EP1973791B1 - 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 invention relates to a package consisting of a container for products and arranged on this container device for receiving additive portions.

State of the art

There has long been a need to be able to individually customize products or to have them customized by the customer to a certain extent. A particularly suitable medium for the individualization of a product is its packaging, since this forms the direct interface between consumer and product.

Therefore, it is desirable to couple means for individualizing or further functionalizing a product directly with the packaging of a product.

In particular, in the field of perfuming products such as detergents, detergents and the like, it is currently still common to sell the entire sales unit with a specific fragrance. Often, however, the user desires that for different fields of application, a different fragrance is released by a cleaning product. For example, it is desirable for a toilet cleanser to emit a more intense fragrance than in the home, where intense fragrances are often more likely to be distracting. So far, it has therefore been necessary to use a variety of special cleaners with the corresponding scents, although the cleaning active preparations are the same or at least very similar.

Especially with very aggressive cleaning preparations, there is also the problem that the aggressive cleaning components also decompose the fragrances persisting in the preparations, so that they have only a low storage stability.

In addition to the preparation of individually scented products, there is a further need that a product package is designed such that the fragrance of the product contained in the package olfactometrisch perceptible

Finally, packaging is also increasingly functionalized in that fragrance-emitting means are arranged on the packaging, which release a certain fragrance into the environment of the packaging and thus assume the additional function of a room freshener.

For the demand-oriented single portioning of products, the use of blister packs is common, for example in the field of drug delivery. Here, individual drug dosages, for example in the form of tablets, each packaged in a chamber of a blister pack.

Typically, such a blister pack consists of a first surface element, in which a plurality of individual, usually cup-shaped, mutually separate cavities for receiving product doses are formed and a second surface element, which is connected areally with the first surface element and closes the cavities.

Usually, the first surface element, in which the cavities are introduced, consists of a plastic film piece in which the cavities are formed, for example by deep drawing.

The second surface element occluding the cavities is made of a material which is sufficiently strong to prevent inadvertent opening, but which can be removed by applying a corresponding pressure, e.g. by thumb pressure or tearing the film with a fingernail, leaves open. By pressure on a chamber of the blister pack pressure is exerted on the product located in the chamber, that then finally pierces the lower film.

A blister pack can also be designed so that the second, the cavities occluding surface element is made firmer in such a way that the cup-shaped cavities of the first surface element are opened by the applied pressure and the second, the cavities occluding surface element remains undamaged.

Out DE4239082 the use of such blister packs for perfume emitting substances is 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.

The disadvantage of this solution is that the blister pack is not permanently connected to a carrier object. Thus, the blister pack can always be completely detached from the carrier object, such as the human skin. However, in particular for sales packaging, this is undesirable and so disadvantageous that a blister pack may inadvertently fall off the sales package or, for criminal intent, be removed from the sales container, for example due to adhesive failure.

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 It is known to arrange fragrance emitting substances in a closure flap of a container. In this case, fragrance-emitting substances are arranged in a chamber of the container closure, this chamber being sealed with a film which can be removed for use of the room freshener cap, so that fragrance can be released from the closure flap to the environment. A disadvantage of this solution is the comparatively large and thus unwieldy for the consumer form of this closure. As a result of the fact that the inner volume of the closure is almost completely filled with a fragrance, practically no dosing volume is available any more, so that the closure can generally not be used as a dosing device, as for example for closures of softener or floor cleaner. Due to the necessarily enlarged design compared to conventional closures, also increases the storage requirements for such equipped container, which inevitably leads to increased logistics costs.

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.

This solution has the disadvantage that the production of a corresponding container is expensive and technically complicated. In addition, large areas are needed, which significantly limits the space for advertising and / or descriptive labels. This also appreciably negatively affects the overall aesthetic impression of the container. Another disadvantage of this solution is that no pasty or gelatinous preparations can be dosed and removed.

WO2004 / 084954A2 discloses a bottle having a structure disposed at the bottle opening and including cavities for holding perfume. A disadvantage of this solution is that the cavities are not individually detached from the structure and therefore allow fragrance delivery only in the immediate vicinity of the bottle.

Object of the invention

It is therefore an object of the present invention to provide a packaging which can be produced cost-effectively, which makes it possible to provide individually packaged portionable additive units in a container in a simple and easy-to-use manner.

The object is achieved by a packaging unit with the Merkmaten of claim 1.

For the purposes of this application, the term packaging unit is understood to mean the entirety of the container, container opening and closure.

The receiving means is formed as a substantially dimensionally stable body to which individual additive portions are fixable.

The additive portions are each at least partially enclosed by a flexible or dimensionally stable container in such a way that the additive in the portion is not unintentionally released. The additive portions are releasably connected to the receiving means.

The additive portions can be formed, for example, by a substantially flexible blister packaging, blister packaging or contour packaging, which are then connected in a suitable manner to the receiving means for fixing to the container.

It is also conceivable to form the additive portions as a dimensionally stable container such as a closable cup or vial, which is then releasably fixable in the packaging unit.

The receiving means for the additive portions may be secured to the container by releasable connections that appear appropriate to the person skilled in the art. In particular, the fixation on the container material, positive and / or non-positive, for example, by one or more of the types of compounds from the group of snap-in compounds, Velcro, compression joints, fusions, adhesive bonds, welds, solder joints, screw, wedge, clamps or bounce joints respectively.

The content of the additive portions may, for example, consist of one or more identical or different products such as, for example, fragrances, Cleaning substances, dyes, surfactants, fungicides, enzymes, hygroscopic substances and the like exist.

According to a particular embodiment of the invention, it is possible for the container of the additive portions to consist, at least in part, of a material which allows a diffusive delivery of product enclosed in the additive portions to the environment. Additionally, in this case, the additive portion may be covered by an additional protective film which initially prevents product delivery to the environment. The protective film can be removed, for example, by tearing off or rubbing off an additive portion, so that then additive product can be released to the environment.

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

be used. In particular, cans may be a pruned can, a can, a can lid, a retracted can, a fold lid can, a fold lid fill can, a folded can, a drawn can, a can, a siphon, a tearing can, a sippy can, a slip lid can, or a stepped can.

Barrels may be selected from the group of belly drums, stave casks, caissons, garage barrels, semi-cauldrons, pack barrels, reel drums, heavy barrels, bead drums or roll bead drums.

For example, a bottle may be an aerosol bottle, a look-through bottle, a beverage bottle, especially ale bottle, goitre bag, goitre bottle, flail bottle, stony bottle, stubby bottle, vichy bottle, wide neck bottle, and mega plate bottle, squeeze bottle, dropper bottle, packaging bottle like something a bottle.

For the purposes of this application, cartons, in particular folding cartons, such as erecting boxes, passage boxes, folded bottom boxes, folded cardboard boxes, folded boxes with inner lining, are to be understood as boxes. Belt folding cartons, sliding cartons, Steckbodenschachteln, Stülpdeckelfaltschachteln and top lid boxes, window boxes, cap boxes such as cover cap boxes or Rändelkappenschachteln, and flap lid boxes, hull boxes, sliding boxes, chip boxes, slip-lid boxes, carrying boxes or shipping boxes understood.

The opening of the container may in particular be a push-in flap, sleeve, in particular outer sleeve, and mouthpiece or mouthpiece or valve carrier, band mouthpiece, crown cork mouthpiece, hole mouthpiece, screw mouthpiece, spray mouthpiece, bunghole or taphole.

The closure can be a closure means from the group of the lid, tear-off, Abrolldeckel, Aufreißdeckel, essay lid, Eindrückdeckel, Einsteckdeckel, Falzdeckel, Foliendeckel, flap lid, cam cover, bayonet cover, groove cover, hinge lid, sliding lid, insertion cover, snap lid, clamping lid, screw cap , Slip-on covers, over-lids, push-in latches, flaps, outer flaps, inner flaps, closure flaps, shims, bungs, plugs, screw plugs, stoppers, handle plugs, ground plugs, cap caps, tube caps, crown caps, screw caps, valve caps, cap caps, bottle caps, tear-off caps, crimp caps and pegs.

The closure and / or opening of the container may optionally include metering and removal aids, such as an aerosol valve, spout, spray cap, spray head, atomizer, dosing device, dosing cap, dosing nozzle or dropper.

In the context of this application, additive is understood as meaning a substance or substance mixture which is suitable for achieving or influencing a property of the product by mixing with the product contained in the container, in particular improving, producing, highlighting, attenuating, accelerating a temporal process or to slow down, to initiate, inhibit or catalyze a reaction. Furthermore, the term "additive" should also be understood to mean a substance or a substance mixture which is suitable for achieving or influencing a property of the container, in particular fragrance and / or active substance delivery, adsorption or absorption on or in the container.

The additive may, for example, one or more substances from the group of fragrances, bleaching agents, cleaning substances, solvents, surfactants, dyes, enzymes, hygroscopic substances, flame retardants, hardeners, leveling agents, wetting agents, dispersants, foaming agents, defoamers, deaerators, corrosion inhibitors, biocides, water softeners , Preservatives, emulsifiers, stabilizers, vitamins, minerals and the like.

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

The additive portions of the receiving means may contain the same or different products. For example, it would be conceivable to arrange substances with different scents in the additive portions in order to allow different perfuming of the contents of the container or of the container itself. For example, when using a fragrance-neutral cleaning liquid, the first with water to a Wischzubereitung is mixed, with each Wischwasserzubereitung another fragrance from the receiving means for the additive portions are added. This prevents on the one hand the olfaktometrische adaptation to a particular fragrance, on the other hand, a fragrance can be selected according to the requirements of a specific application space (toilet, living room, kitchen). This then no longer requires the use of several specially perfumed cleaning substances, which is also desirable in terms of environmental protection and resource conservation.

Another significant advantage of the invention is its simple and thus cost-effective production. It is thus possible to have the receiving means for the additive portions completely independent of a container. Receiving means for the additive portions is subsequently attached to the container according to the disclosed teaching of the invention.

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

Thus, for example, it is also possible, after complete consumption of the additive portions, to remove them from the container and to arrange a new unused receiving agent for additive portions on the container.

Polymeric carrier material

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

For the fragrance-containing particles are generally all polymers or polymer mixtures, which meet the above criteria with respect to the melting or Meet softening temperature. Preferred scent delivery systems in the context of the present application are characterized in that the polymeric carrier material comprises at least one substance selected from the group consisting of ethylene / vinyl acetate copolymers, low or high density polyethylene (LDPE, HDPE) or mixtures thereof, polypropylene, polyethylene / polypropylene copolymers, Polyether / polyamide block copolymers, styrene / butadiene (block) copolymers, styrene / isoprene (block) copolymers, styrene / ethylene / butylene copolymers, acrylonitrile / butadiene / styrene copolymers, acrylonitrile / butadiene copolymers, polyetheresters, Polyisobutene, polyisoprene, ethylene / ethyl acrylate copolymers, polyamides, polycarbonate, polyester, polyacrylonitrile, polymethyl methacrylate, polyurethanes, polyvinyl alcohols.

Polyethylene (PE) is a collective name for polymers belonging to the polyolefins with groupings of the type

CH ₂ -CH ₂

as a characteristic basic unit of the polymer chain. Polyethylenes are 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 Copolymerization of 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 of the polyethylenes from low-pressure process are largely linear and unbranched. These polyethylenes, abbreviated to 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 referred to as products with high or ultra-high molar mass (about 200 000-5 000 000 g / mol or 3 000 000-6 000 000 g / mol) under the short name HD-HMW-PE or UHMW-HD-PE offered. Also, medium density (MDPE) products from blends 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) are only slowly gaining market significance.

Polyethylenes have a very low permeability to water vapor, the diffusion of gases and of aromatic substances and ethereal substances by polyethylenes is relatively high. The mechanical properties are strongly dependent on the molecular size and structure of the polyethylenes. In general, the degree of crystallinity and density of polyethylenes increase 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. With the same density increase with increasing molecular weight of the polyethylene tear strength, elongation, shock resistance, impact resistance and creep strength. Depending on the mode of operation in the polymerization, products with paraffin wax-like properties (MR around 2000) and products with the highest toughness. (MR over 1 million) received.

The processing of the polyethylene types can be carried out according to all methods customary for thermoplastics.

Polypropylene (PP) is the name for thermoplastic polymers of propylene with the general formula:

- (CH ₂ -CH [CH 3]) _n -

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

Polypropylene is characterized by high hardness, resilience, stiffness and heat resistance. Short-term heating of articles made of polypropylene is possible even up to 140 ° C. At temperatures below 0 ° C, some embrittlement of the polypropylenes occurs, which, however, can be shifted to much lower temperature ranges by copolymerization of the propylene with ethylene (EPM, EPDM). In general, the impact resistance of polypropylene can be improved by modification with elastomers. The chemical resistance is good as with all polyolefins. An improvement in the mechanical properties of the polypropylene is achieved by reinforcement with talc, chalk, wood flour or glass fibers. Polypropylenes are even more sensitive to oxidation and light than PE, which is why the addition of stabilizers (antioxidants, light stabilizers, UV absorbers) is required.

Polyether is a comprehensive term in the field of macromolecular chemistry for polymers whose organic repeating units are held together by ether functionalities (COC). According to this definition, a variety of structurally very different. Polymer to the polyethers, z. B. the polyalkylene glycols (polyethylene glycols, polypropylene glycols and polyepichlorohydrins) as polymers of 1,2-epoxides, epoxy resins, Polytetrahydrofurans (polytetramethylene glycols), polyoxetanes, polyphenylene ethers (see polyarylethers) or polyetheretherketones (see polyether ketones). Polymers with pendant ether groups, such as the cellulose ethers, starch ethers and vinyl ether polymers, are not included among the polyethers.

The group of polyethers also includes functionalized polyethers, d. H. Compounds having a polyether backbone laterally attached to their backbones still carry other functional groups, e.g. As carboxy, epoxy, allyl or amino groups, etc. are widely used block copolymers of polyethers and polyamides (so-called. Polyetheramides or polyether block amides, PEBA).

Polyamides (PA) are polymers whose basic building blocks are held together by amide bonds (-NH-CO-). Naturally occurring polyamides are peptides, polypeptides and proteins (Ex .: protein, wool, silk). The synthetic polyamides, with a few exceptions, are thermoplastic, chain-like polymers, some of which have attained great industrial importance as synthetic fibers and materials. According to the chemical structure, the so-called homo-polyamides can be divided 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 of only a single monomer by z. B. polycondensation of a ω-aminocarboxylic acid (1) (polyamino acids) or by ring-opening polymerization of cyclic amides (lactams) (2).

In addition to the homopolyamides, some co-polyamides have gained importance. It is customary in these a qualitative and quantitative indication of the composition z. B. PA 66/6 (80:20) for from 1,6-hexanediamine, adipic acid and ε-caprolactam in a molar ratio 80:80:20 prepared polyamides. Because of their particular properties, polyamides which contain exclusively aromatic radicals (for example, those of p-phenylenediamine and Terephthalic acid), under the Gattungsbez. Aramids or polyaramides summarized (Ex .: Nomex®).

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

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

Branched and crosslinked polyesters are obtained in the polycondensation of trihydric polyhydric alcohols with polyfunctional carboxylic acids. The polyesters are generally also the polycarbonates (carbonic acid polyester) counted. AB type polyesters (I) are u. a. Polyglycolic acids, polylactic acids, polyhydroxybutyric acid [poly (3-hydroxybutyric acid), poly (ε-caprolactone) s and polyhydroxybenzoic acids.

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

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

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

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

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

Polyurethane foams are formed in the polyaddition, when water and / or carboxylic acids are present, because these react with the isocyanates with elimination of the uplifting and foaming carbon dioxide. With Polyalkylenglykolethem as diols and water as a reaction component to get soft polyurethane foams, with polyols and propellants from CFCs (especially R 11) is obtained rigid polyurethane foams and structural or integral foams. Additionally required auxiliaries are here z. As catalysts, emulsifiers, foam stabilizers (especially polysiloxane-polyether copolymers), pigments, aging and flame retardants. In the 1970s, so-called RIM technology was developed for the manufacture of even complicated shaped objects made of polyurethane foam (reaction injection molding). The RIM-Verf. is due to rapid dosing and mixing of the components, injection of the reactive mixture into the mold and rapid curing; the cycle time is only a few 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%).

Commercial polyvinyl alcohols are used as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500

(Molar masses of about 4000 to 100,000 g / mol) offered. The polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

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

Polyvinyl alcohols of a certain molecular weight range are preferably used as 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 of the present invention, the polymeric carrier material of the particles consists at least partly of ethylene / vinyl acetate copolymer. A further preferred subject of the present application is therefore a scent delivery system, characterized in that the polymeric carrier material at least 10 wt .-%, preferably at least 30 wt .-%, particularly preferably at least 70th Contains% by weight of ethylene-vinyl acetate copolymer, preferably made entirely of ethylene-vinyl acetate copolymer.

Ethylene-vinyl acetate copolymers is the name for copolymers of ethylene and vinyl acetate. The preparation of this polymer is basically carried out in a process similar to that of the production of low density polyethylene (LDPE). With an increasing proportion of vinyl acetate, the crystallinity of the polyethylene is interrupted and in this way the melting and softening points or the hardness of the resulting products are reduced. The vinyl acetate also makes the copolymer more polar and thus improves its adhesion to polar substrates.

The ethylene-vinyl acetate copolymers described above are widely available commercially, for example under the tradename Elvax ^® (Dupont). In the present invention, particularly suitable polyvinyl alcohols are, for example Elvax ^® 265, Elvax ^® 240, Elvax ^® 205W, Elvax ^® 200W, as well as Elvax ^® 360th

Some particularly suitable copolymers and their physical properties are shown in the following table: product name % By weight of vinyl acetate (based on the total weight) melting point Elvax ^® 40W 40 47 ° C Elvax ^® 150 33 63 ° C Elvax ^® 265 28 75 ° C Elvax ^® 240 28 74 ° C Elvax ^® 205 W 28 72 ° C Elvax ^® 200 W 28 71 ° C Elvax ^® 360 25 78 ° C Elvax ^® 460 18 88 ° C Elvax ^® 660 12 96 ° C Elvax ^® 760 9 100 ° C

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

Fragrance delivery systems according to the invention contain the polymeric support materials in the form of particles. The spatial form of these particles is limited only by the technical possibilities in their production. As a spatial form come thus all reasonable manageable configurations into consideration, for example, so cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with a circular or oval cross-section. This last embodiment comprises tablet-shaped particles up to compact cylinder pieces with a height-to-diameter ratio above 1. Further possible spatial forms are spheres, hemispheres or "elongated spheres" in the form of ellipsoidal capsules as well as regular polyhedra, for example tetrahedron, hexahedron, octahedron, Dodecahedron, icosahedron. It is also conceivable star-shaped formations with three, four, five, six or more tips or completely irregular body, which may be designed, for example, motivic. Depending on the field of application of the agents according to the invention, suitable motifs are, for example, animal figures, such as dogs, horses or birds, floral motifs or the representation of fruits. The motivic design can also refer to inanimate objects such as vehicles, tools, household items or clothing. The surface of the solid particles may have unevenness depending on the type of the selected manufacturing process and / or a selected coating. Owing to the numerous design possibilities for the particles, the agents according to the invention are distinguished not only by advantages in their preparation. Due to the various forms of the perfume-containing particles are also visually clearly perceptible to the consumer and allow through the targeted spatial design of these particles for product acceptance particularly advantageous visualization of the fragrances contained in the compositions of the invention or other optional active substances contained in these agents. Thus, for example, the different modes of action of individual active substances (eg cleaning and additional functions such as glass protection, silver protection, etc.) can be illustrated by the optically perceptible multiphase of these agents.

In the context of the present application, particles are summarized as particles which have a solid, ie dimensionally stable, non-flowable consistency which is solid at room temperature. Preferred particles have an average diameter of 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 be carried out on all the skilled person for processing these substances known methods. In the context of the present invention, extrusion is preferably preferred by injection molding and spraying into polymer granules.

fragrances

As perfume oils or fragrances, individual fragrance compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons, can be used in the context of the present invention. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8-18 C atoms, citral, citronellal, Citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the Jonone, α-isomethylionone and methylatedryl ketone to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

The general description of the perfumes that can be used (see above) generally represents the different substance classes of fragrances. To be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role plays. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note" or "body note" ) and "base note" (end note or dry out). Since odor perception is also largely based on the odor intensity, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note consists for the most part of less volatile, ie adherent fragrances. For example, in the composition of perfumes, more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly. In the subsequent classification of the fragrances in "lighter volatile "or" adherent "fragrances is so about the olfactory impression and whether the corresponding fragrance is perceived as the head or middle note, nothing said.

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, Stem Oil, Turpentine Oil, Thuja Oil, Thyme oil, Verbe oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon oil, citronella 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 following compounds and mixtures thereof: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, Benzaldehyde, 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, muscone, 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, Pulegon, Saf rol, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, 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.

Preferably, the plastic particles are loaded at a temperature of 15 to 30 ° C, preferably from 20 to 25 ° C, with the selected perfume. For this purpose, the particles are mixed with the appropriate amount of perfume and mixed. In any case, the temperature should be 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 of the polymeric carrier material or included in the particle further perfume carrier materials, which may swell slightly in the course of this process.

Other active substances

As mentioned above, agents according to the invention may contain, in addition to the ingredients required for scenting and deodorization, further active substances. Accordingly, other product groups which contain further preferred substances in addition to the abovementioned constituents according to the invention can be distinguished from the agents which serve exclusively for scenting.

dyes

A first of these optionally usable preferred substances are the dyes. For this purpose, all dyes are generally suitable, which are known to the skilled person as suitable for coloring plastics or as soluble in perfume oils. It is preferable to select the dye according to the fragrance used; For example, lemon fragrance particles are preferably yellow in color, while for apple or herb fragrance particles, a green color is preferred. Preferred dyes have a high storage stability and insensitivity to the other ingredients of the agents and to light. If the agents according to the invention are used in connection with textile or dishwashing, the dyes used should have no pronounced substantivity towards textile fibers, glass, plastic dishes or ceramics in order not to stain them.

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 Gras-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 also be included.

In a preferred embodiment, the dye additionally has an indicator function in addition to its aesthetic effect. As a result, the consumer of the current state of consumption of the deodorant is displayed, so that he receives in addition to the lack of fragrance impression, which may for example be based on a habituation effect on the part of the user, another reliable indication when the deodorant is to be replaced by 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 effected, for example, 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 perfume is not consumed high, 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 constituents of compositions according to the invention are substances such as antimicrobial agents, germicides, fungicides, antioxidants or corrosion inhibitors, with the aid of which additional benefits, such as, for example, disinfection or corrosion protection, can be realized.

For controlling microorganisms, the compositions of the invention may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats and bactericides, fungistatics and fungicides, etc. Important substances from these Groups include, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate.

antioxidants

In order to prevent undesirable changes to the agents or the textiles treated by oxygen and other oxidative processes, for example, the compositions may contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

If the agents according to the invention are used in dishwashers, then these means for protecting the items to be washed or the machine can contain corrosion inhibitors, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds used. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts, which are selected from the group of manganese and / or cobalt salts and / or - complex, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of Cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

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

The metal salts or metal complexes used should be at least partially soluble in water. The counterions suitable for salt formation comprise all customary mono-, di- or tri-positively negatively charged inorganic anions, eg. As oxide, sulfate, nitrate, fluoride, but also organic anions such. 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" within the meaning of the invention is, 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, depending on whether there is a cationic or an anionic charge surplus Cations, for example sodium, potassium and ammonium ions, for charge balance Suitable complexing agents are, for example, citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The well-known in chemistry definition for "oxidation state" is eg 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, from the SO ₃ production (contact method) known mixture of pentavalent and tetravalent vanadium (V ₂ O ₅ , VO ₂ , V ₂ O ₄ ) is suitable, as well as by diluting a Ti (SO ₄ ) ₂ solution resulting titanyl sulfate, TiOSO ₄ -.

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

Means for preventing glass corrosion

An important criterion for the evaluation of a machine dishwashing detergent, apart from its cleaning performance, is the visual appearance of the dry dishes after cleaning. Possibly occurring calcium carbonate deposits on dishes or in the machine interior, for example, can affect the customer satisfaction and thus have causal influence on the economic success of such a detergent. Another long-standing problem with automatic dishwashing is the corrosion of glassware, which can usually be manifested by the appearance of turbidity, streaks and scratches, but also by iridescence of the glass surface. The observed effects are based essentially on two processes, on the one hand the escape of alkali and alkaline earth ions from the glass in connection with a hydrolysis of the silicate network, on the other hand in a deposition of silicate compounds on the glass surface.

The stated problems can be solved with the agents according to the invention if, in addition to the abovementioned mandatory and optionally optional ingredients, certain glass corrosion inhibitors are incorporated in the compositions. Preferred agents according to the invention therefore additionally comprise one or more magnesium and / or zinc salts and / or magnesium and / or zinc complexes.

A preferred class of compounds that can be added to the compositions of the invention to prevent glass corrosion are insoluble zinc salts. These can accumulate on the glass surface during the dishwashing process, preventing the dissolution of metal ions from the glass network and the hydrolysis of the silicates. In addition, these insoluble zinc salts also prevent the deposition of silicate on the glass surface, so that the 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 according to the invention, insoluble zinc salts are zinc silicate, zinc carbonate, zinc oxide, basic Zinc carbonate (Zn ₂ (OH) ₂ CO ₃ ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (PO ₄ ) ₂ , and zinc pyrophosphate (Zn ₂ (P ₂ O ₇ )).

The zinc compounds mentioned are used in the compositions according to the invention in amounts which have a content of the zinc ions of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0 wt .-%, each based on the agent without the container cause. The exact content of the agents on the zinc salt or zinc salts is of course dependent on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration should be in the inventive compositions.

Another preferred class of compounds are magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid. The effect of this is that even with repeated use, the surfaces of glassware do not change corrosively, in particular, no turbidity, streaks or scratches, but also iridescence of the glass surfaces are not caused.

Although according to the invention all magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids may be contained in the claimed agents, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids are derived 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.

A further preferred subject matter of the present application is therefore a scent delivery system which contains further active substances, in particular active substances from the group of perfume carriers, dyes, antimicrobial agents, germicides, fungicides, antioxidants or corrosion inhibitors.

bleach

In addition to the above-mentioned active substances, the agents according to the invention, in particular means for use in dishwashers, textile washing machines or dryers, of course, have all the active substances usually contained in textile or dishwashing or textile or dish care, wherein substances from the group bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, dyes, hydrotropes, foam inhibitors, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, crease inhibitors, 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 are then in addition to the repeated scenting for one or more care or cleaning of textiles or dishes.

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 Peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxy carboxylic 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.

If the agents according to the invention are used in combination with automatic dishwashing detergents, they may contain bleach activators in order to achieve an improved bleaching effect during cleaning at temperatures of 60 ° C. and below. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular 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 the 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-CNX^-, (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 also be -H and X is an anion, wherein 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 -CNX ^- , (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, whereby from the group of these substances turn the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- in which X ^{- is} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate becomes.

In addition to or in place of the conventional bleach activators, so-called bleach catalysts can also be incorporated into the compositions. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

surfactants

Preferred agents in the context of the present application contain one or more surfactants from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.

Preferred anionic surfactants in acid form are one or more substances from the group of carboxylic acids, sulfuric acid half esters and sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylaryl sulfonic acids. In order to have sufficient surface-active properties, the compounds mentioned should have longer-chain hydrocarbon radicals, ie at least 6C atoms in the alkyl or alkenyl radical. Usually, the C chain distributions of the anionic surfactants are 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 Use 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 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 preferable not to use the pure species, but technical mixtures of the individual acids, as they are accessible from lipid cleavage. 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 wt .-% C ₁₈ , 1 wt .-% C ₁₈ ), palm kernel oil fatty acid (about 4 wt .-% C ₈ , 5 wt.% C ₁₀ , 50 wt .-% 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% by weight C ₁₆ , 2% by weight C ₁₆ , 2% by weight C ₁₇ , 17% by weight C ₁₈ , 44% by weight C _{18 '} , 3% by weight 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 wt.% C _{16 '} , 1 wt.% C ₁₇ , 2 wt.% C ₁₈ , 70 wt.% C _18' , 10 wt.% C _{18 "} , 0.5 wt. 1% by weight of C ₁₂ , 2% by weight of C ₁₄ , 45% by weight of C ₁₆ , 2% by weight of C ₁₇ , 47% by weight of C _{17 '''} ), technical grade palmitic / stearic acid. % C ₁₈ , 1% by weight C _{18 '} ) and soybean oil fatty acid (about 2% by weight C ₁₄ , 15% by weight C ₁₆ , 5% by weight C ₁₈ , 25% by weight 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, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the relevant alkyl ether sulfuric acids.

Alkane sulfonic acids and olefin sulfonic acids can also be used in the context of the present invention as anionic surfactants in acid form. Alkanesulfonic acids can be terminally attached to the sulfonic acid group (primary Alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), only the secondary alkanesulfonic acids being of commercial importance. These are prepared by sulfochlorination or sulfoxidation of linear hydrocarbons. In the sulfochlorination according to Reed n-paraffins are reacted with sulfur dioxide and chlorine under irradiation with UV light to the corresponding sulfochlorides which, upon hydrolysis with alkalis directly the alkanesulfonates, upon reaction with water, the alkanesulfonic provide. Since di- and Polysulfochloride and chlorinated hydrocarbons can occur as by-products of the radical reaction in the sulfochlorination, the reaction is usually carried out only up to degrees of conversion of 30% and then terminated.

Another process for producing alkanesulfonic acids is sulfoxidation in which n-paraffins are reacted with sulfur dioxide and oxygen under UV light irradiation. This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylsulfonyl radicals. The reaction with unreacted paraffin provides an alkyl radical and the alkylpersulfonic acid which decomposes into an alkyl peroxysulfonyl radical and a hydroxyl radical. 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. In order to keep the yield of the two end products alkyl sulfonic acid and sulfuric acid as high as possible and to suppress side reactions, this reaction is usually carried out only up to degrees of conversion of 1% and then terminated.

Olefinsulfonates are produced industrially by reaction of α-olefins with sulfur trioxide. Intermediate zwitterions form, which cyclize to form so-called sultones. Under suitable conditions (alkaline or acid hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkensulfonic acids, both of which can likewise be used as anionic surfactant acids.

Alkyl benzene sulfonates as powerful anionic surfactants have been known since the 1930's. At that time, alkylbenzenes were prepared by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution. In the early 1950's propylene was tetramerized into branched α-dodecylene to produce alkylbenzenesulfonates and the product was reacted via a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride to tetrapropylenebenzene, which was subsequently sulfonated and neutralized. This economic possibility of producing tetrapropylene benzene sulfonates (TPS) led to the breakthrough of this class of surfactants, which subsequently displaced soaps as the major surfactant in detergents and cleaners.

Due to the lack of biodegradability of TPS, there was a need to present new alkylbenzenesulfonates that are characterized by improved environmental performance. These requirements are met by linear alkylbenzenesulfonates, which are today almost exclusively produced alkylbenzenesulfonates and are referred to by the abbreviation ABS or LAS.

Linear alkylbenzenesulfonates are prepared from linear alkylbenzenes, which in turn are accessible from linear olefins. For this purpose, large-scale petroleum fractions are separated with molecular sieves in the n-paraffins of the desired purity and dehydrogenated to the n-olefins, resulting in both α- and i-olefins. The resulting olefins are then reacted in the presence of acidic catalysts with benzene to the alkylbenzenes, the choice of the Friedel-Crafts catalyst has an influence on the isomer distribution of the resulting linear alkylbenzenes: When using aluminum trichloride, the content of the 2-phenyl isomers in the mixture with the 3-, 4-, 5- and other isomers at about 30 wt .-%, however, hydrogen fluoride is used as the catalyst, the content of 2-phenyl isomer can be Lower to about 20 wt .-%. The sulfonation of linear alkylbenzenes finally succeeds today industrially with oleum, sulfuric acid or gaseous sulfur trioxide, the latter having by far the greatest importance. For the sulfonation special film or tube bundle reactors are used which provide as product a 97 wt.% Alkylbenzenesulfonic acid (ABSS), which can be used in the context of the present invention as anionic surfactant acid.

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 in this case to prepare and use the alkali metal salts and, among these, preferably 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 above-mentioned anionic surfactants in their acid form may be used alone or in admixture with each other. But it is also possible and preferred that the anionic surfactant in acid form prior to addition to the / the support material (ien) further, preferably acidic, ingredients of detergents and cleaning agents in amounts of 0.1 to 40 wt.%, Preferably from 1 to 15% by weight and in particular from 2 to 10% by weight, in each case based on the weight of the mixture to be reacted.

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

Also cationic surfactants can be used with advantage as an active substance. The cationic surfactant can be added directly to the mixer in its delivery form, or can be sprayed onto the solid carrier in the form of a liquid to pasty cationic surfactant formulation. Such cationic surfactant formulations can be prepared, for example, by mixing commercial cationic surfactants with excipients such as nonionic surfactants, polyethylene glycols or polyols. Also, lower alcohols such as ethanol and isopropanol can be used, and the amount of such lower alcohols in the liquid cationic surfactant preparation should be below 10% by weight for the reasons mentioned above.

Suitable cationic surfactants for the compositions according to the invention are all customary substances, with cationic surfactants having textile-softening action being 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 the 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 can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably 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.

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

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

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 obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

It is particularly preferred for many applications when the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5, and most preferably between 5: 1 and 1: 2. Preference is given to containers according to the invention which contain 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% by weight, based in each case on the weight of the enclosed solids.

As already mentioned, the use of surfactants in automatic dishwashing detergents is preferably restricted to the use of small quantities of nonionic surfactants. Inventive agent for therefore, automatic dishwashing preferably contains 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.

In particular, in machine dishwashing detergents it is preferred that they contain a nonionic surfactant having a melting point above room temperature, preferably a nonionic surfactant having 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 which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.

A particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and especially 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 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of 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 polyoxypropylene 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, isoPropyl, 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. If x stands for 3, for example, the radical R ³ be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined together in any order, for example (EO) (PO) (EO), (EO) (EO ) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO). The value 3 for x has been 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 ^according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5 percent by weight, based on active protein. The protein concentration can be determined 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 of these are the subtilisins BPN 'and Cadsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, 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 under from Novozymes under the name Termamyl ^® and from Genencor available 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.

Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948); Likewise, fusion products of said molecules 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® 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.

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

A useful fungal, endoglucanase (EG) -rich cellulase preparation, or its further developments are offered by Novozymes under the trade name Celluzyme ^®. The products Endolase® ^® and Carezyme ^®, likewise available from Novozymes, are based on the 50 kD EG and 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® ^®. Further commercial products of the company 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 be oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases). contain. Suitable commercial products Denilite® ^® 1 and 2 from Novozymes should be mentioned. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

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

The purification of the relevant enzymes is conveniently carried out by per se established methods, for example via precipitation, sedimentation, Concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.

The agents of the invention may be added to the enzymes in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.

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

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

A protein and / or enzyme contained in an agent according to the invention can be used especially during storage against damage such as

Inactivation, denaturation or decay may be protected by, for example, physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Compositions according to the invention may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

One group of stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, including, in particular, derivatives with aromatic groups, for example 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.

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

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or, such as cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. 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 agents and antioxidants such as sodium sulfite or reducing sugars enhance the stability of the enzymes to oxidative degradation.

Preference is given to using combinations of stabilizers, for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers can be enhanced by combination with boric acid and / or boric acid derivatives and polyols and further enhanced according to the additional use of divalent cations, such as calcium ions.

Particularly preferred in the context of the present invention is the use of liquid enzyme formulations. Here, agents according to the invention are preferred which additionally contain enzymes and / or enzyme preparations, preferably solid and / or liquid protease preparations and / or amylase preparations, in amounts of from 1 to 5% by weight, preferably from 1.5 to 4.5 and in particular from 2 to 4 wt .-%, each based on the total agent.

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.

Figur 1:

Behältnis mit an der Behältnisöffnung angeordneter Blisterverpackung in perspektivischer Aufsicht

Figur 2a:

Blisterverpackung zur Anordnung an einer Behältnisöffnung mit einer Vielzahl von kleinen Portionen

Figur 2b:

Blisterverpackung zur Anordnung an einer Behältnisöffnung mit größeren Portionen

Figur 2c:

Blisterverpackung zur Anordnung an einer Behältnisöffnung mit segmentweise abtrennbaren Portionen

Figur 2d:

Blisterverpackung zur Anordnung an einer Behältnisöffnung mit Knicklinien

Figur 2e:

Blisterverpackung zur Anordnung an einer Behältnisöffnung im eingeknickten Zustand

Figur 3a:

Blisterverpackung im Querschnitt

Figur 3b:

Blisterverpackung im Querschnitt mit einer permeablen und einer Siegelmembran

Figur 4a:

Blisterverpackung mit Snap-In Verschluss

Figur 5a:

formstabiles Aufnahmemittel für Additivportionen in der Aufsicht

Figur 5b:

formstabiles Aufnahmemittel für Additivportionen im Querschnitt

The invention will be explained in more detail with reference to the following figures. The in the FIGS. 1 to 4 illustrated blister packs are not part of the invention.

FIG. 1:

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

FIG. 2a:

Blister pack for placement on a container opening with a plurality of small portions

FIG. 2b:

Blister pack for placement on a container opening with larger portions

FIG. 2c:

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

FIG. 2d:

Blister pack for placement on a container opening with fold lines

FIG. 2e:

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

FIG. 3a:

Blister packaging in cross section

FIG. 3b:

Blister pack in cross-section with a permeable and a sealed membrane

FIG. 4a

Blister packaging with snap-in closure

FIG. 5a

dimensionally stable receiving means for additive portions in the supervision

FIG. 5b:

dimensionally stable receiving means for additive portions in cross section

FIG. 1 shows an embodiment in which a blister pack (3) over the closure and pouring cylinder of the container (1) plugged into the container (1) is fixed. On the lock and Spout cylinder is a closure (2) arranged, which has a circumferential shoulder (2a).

A detail view of an embodiment of the blister pack is shown in FIG Figure 2a-e shown.

The blister pack (3) has an opening (4) which can be inserted over the spout cylinder (2) of the container (1). In a further, not shown embodiment, it is also possible that the blister pack (3) with the opening (4) via the closure (2) of the container (1) inserted can be fixed.

The opening (4) of the blister pack (3) can be completely or only partially closed, wherein 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 one or more blister elements (5a, 5b), which each have a plurality of cavities (6), which are usually arranged distributed over the surface (5a, 5b) of the blister pack (3).

The collar (7) is designed such that the closure (2) in its closed position exerts a clamping force acting on the collar (7) substantially perpendicular to the blister plane. 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 does not come off the container (1) but is held by the shoulder (2a) of the closure (2) on the container (1). The shoulder (2a) of the closure (2) is to be chosen so that it can at least partially act on the surface surrounding the opening (4) of the blister pack (1).

In one embodiment, the blister pack (1) has a circular opening (4) and two arranged radially to the opening

Surface elements (5a, 5b). The blister pack (3) is designed such that the two legs (5a, 5b) of the blister pack (3) can each be raised at their distal ends.

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

FIG. 2b shows a further embodiment in which the cavities (6) of the blister pack (3) extend substantially across the area on the collar (7) arranged Blisterelemente (5a, 5b). These cavities (6) are particularly suitable for receiving larger product portions, as is necessary, for example, for long-lasting scenting of the surroundings of the blister pack (3).

Figure 2c shows a further embodiment of a blister pack (3) for fixing to an outlet cylinder of a container (1). The blister pack (3) has cavities (6), the perforations (8) enclosing the cavities (6) individually configure the cavities (6) separable from the blister pack (3).

Instead of a perforation (8), other means which appear suitable to a person skilled in the art for separating a portion from the blister pack (3) may also be provided.

It is also possible to provide the perforation (8) only on the foil sealing the cavities (6), so that a segment-by-segment opening of the blister pack (3) is possible by peeling off the corresponding foil section.

Figure 2d shows a blister pack (3), with an opening (4) which is completely or partially enclosed by a collar (7). On the collar (7) has a web (13) is arranged, which has at least one predetermined bending line (8).

According to one embodiment, the web (13) has two spaced predetermined bending lines (9). The distance (b) of the two spaced predetermined bending lines (9) is to be chosen so that it substantially corresponds to the height of the spout cylinder (14).

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

At the end of the web (13) remote from the collar (7) a blister element is arranged, which comprises a product-filled cavity (11) which is completely enclosed by a rim (10).

FIG. 2e shows the blister pack according to Figure 2d slipped over the closure cylinder (14) of a container (1). The blister pack (3) is folded along its predetermined bending lines (9) in each case by 90 ° such that the filled cavity (11) is positioned directly above the opening of the closure cylinder.

The cavity (11) of the blister pack (3) is designed such that it can be inserted substantially completely into the opening of the closure cylinder (14).
According to a particularly preferred embodiment, the upper side of the edge (10) rests directly on the wall of the closure cylinder (14) in the folded-in state of the blister package.

In a further embodiment, the edge (10) additionally comprises means which cooperate with the closure cylinder such that the blister pack (3) against lateral slippage on the Locking cylinder is secured. This can for example be realized by a correspondingly shaped circumferential groove or nose on the edge (10) of the blister pack (3).

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

FIG. 3a shows a cross section through a representative cavity (6,11) of a blister pack (3). In the simplest embodiment, the cavity (6) filled with product (16) is formed by a lower film (17) and sealed by a sealing film (15). The material of the sealing film (15) is to be selected 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 which is sufficiently strong to prevent inadvertent opening, but which can be removed by applying a corresponding pressure, e.g. by thumb pressure or tearing the film with a fingernail, leaves open. By pressure on a cavity (6) of the blister pack (3), pressure is exerted on the product (16) located in the cavity (6), so that finally the sealing film (15) pierces.

The sealing film can also be at least partially opened to the cavity by tearing, puncturing, rubbing, peeling, by contact with water, by heat, in particular by the heat of the human skin, or other suitable measures.

According to a further embodiment, the blister pack (3) can also be designed in such a way that the film (17) forming the cavity (6) is made firmer in such a way that the cavity (6) forming film (17) is opened by the applied pressure and the cavity (6) closing the sealing film (15) remains undamaged.

FIG. 3b shows a further developed embodiment of the blister pack (3) which in addition to the sealing film (15) comprises a permeable membrane (18). The permeable membrane (18) is arranged between the film (17) forming the cavity (6) and the sealing film (15), wherein the sealing film (15) is preferably arranged flat on the permeable membrane (18) by means of a releasable adhesive bond.

The material and the properties of the permeable membrane (18) are to be selected such that at least one substance of the product (16) can be released from the cavity (6) through the permeable membrane (18) to the environment. In the simplest case, the permeable membrane (18) is a grid suitable for retaining corresponding solids in the cavity.

In particular, the properties of the permeable membrane (18) should be chosen such that fragrances can be released from a liquid, gelatinous or solid product from a cavity (6) to the environment.

The permeable membrane (18) is preferably adhesively bonded to the film (17) forming the cavity (6) such that the permeable membrane (18) closes the cavities (6). The adhesive forces between the permeable membrane (18) and the film (17) forming the cavity (6) are preferably greater than the bond strengths between the permeable membrane (18) and the sealing film (15), so that when the sealing film (15) is pulled off the permeable membrane (18) adheres to the blister pack (3) and closes the cavities (6).

FIG. 4a shows a further embodiment in which on the blister pack (3) a snap-in connection element (19) is arranged, which with a corresponding receptacle (20) on the packaging unit (1,2,14), form-fitting, preferably releasably connectable , It goes without saying that the Blister (3) may also have a plurality of snap-in connections (19,20).

In a particularly preferred embodiment, the blister pack (3) can also be fixed by a corresponding snap-in connection on the closure (2) of the container (1).

According to a particularly preferred embodiment, the blister pack is at least partially equipped with an adhesive layer which is covered with a releasable sealing film, whereby the blister pack (3) or individual portions (6) of the blister pack (3) can be fixed to surfaces.

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

Fig. 5a shows a dimensionally stable receiving means according to the invention. (3) for additive portions (21) in the supervision. The receiving means (3) has a plurality of receiving openings (22) for additive portions (21). A receiving opening (22) interacts with an additive portion (21) such that the additive portion (21) is releasably fixed in the receiving opening (22). This can be realized, for example, by form, force or material connection between the additive portion (21) and the receiving opening (22). The fixation is to be designed in each case such that the additive portion (21) can not undesirably fall out of the receiving opening (22) during transport or storage, for example.

In a preferred embodiment of the invention, the additive portion (21) is fixed in a receiving opening (22) by a releasable interference fit. In a further preferred embodiment, the fixation between additive portion (21) and receiving opening (22) is 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 seals the additive portion (21) from the environment. The closure is advantageously designed such that the additive portion (21) is liquid-tight against the environment closed. Particularly preferably, the closure is designed in such a way that the additive portion (21) can be sealed substantially tightly against the emission of fragrances.

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

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

Furthermore, it is conceivable to equip the additive portion (21) with sealed openings. The openings may be designed as bores through the shell, bottom and / or top surface of the additive portion (21). However, any other suitable shape for the openings is conceivable, such as slots, grates, 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. In the In particular, sealing can 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) is 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) could also have openings on the lateral surface.

Non-flowable in this context means that the substance contained in an additive portion can not escape through the openings into the environment. This can be achieved, for example, by using a solid or solid granules, wherein, for example, the solid granules are dimensioned such that they do not fit through the openings or the solid is fixed in the portion volume.

The additive portions can be arranged in the receiving means (3) in two positions. In a first closed position, the openings of the additive portion (21) are completely closed by the mantle or bottom surface of the receiving opening (22).

As in FIG. 5b can be arranged by removing an additive portion (21) from the receiving opening (22) the additive portion (21) in a second position in a receiving opening (3) of the receiving means (3), in which the openings of the additive portion (21) with the Environment corresponds and components of the additive in the portion (21) substance, preferably diffusely, are released to the environment.

In addition, in this case, the opening or openings of the additive portion (21) may be covered by a protective film, which is initially a diffusive

Product delivery to the environment prevented. 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 (3) has an opening (4) which is connected to the opening of the container in a positive, non-positive or materially releasable manner. In a preferred embodiment of the invention, the receiving means (3) has 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, wherein the opening (4) is designed such that it prevents at least a simple release of the receiving means from the container. Alternatively, it is also possible to detachably connect the receiving means (3) with the closure of the container in a positive or cohesive manner.

Claims (10)

1. A packaging unit, comprising a container (1) for receiving a product, a closure (2) as well as an opening (14), which can be closed by the closure (2), for discharging the product from the container (1), wherein the packaging unit (1, 2, 14) has at least one receiving means (3) for a plurality of additive portions (21) each of which being less than 50 ml, wherein the additive (16) includes at least one substance from the group of the fragrances, colorants or surfactants and the receiving means (3) for additive portions (21) is detachably fixable to the packaging unit (1, 2, 14), the receiving means (3) is essentially dimensionally stable and includes receiving openings (22), characterized in that the additive portions (21) are detachably fixable in an interlocking, frictional and/or materially bonded manner in the receiving openings (22), and respectively have at least one opening that cooperates in such a way with the receiving openings (22) that the opening of an additive portion (21) fixed in the receiving opening (22) is closed.
2. The packaging unit according to claim 1 characterized in that the receiving means (3) includes a first means (4) for fixing the receiving means (3) to the packaging unit (1, 2), said first means cooperating in such a way with a second means (2, 14) that is arranged on the packaging unit (1, 2, 14) such that the receiving means (3) is detachably fixable in an essentially interlocking, frictional and/or materially bonded manner to the packaging unit (1, 2, 14).
3. The packaging unit according to claim 2 characterized in that the first fixing means arranged on the receiving means (3) is an opening (4) that cooperates with the second means that is arranged on the packaging unit (1,2,14) for fixing the receiving means (3) in such a way that the opening (4) of the receiving means (3) is pluggable through the second means (2,14) arranged on the packaging unit (1,2,14).
4. The packaging unit according to claim 2 or 3 characterized in that the first and second means for fixing the receiving means (3) on the packaging unit (1,2,14) form a snap-in connection.
5. The packaging unit according to one or more of the previous claims characterized in that the plurality of the additive portions are formed as a blister pack.
6. The packaging unit according to claim 5 characterized in that the blister pack (3) comprises an adhesive portion with an adhesive layer, which is covered with a detachable sealing film.
7. The packaging unit according to claim 1 characterized in that the at least one opening of the additive portions (21) is closable with a closure means.
8. The packaging unit according to claim 1 or 7 characterized in that at least one additive portion (21) contains a non-free flowing substance (16).
9. The packaging unit according to one or more of the previous claims characterized in that the products (16) located in the additive portions (21) are from at least two groups, which differ in regard to their fragrance, surfactant, and/or dye composition.
10. The packaging unit according to one or more of the previous claims characterized in that at least a part of the receiving means (3) is adhesively bonded to the packaging unit (1,2,14).

Images