinyl acetate copolymer, preferably completely Ethylene / vinyl acetate copolymer is made.

Is ethylene / vinyl acetate copolymers the name for Copolymers of ethylene and vinyl acetate. The production of this polymer basically takes place in one of the manufacture of low density polyethylenes (LDPE; low density polyethylene) comparable process. 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 resulting products reduced. The vinyl acetate does that Copolymer is also more polar and thus improves its adhesion polar substrates.

The ethylene / vinyl acetate copolymers described above are widely available commercially, for example under the tradename Elvax ^® (Dupont). Polyvinyl alcohols which are particularly suitable in the context of the present invention are, for example, Elvax ^® 265, Elvax ^® 240, Elvax ^® 205 W, Elvax ^® 200 W and Elvax ^® 360.

Some particularly suitable copolymers and their physical properties can be found in the table below:

In the context of the present invention, especially in the area of scenting the interior of automatic dishwashers fragrance delivery systems are particularly preferred, in which as a polymer support material Ethylene / vinyl acetate copolymer is used and this copolymer 5 to 50% by weight of vinyl acetate, preferably 10 to 40% by weight of vinyl acetate and in particular 20 to 30 wt .-% vinyl acetate, each based on the total weight of the copolymer.

Fragrance delivery systems according to the invention contain the polymeric carrier materials in the form of particles. The spatial shape of these particles is only limited by the technical possibilities in their manufacture. All sensibly manageable configurations are thus considered as the spatial shape, for example, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment comprises tablet-shaped particles up to compact cylindrical pieces with a ratio of height to diameter above 1. Further possible spatial shapes are spheres, hemispheres or "elongated spheres" in the form of elipsoid capsules as well as regular polyhedra, for example tetrahedra, hexahedron, octahedron, Dodecahedra, icosahedra, conceivable star-shaped configurations with three, four, five, six or more points or completely irregular bodies, which can be motif-shaped, for example. Depending on the field of use of the agents according to the invention, animal figures such as dogs are suitable as motifs , Horses or birds, floral motifs or the depiction of fruits, but the motif can also relate to inanimate objects such as vehicles, tools, household items or objects get clothes. The surface of the solid particles can have bumps depending on the type of manufacturing process chosen and / or a coating selected. Because of the numerous design options for the particles, the agents according to the invention are not only distinguished by advantages in their manufacture. Due to the wide variety of configurations, the fragrance-containing particles are also visually clearly perceptible to the consumer and, through the targeted spatial configuration of these particles, enable a visualization of the fragrances contained in the agents according to the invention, or other active substances optionally contained in these agents, which is particularly advantageous for product acceptance. The optically perceptible multiphase nature of these agents can, for example, illustrate the different modes of action of individual active substances (e.g. cleaning and additional functions such as glass protection, silver protection, etc.).

As particles are within the present application summarizes particles, which one at room temperature fixed, that is dimensionally stable, non-flowable consistency exhibit. Preferred particles have an average diameter from 0.5 to 20 mm, preferably from 1 to 10 mm and in particular from 3 to 6 mm.

The assembly of the polymer support materials to the particles described above can all the skilled person known processes for processing these substances. Extrusion is preferred in the context of the present invention injection molding and spraying preferred to polymer granules.

Scent delivery systems according to the invention include next to a container furthermore fragrance-containing particles based on polymeric carrier materials, where the weight fraction of the fragrance (s), based on the total weight of the particles, preferably 1 to 70% by weight, preferably 10 to 60% by weight, particularly preferably 20 to 50% by weight, in particular 30 up to 40% by weight.

As perfume oils or fragrances can in Individual fragrance compounds within the scope of the present invention, e.g. synthetic products of the ester, ether, aldehyde type, Ketones, alcohols and hydrocarbons can be used. fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Count among the ethers e.g. benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 Carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly the terpenes like limes and pinene. However, mixtures are preferred different fragrances, which together make an appealing Generate fragrance. Such perfume oils can also natural Contain fragrance mixtures as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Likewise suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as Orange blossom oil, neroliol, Orange peel oil and Sandalwood oil.

The general description of the usable perfumes (see above) generally represents the different classes of substances of fragrances. In order to be perceptible, a fragrance must be volatile, being in addition to the nature of the functional groups and the structure the molecular weight also plays an important role in the chemical compound plays. Most fragrance substances have molecular weights of up to around 200 Dalton while Molar masses of 300 daltons and above rather an exception. Because of the different volatility changed by fragrances the smell of one composed of several fragrances perfumes or fragrance during of evaporation, whereby the odor impressions in "top note", "Heart or middle note" and "base note" (end note or dry out) divided. Because the smell perception too a big one The top note is partly based on the intensity of the smell of a perfume or fragrance not only from volatile compounds, while the Base note for the most part from less volatile, i.e. non-stick fragrances. When composing perfumes can be easier volatile Fragrances are bound to certain fixatives, for example, which prevents it from evaporating too quickly. The following Classification of the fragrances into "more volatile" or "adhesive" fragrances is over the smell impression and above, whether the corresponding fragrance is perceived as a top or heart note nothing is said.

By means of a suitable selection of the fragrances or perfume oils mentioned, it is possible in this way for agents according to the invention to influence both the product odor directly when the brand-new agent is opened and the scent of use, for example when used in a dishwasher. These fragrance impressions can of course be the same, but can also differ. For the latter odor impression, the use of more adhesive fragrances is advantageous, while more volatile fragrances can also be used for product scenting. Adhesive fragrances that can be used in the context of the present extension are, for example, the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, Bay oil, bergamot oil, Champacablütenöl, silver fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, Fichtennandelöl, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, Helichrysumöl, Ho oil, ginger oil, iris oil, cajeput oil, calamus oil, camomile oil, camphor oil, Kanagaöl, cardamom oil, Cassia oil, pine needle oil, Kopaïvabalsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, lemon balm oil, musk grain oil, myrrh oil, clove oil, neroli oil, niaouli oil, orangel oil, orolibum oil, peri oil oil Peppermint oil, allspice oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, spik oil, star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, winter green oil, ylang ylang oil, hyssop oil, cinnamon oil, cinnamon oil, cinnamon oil, cinnamon oil, cinnamon oil, cinnamon oil Lemon oil, lemon oil and cypress oil. However, the higher-boiling or solid odorants of natural or synthetic origin can also be used in the context of the present invention as adherent odorants or odorant mixtures, that is to say fragrances. These compounds include the compounds mentioned below and mixtures of these: ambrettolide, α-amyl cinnamaldehyde, anethole, anisaldehyde, anis alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzyl benzate, boryl formate benzyl, benzyl benzyl benzate, boryl formate benzyl benzate, benzyl formate benzyl benzate, benzyl formate benzyl benzate, benzyl formate benzyl benzate, benzyl formate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzyl benzate , Bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchylacetate, geranyl acetate, geranyl formate, heliotropine, heptinocarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroquinone dimethyl ether, hydroquinone dimethyl ether, hydroquinone dimethyl ether, hydroquinone dimethyl ether , Isoeugenol methyl ether, isosafrol, jasmon, camphor, Karvakrol, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl-n-amyl ketone, methyl anthranilic acid ester, p-methylacetophenone, methyl chavikol, p-methyl quinaphtholine, nyl-β-methyl -nonylacetaldehyde, methyl-n-nonylketone, muscon, β- Naphthol ethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonyl aldehyde, nony alcohol, n-octyl aldehyde, p-oxy-acetophenone, pentadecanolide, β-phenyl ethyl alcohol, phenylacetaldehyde dimethyl acetal, phenyl acetic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid, salicylic acid acid, Santalol, Skatol, Terpineol, Thymen, Thymol, γ-undelactone, Vanilin, Veratrumaldehyde, Cinnamaldehyde, Cimate Alcohol, Cinnamic Acid, Ethyl Cinnamate, Benzyl Cinnamate. The more volatile fragrances include, in particular, the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyisothiocyanates (alkyl mustards), butanedione, limonene, linalool, linaylacetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinylacetate, citral, citronellal.

The plastic particles are preferred at a temperature of 15 to 30 ° C, preferably from 20 to 25 ° C, with the chosen Load fragrance. For this, the particles with the appropriate Amount of fragrance added and mixed. In any case but the temperature below the melting or decomposition temperature of the plastic and also below the flash point of the perfume oil. The fragrance is primarily through adhesion, diffusion and / or capillary forces of the polymeric carrier material or taken up by further perfume carrier materials contained in the particle, which may swell slightly in the course of this process.

As mentioned above, agents according to the invention except the components necessary for scenting and deodorization Contain active substances. Of the means which exclusively the Fragrance, different product groups can be distinguished, which additional to the above-mentioned ingredients according to the invention further preferred Contain substances.

A first of these can be used optionally preferred substances are the dyes. Generally suitable for this all Dyes, which the person skilled in the art is suitable for coloring Plastics or as soluble in perfume oils are known. It is preferred to use the dye according to the one used Select fragrance; for example, particles with a lemon scent preferably have one yellow color on while for particles with apple or herbal fragrance a green Color is preferred. Preferred dyes have a long shelf life and insensitivity across from the rest Ingredients of the agents and against light. Are the agents of the invention used in connection with cleaning textiles or dishes, the dyes used should not have a pronounced substantivity towards textile fibers, Glass, plastic dishes or ceramics are not included to stain.

Suitable dyes and dye mixtures are commercially available under various trade names and are offered by companies such as BASF AG, Ludwigshafen, Bayer AG, Leverkusen, Clariant GmbH, DyStar Textilfarben GmbH & Co. Deutschland KG, Les Colorants Wackherr SA and Ciba Specialty Chemicals. Suitable fat-soluble dyes and dye mixtures include, for example, Solvent Blue 35, Solvent Green 7, Solvent Orange 1 (Orange au Gras-W-2201), Sandoplast Blau 2B, Fettgelb 3G, Iragon ^® Red SRE 122, Iragon ^® Green SGR 3, Solvent Yellow 33 and Solvent Yellow 16, but other dyes can also be included.

In a preferred embodiment, the dye also has an indicator function in addition to its aesthetic effect. This indicates to the consumer the current state of consumption of the deodorant, so that in addition to the lack of a scent impression, which can also occur, for example, due to a habituation effect on the part of the user, he receives a further reliable indication of when the Ge dishwasher deodorant must be replaced with a new one.

The indicator effect can be different Because of being achieved: On the one hand, a dye can be used which escapes from the particles during the period of use. This can, for example, by the ingredients contained in the dishwashing detergent be effected. To do this, a Dye can be used that adheres well to the particles or diffuses slowly out of them to ensure that the discoloration does not too early, namely if the fragrance has not yet been used up, is finished. on the other hand can also be caused by a chemical reaction or thermal decomposition a color change can be caused.

Other preferred components of agents according to the invention are substances such as antimicrobial agents, germicides, fungicides, Antioxidants or corrosion inhibitors, with the help of which Additional benefits, such as disinfection or corrosion protection let it be realized.

To fight microorganisms can the agents according to the invention contain antimicrobial agents. A distinction is made here depending on the antimicrobial spectrum and mechanism of action between Bacteriostatics and bactericides, fungistats and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, Alkyl arlyl sulfonates, halophenols and phenol mercuric acetate.

To unwanted, due to exposure to oxygen and other oxidative processes caused changes in the agents according to the invention or to prevent the treated textiles, for example Contain antioxidants. This connection class includes, for example substituted phenols, hydroquinones, pyrocatechols and aromatic Amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Are the agents of the invention in automatic dishwashers used, so can these means to protect the dishes or the machine contain corrosion inhibitors, especially Silver protective agents in the field of automatic dishwashing have special meaning. The known substances can be used the state of the art. In general, silver protection agents in particular selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. To be used particularly preferably are benzotriazole and / or alkylaminotriazole. One finds in cleaner formulations about that out often Active chlorine-containing agents that clearly corrode the silver surface can reduce. Chlorine-free cleaners contain oxygen and nitrogen in particular organic redox-active compounds, such as di- and trihydric phenols, z. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Prefers here are the transition metal salts, the selected are from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used for prevention corrosion on the wash ware be used.

Instead of or in addition to the silver protective agents described above, for example the Benzotriazoles in the agents according to the invention redox-active substances are used. These substances are preferably inorganic redox-active substances from the group the manganese, titanium, zirconium, hafnium, vanadium, cobalt and Contains cerium salts and / or complexes, the metals preferably are in one of the oxidation states II, III, IV, V or VI.

The metal salts used or Metal complexes are said to be at least partially soluble in water. The counterions suitable for salt formation include all customary ones one, two or three times negatively charged inorganic anions, z. B. oxide, sulfate, nitrate, fluoride, but also organic anions such as B. stearate.

Metal complexes in the sense of the invention are compounds consisting of a central atom and one or more Ligands and optionally one or more the above Anions exist. The central atom is one of the above metals in one of the above Oxidation states. The ligands are neutral molecules or Anions that are monodentate or multidentate are; the term "ligand" in the sense of the invention is e.g. in "Römpp Chemie Lexicon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, Page 2507 "closer explained. Complete the charge of the central atom and the Charge of the ligand (s) not to zero, depending on whether there is a cationic or an anionic excess of charge, either one or more of the above Anions or one or more cations, e.g. B. sodium, potassium, ammonium ions for charge balance. suitable Complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The definition common in chemistry for oxidation level is e.g. in Römpp C Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, Page 3168 "reproduced.

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 that preferred agents according to the invention are characterized in that the metal salts and / or metal complexes are selected are 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 .

These metal salts or metal complexes are generally commercially available substances which can be used in the agents according to the invention for the purpose of protecting against silver corrosion without prior cleaning. For example, the mixture of pentavalent and tetravalent vanadium (V ₂ O ₅ , VO ₂ , V ₂ O ₄ ) known from SO ₃ production (contact process) is suitable, as is that by diluting a Ti (SO ₄ ) ₂ - Solution of titanyl sulfate, TiOSO ₄ .

The metal salts mentioned and / or Metal complexes are in the agents according to the invention, preferably in an amount of 0.05 to 6% by weight, preferably 0.2 to 2.5% by weight, based on the total agent without the container.

Another important criterion to assess a machine dishwashing detergent is in addition to its cleaning performance the visual appearance of the dry dishes after they are done Cleaning. Possible calcium carbonate deposits Dishes or inside the machine can, for example, improve customer satisfaction impair and thus have causal Influence on the economic success of such a cleaning agent. Another longstanding problem with machine dishwashing is the corrosion of glassware, which is usually characterized by the appearance of cloudiness, streaks and scratches but can also manifest by iridescence of the glass surface. They watched Effects are essentially based on two processes, the Leakage of alkali and alkaline earth ions from the glass in combination with hydrolysis of the silicate network, on the other hand in one Deposition of silicate compounds on the glass surface.

The problems mentioned can with the agents according to the invention solved if in addition to the above-mentioned mandatory and optionally optional Ingredients certain glass corrosion inhibitors in the agents be incorporated. Preferred agents according to the invention therefore additionally contain a or more magnesium and / or zinc salts and / or magnesium and / or Zinc complexes.

A preferred class of compounds the agents according to the invention for preventing glass corrosion can be added are insoluble Zinc salts. these can yourself during the dishwashing process on the glass surface accumulate and prevent metal ions from dissolving there from the glass network as well as the hydrolysis of the silicates. Prevent additionally these insoluble Zinc salts also the deposit of silicate on the glass surface, so that this Glass is protected from the consequences described above.

Insoluble zinc salts in the sense of this preferred embodiment are zinc salts which have a solubility of at most 10 grams of zinc salt per liter of water at 20 ° C. Examples of particularly insoluble zinc salts preferred according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn ₂ (OH) ₂ CO ₃ ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (PO ₄ ) ₂ ), and zinc pyrophosphate (Zn ₂ (P ₂ O ₇ )).

The zinc compounds mentioned are in the agents according to the invention used in amounts that contain zinc ions between the agents 0.02 and 10 wt .-%, preferably between 0.1 and 5.0 wt .-% and in particular between 0.2 and 1.0% by weight, in each case based on the Means without the container. The exact content of the agents in the zinc salt or zinc salts is naturally dependent on the type of zinc salts - each less soluble the zinc salt used, the higher its concentration should be in the. agents according to the invention his.

Another preferred class of Compounds are magnesium and / or zinc salts) at least one monomeric and / or polymeric organic acid. These also cause repeated use does not change the surfaces of glassware, especially no cloudiness, Streaks or scratches but also no iridescence on the glass surfaces become.

Although according to the invention all magnesium and / or zinc salts) of monomeric and / or polymeric organic acids in the claimed agents may be included, as above described, the magnesium and / or zinc salts monomeric and / or polymeric organic acids from the groups of unbranched saturated or unsaturated Monocarboxylic acids, the branched saturated or unsaturated Monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, of oxo acids, of amino acids and / or of polymeric carboxylic acids prefers. Within these groups, within the scope of the present According to the invention, the acids mentioned below are preferred:

The spectrum of the preferred according to the invention Zinc salts of organic acids, preferably organic carboxylic acids, ranges from salts that are difficult or insoluble in water, so a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility have up to such salts that are soluble in water above 100 mg / L, preferably above 500 mg / L, particularly preferred above 1 g / L and especially above 5 g / L (all solubilities at 20 ° C water temperature). The first group of zinc salts include, for example, zinc citrate, the zinc oleate and the zinc stearate, to the group of soluble Zinc salts belong for example zinc formate, zinc acetate, zinc lactate and the zinc gluconate:

In a further preferred embodiment of the present invention contain the agents according to the invention at least one zinc set, but no magnesium salt of an organic one Acid, wherein it is preferably at least one zinc set of an organic Carboxylic acid, particularly preferably a zinc salt from the group of zinc stearate, Zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate is. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

A preferred agent in the context of the present invention contains zinc set in amounts of 0.1 to 5% by weight, preferably 0.2 to 4% by weight and in particular 0.4 to 3% by weight, or zinc in oxidized form (calculated as Zn ²⁺ ) in amounts from 0.01 to 1% by weight, preferably from 0.02 to 0.5% by weight and in particular from 0.04 to 0.2% by weight , each based on the agent without the container.

Another preferred item The present application is therefore a fragrance delivery system which further active substances, in particular active substances from the group the perfume carrier, dyes, antimicrobial agents, germicides, fungicides, antioxidants or contain corrosion inhibitors.

The container for the fragrance-containing particles preferably consists of a water-insoluble material, and is preferred from a textile material and / or a polymer and / or a Made of polymer mixture.

Under the term "polymers" are polymers, polyadducts in the context of the present application and polycondensates combined.

As polymers in this Application referred to such high molecular weight compounds whose Structure follows a chain growth mechanism. preferred In the context of the present application, polymers are polyethylene, Polypropylene, poly-1-butene, Poly-4-methyl-1-pentene, polyvinyl chloride, polyvinylidene chloride, Polyacrylonitrile and / or polystyrene.

Polyadducts are created by polyaddition, in other words, polyreactions in which repetitions are repeated and independent of each other linking reactions of bis- or polyfunctional starting materials (monomers) via reactive Finally, oligomers Polymers are created. Preferred polyadducts are polyurethanes.

Polycondensates are created like that Polyadducts through repetitive and independent linking reactions discrete oligomers and monomers, but in contrast to polyaddition At the same time, low-molecular compounds are split off. Preferred polycondensates in the context of the present invention are Polyamides, polycarbonates and polyesters.

In summary, the containers contain Incorporation of the fragrance-containing particles at least partially Polyethylene, 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, polyester, polyacrylonitrile, polymethyl methacrylate or polyurethanes.

A detailed description of this Polymers can be found at the beginning of this description. To those there versions is referred to here to avoid repetition.

Polymers are characterized by a special versatility in terms of processability. Plastics can by extrusion or injection molding processed as shaping as by drawing processes. At the Drawing (thermoforming) is a preheated plastic sheet or -foil between the two parts of the tool, the positive and the negative, introduced and then squeezed them together, which gives the plastic part its shape. The so-called cold working is similar; here, however, the plate or film to be deformed is not preheated. If there is no negative tool, one speaks of deep drawing. In the context of the present invention, the above-mentioned containers can be all processes known to the person skilled in the art, in particular by extrusion, injection molding, Thermoforming or blow molding. The containers must be in in any case, the leak of the fragrance and optional other active ingredients enable, why use both with openings provided container as well as the at least partial use of permeable container materials how permeable membranes are suitable.

As "textile material" referred to in the context of the present application such substances, that can be processed into textile fabrics. Among the preferred count textile materials in addition to synthetic polymers such as nylon, polyester, polyacrylic or polyolefins also plant materials such as cotton or other cellulosic materials.

In addition to the blister packs, such as those that can be produced by deep-drawing processes, as well as injection-molded or blow-molded containers in the form of cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section, are suitable as spatial shapes for the container. This last embodiment comprises tablet-shaped containers up to compact cylinder pieces with a ratio of height to diameter above 1. Further possible spatial shapes are spheres, hemispheres or "elongated spheres" in the form of elipsoid capsules as well as regular polyhedra, for example tetrahedra, hexahedron, octahedron, Dodecahedron, icosahedron, star-shaped configurations with three, four, five, six or more tips or completely are also conceivable irregular bodies, which can be motivated, for example. Depending on the field of use of the agents according to the invention, suitable motifs are, for example, animal figures such as dogs, horses or birds, floral motifs or the representation of fruits. The motivic design can also refer to inanimate objects such as vehicles, tools, household items or clothing. The surface of the solid particles can have bumps depending on the type of manufacturing process chosen and / or a coating selected.

Other suitable container shapes are bags, nets, sacks, Pouches or sachets, which are made, for example, of foils, fleeces, Fabrics or knitted fabrics can be made and their pore or Mesh size as well as in the aforementioned injection molding, blow molding or deep-drawn bodies must be less than the diameter of the particles to prevent them from trickling out.

The aforementioned containers can be filling the fragrance-containing particles by sewing, welding or Be sealed sealed.

The procedures described above for Packaging of the containers means according to the invention are usually as well optically how to direct the ultimate purpose of these funds. The agent according to the invention can for example, in addition to the fragrance-containing particles, other active substances contain.

These active substances can within of the container in a mixture or a mixture with the fragrance-containing particles but can also be made up separately from these particles. there can this optional additional Active substances both in the form of a single dose, for example for the one time Disinfection of a dishwasher, but can also be used in the form of multiple dosing.

In addition to the above Active substances can the agents according to the invention, especially funds for use in dishwashers, Textile washing machines or dryers, all of course usually in funds for the cleaning of textiles or dishes or the care of textiles or dishes Contain contained active substances, substances from the Group of bleaching agents, bleach activators, polymers, builders, Surfactants, enzymes, electrolytes, pH adjusting agents, fragrances, perfume carriers, dyes, Hydrotropes, foam inhibitors, anti-redeposition agents, optical Brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, Color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, phobing and impregnating agents, Swelling and sliding solid, non-aqueous solvents, fabric softener, protein hydrolyzate, and UV absorbers are particularly preferred. Such combination products in addition to repeated scenting, they are also suitable for or repeated care or cleaning of textiles or dishes.

Bleaching agents and bleach activators can be included in the agents according to the invention as important components of washing or cleaning agents. Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaches which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Detergent tablets for automatic dishwashing can also contain bleaches from the group of organic bleaches. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxyaloacidoperoxycaproic acid (Pε) )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxydiperoxybiperyldoxybiperyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutanoic acid, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

If the agents according to the invention are used in combination with automatic dishwashing agents, they can contain bleach activators in order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C. and below. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acy lated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

in der R¹ für -H, -CH₃, einen C_2–24-Alkyl- oder -Alkenylrest, einen substituierten C_2–24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1–24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1–24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.Further bleach activators which are preferably used in the context of the present application are compounds from the group of the cationic nitriles, in particular cationic nitrile of the formula

in which R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a C _1-24 alkyl group, or for a substituted alkyl or alkenylaryl radical with a C _1-24 alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -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 , - (CH ₂ CH ₂ -O) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

enthalten, in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt und Verbindungen der Formeln (CH₃)₃N)⁽⁺⁾CH₂-CN X^–, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^–, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^– besonders bevorzugt sind, wobei aus der Gruppe dieser Substanzen wiederum das kationische Nitril der Formel (CH₃)₃N⁽⁺⁾CH₂-CN X^–, in welcher X^– für ein Anion steht, das aus der Gruppe Chlorid, Bromid, Iodid, Hydrogensulfat, Methosulfat, p-Toluolsulfonat (Tosylat) oder Xylolsulfonat ausgewählt ist, besonders bevorzugt wird.A particularly preferred agent according to the invention is a cationic nitrile of the formula

contain, in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , where R ^{4 can} additionally be -H and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N) ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{- are} particularly preferred, from the group of these substances again the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , in which X ^{- stands} for an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate ) or xylene sulfonate is selected, is particularly preferred.

In addition to the conventional Bleach activators or in their place can also be so-called bleach catalysts be incorporated into the funds. These substances are are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes are used as bleaching catalysts usable.

In addition to the ingredients mentioned Bleaching agents and bleach activators are builders other important ingredients of detergents or cleaning agents. In the agents according to the invention can all usually builders used in these agents, in particular So zeolites, silicates, carbonates, organic cobuilders and - where no ecological There are prejudices against their use - including phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. Within the scope of this invention, un ter the term "amorphous" also understood "X-ray amorphous". This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite that can be used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula n Na ₂ O · (1-n) K ₂ O · Al ₂ O ₃ · (2–2.5) SiO ₂ · (3.5–5.5) H ₂ O can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, there is also a stake of the well-known phosphates possible as builder substances, provided that such use is not avoided for ecological reasons should be. The sodium salts of the orthophosphates are particularly suitable, the pyrophosphates and especially the tripolyphosphates. To avoid of repetitions is for a detailed Description of these phosphates on the above statements directed.

Usable organic builders are, for example, those in the form of their alkali and especially sodium salts usable polycarboxylic acids, like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, Sugar acids, amino carboxylic acids, nitrilotriacetic (NTA), provided that such use is not for ecological reasons objectionable, and mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, sugar acids and mixtures of these.

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

Are the agents of the invention with automatic dishwashing used, are water-soluble Builder preferred as they work on dishes and hard surfaces tend to be less likely to form insoluble residues. Usual builder are the low molecular weight polycarboxylic acids and their salts, the homopolymers and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and silicates. Prefers are used to manufacture tablets for machine dishwashing trisodium citrate and / or Pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class the disilicates and / or metasilicates used. Particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate. A builder system is also particularly preferred, which is a mixture of tripolyphosphate and sodium carbonate and sodium disilicate contains.

As organic cobuilders, in the cleaning agents in the context of the present invention in particular Polycarboxylates / polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used become. These classes of substances are described below.

Usable organic builders are, for example, those that can be used in the form of their sodium salts polycarboxylic being under polycarboxylic acids such carboxylic acids can be understood that carry more than one acid function. For example these are citric acid, adipic acid, Succinic acid, Glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), unless such use for ecological reasons objectionable, and mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, methylglycine, sugar acids and mixtures of these.

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

Polymers are also used as builders Suitable polycarboxylates, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular Polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol exhibit. Because of their superior solubility can from this group, in turn, the short-chain polyacrylates, the molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1200 to 4000 g / mol, have, be preferred.

Are particularly preferred in the agents according to the invention both polyacrylates and copolymers of unsaturated Carboxylic acids, Containing sulfonic acid Monomers and optionally other ionic or nonionic Monomers used. The copolymers containing sulfonic acid groups will be detailed in the following described.

• i) ungesättigten Carbonsäuren
• ii) Sulfonsäuregruppen-haltigen Monomeren
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

enthalten.However, it is also possible to provide products according to the invention which, as so-called “3-in-1” products, combine the conventional cleaners, rinse aids and a salt replacement function. For this purpose, automatic dishwashing detergents according to the invention are preferred which additionally contain 0.1 to 70% by weight of copolymers out

• i) unsaturated carboxylic acids
• ii) Monomers containing sulfonic acid groups
• iii) optionally further ionic or nonionic monomers

contain.

These copolymers cause the Such items treated dishes in subsequent cleaning operations clearly become cleaner than dishes that have been washed using conventional means.

As an additional positive effect occurs a shortening the drying time of the dishes treated with the detergent on, i.e. the consumer can after the cleaning program the dishes earlier Take out of the machine and use again. Under drying time is part of the teaching of the invention in general the literal meaning understood, that is, the time that passes until one in a dishwasher treated dish surface has dried, but especially the time that passes until 90% one with a detergent or rinse aid in concentrated or diluted form treated surface is dried.

In the context of the present invention, unsaturated carboxylic acids of the formula 1 are preferred as monomers, R ¹ (R ² ) C = C (R ³ ) OOOH (I) 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, with -NH ₂ , -OH or -OOOH substituted alkyl or alkenyl radicals as defined above or represents -OOOH or -OOOR ⁴ , where 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 formula I 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) preferred.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula II R ⁵ (R ⁶ ) C = C (R ¹ ) -X-SO ₃ H (II), in which R ⁵ to R ¹ 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 -OOOH as defined above or for -OOOH or -OOOR ⁴ R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present 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 IIa, IIb and / or IIc, H ₂ C = CH-X-SO ₃ H (IIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (IIb), HO ₃ SX- (R ⁶ ) C = C (R ¹ ) - X-SO ₃ HH ₂ C = CH-X-SO ₃ H (IIa), H ₂ C = C (CH ₃ ) -X-SO ₃ HH ₂ C = CH-X-SO ₃ H (IIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (IIb), HO ₃ SX- (R ⁶ ) C = C (R ¹ ) -X-SO ₃ H (IIc), (IIb), HO ₃ SX- (R ⁶ ) C = C (R ¹ ) -X-SO ₃ H (IIc), (IIc), in which R ⁶ and R ^{1 are} independently selected from -N, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present 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 (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula IIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula IIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula IIa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CN ₃ ) CH ₂ - in formula IIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (O) NH- CH ₂ CH (OH) CH ₂ - in formula IIb), allylsulfonic acid (X = CH ₂ in formula IIa), methallylsulfonic acid (X = CH ₂ in formula IIb), allyloxybenzenesulfonic acid (X = - CH ₂ -OC ₆ H ₄ - in Formula IIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula IIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid (X = CH ₂ in Formula IIb), styrene sulfonic acid (X = C ₆ H ₄ in formula IIa), vinyl sulfonic acid (X not present in formula IIa), 3-sulfopropyl acrylate (X = -C (O) NN-CH ₂ CH ₂ CH ₂ - in formula IIa ), 3-p sulfopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula IIb), sulfomethacrylamide (X = -C (O) NH- in formula IIb), sulfomethyl methacrylamide (X = -C (O) NH- CH ₂ - in formula IIb) and water-soluble salts of the acids mentioned.

As another ionic or non-ionic Monomers are particularly suitable ethylenically unsaturated compounds. Preferably is the content of those used according to the invention Polymers on monomers of group iii) less than 20% by weight, based on the polymer. Polymers to be used with particular preference only from monomers of groups i) and ii).

• i) ungesättigten Carbonsäuren der Formel I. R¹(R²)C=C(R³)OOOH (I) 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 -OOOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -OOOH oder -OOOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• ii) Sulfonsäuregruppen-haltigen Monomeren der Formel II R⁵(R⁶)C=C(R¹)-X-SO₃H (II) in der R⁵ bis R¹ 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 -OOOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -OOOH oder -OOOR⁴ 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)
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

besonders bevorzugt.In summary, copolymers are made of

• i) unsaturated carboxylic acids of formula I. R ¹ (R ² ) C = C (R ³ ) OOOH (I) 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, with -NH ₂ , -OH or -OOOH substituted alkyl or Al kenyl radicals as defined above or represents -OOOH or -OOOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
• ii) Monomers of the formula II containing sulfonic acid groups R ⁵ (R ⁶ ) C = C (R ¹ ) -X-SO ₃ H (II) in which R ⁵ to R ¹ 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 -OOOH substituted alkyl or alkenyl radicals as defined above or represents -OOOH or -OOOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present 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 ionic or nonionic monomers

particularly preferred.

• i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln IIa, IIb und/oder IIc: H₂C=CH-X-SO₃H (IIa), H₂C=C(CH₃)-X-SO₃H (IIb), HO₃S-X-(R⁶)C=C(R¹)-X-SO₃HH₂C=CH-X-SO₃H (IIa), H₂C=C(CH₃)-X-SO₃HH₂C=CH-X-SO₃H (IIa), H₂C=C(CH₃)-X-SO₃H (IIb), HO₃S-X-(R⁶)C=C(R¹)-X-SO₃H (IIc),(IIb), HO₃S-X-(R⁶)C=C(R¹)-X-SO₃H (IIc),(IIc), in der R⁶ und R¹ 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)- 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 ionischen oder nichtionogenen Monomeren.

Particularly preferred copolymers consist of

• i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid
• ii) one or more monomers of the formulas IIa, IIb and / or IIc containing sulfonic acid groups: H ₂ C = CH-X-SO ₃ H (IIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (IIb), HO ₃ SX- (R ⁶ ) C = C (R ¹ ) - X-SO ₃ HH ₂ C = CH-X-SO ₃ H (IIa), H ₂ C = C (CH ₃ ) -X-SO ₃ HH ₂ C = CH-X-SO ₃ H (IIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (IIb), HO ₃ SX- (R ⁶ ) C = C (R ¹ ) -X-SO ₃ H (IIc), (IIb), HO ₃ SX- (R ⁶ ) C = C (R ¹ ) -X-SO ₃ H (IIc), (IIc), in which R ⁶ and R ^{1 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) - 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 ionic or nonionic monomers.

The copolymers, which are contained in the medium can the monomers from groups i) and ii) and, if appropriate, iii) Contained in varying amounts, with all representatives from the group i) with all Representatives from group ii) and all representatives from the Group iii) can be combined. Especially preferred polymers have certain structural units that are described below.

For example, agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula III - [CH ₂ -CHCOOH] _m [CH ₂ -CHC (O) -Y-SO ₃ H) P (III), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) with n = 0 to 4, represents -O- (C ₆ H ₄ ) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

These polymers are produced by copolymerization of acrylic acid with a sulfonic acid group-containing acrylic acid derivative. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula IV - [CH ₂ -C (CH ₃ ) OOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (IV), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) - 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.

Completely analogously, acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Agents according to the invention which contain one or more copolymers which have structural units of the formula V - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (V), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) with n = 0 to 4, represents -O- (C ₆ H ₄ ) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are preferred, likewise a preferred embodiment of the present invention, just as agents are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula VI - [CH ₂ -C (CH ₃ ) OOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (VI), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) with n = 0 to 4, represents -O- (C ₆ H ₄ ) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula VII - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VII), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is preferred, and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula VIII - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (VIII), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) - 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.

In summary, automatic dishwashing agents according to the invention are preferred which contain, as ingredient b), one or more copolymers which have structural units of the formulas III and / or IV and / or V and / or VI and / or VII and / or VIII - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (III), - [CH ₂ -C (CH ₃ ) OOOH] _m - [CH ₂ -CHC ( O) -Y-SO ₃ H) _p - (IV), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (V), - [CH ₂ -C (CH ₃ ) OOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (VI), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VII), - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - [ CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (III), - [CH ₂ -C (CH ₃ ) OOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H) _p - (IV), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (V), - [ CH ₂ -C (CH ₃ ) OOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (VI), - [HOOCCH-CHCOOH] _m - [CH ₂ - CHC (O) -Y-SO ₃ H] _p - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (III), - [CH ₂ -C ( CH ₃ ) OOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H) _p - (IV), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (V), - [CH ₂ -C (CH ₃ ) OOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (III), - [CH ₂ -C (CH ₃ ) OOOH] _m - [CH ₂ -CHC (O ) -Y-SO ₃ H) _p - (IV), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (III), - [CH ₂ -C (CH ₃ ) OOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H) _p - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC ( O) -Y-SO ₃ H] _p - (III), - [CH ₂ -C (CH ₃ ) OOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H) _p - (IV), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (V), - [CH ₂ -C (CH ₃ ) OOOH] _m - [ CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (VI), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VII), - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (VIII), (IV), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (V), - [CH ₂ -C (CH ₃ ) OOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (VI), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VII), - [HOOCCH-CHCOOH ] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (VIII), (V), - [CH ₂ -C (CH ₃ ) OOOH] _m - [CH ₂ - C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (VI), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VII) , - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (VIII), (VI), - [HOOCCH-CHCOOH] _m - [CH ₂ - CHC (O) -Y-SO ₃ H] _p - (VII), - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (VIII), (VII), - [HOOCCH-CHCOOH] _m - [CH ₂ -C ( CH ₃ ) C (O) OY-SO ₃ H] _p - (VIII), (VIII), contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, 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, are preferred.

In the polymers, the sulfonic acid are wholly or partly in neutralized form, i.e. that the acid Hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular can be exchanged for sodium ions. Appropriate means, which are characterized in that the sulfonic acid groups Partially or fully neutralized in the copolymer are preferred according to the invention.

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

Such are special with terpolymers preferred, the 20 to 85 wt .-% monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) included.

The molar mass of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the intended use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 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 content of one or more Copolymers in the agents according to the invention can vary depending on the application and the desired product performance, preferred machine according to the invention Dishwashing liquid are characterized in that they the copolymer (s) in amounts of 0.25 to 50% by weight, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular contain from 1 to 15% by weight.

As already mentioned further above, it is particularly preferred to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers in the agents according to the invention. The polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred. Such polyacrylates are commercially available under the trade names Sokalan ^® PA15 or Sokalan ^® PA25 (BASF).

Also suitable are _C opolymere polycarboxylates, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.

The (co) polymeric polycarboxylates can can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility can the polymers also allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

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

Show other preferred copolymers as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and Vinyl acetate.

Are also preferred as others Builder substances polymeric aminodicarboxylic acids, their salts or their precursors to call. Polyaspartic acids or their salts and derivatives.

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

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

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

Another class of substances with cobuilder properties represent the phosphonates. These are in particular around hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9) reacts. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), Diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and the Octa sodium salt of DTPMP. As a builder HEDP is preferably used from the class of the phosphonates. The aminoalkane phosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the agent also bleach contain, be preferred, aminoalkanephosphonates, in particular DTPMP, to use, or to use mixtures of the phosphonates mentioned.

In addition, everyone can Compounds capable of complexes with alkaline earth ions train as cobuilders.

Preferred funds included in the frame the present application one or more surfactants) from the groups the anionic, nonionic, cationic and / or amphoteric Surfactants.

As anionic surfactants in acid form are preferred one or more substances from the group of carboxylic acids, the Schwefelsäurehalbester and the sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylanlsulfonic acids, used. In order to have sufficient surface-active properties, the compounds mentioned should have longer-chain hydrocarbon residues, ie have at least 6 carbon atoms in the alkyl or alkenyl radical. Usually are the C chain distributions the anionic surfactants in the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22 carbon atoms.

Carboxylic acids, which are used as soaps in detergents and cleaning agents in the form of their alkali metal salts, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), only water is used on an industrial scale to split the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. Carboxylic acids which can be used as an anionic surfactant in acid form in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. The preferred compound in the context of the present compound is Use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), triacidic acid (melotinic acid), triacidic acid (melotonic acid), and melonic acid unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-octadecenoic acid) (9c -Octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreic acid ( Linolenic acid) For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids, as can be obtained from fat cleavage. Such mixtures are, for example, cos oil fatty acid (approx. 6% by weight Ca, 6% by weight C ₁₀ , 48% by weight C ₁₂ , 18% by weight C ₁₄ , 10% by weight C ₁₆ , 2% by weight. -% C _18, 8 wt .-% _{C18 ',} 1 wt .-% C _18''), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt .-% C ₁₂ , 15% by weight C ₁₄ , 7% by weight C ₁₆ , 2% by weight C ₁₈ , 15% by weight C _{18 '} , 1% by weight C _18'' ), tallow fatty acid (approx 3 wt% C ₁₄ , 26 wt% C ₁₆ , 2 wt% C _{16 '} , 2 wt% C ₁₇ , 17 wt% C ₁₈ , 44 wt% C _18' , 3% by weight C _{18 ''} , 1% by weight C _{18 '''} ), hardened tallow fatty acid (approx. 2 wt% C ₁₄ , 28 wt% C ₁₆ , 2 wt% C ₁₇ , 63 wt% C ₁₈ , 1 wt% C _{18 '} ), technical oleic acid (approx . 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C _16, 6 wt .-% C _{16 ',} 1 wt .-% C _17, 2 wt .-% C _18, 70% by weight C _{18 '} , 10% by weight C _18'' , 0.5% by weight C _18''' ), technical palmitin / stearic acid (approx. 1% by weight C ₁₂ , 2% by weight) .-% C ₁₄ 45 wt .-% C _16, 2 wt .-% C ₁₇ 47 wt .-% _18: 1 wt .-% C _{18 ')} and soybean oil fatty acid (about 2 wt .-% C ₁₄ , 15% by weight 6.5% by weight C ₁₈ , 25% by weight C _{18 '} , 45% by weight C _18'' , 7% by weight C _18''' ).

Sulfuric acid semiesters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the context of the present invention. Their alkali metal, in particular sodium salts, the fatty alcohol sulfates, are commercially available from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the alkyl sulfuric acids concerned and are subsequently neutralized. The fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters. In terms of quantity, the most important industrial process for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with SO ₃ / air mixtures in special cascade, falling film or tube bundle reactors.

Another class of anionic surfactant acids that used according to the invention are the alkyl ether sulfuric acids, their salts, the alkyl ether sulfates, compared to the alkyl sulfates by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts). Alkyl become like the alkyl sulfuric acids synthesized from fatty alcohols, which with ethylene oxide to the concerned Fatty alcohol ethoxylates are implemented. Instead of ethylene oxide propylene oxide can also be used. The subsequent sulfonation with gaseous Sulfur trioxide in short-term sulfonation reactors yields over 98% on the relevant alkyl ether sulfuric acids.

Alkanesulfonic acids and olefin sulfonic acids are also in the context of the present invention as anionic surfactants in acid form used. alkanesulfonic can the sulfonic acid group terminal bound (primary alkane sulfonic acids) or contain along the C chain (secondary alkanesulfonic acids), where only the secondary ones alkanesulfonic have commercial importance. These are by sulfochlorination or Sulfoxidation of linear hydrocarbons produced. In sulfochlorination according to Reed, n-paraffins with sulfur dioxide and chlorine under irradiation with UV light corresponding sulfochlorides implemented in the hydrolysis with alkalis directly deliver the alkanesulfonates, when reacting with water the alkanesulfonic acids. Because in the sulfochlorination, di- and polysulfochlorides as well as chlorinated hydrocarbons can occur as by-products of the radical reaction the reaction usually only carried out up to degrees of implementation of 30% and then canceled.

Another process for making alkanesulfonic acids is sulfoxidation, in the case of n-paraffins under irradiation with UV light with sulfur dioxide and oxygen be implemented. This radical reaction occurs successively Alkylsulfonyl radicals that add oxygen to the alkylpersulfonyl radicals continue to respond. The reaction with unreacted paraffin provides an alkyl radical and the alkyl persulfonic acid, which are converted into an alkyl peroxysulfonyl radical and a hydroxyl radical breaks down. The reaction of the two radicals with unreacted paraffin provides the alkyl sulfonic acids or water, which reacts with alkyl persulfonic acid and sulfur dioxide to form sulfuric acid. To the yield of the two end products alkyl sulfonic acid and Sulfuric acid if possible To keep high and suppress side reactions, this reaction is usually only carried out up to degrees of implementation of 1% and then terminated.

Olefin sulfonates are becoming technical by reaction of α-olefins made with sulfur trioxide. Intermediate hermaphrodites form which cyclize into so-called sultons. Under suitable conditions (alkaline or acidic hydrolysis) these sultones react to hydroxylalkanesulfonic acids or alkensulfonic acids both also as anionic surfactant acids can be used.

Alkylbenzenesulfonates as powerful Anionic surfactants have been around since the 1930s known. At that time, monochlorination of kogasin fractions and subsequent ones Friedel-Crafts alkylation alkylbenzenes made with oleum sulfonated and neutralized with sodium hydroxide solution. beginning of fifties Years have passed to the production of alkylbenzenesulfonates propylene branched α-dodecylene tetramerized and the product over a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride converted to tetrapropylene benzene, the following sulfonated and neutralized. This economic opportunity the production of tetrapropylene benzene sulfonates (TPS) led to Breakthrough of this class of surfactants, which subsequently the soaps as the main surfactant displaced in detergents and cleaning agents.

Because of the lack of biological Degradability of TPS resulted in the need for new alkylbenzenesulfonates to be presented, which are characterized by improved ecological behavior. These requirements are met by linear alkyl benzene sulfonates, which today almost exclusively alkylbenzenesulfonates produced and with the abbreviation ABS or LAS can be used.

Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are accessible from linear olefins. For this purpose, petroleum fractions are separated on an industrial scale with molecular sieves into the n-paraffins of the desired purity and dehydrated to the n-olefins, resulting in both α- and i-olefins. The resulting olefins are then added to benzene in the presence of acidic catalysts the alkylbenzenes, the choice of the Friedel-Crafts catalyst having an influence on the isomer distribution of the linear alkylbenzenes formed: when using aluminum trichloride, the content of the 2-phenyl isomers is in the mixture with the 3-, 4-, 5- and other isomers at approx. 30% by weight. However, if hydrogen fluoride is used as a catalyst, the 2-phenyl isomer content can be reduced to approx. 20% by weight. Finally, the sulfonation of linear alkylbenzenes is now possible on a large industrial scale with oleum, sulfuric acid or gaseous sulfur trioxide, the latter being by far the most important. For the sulfonation, special film or tube bundle reactors are used which deliver a 97% by weight alkylbenzenesulfonic acid (ABSS) as product, which can be used as anionic surfactant acid in the context of the present invention.

in der die Summe aus x und y üblicherweise zwischen 5 und 13 liegt. Erfindungsgemäß bevorzugt als Aniontensid in Säureform sind C_8–16-, vorzugsweise C_9–3-Alkylbenzolsulfonsäuren. Es ist im Rahmen der vorliegenden Erfindung weiterhin bevorzugt, C_8–16-, vorzugsweise C_9–13-Alkybenzolsulfonsäuren einzusetzen, die sich von Alkylbenzolen ableiten, welche einen Tetralingehalt unter 5 Gew.-%, bezogen auf das Alkylbenzol, aufweisen. Weiterhin bevorzugt ist es, Alkylbenzolsulfonsäuren zu verwenden, deren Alkylbenzole nach dem HF-Verfahren hergestellt wurden, so daß die eingesetzten C_8–16-, vorzugsweise C_9–13-Alkybenzolsulfonsäuren einen Gehalt an 2-Phenyl-Isomer unter 22 Gew.-%, bezogen auf die Alkylbenzolsulfonsäure, aufweisen.By choosing the neutralizing agent, a wide variety of salts, ie alkylbenzenesulfonates, can be obtained from the ABSS. For reasons of economy, it is preferred to prepare and use the alkali metal salts and, among them, the sodium salts of the ABSS. These can be described by the general formula IX:

in which the sum of x and y is usually between 5 and 13. According to the invention, preferred as the anionic surfactant in acid form are C _8-16 , preferably C _9-3, alkylbenzenesulfonic acids. In the context of the present invention, it is further preferred to use C _8-16 , preferably C _9-13 alkylbenzenesulfonic acids which are derived from alkylbenzenes which have a tetralin content below 5% by weight, based on the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes have been prepared by the HF process, so that the C _8-16 -, preferably C _9-13- alkylbenzenesulfonic acids used have a 2-phenyl isomer content of less than 22% by weight , based on the alkylbenzenesulfonic acid.

The anionic surfactants mentioned above in its acid form can used alone or in a mixture with one another. But it is also possible and preferred that the Anionic surfactant in acid form before adding to the substrate (s)) further, preferably acidic, ingredients of detergents and cleaning agents in amounts from 0.1 to 40% by weight, preferably from 1 to 15% by weight and in particular from 2 to 10% by weight, in each case based on the weight the mixture to be reacted.

Of course it is also possible that Use anionic surfactants partially or fully neutralized. These salts can then as a solution, Suspension or emulsion are present in the granulating liquid, but also as a solid be part of the solid bed. As cations for such Anionic surfactants are available in addition to the alkali metals (in particular here according to claim and K salts) ammonium and mono-, di- or triethanolalkonium ions on. Instead of mono-, di- or triethanolamine you can also the analog representatives of mono-, di- or trimethanolamine or those of the higher alkanolamines Alcohols quaternized and present as a cation.

Cationic surfactants can also be used Use advantage as active substance. The cationic surfactant can be in be delivered directly to the mixer in its delivery form, or in Form of a liquid to pasty Cationic surfactant preparation form are sprayed onto the solid carrier. Let such cationic surfactant preparation forms by mixing commercially available cationic surfactants with auxiliaries such as nonionic surfactants, polyethylene glycols or polyols. Lower alcohols such as ethanol and isopropanol can also be used the amount of such lower alcohols in the liquid cationic surfactant formulation for the reasons mentioned above should be below 10% by weight.

Suitable cationic surfactants for the agents according to the invention all usual Substances are considered, cationic surfactants with fabric softening Effect are clearly preferred.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1–6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8–28- Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.The agents according to the invention can contain one or more cationic, fabric softening agents of the formulas X, XI or XII as cationic active substances with fabric softening effect:

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

In preferred embodiments of the present invention, the compositions additionally contain nonionic surfactant (s) as an active substance.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular in 2-position methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 C atoms and G is the symbol which stands for a glycose unit with 5 or 6 C atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferred nonionic surfactants, either as the sole nonionic Surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters.

Also non-ionic surfactants of the type the amine oxides, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half from that.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula XIII,

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R' für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1–4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula XIV,

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 'represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this remainder.

[Z] is preferably by reductive Obtained amination of a reduced sugar, for example glucose, Fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy substituted compounds can then by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

It is special for many applications preferred if the ratio from anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably is between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. Prefers are containers according to the invention which Surfactant (s), preferably anionic (s) and / or nonionic surfactant (s), in amounts of 5 to 80% by weight, preferably 7.5 to 70% by weight, particularly preferably from 10 to 60% by weight and in particular from 12.5 up to 50 wt .-%, each based on the weight of the enclosed Solids.

As already mentioned, the use of surfactants in cleaning agents for automatic dishwashing is preferably limited to the use of nonionic surfactants in small amounts. Agents for automatic dishwashing according to the invention therefore preferably contain only certain nonionic surfactants, which are described below. Usually only weakly foaming nonionic surfactants are used as surfactants in automatic dishwashing detergents. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin are 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Especially with cleaning agents for the machine dishwashing it is preferred that this one contain nonionic surfactant that has a melting point above Has room temperature, preferably a nonionic surfactant a melting point above 20 ° C. Nonionic surfactants to be used with preference have melting points above 25 ° C, particularly preferably to be used nonionic surfactants have melting points between 25 and 60 ° C, in particular between 26.6 and 43.3 ° C.

Suitable nonionic surfactants, the melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants, which can be solid or highly viscous at room temperature. Become used at room temperature highly viscous nonionic surfactants, it is preferred that these a viscosity above 20 Pas, preferably above 35 Pas and in particular above Have 40 Pas. Also nonionic surfactants, which are waxy at room temperature Have consistency are preferred.

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

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

A particularly preferred nonionic surfactant which is solid at room temperature is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide , Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

The nonionic surfactant that is solid at room temperature preferably has additional Propylene oxide units in the molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or Alkylphenols additionally Have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes preferably more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight such non-ionic surfactants.

Further particularly preferably to be used Contains nonionic surfactants with melting points above room temperature 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.

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

Another preferred surfactant can be represented by the formula R ¹ O (CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _x [CH ₂ CH (OH) R ² ] describe in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1, 5 and y represents a value of at least 15.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if x ≥ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15.

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

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

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

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

Furthermore are for this Purpose of the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948); are as well Fusion products of the molecules mentioned can be used.

In addition, the further developments of the α-amylase from Aspergillus niger and A. onzae available under the trade names Fungamyl ^® from Novozymes are suitable. Another commercial product is the Amylase-LT ^® .

Agents according to the invention can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to produce peracids from suitable precursors in sifu. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^® , Lipolase ^® Ultra, LipoPrime ^® , Lipozyme ^® and Lipex ^® . Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. Lipase ^® , Lipase AP ^® , Lipase M-AP ^θ and Lipase AML ^® available. The Genencor company can use, for example, the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium so1anii. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention, also the product Lumafast ^® from Genencor.

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

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

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

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

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

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

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

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

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

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

A group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, Borax, boric acids, boronic acids or their salts or esters are used, especially derivatives with aromatic groups, such as ortho, meta or para substituted phenylboronic, or their salts or esters. Furthermore, peptide aldehydes, this means Suitable oligopeptides with reduced C-terminus. As a peptide Protease inhibitors include ovomucoid and leupeptin mention; an additional Option is the formation of fusion proteins from proteases and peptide inhibitors.

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

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

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

Reducing agents and antioxidants such as sodium sulfite or reducing sugars increase the stability of the enzymes across from oxidative decay.

Combinations of are preferred Stabilizers used, for example from polyols, boric acid and / or Borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing Salt. The effect of peptide-aldehyde stabilizers can by the combination with boric acid and / or boric acid derivatives and polyols increased and according to the additional use of divalent cations, such as calcium ions reinforced become.

Is particularly preferred in the frame of the present invention the use of liquid enzyme formulations. Here are agents according to the invention preferred that in addition Enzymes and / or enzyme preparations, preferably solid and / or liquid Protease preparations and / or amylase preparations, in amounts of 1 to 5% by weight, preferably from 1.5 to 4.5 and in particular from 2 to 4% by weight, in each case based on the entire average.

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

In order to bring the pH of solutions of the washing or cleaning agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or bases can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. Usually the amount exceeds this adjusting agent does not contain 1% by weight of the total formulation.

As a hydrotrope or solubilizer are substances that are present in others because of their presence a certain solvent practically insoluble Compounds in this solvent soluble or make emulsifiable (solubilization). There are solution mediators with the slightly soluble Substance is a molecular compound and those that work through micell formation. One can also say that only solution brokers a so-called latent solvent lend its solvency. With water as (latent) solvent one speaks instead of solution brokers mostly from hydrotropes, in certain cases better from emulsifiers.

Foam inhibitors which can be used in the agents according to the invention include soaps, oils, fats, paraffins or silicone oils, which can optionally be applied to carrier materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the aforementioned materials. Agents preferred in the context of the present application contain paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are structured according to the scheme (R ₂ SiO) _x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids with a molecular weight between 1000-150,000, and viscosities between 10 u. 1,000,000 mPas.

Suitable anti-redeposition agents, which are also referred to as soil repellents are, for example, nonionic Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30 wt .-% and of hydroxypropyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether and the polymers of phthalic acid and / or known from the prior art terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.

Optical brighteners (so-called "white tones") can agents according to the invention can be added to the graying and yellowing of the treated Eliminate textiles. These substances pull on the fiber and cause a brightening and feigned bleaching effect by they invisible ultraviolet radiation in visible long-wave Convert light, being the ultraviolet absorbed from sunlight Light as a slightly bluish Fluorescence is emitted and with the yellow tone of the grayed or yellowed laundry pure white results. Suitable compounds come from the substance classes, for example the 4.4 '' diamino-2.2 '' stilbene disulfonic acids (flavonic acids), 4.4 '' distyryl biphenyls, Methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid, Benzoxazole, Benzisoxazole and Benzimidazole systems and the pyrene derivatives substituted by heterocycles.

Graying inhibitors have that Task, the detached from the fiber Keep dirt suspended in the fleet and keep it moving to prevent the dirt. For this purpose, water-soluble colloids are usually more organic Suitable in nature, for example the water-soluble salts of polymeric carboxylic acids, glue, Gelatin, salts of ether sulfonic acids of strength or the cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water soluble, polyamides containing acidic groups are suitable for this purpose. Farther can be soluble Starch preparations and other than the above starch products use, e.g. degraded starch, aldehyde etc. Polyvinyl pyrrolidone is also useful. As graying inhibitors cellulose ethers such as carboxymethyl cellulose (sodium salt) can also be used, Methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures.

Because textile fabrics, especially from Rayon, rayon, cotton and their blends, for wrinkling can, because the individual fibers prevent bending, kinking. Pressing and squeezing The agents according to the invention can be sensitive across the grain contain synthetic anti-crease agents. These include, for example synthetic products based on fatty acids, fatty acid esters. fatty acid amides, -alkyl esters, -alkylolamides or fatty alcohols, mostly with Ethylene oxide are implemented, or products based on lecithin or modified phosphoric acid ester. One in particular textile finishing Suitable care and substance is the cottonseed oil, which for example by pressing out the brown, cleaned cotton seeds and refining with about 10% sodium hydroxide or by extraction made with hexane at 60-70 ° C can be. Such cotton oils contain 40 to 55 wt .-% linoleic acid, 16 to 26 wt .-% oleic acid and 20 to 26% by weight palmitic acid. More on fiber smoothing and fiber care particularly preferred agents are the glycerides, in particular the monoglycerides of fatty acids such as glycerol monooleate or glycerol monostearate.

To combat microorganisms, the agents according to the invention can contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halogenophenols and phenol mercuric acetate, where these compounds can also be dispensed with entirely in the case of the agents according to the invention.

To unwanted, due to exposure to oxygen and other oxidative processes caused changes in the washing and To prevent cleaning agents and / or the treated textiles, can the agents according to the invention Contain antioxidants. This connection class includes, for example substituted phenols, hydroquinones, pyrocatechols and aromatic Amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

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

Phobing and impregnation processes are used to finish Textiles with substances that prevent the deposition of dirt or make it easier to wash out. Preferred phobic and impregnating are perfluorinated fatty acids, also in the form of their aluminum u. Zirconium salts, organic silicates, silicones, polyacrylate with perfluorinated alcohol component or with perfluorinated acyl or sulfonyl radical-coupled, polymerizable compounds. Also Antistatic agents can be included. The dirt-repellent finish with phobing and impregnating agents is often classified as an easy-care kit. The intrusion the impregnating agent in the form of solutions or emulsions of the active substances concerned can be added by adding Wetting agents that reduce the surface tension are facilitated. On Another area of application of phobing and impregnating agents is water-repellent equipment of textile goods, tents, tarpaulins, leather etc., in contrast to that the tissue pores are not closed to make them waterproof, the fabric therefore remains breathable (hydrophobic). The one for waterproofing coat the water repellant used Textiles, leather, paper, wood etc. with a very thin layer hydrophobic groups, such as longer ones Alkyl chains or siloxane groups. Suitable water repellents are z. B. paraffins, waxes, metal soaps, etc. with additives Aluminum or zirconium salts, quaternary ammonium compounds with long-chain Alkyl residues, urea derivatives, fatty acid-modified melamine resins, Chromium complex salts, silicones, tin organic compounds and glutardialdehyde as well as perfluorinated compounds. The hydrophobic materials feel does not look greasy; nevertheless - similar to greased substances - water drops pearl on them without wetting. So z. B. silicone-impregnated Textiles a soft touch u. are water u. stain-resistant; Stains from ink, wine, fruit juices and the like are easier to remove.

To care for the textiles and improve the textile properties such as a softer ^"hand` (lubricant) and reduced electrostatic charge can contain (increased comfort) means softener according to the invention. The active ingredients in fabric softener formulations are "esterquats", quaternary ammonium compounds having two hydrophobic moieties such as for example, disteraryldimethylammonium chloride, which, however, due to its insufficient biodegradability, is increasingly being replaced by quaternary ammonium compounds which contain ester groups in their hydrophobic residues as predetermined breaking points for biodegradation. Such "esterquats" with improved biodegradability can be obtained, for example, by mixing mixtures of methyldiethanolamine and / or triethanolamine esterified with fatty acids and the reaction products then quaternized with alkylating agents in a manner known per se. Dim is also suitable as a finish ethylolethylenharnstoff.

To improve water absorption, the Rewettability of the treated textiles and for relief of ironing of the treated textiles can in the agents according to the invention, for example Silicone derivatives are used. These also improve that rinse behavior of the agents according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups one to five Have carbon atoms and are partially or completely fluorinated. preferred Silicones are polydimethylsiloxanes, which may be derivatized could be and then are amino-functional or quaternized or Si-OH-, Si-H- and / or have Si-Cl bonds. Other preferred silicones are the polyalkylene oxide modified polysiloxanes, i.e. polysiloxanes, which have, for example, polyethylene glycols and the polyalkylene oxide-modified Dimethylpolysiloxanes.

Because of their fiber-caring effect, protein hydrolyzates are further active substances preferred in the field of detergents and cleaning agents in the context of the present invention. Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins). According to the invention, protein hydrolyzates of both vegetable and animal origin can be used. Animal protein hydrolyzates are, for example, elastin, collagen, Ke Ratine, silk and milk protein protein hydrolyzates, which can also be in the form of salts. According to the invention, the use of protein hydrolysates of plant origin, e.g. B. soy, almond, rice, pea, potato and wheat protein hydrolyzates. Although the use of the protein hydrolyzates as such is preferred, amino acid mixtures or individual amino acids, such as arginine, lysine, histidine or pyrroglutamic acid, which have otherwise been obtained, can optionally be used in their place. It is also possible to use derivatives of the protein hydrolyzates, for example in the form of their fatty acid condensation products.

The deodorization and scenting of clear by means of the agents according to the invention takes place, as explained at the beginning, by placing these agents in a room and then heating them up Temperatures between 30 and 150 ° C. Another subject of the present application is therefore a Process for deodorising and scenting rooms, characterized in that the existence Fragrance delivery system according to one of claims 1 to 10 introduced into the room is and heated to temperatures between 30 and 150 ° C.

Generally are suitable for scenting all rooms, but especially the interiors of buildings, vehicles or technical devices, but preferably the interiors of textile washing machines, dryers or dishwashers.

The use of fragrance delivery systems according to the invention Another object is the deodorization and scenting of rooms of the present application.

Claims (12)

Fragrance delivery system comprising a container and particles for deodorization and scenting of rooms, which contain at least one polymeric carrier material and at least one fragrance, characterized in that the polymeric carrier material has a melting or softening point between 30 and 150 ° C. Fragrance delivery system according to claim 1, characterized in that the polymer support material a melting or softening point between 40 and 125 ° C, preferably between 60 and 100 ° C, particularly preferably from 70 to 90 ° C. and in particular between 75 and 80 ° C. Fragrance delivery system according to one of claims 1 or 2, characterized in that this polymeric carrier material at least one 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, polyester, polyacrylonitrile, polymethyl methacrylate, Polyurethanes that contain polyvinyl alcohols. Fragrance delivery system according to one of claims 1 to 3, characterized in that this polymeric carrier material at least 10% by weight, preferably at least 30% by weight, particularly preferably contains at least 70% by weight of ethylene / vinyl acetate copolymer, preferably Completely is made of ethylene / vinyl acetate copolymer. Fragrance delivery system according to one of Claims 1 to 4, characterized in that that as polymeric carrier material Ethylene / vinyl acetate copolymer is used and this copolymer 5 to 50% by weight of vinyl acetate, preferably 10 to 40% by weight of vinyl acetate and in particular 20 to 30 wt .-% vinyl acetate, each based on the total weight of the copolymer. Fragrance delivery system according to one of Claims 1 to 5, characterized in that that the Weight fraction of the fragrance (s) 1 to 70 wt .-%, preferably 10 to 60% by weight, particularly preferably 20 to 50% by weight, in particular 30 to 40% by weight, based in each case on the total weight of the particles, is. Fragrance delivery system according to one of claims 1 to 6, characterized in that these an average diameter of 0.5 to 20 mm, preferably of Have 1 to 10 mm and in particular from 3 to 6 mm. Fragrance delivery system according to one of claims 1 to 7, characterized in that these further active substances from the group of perfume carriers, dyes, antimicrobial Active substances, germicides, fungicides, antioxidants or corrosion inhibitors contain. Fragrance delivery system according to one of Claims 1 to 8, characterized in that that this container from a water-insoluble Material, preferably a textile material or a polymer or a polymer blend is made. Process for deodorising and scenting rooms, thereby characterized that a Fragrance delivery system according to one of claims 1 to 9 introduced into the room is and heated to temperatures between 30 and 150 ° C. A method according to claim 10, characterized in that it is in the rooms around the interiors of buildings, Vehicles or technical devices, preferably around the interiors of textile washing machines, dryers or dishwashers is. Use of fragrance delivery systems according to one of claims 1 to 9 for deodorization and scenting of rooms.