DE102006002864A1 - Packaging Unit - Google Patents

Abstract

A packaging unit has a container (1) for holding a product, a closure (2) and an opening or closure cylinder (14) for dispensing product from the container (1). The closure (2) closes the opening (14). The packaging unit has at least one receiving means (3), for a plurality of additive portions (6, 11, 21) of in each case less than 50 ml, which may be blister packs. The additive (16) held in the additive portions (6, 11, 21) may be one or more aromatic, colorant or surfactant. The receiving means (3) for additive portions (6, 11, 21) can be fixed releasably to the packaging unit.

Description

The The invention relates to a package consisting of a container for products and one on this container arranged device for receiving additive portions.

State of the art

It has long been a need in being able to customize products or customized individualized by the customer to a certain extent. A particularly suitable medium for individualizing a product represents its packaging as this is the immediate interface between Consumer and product training.

Therefore it is desirable Means for individualization or further functionalization of a Product directly to the packaging of a product.

Especially in the field of perfuming of products such as detergents, detergents and the like, it is still common, the entire sales unit to sell with a specific scent. Often, however, the user desires that for different uses a different scent through a cleaning product is delivered. For example, it is desirable that a cleaning agent for the toilet area emits a more intense fragrance than in the living area, in the intense scents often rather than disturbing be felt. So far it was necessary, a variety of Special cleaners with the appropriate fragrances to use, although the cleaning-active preparations are the same or at least very similar.

Just In addition, with very aggressive cleaning preparations exists the problem that the aggressive cleaning components include the in the preparations decompose fragrances that persist so that these only a short shelf life exhibit.

Next the preparation individually perfumed Products, there is another need that a product packaging is designed such that the fragrance of the packaging contained Product is olfactometrically noticeable.

Finally Packaging increasingly also functionalized that on the packaging fragrance emitting means are arranged, the one release certain fragrance into the environment of the packaging and so on additional Take over the function of a room freshener.

to individual portioning of products according to requirements is the use Of blister packs, for example, in the field of drug delivery usual. in this connection are individual drug doses, for example in the form of tablets, each packaged in a blister pack chamber.

Usually If such a blister pack consists of a first surface element, in that a variety of individual, usually cup-shaped, separate cavities are designed for receiving product doses and a second Surface element, which flat with the first surface element connected and the cavities closes.

Usually is the first surface element, in that the cavities are introduced, from a plastic film piece in which the cavities, for example be formed by deep drawing.

The second, the cavities closes surface element is made of a material that is strong enough to prevent unintentional opening avoid, however, by applying an appropriate pressure, e.g. by thumb pressure or tearing the film with a fingernail, leaves open. By pressure on a chamber of the blister pack will put pressure on in the Chamber product is exercised, that finally the lower foil pierces.

A Blister packaging can also be designed so that the second, the cavities occlusive surface element, in this way made firmer is that the cup-shaped wells of the first surface element opened by the applied pressure and the second, the cavities closes surface element undamaged remains.

Out DE4239082 is the use of such blister packs for perfume emitting substance known. The blister pack consists of a plurality of perfume-filled chambers, the back of the blister pack being provided with an adhesive layer which can be adhered to a garment or human skin.

adversely in this solution is that the blister pack is not unsolvable with a carrier object is connectable. So the blister pack can always completely from Carrier object, such as the human skin, are replaced. Especially for sales packaging However, this is not desirable and in such disadvantageous that a blister pack unintentionally, for example, by failure of the adhesive, from the sales packaging fall, or, with criminal intent, removed from the sales container becomes.

Furthermore, the product in the cup-shaped depressions of the blister pack can not be released by destruction of the lower film, as this lower film according to the teaching DE4239082 sticks to the carrier object over the entire surface. Thus, it is unavoidable that in the destruction of a cup-shaped cavity to release a portion of product, this product comes into contact with the user's hands. For many applications, such as in the dosage of cleaning substances or highly concentrated fragrance oils, this is undesirable.

Out WO2004 / 084660 is known, perfume emitting substances in one Closure flap of a container to arrange. Here are in a chamber of the container closure perfume emitting substances arranged, said chamber having a Foil sealed, which removes the use of the room freshener cap Can be, so that perfume from the flap to the environment can be delivered. A disadvantage of this solution is the comparatively size and thus for the consumer unwieldy form of this closure. As a result of that the inner volume of the closure almost completely with filled with a perfume is virtually no dosing available, so that the closure is not usually used as a doser, such as at closures of softener or floor cleaner, can be used. By the necessarily enlarged design compared to usual closures is also increasing the storage requirement for so equipped Container, which inevitably increased too Logistics costs leads.

CA983437 discloses a container for medical applications where it is necessary to take a prescribed dose of a tablet or capsule in conjunction with a liquid. For this purpose, a container according to CA983437 via means for receiving the individual cans on the outer wall of the container. These are depressions in the outer wall, in which the individual doses can be inserted or placed. The cans located in the wells are then fixed with adhesive tape in the wells. To remove a dose, the adhesive tape can then be lifted and withdrawn, so that a dose is released and can be removed from the recess of the outer wall of the container.

These solution has the disadvantage that the production of a corresponding container expensive and technically complicated. In addition, large areas are needed, which the place for Significantly restricts advertising and / or descriptive labels. Also becomes thereby the aesthetic one Overall impression of the container noticeably negatively influenced. Another disadvantage of this solution is that is not pasty or gel-like preparations can be dosed and removed.

Task of invention

task The present invention is therefore an inexpensive to produce To create packaging that allows individually packaged portionable Additive units in a simple and easy to use way on a container provide.

The The object is achieved by a packaging unit comprising a container for receiving a product, a closure and a closable by the closure opening for removal of the product from the container wherein the packaging unit at least one receiving means for a plurality of additive portions of less than 50 ml, wherein the Additive at least one substance from the group of fragrances, Dyes or surfactants and comprises the receiving means for the additive portions solvable can be fixed to the packaging unit.

Under Packaging unit in the sense of this application is the entirety from container, Container opening and Closure understood.

The Receiving means for a plurality of product portions can be used, for example, as a tear-off pack, pillow pack, Shrink wrap, blister pack, blister pack, blister pack, contour pack, Blister pack, Skin pack, stretch wrap, strip pack, vacuum pack, combination pack, multi-component pack, Multipack, Multipart pack, portion pack, multipack or multipack accomplished be.

Especially the receiving means can also be considered as substantially dimensionally stable body be formed, to which individual additive portions are fixable.

The Additive portions are each of such a flexible or dimensionally stable container at least partially enclosed that in the serving Additive is not released unintentionally. The additive portions can solvable or be firmly connected to the receiving means.

The Additive portions can for example, by a substantially flexible blister pack, blister pack or contour wrapping are formed, which then suitably are connected to the receiving means for fixing to the container.

It is also conceivable, the additive portions as a dimensionally stable container like for example, a closable Cups or vials auszuformen, which then, preferably, releasably in the packaging unit can be fixed.

The Receiving means for the additive portions can be prepared by soluble compounds which appear suitable to the person skilled in the art on the container be attached. In particular, the fixation on the container material, form- and / or non-positively for example, by one or more of the connection types the group of snap-in connections, Kletverbindungen, press connections, Fusible links, glued joints, welded joints, solder joints, Screw connections, wedge connections, clamp connections or bounce connections respectively.

Of the Content of the additive portions, for example, from one or more identical or different products such as, fragrances, Cleaning substances, dyes, surfactants, fungicides, enzymes, hygroscopic substances and the like exist.

According to one particular embodiment the invention it is possible that the container the additive portions consist at least partially of a material, a diffusive release of trapped in the additive portions Product allowed to the environment. In addition, in this case the additive portion of an additional Protective film to be covered, the first to a product delivery the environment prevents. The protective film can for example by Tear off or rubbing away from an additive portion so that then additive product can be delivered to the environment.

The Invention is particularly suitable for dimensionally stable containers such as cups, cans, buckets, barrels, bottles, Canisters, pitchers, boxes, drums or tubes, but can also for flexible containers like bags or sacks be used.

at Cans may in particular be a stretched can, Press-in lid box, retracted Box, folding lid box, folding lid filling box, folded box, Pulled box, Piston box, Winding box, Zipper tape box, Sick box, Slip lid box or step edge can trade.

Barrels can be out the group of belly barrels, Stave barrels, Sealing barrels, Garage barrels, Half sealing barrels, Pack barrels, Roll hoop drums, Heavy barrels, channel drums or roll bead barrels selected become.

A Bottle can be used, for example, as an aerosol bottle, see-through bottle, Beverage bottle, especially Ale bottle, Bocksbeutel, Kropfhalsflasche, Schlegelflasche, Steinie Bottle, Stubby Bottle, Vichy Bottle, Wide Neck Bottle, as well Megapat bottle, squeeze bottle, dropper bottle, packaging bottle like something a bottle, running be.

Among boxes for the purposes of this application are in particular folding boxes such as Aufrichtschachteln, passage boxes, Faltbodenschachteln, Falthüllenschachteln, cartons with inner lining, belt folding boxes, Schiebefaltschachteln, Steckbodenschachteln, Stülpdeckelfaltschachteln and Aufsatzdeckelschachteln, window boxes, cap boxes such as reference caps boxes or knurled cardboard boxes, as well as flap lid boxes, hull boxes, sliding boxes, chip boxes, slip-on lid boxes, carrying boxes or shipping boxes understood.

at the opening of the container in particular, it may be a push-in flap, cuff, in particular Outer collar, as well as mouthpiece or mouth or valve carrier, Band mouthpiece Kronenkorkmundstück, Hole mouthpiece Schraubmundstück, Extrusion die, Bunghole, or tap hole act.

at The closure may be a closure means from the group of Lid, tear-off lid, roll-down lid, The easy open end, Attachment lid, push-in lid, Push-in lid, folding lid, folio lid, flap lid, cam cover, Bayonet cover, groove cover, hinged lid, sliding cover, Insertion cover, snap-on lid, clamping lid, screw cap, slip-on lid, over-lids, Insertion tabs, flaps, outer flaps, inner flaps, closing flaps, Washers, plugs, plugs, screw plugs, stubble, grip plugs, Grinding plugs, sealing caps, Tube caps, Crown corks, screw caps, valve caps, caps, Bottle caps, tear-off capsules, Bördelkapseln and cones act.

Of the Closure and / or the opening of the container can optionally have metering and removal aids, such as an aerosol valve, a spout, a spray cap, a spray head, a nebulizer, one Dosing device, a dosing, a dosing or a dropper.

Under Additive in the context of this application is a substance or substance mixture understood, which is suitable by mixing with the container located in the Product to achieve or influence a property of the product In particular, to improve, manufacture, highlight, mitigate, one speeding up or slowing down a reaction process initiate, inhibit or catalyze. Further, under Additive also be understood a substance or a mixture of substances, which is suitable to achieve a property of the container or to influence, in particular fragrance and / or drug delivery, adsorption or absorption on or in the container.

The Additive may, for example, one or more substances from the Group of perfumes, bleaching agents, cleaning substances, solvents, Surfactants, dyes, enzymes, hygroscopic substances, flame retardants, Harder, Leveling agents, wetting agents, dispersants, foaming agents, defoamers, deaerators, corrosion inhibitors, Biocides, water softeners, Preservatives, emulsifiers, stabilizers, vitamins, minerals and the like.

By the realizable with the invention spatial separation between certain additive active substances (fragrance, enzymes, bleach, etc.) and the actual product as well as arranged directly on the container portionable additive units, the product in the container is on simple way to assemble.

The Additive portions of the receiving means may be the same or different Products include. That's how it is For example, it is conceivable substances with different scents in to arrange the additive portions to different perfumes the contents of the container or to allow the container itself. So, for example when using a fragrance-neutral cleaning fluid the first is mixed with water to a wiping preparation, with each wiping water preparation another perfume from the receiving means for the additive portions added become. This prevents on the one hand the olfaktometrische adjustment to a certain fragrance, on the other hand, a fragrance according to the requirements a special application room (toilet, living room, kitchen). This does not require the use of several special ones perfumed Cleaning substances, which also means environmental protection and resource conservation desirable is.

One Another significant advantage of the invention is its simple and thus cost-effective Production. So it is possible the receiving means for the additive portions completely independently from a container to have finished. Receiving means for the additive portions is subsequently according to the disclosed Teaching the invention on the container attached.

The Receiving means for the additive portions are solvable by the consumer at any time, thereby the receiving means for the additive portions according to a preferred embodiment the invention also to objects outside of the product container can be fixed.

For example, it is also possible, after complete consumption of the additive portions to remove them from the container and a new unused absorption means for additive portions on the container assign.

Polymeric carrier material

According to one preferred embodiment invention, the active additive substances are on or in a polymeric carrier material bound. Fragrances in or on a polymeric are particularly preferred support material bound.

For the perfume-containing Particles are generally all polymers or polymer mixtures, which are the above-mentioned criteria regarding the melting or softening temperature fulfill. In the context of the present application preferred scent delivery systems are characterized in that the polymeric carrier material at least one substance from the group comprising ethylene / vinyl acetate copolymers, Low or high density polyethylene (LDPE, HDPE) or blends the same, 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, polymethylmethacrylate, Polyurethanes, polyvinyl alcohols contains.

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 usually prepared by polymerization of ethylene by two fundamentally different methods, the high pressure and the low pressure process. The resulting products are accordingly often referred to as high pressure polyethylenes and low pressure polyethylenes, respectively; they differ mainly in their degree of branching and, consequently, in their degree of crystallinity and their density. Both methods can be carried out as solution polymerization, emulsion polymerization or gas phase polymerization.

When high-pressure method branched low-density polyethylenes fall at (about .915 to .935 g / cm ³⁾ and crystallinity of about 40-50%, obtained as LDPE-type (low density polyethylene), respectively. Products with a higher molecular weight and the resulting improved strength and ductility have the abbreviation HMW-LDPE (HMW = high molecular weight). By copolymerizing the ethylene with longer-chain olefins, in particular with butene and octene, the pronounced degree of branching of the polyethylenes produced in the high-pressure process can be reduced; the copolymers have the abbreviation LLD-PE (linear low density polyethylene).

The macromolecules The polyethylenes from low-pressure process are largely linear and unbranched. These polyethylenes, abbreviated HDPE (from E high density polyethylene) have degrees of crystallinity of 60-80% and a density of about 0.94-0.965 g / cm3. They are considered high and ultra high molecular weight products (about 200 000-5 000 000 g / mol or 3 000 000-6 000 000 g / mol) under the abbreviation 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 polyethylenes with densities <0.918 g / cm3 (VLD-PE, from E very low density polyethylene) win only slow market meaning.

polyethylenes have a very low water vapor permeability, the diffusion of Gases as well as flavorings and ethereal substances by polyethylenes quite high. The mechanical properties are highly dependent on Molecular size and structure the polyethylene. In general, the degree of crystallinity and the density of polyethylenes are increasing with decreasing degree of branching and with shortening of the side chains. With the density increase shear modulus, hardness, yield strength and melting range; it decreases from shock resistance, transparency, swellability and solubility. At the same density, the molecular weight of the polyethylenes increases Tear resistance, Elongation, shock resistance, impact resistance and creep resistance to. Depending on how you work in the polymerization you can products with paraffin wax-like Properties (MR around 2000) and products with highest toughness (MR over 1 million) receive.

The Processing of polyethylene types can be done after all for thermoplastics Methods are done.

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

Base for the Polypropylene manufacturing was the evolution of the process stereospecific polymerization of propylene in the gas phase or in suspension by Natta. This is done with Ziegler-Natta catalysts, increasingly but also initiated by metallocene catalysts and leads either to highly crystalline isotactic or less crystalline syndiotactic or to amorphous atactic polypropylenes.

polypropylene characterized by high hardness, Resilience, Stiffness and heat resistance. Short-term heating of objects made of polypropylene is even possible up to 140 ° C. At temperatures below 0 ° C occurs a certain embrittlement the polypropylene, but by copolymerization of propylene with ethylene (EPM, EPDM) to much lower temperature ranges can be moved. In general, the impact resistance can be of polypropylene by modification with elastomers. The chemical resistance is good as with all polyolefins. An improvement of the mechanical Properties of the polypropylenes are achieved by reinforcement with Talc, chalk, wood flour or glass fibers. Polypropylenes are in even stronger Dimensions as PE oxidation and photosensitive, which is why the addition of stabilizers (Antioxidants, light stabilizers, UV absorbers) is required.

polyether is one in the field of Macromolecular Chemistry Designation for Polymers whose organic repeating units are characterized by ether functionalities (C-O-C) held together. According to this definition belongs one Variety of structurally very different polymers to the polyethers, e.g. the polyalkylene glycols (polyethylene glycols, polypropylene glycols and polyepichlorohydrins) as polymers of 1,2-epoxides, epoxy resins, Polytetrahydrofurans (polytetramethylene glycols), polyoxetanes, polyphenylene ethers (see polyaryl ether) or polyetheretherketones (see Polyetherketone). Not the polyethers are polymers with pendant ether groups calculated, as u.a. the cellulose ethers, starch ethers and vinyl ether polymers.

to Group of polyethers count furthermore also functionalized polyethers, d. H. Connections with a polyether scaffold, the laterally attached to their main chains still other functional Groups wear such as Carboxy, epoxy, allyl or amino groups etc. Versatile are block copolymers of polyethers and polyamides (so-called polyetheramides or polyether block amides, PEBA).

When Polyamides (PA) are called polymers whose basic building blocks held together by amide bonds (-NH-CO-). Naturally occurring Polyamides are peptides, polypeptides and proteins (Ex .: protein, wool, Silk). The synthetic polyamides are, with a few exceptions thermoplastic, chain-shaped Polymers, some of which are large have achieved technical importance as synthetic fibers and materials. After the chemical structure, the so-called homo-polyamides can be into two groups, the aminocarboxylic acid types (AS) and the diamine-dicarboxylic acid types (AA-SS, where A denotes amino groups and S denotes carboxy groups). The former are made from only a single monomer by e.g. polycondensation an ω-aminocarboxylic acid (1) (Polyamino) or by ring-opening Polymerization of cyclic amides (lactams) (2) prepared.

Next The homopolyamides also some co-polyamides have gained importance. It is usual in these a qualitative and quantitative statement of the composition e.g. PA 66/6 (80:20) for from 1,6-hexanediamine, adipic acid and ε-caprolactam in molar ratio 80:80:20 manufactured polyamides.

Because of their special properties, polyamides which contain exclusively aromatic radicals (for example those from p-phenylenediamine and terephthalic acid) are classified under the generic reference. Aramids or polyaramides summarized (Ex .: Nomex ^® ).

The most frequently used polyamide types (in particular PA 6 and PA 66) consist of unbranched chains with average molar masses of 15,000 to 50,000 g / mol. You are in solid state semi-crystalline and have degrees of crystallization of 30-60%. An exception are polyamides of building blocks with side chains or co-polyamides of strong different components, which are largely amorphous. In contrast to the generally milky-opaque, semi-crystalline polyamides These are almost crystal clear. The softening temperature of the most common Homo-polyamides are between 200 and 260 ° C (PA 6: 215-220 ° C, PA 66: 255-260 ° C).

polyester is the collective name for Polymers whose basic building blocks are held together by ester bonds (-CO-O-) become. After their chemical structure, the so-called Homopolyesters can be divided into two groups, the hydroxycarboxylic acid types (AB polyester) and the dihydroxy-dicarboxylic acid types (AA-BB polyester). The former are made of only a single monomer by e.g. polycondensation an ω-hydroxycarboxylic acid 1 or by ring-opening polymerization cyclic ester (lactone) 2 produced.

branched and crosslinked polyesters are used in the polycondensation of three or polyhydric alcohols with polyfunctional carboxylic acids. The polyesters are generally also the polycarbonates (polyester carbonic acid) expected. AB type polyester (1) are u. a. Polyglycolic acids, polylactic acids, polyhydroxybutyric acid [poly (3-hydroxybutyric acid), poly (ε-caprolactone) e and polyhydroxybenzoic acids.

Purely Aliphatic AA-BB type polyesters (II) are aliphatic polycondensates Diols and dicarboxylic acids, the u. a. as products with terminal Hydroxy groups (as polydiole) for the preparation of polyester polyurethanes [e.g. Polytetramethylene]. The largest technical significance in terms of quantity AA-BB type polyester of aliphatic diols and aromatic dicarboxylic acids, in particular the polyalkylene terephthalates, with polyethylene terephthalate (PET), Polybutylene terephthalate (PBT) and poly (1,4-cyclohexanedimethylene terephthalate) s (PCDT) as the most important representative. These types of polyesters can by Co-use of other aromatic dicarboxylic acids (for example isophthalic acid) or by using diol mixtures in the polycondensation in their Properties widely varied and different application areas customized become.

Purely Aromatic polyesters are the polyarylates, which include u.a. which include poly (4-hydroxybenzoic acid). In addition to the previously mentioned saturated Polyesters can also be unsaturated polyesters from unsaturated Dicarbonsäunen produced as polyester resins, especially as unsaturated polyester resins (UP resins), have achieved technical importance.

polyester are usually thermoplastics. Products based on aromatic Possess dicarboxylic acids pronounced material character. The purely aromatic polyarylates are characterized by high thermal stability.

When Polyurethanes (PUR) are polymers in whose macromolecules the Repeating units are linked by urethane groups -NH-CO-O-. Polyurethanes are generally prepared by polyaddition from or higher quality Alcohols and isocyanates obtained.

ever optional and stoichiometric relationship The starting materials are thus polyurethanes with very different mechanical properties as components of adhesives and paints (polyurethane resins), as ionomers, as thermoplastic Material for Stock parts, rollers, tires, rollers are used and as more or less hard elastomers in fiber form (elastofibres, short. PUE for these elastane or spandex fibers) or as polyether or polyester urethane rubber (EU or AU)

Polyurethane foams are produced in the polyaddition, when water and / or carboxylic acids are present, because these react with the isocyanates with elimination of impulsive and foaming carbon dioxide. With polyalkylene glycol ethers as diols and water as the reaction component to get to flexible polyurethane foams, with Polyols and propellants from CFCs (especially R 11) are obtained rigid polyurethane foams and structural or integral foams. Additional auxiliaries needed are here e.g. Catalysts, emulsifiers, foam stabilizers (especially polysiloxane-polyether copolymers), Pigments, aging and flame retardants. To the manufacturer of too complicated shaped objects made of polyurethane foam in the 70s, the so-called RIM technology developed (reaction injection molding). The RIM Avail. based on rapid dosing and mixing of components, Injection of the reactive mixture into the mold and rapid curing; the Cycle time is just minutes. Using RIM technology u.a. Car body parts, Shoe soles, window profiles and television housing generated.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs enthalten.Polyvinyl alcohols (PVAL, occasionally also PVOH) is the term for polymers of the general structure

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

Commercially available polyvinyl alcohols be as white-yellowish Powders or granules with degrees of polymerization in the range of approx. 100 to 2500 (molecular weights of about 4000 to 100,000 g / mol) offered. The polyvinyl alcohols are characterized by the manufacturers by indicating the degree of polymerization of the starting polymer, the Hydrolysis degree, the saponification number or the solution viscosity.

polyvinyl alcohols are dependent soluble in the degree of hydrolysis in water and a few highly polar organic solvents (Formamide, dimethylformamide, dimethyl sulfoxide); of (chlorinated) Hydrocarbons, esters, fats and oils are not attacked. Polyvinyl alcohols are classified as toxicologically harmless and are at least partially biodegradable biologically. The water solubility can be by post-treatment with aldehydes (acetalization), by Complexation with Ni or Cu salts or by treatment with dichromates, boric acid or reduce borax. The coatings of polyvinyl alcohol are broad impenetrable for Gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, however allow water vapor to 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 whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 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 The present invention is the polymeric carrier material the particle at least partially of ethylene / vinyl acetate copolymer. Another preferred subject of the present application is therefore a fragrance delivery system, characterized in that the polymeric support material at least 10% by weight, preferably at least 30% by weight, more preferably contains at least 70 wt .-% ethylene / vinyl acetate copolymer, preferably completely Ethylene / vinyl acetate copolymer is produced.

Ethylene / vinyl acetate copolymers is the name for Copoylmers of ethylene and vinyl acetate. The production of this polymer takes place in principle in one of the production of low density polyethylene (LDPE; low density polyethylene) comparable methods. 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 also 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). In the present invention, particularly suitable polyvinyl alcohols are, for example Elvax ^® 265, Elvax ^® 240, Elvax ^® 205W, Elvax ^® 200W, as well as Elvax ^® 360th

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

in the Frame of the present invention, especially in the field of scenting the interiors fragrance delivery systems are particularly preferred in which as polymeric 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 dispensing systems according to the invention contain the polymeric support materials in the form of particles. The spatial form of these particles is merely through the technical possibilities limited in their manufacture. As a form of space so come all reasonable manageable configurations into consideration, for example, cubes, cuboids and corresponding Room elements with flat side surfaces and in particular cylindrical Embodiments with circular or oval section. This last embodiment includes tableted Particles up to compact cylinder pieces with a ratio of Height to diameter above 1. Other possible Spatial forms are spheres, hemispheres or "stretched spheres" in the form of ellipsoidal capsules as well like regular ones Polyhedra, for example tetrahedron, hexahedron, octahedron, dodecahedron, Icosahedron. Also conceivable are star-shaped formations with three, four five, six or more tips or completely irregular bodies that for example, can be designed motivically. As motives are suitable dependent on from the field of application of the agents according to the invention, for example animal figures, like dogs, horses or birds, floral motifs or the representation of fruits. The motivic design can but also on inanimate objects such as vehicles, tools, Household items or clothing. The surface of the solid particles can dependent on on the type of chosen Manufacturing process and / or a selected coating bumps exhibit. Due to the numerous design options for the Particles are not only the advantages of the agents according to the invention during their production. Due to the manifold forms of design In addition, the perfume-containing particles are optically clear to the consumer perceptible and allow through the targeted spatial design this particle one for the product acceptance particularly advantageous visualization of in the agent of the invention contained fragrances, or further optional in these agents contained active substances. So can through the visually perceptible Polyphase of these means, for example, the different Mode of action of individual active substances (for example, cleaning and additional functions as glass protection, silver protection etc.) are clarified.

When Particles are summarized in the context of the present application particles which a solid at room temperature, that is dimensionally stable, non-flowable consistency exhibit. Preferred particles have a mean diameter from 0.5 to 20 mm, preferably from 1 to 10 mm and in particular from 3 to 6 mm.

The preparation of the polymeric support materials to the particles described above can all methods known to those skilled in the processing of these substances take place. In the context of the present invention, extrusion is preferably preferred by injection molding and spraying into polymer granules.

fragrances

When Perfume oils or Fragrances can in the context of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, Ketones, alcohols and hydrocarbons are used. fragrance compounds the type of esters are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Count to the Ethern for example, benzyl ethyl ether, to the aldehydes e.g. the linear ones Alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, α-isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly the terpenes like limonene and pinene.

Prefers However, mixtures of different fragrances are used, the together create an appealing scent. 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. Also Muscat, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum oils are also suitable Orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

The general description of the applicable perfumes (see above) provides in general the different substance classes of fragrances To be perceptible, one must Perfume be volatile, besides the nature of the functional groups and the structure the molecular weight of the chemical compound also plays an important role plays. So most perfumes have molecular weights up to about 200 Dalton, while Molar masses of 300 daltons and above rather an exception. Due to the different volatility changed by fragrances the smell of a compound of several fragrances perfumes or perfume during vaporizing, whereby the odor impressions in "top note", "middle note" body) and "base note" (end note or dry divided out). Because the smell perception to a large extent also on the smell intensity is based, the top note of a perfume or fragrance is not alone from volatile Connections while the base note for the most part from less volatile, i.e. adherent fragrances. When composing perfumes can be easier volatile For example, fragrances can be bound to specific fixatives. which prevents it from evaporating too quickly. At the following Classification of the fragrances in "lighter volatile or "adherent" fragrances So over the smell impression and about it, whether the corresponding fragrance is perceived as head or middle note, nothing testified.

By means of a suitable selection of said fragrances or perfume oils, the product smell can be influenced in this way for agents according to the invention immediately upon opening the brand-new composition as well as the use fragrance, for example when used in a dishwashing machine. These fragrance impressions can of course be the same, but can also differ. For the latter odor impression, the use of adhesive odoriferous substances is advantageous, while also more volatile odoriferous substances can be used for product scenting. Adhesion-resistant fragrances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamot oil, Champacablütenöl, Edel fir oil, Edeltannenzapfen oil, Elemiöl, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, Guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine oil, copaia balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, Musk Grain Oil, Myrrh Oil, Clove Oil, Neroli Oil, Niaouli Oil, Olibanum Oil, Orange Oil, Origanum Oil, Palmarosa Oil, Patchouli Oil, Peru Balsam Oil, Petitgrain Oil, Pepper Oil, Peppermint Oil, Pimento Oil, Pine Oil, Rose Oil, Rosemary Oil, Sandalwood Oil, Celery Oil, Spik Oil, Star Aniseed Oil, Turpentine Oil, Thuja Oil, Thyme oil, verb ena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon oil, lemon oil, lemon oil and cypress oil. But also the higher-boiling or solid fragrances of natural or synthetic origin can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances. These compounds include the compounds listed below and mixtures thereof: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, Ben ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol, bornyl acetate, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptincarboxylic acid methyl ester, Heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole, jasmon, camphor, karvakrol, karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilate, p-methylacetophenone, Methylchavikole, p-methylquinoline, methyl-β-naphthylketone, methyl-n-nonylacetaldehyde, methyl-n-nonylketone, muskon, β-naphtholethyl ether, β-naphtholmethyl ether, nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p- Oxy-acetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegone, safrole, salicylsä ureisoamyl ester, salicylic acid methyl ester, hexyl salicylate, cyclohexyl salicylate, santalol, skatole, terpineol, thymes, thymol, γ-undelactone, vaniline, veratrum aldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, cinnamic acid ethyl ester, cinnamic acid benzyl ester. 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 readily volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.

Prefers The plastic particles are at a temperature of 15 to 30 ° C, preferably from 20 to 25 ° C, with the selected one Laden with fragrance. For this purpose, the particles with the corresponding Amount of the fragrance added and mixed. In any case, should the temperature but below the melting or decomposition temperature of the plastic and also below the flash point of the perfume oil. The fragrance is primarily by adhesion, diffusion and / or capillary forces from the polymeric carrier material or of further perfume carrier materials contained in the particle, which may swell slightly during this process.

Other active substances

As previously mentioned, can inventive agent except the ingredients necessary for perfuming and deodorising more Active ingredients included. Of the means which exclusively the Serving scenting, therefore, further product groups can be distinguished, which in addition to the aforementioned inventive components further preferred Contain substances.

dyes

A The first of these optionally usable preferred substances are the Dyes. For this purpose, all dyes are generally suitable, the Professional as suitable for coloring of plastics or as soluble in perfume oils are known. It is preferable to use the dye according to the one used Select fragrance; For example, lemon fragrance particles preferably have one yellow paint on while for particles with apple or herb scent a green Color is preferred. Preferred dyes have a high storage stability and insensitivity across from the rest Ingredients of the agents and against light. Will the agents of the invention used in connection with textile or dishwashing, should the dyes used have no pronounced substantivity towards textile fiber, Glass, plastic utensils or ceramics do not have these to stain.

Suitable dyes and dye mixtures are commercially available under various trade names and are offered, inter alia, by the companies BASF AG, Ludwigshafen, Bayer AG, Leverkusen, Clariant GmbH, DyStar Textile dyes GmbH & Co. Germany 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 grass-W-2201), Sandoplast Blue 2B, Fat Yellow 3G, Iragon ^® Red SRE 122 Iragon ^® Green SGR 3, Solvent Yellow 33 and Solvent Yellow 16, but other dyes may be included.

In a preferred embodiment the dye has in addition to its aesthetic effect in addition a Indicator function. This will give the consumer the current consumption status of the deodorant so that he in addition to the lack of fragrance impression, for example, on a habituation can be based on the part of the user, another reliable indication gets when to replace the deodorant with a new one.

The indicator effect can be achieved in various ways: On the one hand, a dye can be used, which escapes from the particles during the period of application. This can be, for example caused by the ingredients contained in the dishwashing detergent. For this purpose, a dye must be used, which adheres well to the particles or only slowly diffuses out of them to ensure that the discoloration is not too early, namely, when the fragrance is not consumed, is completed. On the other hand, a color change can also be caused by a chemical reaction or thermal decomposition.

Antimicrobial agents, Germicides, fungicides

Further preferred ingredients of the invention are substances such as antimicrobial agents, germicides, fungicides, antioxidants or corrosion inhibitors, with the help of additional benefits, such as the disinfection or corrosion protection can be realized.

to fight of microorganisms can the agents according to the invention contain antimicrobial agents. Here one differentiates depending on antimicrobial spectrum and mechanism of action between Bacteriostats and bactericides, fungistats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, Alkylarlyl sulfonates, halophenols and phenol mercuriacetate.

antioxidants

Around unwanted, caused by oxygen and other oxidative processes changes on the inventive compositions or to prevent the example treated textiles, the Contains medium antioxidants. For example, this class of connection includes substituted phenols, hydroquinones, catechols and aromatic Amines and organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Become the agents according to the invention in dishwashers used, so they can Means for protecting the items to be washed or the machine contain corrosion inhibitors, with particular silver protectants in the field of automatic dishwashing a special meaning to have. Can be used, the known substances of the prior Technology. General can especially silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, Alkylaminotriazole and the transition metal salts or complexes are used. Particularly preferable to use are benzotriazole and / or alkylaminotriazole. One finds in cleaner formulations about that often out Active chlorine-containing agents, the corrosion of the silver surface clearly can diminish. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds used. Also salt and complex inorganic compounds, such as salts The metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preference is given here to 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. Also can Zinc compounds used to prevent corrosion of items to be washed become.

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

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

Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally additionally one or more of the abovementioned anions. The central atom is one of the above-mentioned metals in one of the abovementioned oxidation states. The ligands are neutral molecules or anions that are mono- or polydentate; The term "ligands" in the context of the invention is explained in more detail, for example, in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507". If, in a metal complex, the charge of the central atom and the charge of the ligand (s) are not zero, either one or more of the abovementioned anions or one or more cations, for example sodium, provides, depending on whether there is a cationic or an anionic charge excess , Potassium, ammonia umionen, for charge balancing. Suitable complexing agents are, for example, citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The common in chemistry Definition for "oxidation state" is e.g. in "Römpp Chemie 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 in that preferred agents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [ 1-hydroxyethane-1,1-diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ .

In these metal salts or metal complexes are generally commercially available substances that can be used for the purpose of silver corrosion protection without prior purification in the compositions of the invention. Thus, for example, the mixture of pentavalent and tetravalent vanadium (V ₂ O ₅ , VO ₂ , V ₂ O ₄ ) known from the SO ₃ preparation (contact method) is suitable, as is the case by diluting a Ti (SO ₄ ) ₂ - Solution resulting titanyl sulfate, TiOSO ₄ .

The mentioned metal salts and / or metal complexes are in the inventive compositions, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, based on the total agent without the container included

Means to Prevention of glass corrosion

One important criterion for the evaluation of a machine dishwashing detergent is in addition to its cleaning performance, the visual appearance of dry dishes after cleaning. Eventually occurring Calcium carbonate deposits on dishes or in the machine interior, for example, customer satisfaction impair and have causal Influence on the economic success of such a cleaning agent. Another longstanding problem with automatic dishwashing is the corrosion of glassware, usually due to the appearance of cloudiness, streaks and scratches, but also by iridescence of the glass surface can express. The observed Effects are based essentially on two processes, for a leakage of alkali and alkaline earth ions from the glass in Connection with a hydrolysis of the silicate network, on the other hand in a deposit of silicate compounds on the glass surface.

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

A preferred class of compounds used to prevent glass corrosion the agents according to the invention can be added are insoluble Zinc salts. these can while the dishwashing process attach to the glass surface and prevent that there in solution go of metal ions from the glass network as well as the hydrolysis of the Silicates. additionally prevent these insoluble Zinc salts also the deposition of silicate on the glass surface, so that this Glass is protected from the consequences described above.

Insoluble zinc salts in the context of this preferred embodiment are zinc salts which have a solubility of a maximum of 10 grams of zinc salt per liter of water at 20 ° C. Examples of particularly preferred insoluble zinc salts 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 mentioned zinc compounds are in the inventive compositions used in amounts containing a level of zinc ions between 0.02 and 10 wt .-%, preferably between 0.1 and 5.0 wt .-% and in particular between 0.2 and 1.0 wt .-%, each based on the Agent without the container, effect. The exact content of the agent on the zinc salt or zinc salts is naturally dependent on the type of zinc salts - ever less soluble the zinc salt used is, the higher its concentration should be in the inventive compositions be.

A Another preferred class of compounds are magnesium and / or Zinc salts) of at least one monomeric and / or polymeric organic Acid. These cause that too when used repeatedly, the surfaces of glassware are not corrosively changed, in particular no cloudiness, Streaks or scratches but also no iridescence of the glass surfaces caused become.

Although according to the invention all magnesium and / or zinc salts) of monomeric and / or polymeric organic acids may be contained in the claimed compositions, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids are selected 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, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred. Within these groups, the acids mentioned below are again preferred in the context of the present invention:
The spectrum of the inventively preferred zinc salts of organic acids, preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / L, preferably below 10 mg / L, in particular have no solubility, to such Salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate:
In a further preferred embodiment of the present invention, the agents according to the invention comprise at least one zinc salt but no magnesium salt of an organic acid, which is preferably at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt selected from zinc stearate, zinc oleate, zinc gluconate, zinc acetate , Zinc lactate and / or zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

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

One Another preferred subject of the present application is therefore a fragrance delivery system containing other active substances, in particular Active substances from the group of perfume carriers, dyes, antimicrobial Agents, germicides, fungicides, antioxidants or corrosion inhibitors contain.

bleach

In addition to the abovementioned active substances, the agents according to the invention, in particular funds for use in dishwashers, Textile washing machines or dryers, of course, all usually in funds for the textile or dishwashing or the textile or dish care having active substances contained, wherein substances from the Group of bleaching agents, bleach activators, polymers, builders, Surfactants, enzymes, electrolytes, pH adjusters, Fragrances, perfume carriers, dyes, Hydrotrope, foam inhibitors, anti redeposition agents, optical Brightener, grayness inhibitors, inlet preventer, anti-crease agents, Dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, repellents and impregnating agents, Swelling and anti-slip agents, non-aqueous solvents, fabric softeners, protein hydrolysates, 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 crockery.

As important constituents of detergents or cleaners, bleaching agents and bleach activators may be present in the compositions according to the invention, among other constituents. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Dishwashing detergent tablets may also contain bleaches from the group of organic bleaches. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzo (c) the aliphatic or substituted aliphatic peroxyacids such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid , N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-Terephthaloyl-di (6-aminopercaproic acid) can be used.

Become the agents according to the invention used in combination with automatic dishwashing detergents, these can Bleach activators are included to assist in cleaning at temperatures of 60 ° C and including achieving an improved bleaching effect. As bleach activators can Compounds which, under perhydrolysis conditions, are aliphatic peroxycarboxylic acids preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O and / or N-acyl groups of said carbon atom number and / or optionally substituted Wear benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated 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 preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles 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 having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having 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 where 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.In particularly preferred inventive agents is a cationic nitrile of the formula

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 also be -H and X is an anion, where 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, wherein in turn from the group of these substances the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^(-) , in which X ^{- represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate ( Tosylate) or xylene sulfonate is particularly preferred.

In addition to The conventional bleach activators or in their place may also so-called bleach catalysts are incorporated into the agents. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.

surfactants

preferred Means contain in the context of the present application one or more Surfactants) from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.

When 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 alkylsulfuric acids and the alkylarylsulfonic acids, used. To have sufficient surface-active properties the compounds mentioned should have longer hydrocarbon radicals feature, that is, have at least 6 C atoms in the alkyl or alkenyl radical. Usually, the C-chain distributions are the anionic surfactants in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.

Carboxylic acids, which are used in the form of their alkali metal salts as soaps in detergents and cleaners, are obtained industrially, for the most part, from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage. 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. are preferred in the context of the present invention of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and the 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-octadecadienoic acid (linoleic acid), 9t, 12t- Octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c octadecatrienoic acid ( For reasons of cost, it is preferred not to use the pure species, but technical mixtures of the individual acids, as they are accessible from lipolysis. Such mixtures are, for example, coconut oil fatty acid (about 6 wt .-% C ₈ , 6 wt .-% C ₁₀ , 48 wt .-% C ₁₂ , 18 wt .-% C ₁₄ , 10 wt .-% C ₁₆ , 2 wt % C ₁₈ , 8% by weight C _{18 '} , 1% by weight C _{18 "} ), palm kernel oil fatty acid (about 4% by weight C ₈ , 5% by weight C ₁₀ , 50% by weight). % C ₁₂ , 15 wt .-% C ₁₄ , 7 wt .-% C ₁₆ , 2 wt .-% C ₁₈ , 15 wt .-% C _{18 '} , 1 wt .-% C _18'' ), tallow fatty acid ( about 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 wt .-% C _18'' , 1 wt .-% C _18''' ), hardened tallow fatty acid (about 2 wt .-% C ₁₄ , 28 wt .-% C ₁₆ , 2 wt .-% C ₁₇ , 63 wt .-% C ₁₈ , 1 wt .-% C _{18 '} ), technical oleic acid (about 1 wt .-% C ₁₂ , 3 wt .-% C ₁₄ , 5 wt .-% C ₁₆ , 6% by weight C _{16 '} , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _18' , 10% by weight C _{18 "} , 0.5% by weight % C _{18 '''} ), technical palmitic / stearic acid (about 1 wt .-% C ₁₂ , 2 wt .-% C ₁₄ , 45 wt .-% C ₁₆ , 2 wt .-% C ₁₇ , 47 wt. % C ₁₈ , 1% by weight C _{18 '} ) and soybean oil fatty acid (about 2% by weight C ₁₄ , 15 wt .-% C ₁₆ , 5 wt .-% C ₁₈ , 25 wt .-% C _{18 '} , 45 wt .-% C _18'' , 7 wt .-% C _18''' ).

Sulfuric acid semi-esters 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 salts, in particular sodium salts, the fatty alcohol sulfates are industrially available from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, sulfamic acid or sulfur trioxide to the respective alkyl sulfuric acids and subsequently neutralized. The fatty alcohols are thereby obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters. The quantitatively most important industrial process for the production of fatty alkylsulfuric acids is the sulfation of the alcohols with SO ₃ / air mixtures in special cascade, falling film or tube bundle reactors.

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

Also alkanesulfonic and olefinsulfonic acids are 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 along the C chain (secondary alkanesulfonic acids), wherein only the secondary alkanesulfonic have commercial significance. These are by sulfochlorination or Sulfoxidation of linear hydrocarbons. In the sulfochlorination According to Reed, n-paraffins with sulfur dioxide and chlorine under irradiation reacted with UV light to the corresponding sulfochlorides, the upon hydrolysis with alkalis directly the alkanesulfonates, upon reaction with water the alkanesulfonic acids, deliver. As in the sulfochlorination di- and Polysulfochloride as well Chlorinated hydrocarbons as by-products of the radical reaction may occur, the reaction usually becomes only up to implementation levels of 30% performed and then canceled.

One another process to Preparation of alkanesulfonic acids is the sulfoxidation, in which n-paraffins under irradiation with UV light can be reacted with sulfur dioxide and oxygen. at This radical reaction generates successive alkylsulfonyl radicals, which react further with oxygen to the Alkylpersulfonylradikale. The reaction with unreacted paraffin yields an alkyl radical and the alkylpersulfonic acid, which is an alkyl peroxysulfonyl radical and a hydroxyl radical decays. The reaction of the two radicals with unreacted paraffin provides the alkylsulfonic acids or water which reacts with alkylpersulfonic acid and sulfur dioxide to form sulfuric acid. To the yield of the two end products alkylsulfonic acid and Sulfuric acid as possible To keep high and suppress side reactions, this reaction usually becomes only up to implementation levels of 1% performed and then canceled.

olefin be technically by reaction of α-olefins with sulfur trioxide produced. Intermediate zwitterions, which form Cyclize to so-called sultones. Under suitable conditions (alkaline or acidic hydrolysis), these sultones react to form Hydroxylalkansulfonsäuren or alkene sulfonic acids, which both also as anionic surfactant acids can be used.

alkylbenzenesulfonates As powerful anionic surfactants have been since the thirties known in the last century. At that time were by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation Alkylbenzenes prepared, which are sulfonated with oleum and sodium hydroxide were neutralized. The early fifties was for manufacturing of alkylbenzenesulfonates propylene to branched α-dodecylene tetramerized and the product over a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride for Tetrapropylenebenzene reacted, which is subsequently sulfonated and neutralized has been. This economic possibility the preparation of tetrapropylene benzene sulfonates (TPS) led to Breakthrough of this class of surfactants, which are the soaps as the main surfactant in detergents and cleaners.

by virtue of The lack of biodegradability of TPS made it necessary to represent new alkylbenzenesulfonates, characterized by an improved ecological Characterize behavior. These requirements are met by linear alkyl benzene sulfonates Fulfills, which today almost exclusively produced alkylbenzenesulfonates are and with the abbreviation ABS or LAS are occupied.

linear Alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are accessible from linear olefins. To do this industrially Petroleum fractions with molecular sieves in the n-paraffins of the desired Purity separated and dehydrogenated to the n-olefins, resulting in both α- and i-olefins. The resulting olefins are then in the presence of acidic catalysts reacted with benzene to the alkylbenzenes, the choice of the Friedel-Crafts catalyst Influence on the isomer distribution of the resulting linear alkylbenzenes has: When using aluminum trichloride, the content of the 2-phenyl isomers in the mixture with the 3-, 4-, 5- and other isomers at ca. 30 wt .-%, however, hydrogen fluoride is used as catalyst, let yourself the content of 2-phenyl isomer to about 20 wt .-% lower. The sulfonation The linear alkylbenzene finally succeeds today industrially with oleum, sulfuric acid or gaseous Sulfur trioxide, the latter having by far the greatest importance. For sulfonation special film or tube bundle reactors are used, the as a product, a 97 wt .-% alkylbenzenesulfonic acid (ABSS) provide, in the Can be used as an anionic surfactant according to the present invention is.

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_9-13-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 here, the alkali metal salts and Among these, it is preferable to prepare and use the sodium salts of ABSS. These can be described by the general formula IX:

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

The The foregoing anionic surfactants in their acid form may be used alone or in admixture be used together. But it is also possible and preferred that the Anionic surfactant in acid form prior to addition to the support material (s) other, preferably acid, ingredients of detergents and cleaners in amounts of from 0.1 to 40% by weight, preferably from 1 to 15% by weight and in particular from 2 to 10 wt .-%, each based on the weight of the mixture to be reacted.

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

Also Cationic surfactants can be used with advantage as an active substance. The cationic surfactant can be delivered directly to the mixer be given or in the form of a liquid to pasty cationic surfactant formulation on the solid support sprayed become. Such cationic surfactant formulations can be, for example by mixing commercial Cationic surfactants with excipients such as nonionic surfactants, polyethylene glycols or produce polyols. Also lower alcohols like ethanol and Isopropanol can be used, the amount of such lower alcohols in the liquid Cationic surfactant preparation form for the reasons mentioned above Should be 10 wt .-%.

When Cationic surfactants come for the agents according to the invention all usual Substances into consideration, whereby cationic surfactants with textile 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 compositions according to the invention may contain as cationic active substances with textile-softening action one or more cationic, textile-softening agents of the formulas X, XI or XII:

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 agents 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 on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, 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 means which, for a particular product, may be an integer or a fractional number. 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, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glykoseeinheit 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; preferably x is 1.2 to 1.4.

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

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide 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.Further suitable surfactants are polyhydroxy fatty acid amides of the formula XIII,

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

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ 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 the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with 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 residue.

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

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

As already mentioned, the use of surfactants in automatic dishwashing detergents is preferably restricted to the use of small quantities of nonionic surfactants. Dishwashing agents according to the invention therefore preferably contain only certain nonionic Surfactants, which are described below. As surfactants, only weakly foaming nonionic surfactants are usually used in automatic dishwashing detergents. Representatives from the groups of anionic, cationic or amphoteric surfactants, however, have less importance. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, 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 means which, for a particular product, may be an integer or a fractional number. 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 for cleaning agents for automatic dishwashing it is preferred that this one Nonionic surfactant containing a melting point above Room temperature, preferably a nonionic surfactant with a melting point above 20 ° C. Preferably used nonionic surfactants have melting points above 25 ° C, particularly preferably 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 said Temperature range, for example, low-foaming nonionic Surfactants which may 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 especially above 40 Pas. Also nonionic surfactants which are waxy at room temperature Consistency are preferred.

Prefers as at room temperature fixed to be used nonionic surfactants derived the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary Alcohols and mixtures of these surfactants with structurally complicated built-up surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants stand out about it out by good foam control.

In a preferred embodiment The present invention is the nonionic surfactant having 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, preferably at least 12 mol, more preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per Mol alcohol or alkylphenol emerged.

A particularly preferred solid at ambient temperature, non-ionic surfactant is derived 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 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide , Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25% by weight, especially preferably up to 20 wt .-% and in particular up to 15 wt .-% of total molecular weight of the nonionic surfactant. Especially preferred nonionic surfactants are ethoxylated monohydroxyalkanols or Alkylphenols, in addition Having polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes preferably more than 30 wt .-%, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight such nonionic surfactants.

More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse 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 polyoxy propylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

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

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

Other 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 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula may 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, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. 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 may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when 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 may be joined 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 selected here by way of example and may well be greater, with the variation width 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 to R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is 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 is} H and x assumes values of 6 to 15.

enzymes

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

Among the proteases, those of the subtilisin type are preferable. Examples are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which are assigned to the subtilases but no longer to the subtilisins in the narrower sense. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ^® variants are derived.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ^® and protease P ^® 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, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

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

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae, which are. Another commercial product is, for example, the amylase ^LT® .

Compositions according to the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^®, Lipolase Ultra ^®, LipoPrime® ^®, Lipozyme® ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. ^Lipase® , Lipase ^AP® , Lipase M- ^AP® and Lipase ^{AML® are} available. By Genencor, for example, the lipases or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products are the originally marketed by Gist-Brocades preparations 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.

Compositions according to the invention can, especially if they are for the treatment of textiles are thought to contain cellulases, depending on the purpose as pure enzymes, as enzyme preparations or in the form of Mixtures in which the individual components advantageously with regard to their different performance aspects. To count these performance aspects in particular contributions to the primary washing performance, for secondary washing performance of the agent (anti-redeposition effect or graying inhibition) and softening (fabric effect), to exerting a "stone washed" effect.

A useful fungal, endoglucanase (EG) -rich cellulase preparation, or its further developments are offered by Novozymes under the trade name Celluzyme ^®. The products Endolase ^® and Carezyme ^® , also available from Novozymes, are based on the 50th kD-EG, respectively 43 kD-EG from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® ^® and Renozyme ^®. Likewise, the 20 kD EG cellulase from Melanocarpus from AB Enzymes, Finland, available under the trade names Ecostone® ^® and Biotouch ^®, can be used. Further 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.

Compositions of the invention may contain other 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 from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, United States. The obtained from B. subtilis β-glucanase is available under the name Cereflo ^® from Novozymes.

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

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

The Purification of the enzymes concerned is conveniently done by itself established methods, for example about precipitation, sedimentation, concentration, Filtration of the liquid Phases, microfiltration, ultrafiltration, exposure to chemicals, Deodorization or suitable combinations of these steps.

Compositions according to the invention can the enzymes are added in any form known in the art become. These include for example, by granulation, extrusion or lyophilization obtained solid preparations or, especially in liquid or gelatinous Means, solutions the enzymes, preferably as possible concentrated, low in water and / or added with stabilizers.

alternative can the enzymes for both the solid as well for the liquid Dosage form can be encapsulated, 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 as in enclosed in a solidified gel or in core-shell type, in which an enzyme-containing core with a water, air and / or Chemikalienundurchlässigen Protective layer coated is. In superimposed layers additional active ingredients, For example, stabilizers, emulsifiers, pigments, bleach or Dyes are applied. Such capsules are after known methods, for example by shaking or Roll granulation or applied in fluid-bed processes. Advantageously Such granules, for example by applying polymeric film-forming agents, low in dust and storage-stable due to the coating.

Farther Is it possible, to assemble two or more enzymes together, so that a single Granules several enzyme activities having.

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

One group of stabilizers are reversible protease inhibitors. Often benzamidine Hy drochloride, borax, boric acids, boronic acids or their salts or esters used, including in particular derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, or their salts or esters. Furthermore, peptide aldehydes, that is oligopeptides with reduced C-terminus are suitable. As peptidic protease inhibitors are, inter alia, ovomucoid and leupeptin to mention; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.

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

low aliphatic alcohols, but especially polyols, such as Glycerine, ethylene glycol, propylene glycol or sorbitol are other often used enzyme stabilizers. Furthermore, di-glycerol phosphate also protects against denaturation due to physical influences. Likewise, calcium salts used, such as calcium acetate or calcium formate as well as 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. Polyamine N-oxide containing polymers act simultaneously as enzyme stabilizers and as dye transfer inhibitors. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkylpolyglycosides can stabilize in accordance with the also the enzymatic components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds perform a dual function as soil release agents and as enzyme stabilizers.

reducing agent and antioxidants like sodium sulfite or reducing sugars increase that stability of the enzymes oxidative decay.

Prefers For example, combinations of stabilizers are used made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing Salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing Salt. The action of peptide-aldehyde stabilizers can be achieved 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 on reinforced become.

Especially Within the scope of the present invention, the use of liquid enzyme formulations is preferred. Here are means according to the invention preferred, in addition Enzymes and / or enzyme preparations, preferably solid and / or liquid Protease preparations and / or amylase preparations, in quantities of 1 to 5 wt .-%, preferably from 1.5 to 4.5 and in particular of 2 to 4 wt .-%, each based on the total agent included.

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

The Invention is illustrated by the in the following figures embodiments explained in more detail. there shows

1 : Container with arranged on the container opening blister pack in perspective view

2a : Blister pack for placement on a container opening with a multitude of small portions

2 B : Blister pack for placement on a container opening with larger portions

2c : Blister pack for placement on a container opening with segmentable separable portions

2d : Blister pack for placement on a container opening with crease lines

2e : Blister pack for placement on a container opening in the folded-in state

3a : Blister pack in cross section

3b : Blister pack in cross section with a permeable and a sealed membrane

4a : Blister pack with snap-in closure

5a : dimensionally stable receiving means for additive portions in the supervision

5b : dimensionally stable absorption means for additive portions in cross section

1 shows a particular embodiment of the invention, in which a blister pack ( three ) over the closure and pouring cylinder of the container ( 1 ), on the container ( 1 ) is fixed. On the lock and spout cylinder is a closure ( 2 ), which has a circumferential shoulder ( 2a ) having.

A detailed view of an embodiment of the blister pack according to the invention is shown in FIG 2a -E shown.

The blister pack ( three ) has an opening ( 4 ), which via the spout cylinder ( 2 ) of the container ( 1 ) can be plugged. In another embodiment, not shown, it is also possible that the blister pack ( three ) with the opening ( 4 ) over the closure ( 2 ) of the container ( 1 ) is fixable.

The opening ( 4 ) of the blister pack ( three ) may be completely or partially closed, with the opening ( 4 ) is designed such that it prevents at least a simple release of the blister pack from the container.

From the collar ( 7 ) extend from one or more blister elements ( 5a . 5b ), each of which has a multiplicity of cavities ( 6 ), usually over the area ( 5a . 5b ) of the blister pack ( three ) arranged distributed.

The collar ( 7 ) is configured such that the closure ( 2 ) in its closed position a force acting substantially perpendicular to the blister plane clamping force on the collar ( 7 ) exercises. The opening ( 4 ) of the blister pack is smaller than the shoulder ( 2a ) of the closure ( 2 ), so that when the container is closed, the blister pack is not removed from the container ( 1 ) but through the shoulder ( 2a ) of the closure ( 2 ) on the container ( 1 ) is held. The shoulder ( 2a ) of the closure ( 2 ) should be chosen so that it is at least partially 4 ) of the blister pack ( 1 ) can act on surrounding surface.

In a particularly preferred embodiment, the blister pack ( 1 ) via a circular opening ( 4 ) and two radially arranged to the opening surface elements ( 5a . 5b ). The blister pack ( three ) is configured such that the two legs ( 5a . 5b ) of the blister pack ( three ) can each be raised at their distal ends.

The blister pack ( 1 ) may be attached, for example, by an adhesive bond to the container. In this case, the adhesive bond only extends in such a way over a partial surface of the blister pack ( 1 ) that the remaining area of the container can be lifted by a product portion of the blister pack ( 1 ) to push out.

2 B shows a further particularly preferred embodiment of the invention, in which the cavities ( 6 ) of the blister pack ( three ) essentially over the area on the collar ( 7 ) arranged blister elements ( 5a . 5b ). These cavities ( 6 ) are particularly suitable for receiving larger product portions, such as, for example, prolonged scenting of the surroundings of the blister pack ( three ) necessary is.

2c shows a further embodiment of a blister pack ( three ) for fixing to an outlet cylinder of a container ( 1 ). The blister pack ( three ) has cavities ( 6 ) passing through the cavities ( 6 ) enclosing perforation ( 8th ) the cavities ( 6 ) individually from the blister pack ( three ) designed separable.

Instead of a perforation ( 8th ) may also other, to those skilled appear appropriate means for separating a portion of the blister pack ( three ) be provided.

It is also possible to use the perforation ( 8th ) only at the cavities ( 6 ), so that a segmental opening of the blister pack ( three ) is possible by removing the corresponding film section.

2d shows a blister pack ( three ), with an opening ( 4 ) by a collar ( 7 ) is completely or partially enclosed. On the collar ( 7 ) is a footbridge ( 13 ) arranged over at least one predetermined bending line ( 8th ).

According to a particularly preferred embodiment of the invention, the bridge ( 13 ) two spaced predetermined bending lines ( 9 ) on. The distance (b) of the two spaced predetermined bending lines ( 9 ) should be chosen so that they are substantially equal to the height of the spout cylinder ( 14 ) corresponds.

The nominal bending line ( 8th ) is usually a substantially linear material weakening in the web ( 13 ), which may be formed for example by perforation, material recesses or material compaction.

On the collar ( 7 ) far end of the bridge ( 13 ) a blister element is arranged so that a product filled with a cavity ( 11 ), which is bounded by a border ( 10 ) is completely enclosed.

2e shows the blister pack according to 2d over the lock cylinder ( 14 ) of a container ( 1 ). The blister pack ( three ) is along its predetermined bending lines ( 9 ) are each bent over by 90 ° such that the filled cavity ( 11 ) is positioned directly over the opening of the lock cylinder.

The cavity ( 11 ) of the blister pack ( three ) is designed such that it substantially completely into the opening of the closure cylinder ( 14 ) is insertable. According to a particularly preferred embodiment, the upper side of the edge ( 10 ) in the folded-in state of the blister pack directly on the wall of the closure cylinder ( 14 ) on.

In another particularly preferred embodiment, the edge ( 10 ) additionally means cooperating with the closure cylinder such that the blister pack ( three ) is secured against lateral slippage on the lock cylinder. This can be done, for example, by an appropriately designed circumferential groove or nose on the edge ( 10 ) of the blister pack ( three ) be realized.

In another embodiment of the invention, it is also possible that the cavity ( 11 ) by a suitable choice of the distance (b) of the predetermined bending lines ( 9 ) and kink the bridge ( 13 ) along the predetermined bending lines ( 9 ) in a correspondingly shaped opening or surface of the closure ( 2 ), which on the lock cylinder ( 14 ), is positionable.

3a shows a cross section through a representative cavity ( 6 . 11 ) of a blister pack according to the invention ( three ). In the simplest embodiment, the product (with 16 ) filled cavity ( 6 ) through a lower film ( 17 ) and through a sealing film ( 15 ) locked. The material of the sealing foil ( 15 ) is to be chosen so that certain substances of the product ( 16 ), in particular fragrances, are not released to the environment.

The bottom foil ( 17 ) is made of a material that is strong enough to prevent inadvertent opening, but can be opened by applying a corresponding pressure, for example by thumb pressure or tearing the film with a fingernail. By pressure on a cavity ( 6 ) of the blister pack ( three ) pressure on the in the cavity ( 6 ) ( 16 ), that finally the sealing film ( 15 ) pierces.

The Sealing film can also be damaged by tearing, Pierce, rub off, peel off, by contact with water, through Warmth, especially by the heat human skin, or other appropriate measures at least partly to the cavity opened become.

According to a further embodiment of the invention, the blister pack ( three ) are also designed so that the cavity ( 6 ) forming film ( 17 ) in such a way that the cavity ( 6 ) forming film ( 17 ) is opened by the applied pressure and the cavity ( 6 ) close continuous sealing film ( 15 ) remains undamaged.

3b shows a further developed embodiment of the blister pack ( three ) in addition to the sealing film ( 15 ) a permeable membrane ( 18 ). The permeable membrane ( 18 ) is between the cavity ( 6 ) forming film ( 17 ) and the sealing film ( 15 ), wherein the sealing film ( 15 ) preferably by a releasable adhesive bond flat on the permeable membrane ( 18 ) is arranged. The material and properties of the permeable membrane ( 18 ) are to be chosen such that at least one substance of the product ( 16 ) from the cavity ( 6 ) through the permeable membrane ( 18 ) can be delivered to the environment. In the simplest case, the permeable membrane ( 18 ) around a grid that is capable of retaining corresponding solids in the cavity.

In particular, the properties of the permeable membrane ( 18 ) so that fragrances from a liquid, gel or solid product from a cavity ( 6 ) can be delivered to the environment.

The permeable membrane ( 18 ) is preferably such with which the cavity ( 6 ) forming film ( 17 ) that the permeable membrane ( 18 ) the cavities ( 6 ) closes. The bond strengths between the permeable membrane ( 18 ) and the cavity ( 6 ) forming film ( 17 ) are preferably greater than the bond strengths between the permeable membrane ( 18 ) and the sealing film ( 15 ), so that when removing the sealing film ( 15 ) the permeable membrane ( 18 ) on the blister pack ( three ) and the cavities ( 6 ) closes.

4a shows a further embodiment of the invention, in which on the blister pack ( three ) a snap-in connector ( 19 ) is arranged such that with a corresponding receptacle ( 20 ) on the packaging unit ( 1 . 2 . 14 ), positively, preferably releasably, is connectable. It goes without saying that the blister pack ( three ) also a plurality of snap-in connections ( 19 . 20 ).

In a particularly preferred embodiment of the invention, the blister pack ( three ) also by a corresponding snap-in connection on the closure ( 2 ) of the container ( 1 ) are fixed.

According to a particularly preferred embodiment of the invention, the blister pack is at least partially provided with an adhesive layer which is covered with a releasable sealing film, whereby the blister pack ( three ) or individual portions ( 6 ) of the blister pack ( three ) are fixable to surfaces.

The in the cavities ( 6 ) ( 16 ) comprise in particular, but not exclusively, one or more substances selected from the group of perfumes, cleaning-active substances, dyes, foaming agents, etc.

5a shows a dimensionally stable receiving means ( three ) for additive portions ( 21 ) in the supervision. The receiving means ( three ) has a plurality of receiving openings ( 22 ) for additive portions ( 21 ) on. A receiving opening ( 22 ) acts with an additive portion ( 21 ) in such a way that the additive portion ( 21 ) in the receiving opening ( 22 ) is releasably fixed. This can be achieved, for example, by form, force or material connection between the additive portion ( 21 ) and the receiving opening ( 22 ) will be realized. The fixation is in each case to be designed such that the additive portion ( 21 ) not undesirable, eg during transport or storage, from the receiving opening ( 22 ) can fall out.

In a preferred embodiment of the invention, the additive portion ( 21 ) in a receiving opening ( 22 ) fixed by a releasable interference fit. In a further preferred embodiment, the fixation between additive portion ( 21 ) and receiving opening ( 22 ) ensured by a detachable snap-in connection.

The receiving openings ( 22 ) can be designed for example as a through hole or as a blind hole. Also, any other, the expert as equally effective obvious opening design is conceivable, such as openings with a rectangular, triangular or oval cross-section.

The additive portion ( 21 ) has a closure which holds the additive portion ( 21 ) closes tightly against the environment. The closure is advantageously designed such that the additive portion ( 21 ) liquid-tight against the environment is closed. Particularly preferably, the closure is designed such that the additive portion ( 21 ) is substantially tightly sealed against the emission of fragrances.

The closure is detachable via force, form or material connection to the additive portion ( 21 ) arranged. In particular, the additive portion ( 21 ) be sealed by the closure via a press fit, a screw cap, a snap-in connection or bonding to the environment.

In a further embodiment, the additive portion ( 21 ) closed with a stopper. The plug is preferably made of an elastic material and is designed such that it absorbs the additive portion ( 21 ) closes at least liquid-tight.

Furthermore, it is conceivable that the additive portion ( 21 ) with sealed openings. The openings can be designed as bores through the shell, bottom and / or top surface of the additive portion ( 21 ) be configured. However, any other suitable shape for the openings is conceivable, such as some slots, grids, etc. The sealing of the openings is designed such that the openings are sealed liquid-tight. In a particularly preferred embodiment, the seal is substantially dense to the emission of fragrances from the portion volume into the environment. The sealing may in particular be a plastic film which is glued to the surface of the additive portion at least partially, preferably detachably. It is also conceivable to seal the openings via a so-called sleeve, wherein a suitable plastic film is pulled tightly around the portion container.

In a further embodiment, the additive portion ( 21 ) filled with a non-flowable substance. In this case, the additive portion may be shaped like a cup having an open end face. Alternatively, the additive portion ( 21 ) also have openings on the lateral surface.

Not means flowable in this context, that in an additive portion located Substance not through the openings can escape into the environment. This can be done, for example, by using a Solid or solid granules can be achieved, for example The solid granules are sized so that it does not pass through the openings fits or the solid is fixed in the portion volume.

The additive portions may be in the receiving means ( three ) are arranged in two positions. In a first closed position, the openings of the additive portion ( 21 ) completely through the mantle or bottom surface of the receiving opening ( 22 ) locked.

As in 5b can be seen by removing an additive portion ( 21 ) from the receiving opening ( 22 ) the additive portion ( 21 ) in a second position in a receiving opening ( three ) of the reception means ( three ) are arranged, in which the openings of the additive portion ( 21 ) corresponds to the environment and components of the additive portion ( 21 ), preferably diffusely, are released to the environment.

In addition, in this case, the opening or openings of the additive portion ( 21 ) be covered by a protective film, which initially prevents a diffusive product delivery to the environment. The protective film can be removed, for example by tearing off or rubbing off, so that then product can be released to the environment.

The receiving means ( three ) has an opening ( 4 ), which is positively, positively or materially releasably connected to the opening of the container. In a preferred embodiment of the invention, the receiving means ( three ) an opening ( 4 ), which can be inserted over the spout cylinder of the container. The opening ( 4 ) can hereby be completely or only partially closed, the opening ( 4 ) is configured such that it prevents at least a simple release of the receiving means from the container. Alternatively, it is also possible for the receiving means ( three ) to be releasably connected to the closure of the container in a positive or cohesive manner.

Claims (15)

Packaging unit comprising a container ( 1 ) for receiving a product, a closure ( 2 ) as well as through the closure ( 2 ) closable opening ( 14 ) for removing the product from the container ( 1 ), characterized in that the packaging unit ( 1 . 2 . 14 ) at least one receiving means ( three ) for a plurality of additive portions ( 6 . 11 . 21 ) each of less than 50 ml, wherein the additive ( 16 ) comprises at least one substance from the group of perfumes, dyes or surfactants and the receiving means ( three ) for additive portions ( 6 . 11 . 21 ) detachable on the packaging unit ( 1 . 2 . 14 ) is fixable. Packaging unit according to claim 1, characterized in that the receiving means ( three ) a first Medium ( 4 . 7 . 19 ) for fixing the receiving means ( three ) on the packaging unit ( 1 . 2 ), with a second, on the packaging unit ( 1 . 2 . 14 ) ( 2 . 14 . 20 ) cooperates such that the receiving means ( three ) releasably, substantially positively, force and / or cohesively, on the packaging unit ( 1 . 2 . 14 ) is fixable. Packaging unit according to one or more of the preceding claims, characterized in that the first, on the receiving means ( three ) fixing means an opening ( 4 ), with the second, on the packaging unit ( 1 . 2 . 14 ) arranged means for fixing the receiving means ( three ) cooperates in such a way that the opening ( 4 ) of the reception means ( three ) on the second, on the packaging unit ( 1 . 2 . 14 ) ( 2 . 14 ) is pluggable. Packaging unit according to one or more of the preceding claims, characterized in that the first and second means for fixing the receiving means ( three ) on the packaging unit ( 1 . 2 . 14 ) form a snap-in connection. Packaging unit according to one or more of the previous ones Claims, characterized in that the plurality of additive portions as Blister packaging are formed. Packaging unit according to claim 5, characterized in that a web ( 13 ) at least two predetermined bending lines ( 9 ), along which the blister pack ( three ) can be hinged such that the cavity ( 11 ) substantially in the opening of the container ( 14 ) is positionable. Packaging unit according to one or more of claims 5 to 6, characterized in that at least a part of a plurality of the cavities ( 6 ) of at least one perforation line ( 8th ) is enclosed in such a way that a single or a group of cavities ( 6 ) along one or more perforation lines ( 8th ) from the blister pack ( three ) is separable. Packaging unit according to one or more of claims 5 to 7, characterized in that the opening of the cavity ( 6 ) closing permeable membrane ( 18 ) between the cavity ( 6 ) forming film ( 17 ) and a removable sealing film ( 15 ) is arranged such that when removing the sealing film ( 15 ), the permeable membrane ( 18 ) adheres to the blister pack and the cavities ( 6 ) closes. Packaging unit according to one or more of claims 5 to 8, characterized in that the blister pack ( three ) has an adhesive portion with an adhesive layer covered with a releasable sealing film. Packaging unit according to one or more of claims 1 to 4, characterized in that the receiving means ( three ) is substantially dimensionally stable and receiving openings ( 22 ), which are designed such that additive portions ( 21 ) by form, material and / or adhesion releasably in the receiving openings ( 22 ) are fixable. Packaging unit according to claim 10, characterized in that the additive portions ( 21 ) have at least one opening which is closable with a closure means. Packaging unit according to one or more of claims 10 to 11, characterized in that the additive portions ( 21 ) have at least one opening with the receiving openings ( 22 ) cooperates such that the opening of a in the receiving opening ( 22 ) fixed additive portion ( 21 ) is closed. Packaging unit according to one or more of claims 10 to 12, characterized in that at least one additive portion ( 21 ) a non-flowable substance ( 16 ) includes. Packaging unit according to one or more of the preceding claims, characterized in that in the additive portions ( 6 . 21 ) ( 16 ) are taken from at least two groups which differ in their perfume, surfactant, and / or dye composition. Packaging unit according to one or more of the preceding claims, characterized in that at least a part of the receiving means ( three ) with the packaging unit ( 1 . 2 . 14 ) is glued.