EP1973800A1 - Container closure - Google Patents

Abstract

Closure (1) for a container, in particular for pourable or flowable products, comprising a closure head (2), a circumferential face (3) which is connected at least partially to the closure head (2), and means (6) which interact with the container in such a way that the discharge opening of the container can be closed by the closure (1), with the result that the closure (1) has means (4) for fixing a plurality of portion containers (7) of in each case less than 50 ml filling volume to the closure (1) and the portion containers (7) are filled with at least one substance from the group of aromatics, colorants or tensides.

Description

 container closure

The invention relates to a closure for a container, in particular for a bottle or a canister for pourable and / or flowable consumer products such as from the group of pharmaceuticals, personal care products, agricultural auxiliaries, building materials, dyes, laundry detergents, dishwashing detergents, adhesives or food.

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. Thus far, it has been necessary to use a variety of specialty cleaners with the appropriate scents, although the detergent-active formulations 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.

From 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 containers, which inevitably leads to increased logistics costs.

CA983437 discloses a container for medical applications in which it is necessary to administer a prescribed dose of a tablet or capsule Compound with a liquid. For this purpose, a container according to CA983437 has 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.

Object of the invention

It is therefore an object of the present invention to provide a closure that allows to preferably provide a plurality of individually packaged portionable product units in a container closure, in a simple and easy to use manner, and allows individual product units without completely separating the closure from the container refer to.

The object is achieved according to the features of claim 1.

A significant advantage of the closure according to the invention is its cost-effective manufacturability. Because no constructive, creative change to the container are necessary, the provision of the product units on the closure from a production and economic point of view is much cheaper, since a container closure is usually injection molded, so that - A -

Consequently, requirements with regard to accuracy and geometrical complexity can usually be fulfilled and are technically controllable. In containers, the blow molding process is frequently used today, with which in particular lightweight bottles can be produced inexpensively, for example, for rinsing and cleaning agents, but complex geometries and especially manufacturing tolerances such as attaching a product unit directly to the container would be necessary, technically and / or economically not are satisfiable.

Furthermore, the solution according to the invention can be easily adapted to existing closures.

By realizable with the invention spatial separation of certain active substances (fragrance, enzymes, bleach, etc.) from a preparation and their portioned arrangement in the closure of the container, the product contained in the container in a simple way to assemble.

The content of the portion containers may consist of one or more identical or different products or additives such as, fragrances, cleaning substances, dyes, enzymes, hygroscopic substances and the like.

For example, it would be conceivable to arrange substances with different scents in the portion containers in order to allow different perfuming of the contents of the container. Thus, for example, when using a fragrance-neutral cleaning liquid which is first mixed with water to form a wiping preparation, another fragrance from a portion container is metered in each wiping water preparation. 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 a plurality of specially perfumed cleaning substances, which is also desirable in terms of environmental protection and resource conservation.

The individually packaged, portionable additive product units are fixed by a suitable positive, non-positive or cohesive connection to the closure. Preferred types of connection are snap-in connections, compression joints, fusible links, adhesive bonds, Velcro connections.

According to a particular embodiment of the invention, the individually packaged, portionable product units have a closure. This can be formed, for example, by a rotatable cap or a desired weakening line, a stopper, a sealing foil on the product unit.

The closure and / or opening of the container may optionally include metering and dispensing 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 perfumes, 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.

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 that meet the above criteria with respect to the melting or softening temperature. Preferred scent-dispensing 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 (about 0.915 to 0.935 g / cm ³⁾ and crystallinity of about 40-50%, which is as LDPE-type (low density polyethylene), respectively. Products with a higher molecular weight and the resulting improved strength and ductility have the abbreviation HMW-LDPE (HMW = high molecular weight). By copolymerizing the ethylene with longer-chain olefins, in particular with butene and octene, the pronounced degree of branching of the polyethylenes produced in the high-pressure process can be reduced; the copolymers have the abbreviation LLD-PE (linear low density polyethylene).

The macromolecules 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 method of polymerization, products with paraffin wax-like properties (MR around 2000) and products with highest toughness (MR over 1 million) can be obtained.

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

Polypropylene (PP) is the name given to thermoplastic polymers of the

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 objects Polypropylene is even possible up to 140 ⁰ 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 (C-O-C). According to this definition, a large number of structurally very different polymers belong to the polyethers, eg. 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 polyarylether) or polyetheretherketones (see. Not to the polyethers polymers with pendant ether groups are calculated, such as. a. the cellulose ethers, starch ethers and vinyl ether polymers.

The group of polyethers also include functionalized polyethers, ie compounds having a polyether skeleton, which laterally attached to their main chains still carry other functional groups such. As carboxy, epoxy, AIIyI or amino groups, etc. are widely used block copolymers of polyethers and polyamides (so-called polyetheramides or polyether block amides, PEBA). AIs 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 special properties, polyamides which contain exclusively aromatic radicals (for example those of p-phenylenediamine and terephthalic acid) are classified under the generic name. Aramids or polyaramides summarized (Ex .: Nomex®).

The most commonly used polyamide types (especially PA 6 and PA 66) consist of unbranched chains with average molecular weights of 15,000 to 50,000 g / mol. They are partially crystalline in the solid state and have degrees of crystallization of 30-60%. An exception are polyamides of building blocks with side chains or co-polyamides of very different components, which are largely amorphous. In contrast to the generally milky-opaque, semi-crystalline polyamides these are almost crystal clear. The softening temperature of the most common homo-polyamides are between 200 and 260 ⁰ C (PA 6: 215-220 ⁰ C, PA 66: 255-260 ⁰ C). Polyester is the collective name for polymers whose basic building blocks are held together by ester bonds (-CO-O-). According to their chemical structure, the so-called homopolyesters can be divided into two groups, the hydroxycarboxylic acid types (AB-polyester) and the dihydroxy-dicarboxylic acid types (AA-BB-polyester). The former are made of only a single monomer by z. B. polycondensation of a ω-hydroxycarboxylic acid 1 or by ring-opening polymerization of cyclic esters (lactones) 2 produced.

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

Pure aliphatic AA-BB type polyesters (II) are polycondensates of aliphatic diols and dicarboxylic acids, the u. a. as hydroxy terminated products (as polydiols) for the preparation of polyester polyurethanes [e.g. B. polytetramethylene adipate]. The most technically significant in terms of quantity are AA-BB type polyesters of aliphatic diols and aromatic dicarboxylic acids, in particular the polyalkylene terephthalates, with polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and poly (1,4-cyclohexanedimethylene terephthalate) s (PCDT) as the most important representatives , These types of polyesters can be widely varied in their properties by using other aromatic dicarboxylic acids (for example isophthalic acid) or by using diol mixtures in polycondensation and can be adapted to different fields of application.

Purely aromatic polyesters are the polyarylates, which include the poly (4-hydroxybenzoic acid) include. In addition to the previously mentioned saturated polyesters, it is also possible to use unsaturated polyesters from unsaturated ones Produce dicarboxylic acids, which have achieved technical importance 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 (elastofasem, 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, the so-called RIM technique was developed for the manufacture of complexly shaped objects made of polyurethane foam (reaction injection molding). The RIM-Verf. is based on rapid dosing and mixing the components, injection of the reactive mixture into the mold and rapid curing; the cycle time is only a few minutes. Among other things, car body parts, shoe soles, window profiles and television casings are produced by means of RIM technology.

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

CH ₂ -CH-CH ₂ -CH-

OH OH

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

contain.

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

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable. The water solubility can be by post-treatment with aldehydes (acetalization), by complexation with Ni or Cu salts or reduce 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.

Preferably, a range of molecular weights are used as materials for the containers polyvinyl alcohols, which is preferable in the invention that the water-soluble or water-dispersible container comprises a polyvinyl alcohol whose molecular weight ranging from 10,000 to 100,000 gmol ^"1, preferably from 11,000 to 90,000 ^{gmol" 1,} more 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 fragrance delivery system, characterized in that the polymeric carrier material contains at least 10 wt .-%, preferably at least 30 wt .-%, particularly preferably at least 70 wt .-% ethylene / vinyl acetate copolymer, preferably completely made of ethylene / vinyl acetate copolymer.

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

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

In the context of the present invention, especially in the field of scenting the interiors, fragrance delivery systems are particularly preferred in which ethylene / vinyl acetate copolymer is used as the polymeric support material and this copolymer contains from 5 to 50% by weight of vinyl acetate, preferably from 10 to 40% by weight. Vinyl acetate and in particular 20 to 30 wt .-% vinyl acetate, each based on the total weight of the copolymer containing. Fragrance delivery systems according to the invention contain the polymeric carrier 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. Particles in the context of the present application are 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 with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, oc-lsomethylionon and methyl cedryl ketone , the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include 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 Muskateller, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.

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 "middle note" as well as "Base note" (end note or dry out) divided. Since odor perception is also largely due to odor intensity, the top note of a perfume does not consist solely of volatile compounds, while the base note is largely made up of less volatile, i. adherent fragrances. For example, in the composition of perfumes, more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly. In the subsequent classification of the fragrances in "more volatile" or "adherent" fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing said.

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 be 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, kanaga oil, cardamom oil, cassia oil, pine oil, copaϊva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, Musk Grain Oil, Myrrh Oil, Clove Oil, Neroli Oil, Niaouli Oil, Olibanum Oil, Orange Oil, Origanum Oil, Palmarosa Oil, Patchouli Oil, Peru Balsam Oil, Petitgrain Oil, Pepper Oil, Peppermint Oil, Pimento Oil, Pine Oil, Rose Oil, Rosemary Oil, Sandalwood Oil, Celery Oil, Spik Oil, Star Aniseed Oil, Turpentine Oil, Thuja Oil, Thyme oil, verb ena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon oil, lemon oil, lemon oil and cypress oil. But also the higher-boiling or solid fragrances of natural or synthetic origin can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances. These compounds include the 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, methylchavikol, 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, pulegone, safrole, salicylic acid isoamyl ester, methyl salicylate, salicylic acid hexyl ester, cyclohexyl salicylate, santalol, skatole, terpineol, thymine, thymol, γ-undelactone, vaniline, veratrumaldehyde, 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 ⁰ 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 absorbed by adhesion, diffusion and / or capillary forces of the polymeric carrier material or of other perfume carrier materials contained in the particle, these being able to 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. From the means which serve exclusively the scenting, therefore, further product groups can be distinguished, which in addition to the contain the aforementioned constituents of the invention further preferred substances.

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, Grease Yellow 3G ₁ Iragon® Red SRE 122, Iragon® Green SGR 3, Solvent Yellow 33 and Solvent Yellow 16, but other dyes may be included.

In a preferred embodiment, the dye 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 next to the lack of fragrance impression, which may for example also be based on a habituation effect on the part of the user, another reliable indication as to when to replace the deodorant with a new one.

The indicator effect can be achieved in various ways: On the one hand, a dye can be used, which escapes from the particles during the period of application. This can be 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 fragrance is not consumed, is completed. On the other hand, a color change can also be caused by a chemical reaction or thermal decomposition.

Antimicrobial agents. Germicides, fungicides

Further preferred 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 are, 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 and organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

If the agents according to the invention are used in dishwashers, then these agents 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 are preferably present in one of the oxidation states II, III, IV, V or VI.

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 above-mentioned. Anions exist. The central atom is one of the o.g. Metals in one of the above Oxidation states. The ligands are neutral molecules or anions that are mono- or polydentate; The term "ligand" within the meaning of the invention is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507" explained in more detail. If, in a metal complex, the charge of the central atom and the charge of the ligand (s) do not add up to zero, either one or more of the above may be provided, depending on whether there is cationic or anionic charge excess. Anions or one or more cations, e.g. As sodium, potassium, ammonium ions, for the charge balance. Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The definition of "oxidation state" common in chemistry is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3168" reproduced.

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [I-

Hydroxyethane-1, 1-diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrFg, CoSO ₄ , Co (NO 3) ₂ , ^Ce ( ^N 3) 3 and their mixtures, so that preferred agents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group consisting of 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 2- ^{V0 Ti0S0} 4' ^K 2 ^{T 'F} 6- ^K 2 ^ZrF 6' ^C ° ^S0 4 ^{'Cθ (NO} λ' ^{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. For example, e.g. that known from SO production (contact method)

Mixture of pentavalent and tetravalent vanadium (VO, VO ₀ , V, O) is suitable, as well as the resulting by diluting a Ti (SO ₄ ) ₂ solution 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, contain

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, affect 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 insoluble zinc salts according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn ₂ (OH) ₂ COa), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (PO-O 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 included in the claimed compositions, 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 2O ⁰ C water temperature). The first group of zinc salts includes, for example, the zinc nitrate, the zinc oleate and the zinc stearate; 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 Zinkeitrat acts. 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 abovementioned active substances, the compositions according to the invention, in particular compositions for use in dishwashers, textile washing machines or dryers, may of course comprise all active substances normally contained in textile or dishwashing or textile or dishwashing agents, 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-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid , N, N-Terephthaloyl-di (6-aminopercaproic acid) can be used. 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 action 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-nonanoyl-succinimide (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.

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

R ¹

I

R ² -N ⁽⁺⁾ - (CH ₂ ) -CN X ⁽ ->,

R ³

in which R ¹ is -H, -CH _3, a C _2-24 -alkyl or -alkenyl radical, a substituted C _2- 24 alkyl or alkenyl group having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a Ci _-24 - Alkyl group, or a substituted alkyl or Alkenylarylrest with a C ₁ . ₂₄ alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ - CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion ,

In particularly preferred inventive agents is a cationic nitrile of the formula

R ⁵ is -N ⁽⁺⁾ - (CH ₂₎ -CN X <^"\

R ^e

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

In addition to 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 salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.

surfactants

Preferred 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 6 carbon 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 (caproic 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), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (Petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatrienoic acid (linolenic acid) It is preferred not to use the pure species, but technical mixtures of the individual acids, as they are accessible from the lipid cleavage Such mixtures are for example coconut oil fatty acid (about 6 wt .-% C ₈ , 6 wt .-% Ci ₀ , 48 % By weight C ₁₂ , 18% by weight C ₁₄ , 10% by weight C ₁₆ , 2% by weight C ₁₈ , 8% by weight C ₁₈ -, 1% by weight C ₁₈ -), Palm kernel oil fatty acid (about 4% by weight C ₈ , 5% by weight C ₁₀ , 50% by weight C ₁₂ , 15% by weight C ₁₄ , 7% by weight C ₁₆ , 2% by weight C ₁₈ , 15% by weight C ₁₈ -, 1% by weight C ₁₈ -), tallow fatty acid (ca. 3% by weight 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 wt .-% C ₁₈ -, 1 wt .-% C ₁₈ -), hardened tallow fatty acid (about 2 wt .-% C ₁₄ , 28 wt .-% C ₁₆ , 2 wt .-% C ₁₇ , 63 wt .-% C ₁₈ , 1 wt .-% C ₁₈ ), technical oleic acid (about 1 wt .-% C ₁₂ , 3 wt .-% C ₁₄ , 5 wt .-% C ₁₆ , 6 wt .-% C ₁₆ -, 1 wt .-% C ₁₇ , 2 wt .-% C ₁₈ , 70 wt .-% C ₁₈ -, 10 wt .-% C ₁₈ -, 0.5 wt .-% C ₁₈ -), technical Palmitin / stearic acid (about 1% by weight of Ci ₂ , 2% by weight of C ₁₄ , 45% by weight of C ₁₆ , 2% by weight of C ₁₇ , 47% by weight of 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% by weight 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 from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters won. The quantitatively most important industrial process for the preparation 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 may contain the sulfonic acid group terminally bound (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), with only the secondary alkanesulfonic acids having commercial significance. These are prepared by sulfochlorination or sulfoxidation of linear hydrocarbons. In sulfochlorination after melting, n-paraffins are reacted with sulfur dioxide and chlorine under UV light irradiation to give the corresponding sulfochlorides which upon hydrolysis with alkalis directly give the alkanesulfonates, when reacted with water the alkanesulfonic acids. 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 irradiated with sulfur dioxide and UV light Oxygen are converted. 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 followed by 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 OC- and i-olefins. The resulting olefins are then reacted in the presence of acidic catalysts with benzene to the alkylbenzenes, the choice of 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 reduced 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 is used in the context of the present invention as anionic surfactant acid.

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: H ₃ C- (C

in which the sum of x and y is usually between 5 and 13. Preferred as anionic surfactant in acid form according to the invention are C _8- i ₆ -, preferably It is within the scope of the present invention further preferably, C _8- I6. preferably C _9- use i ₃ -alkylbenzenesulfonic acids derived from alkylbenzenes having a tetralin content below 5 wt .-%, based on the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes were prepared by the HF process, so that the Cβ-16-, preferably C ₉ -13-alkylbenzenesulfonic acids employed have a content of 2-phenyl isomer below 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. However, it is also possible and preferred that the anionic surfactant in acid form before addition to the / the carrier material (s) further, preferably acidic, ingredients of detergents and cleaners in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, in each case based on the weight of the mixture to be reacted, mixed.

Of course, it is also possible to use the anionic surfactants partially or fully neutralized. These salts can then be present as solution, suspension or emulsion in the granulation liquid, but also as a solid component of the solid bed. 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 can also be the analogous representatives of mono-, di- or trimethanolamine or those of the alkanolamines higher alcohols 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 preparation forms can be prepared, for example, by mixing commercial cationic surfactants with auxiliaries, 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.

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:

R ¹

I

R ¹ -N ⁽⁺⁾ - (CH ₂ ) n TR ² (X)

(CH ₂ ) _n -TR ²

R ¹ R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -CH-CH ₂ (XI)

R ¹ TT

I i

R ² R ²

R ¹

I

R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (XII)

wherein each R ¹ group is independently selected from _Ci-6-alkyl, - alkenyl or hydroxyalkyl groups; each group R ² 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. Preferred ethnic oxylierten alcohols include, for example, C _2- i ₄ alcohols containing 3 EO or 4 EO, n-alcohol with 7 EO, C _3- I ₅ alcohols containing 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 rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, other nonionic surfactants which can also be employed are alkyl glycosides of the general formula RO (G) _x , in which R is a primary straight-chain or methyl-branched, especially methyl-branched, 2-position 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-coconut alkyl-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.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula XIII ₁ I

R-CO-N- [Z] (XIII)

in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^ is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical 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.

The group of polyhydroxy fatty acid amides also includes compounds of the formula XIV,

R ¹ -OR ²

I R-CO-N- [Z] (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 group having 1 to 8 carbon atoms, wherein _Ci-C4 alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxyalkyl residue, whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives this rest. [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. Dishwashing compositions according to the invention therefore preferably contain only certain nonionic surfactants, which are described below. As surfactants, only weakly foaming nonionic surfactants are usually used in automatic dishwashing detergents. Representatives from the groups of anionic, cationic or amphoteric surfactants, however, have less importance. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 C atoms, for example of coconut, palm, tallow or oleyl alcohol, and by preferably 2 to 8 EO per mole of alcohol. Preferred ethnic oxylierten alcohols include, for example, C ^ -u-alcohols with 3 EO or 4 EO, n-alcohol with 7 EO, C _3- I ₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO , Ci _2- i ₈ - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci ₂ -14-alcohol with 3 EO and Ci _2- i ₈ -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 rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are 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 ⁰ C. Preferably used nonionic surfactants have melting points above 25 ° C. , particularly preferably used nonionic surfactants have melting points between 25 and 60 ⁰ C, in particular between 26.6 and 43.3 ⁰ 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 built-up 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 solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _6-2 alcohol), preferably a C ₈ alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won. Of these, the so-called "narrow rank 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.

Further particularly preferred nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75th % 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 polyoxypropyls initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole trimethylolpropane.

Non-ionic surfactants that can 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] χ [CH ₂ ] _k CH (OH) [CH ₂ ] _j 0R ²

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

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

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is 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 can be used to increase the washing, or

Cleaning power contain enzymes, in principle, all in the prior art can be used for these purposes established enzymes. 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 thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the 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 available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α- amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α- amylase from B. amyloliquefaciens is sold 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 S. 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. 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 for example marketed by Novozymes under the trade names Lipolase ^®, Lipolase Ultra ^®, LipoPrime® ^®, Lipozyme® ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. ^Lipase® , Lipase ^AP® , Lipase M- ^AP® and Lipase ^{AML® are} available. By Genencor, for example, the lipases or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention also the product Lumafast® ^® from Genencor.

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 ^® available also from Novozymes based on the 50 kD EG and 43 kD EG possible from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® ^® and Renozyme ^®. Likewise, the 20 kD-EG cellulase from Melanocarpus, from the company AB Enzymes, Finland ^® is 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 lndiAge ^® 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 L from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, USA , The obtained from B. subtilis .beta.-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 according to the invention are either originally derived from microorganisms, such as the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and / or are known per se biotechnological processes produced 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 conventional methods, for example by 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 protected against damage, for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage. 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, such as ortho-.meta or para-substituted phenylboronic acids, or their salts or esters. Furthermore, peptide aldehydes, that is oligopeptides with reduced C-terminus are suitable. As peptidic protease inhibitors are, inter alia, ovomucoid and leupeptin to mention; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.

Other enzyme stabilizers are aminoalcohols, such as up to Ci _2, such as succinic acid, other dicarboxylic acids or salts of said acids, mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic 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 more common 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 Cβ-Ci ₈ 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 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 1 to 5 wt .-%, 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 MgCb in the granules according to the invention is preferred.

Bezuqszeichenhste

1 closure

2 locking head

3 lateral surface

4 receiving opening for portion container

5 dosing volume

6 screw thread

7 portion container

8 substance

9 predetermined breaking point

10 screw thread

11 containers

12 portion volumes

13 portion closure

14 plugs

15 portion opening

16 sealing

17 portion opening

The invention will be explained in more detail with reference to embodiments which are illustrated in the following figures. Show it

Figure 1: closure with receiving openings for portion containers in cross section

Figure 2: closure with receiving openings for portion containers in the supervision

Figure 3: closure with receiving openings for portion containers in the supervision

FIG. 4: Portion container with closure FIG. 5: Portion container with stopper FIG. 6: Portion container with sealed openings FIG. 7: Portion container with non-flowable substance FIG. 8: Closure with portion containers with non-flowable substance in cross section

Description of the figures

FIG. 1 shows a cross-sectional view of the closure 1 according to the invention. The closure 1 has a jacket surface 3 and a closure head 3 which extends over an end face of the jacket surface 3 and thus forms a cup-like metering volume 5 of the closure 1.

The closure 1 has a plurality of receiving openings 4 for portion containers 7. A receiving openings 4 interacts with a portion container 7 such that the portion container 7 is detachably fixed in the receiving opening 4. This can be realized for example by form, force or material connection between the portion container 7 and the receiving opening 4. The fixation is in each case to be designed such that the portion container 7 can not undesirable, for example during transport or storage, fall out of the receiving opening. In a preferred embodiment of the invention, the portion container 7 is fixed in a receiving opening 4 by a releasable interference fit. In a further preferred embodiment, the fixation between portion container 7 and receiving opening 4 is ensured by a detachable snap-in connection.

The closure 1 has an internal thread which corresponds to an external thread formed on the container 11 and permits a preferably liquid-tight closure of the container 11 by the closure 1.

Figure 2 shows the closure 1 with receiving openings 4 for portion containers 7 in the plan. A plurality of receiving openings 4 is in this case arranged concentrically around the center of the closure 1. The receiving openings 4 can be designed as a through hole or as a blind hole. According to the embodiment shown in FIG. 2, a receiving opening 4 is completely enclosed by the closure 1.

FIG. 3 shows a further embodiment of the closure 1 according to the invention, in which the receiving openings 4 are only partially enclosed by the closure 1 in such a way that clip-like openings are formed in which a portion container 7 can be fixed.

FIG. 4 shows a portion container 7 with a closure 13, which tightly seals the portion volume 12 from the environment. The closure 13 is advantageously designed such that the portion volume 12 can be closed in a liquid-tight manner with respect to the environment. Particularly preferably, the closure 13 is designed such that the portion volume 12 is substantially tightly sealed against the emission of fragrances. The closure 13 is detachably connected via force, shape or material connection to the portion container 7. In particular, the portion volume 12 can be sealed tightly by the closure 13 via an interference fit, a screw cap, a snap-in connection or bonding with respect to the environment.

FIG. 5 shows a portion container 7 in which the portion volume 12 is closed with a stopper 14. The plug 14 is preferably made of an elastic material and is designed such that it closes the portion volume 12 at least liquid-tight.

FIG. 6 shows a portion container 7 with sealed openings 15. The openings 15 can be configured as bores through the shell, bottom and / or top surface of the portion container 7. However, any other suitable shape for the openings 15 is conceivable, such as slots, grates, etc.

The seal 16 of the openings 15 is designed such that the openings 15 are sealed liquid-tight. In a particularly preferred embodiment, the seal is substantially dense to the emission of perfumes from the portion volume 12 into the environment.

The sealing can in particular be a plastic film which is glued to the surface of the portion container 7 at least partially, preferably detachably. It is also conceivable to seal the openings 15 via a so-called sleeve, wherein a suitable plastic film is pulled taut around the portion container.

As shown in FIG. 7, the portion container 7 may also be filled with a non-flowable substance 8. In this case, the portion container 7 may be shaped like a cup, which has an open end face 17. Alternatively, the portion container could also have openings 15 on the lateral surface.

Not flowable in this context means that the substance located in the portion volume 12 8 can not escape through the openings 15,17 in 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 15, 17 or the solid is fixed in the portion volume.

FIG. 8 shows the use of the portion containers 7 disclosed in FIG. 7 in a closure 1 according to the invention. The portion containers 7 can be arranged in the closure 1 in two positions. In a first closed position, the openings 17 of the portion container are completely closed by the mantle or bottom surface of the receiving opening.

By removing the portion container 7 from the receiving opening 4, the portion container 7 can be arranged in a second position in a receiving opening 4 of the closure 1, in which the openings 17 of the portion container 7 corresponds to the environment and constituents of the substance contained in the portion container 7 8, preferably diffused, are released to the environment.

In addition, in this case, the opening or openings of the portion container 7 may be covered by a protective film, which initially prevents a diffusive product delivery to the environment. The protective film can be removed, for example by tearing off or rubbing off, so that then product 8 can be released to the environment.

Claims

claims

1. closure (1) for a container, in particular for schüft- or flowable products, comprising a closure head (2), a lateral surface (3) which is at least partially connected to the closure head (2), and means (6), the cooperate with the container such that the dispensing opening of the container through the closure (1) is closable, characterized in that the closure (1) via means (4) for fixing a plurality of portion containers (7) of less than 50 ml filling volume on Closure (1) and the portion containers (7) are at least partially filled with at least one substance from the group of perfumes, dyes or surfactants.

2. Closure according to claim 1, characterized in that an essentially positive, cohesive and / or non-positive connection between the receiving means (4) and the portion containers (7).

3. Closure according to one of the preceding claims, characterized in that the means (4) for receiving the portion containers (7) are designed such that the portion containers (7) are detachably arranged in the receiving means (4).

4. Closure according to one of the preceding claims, characterized in that a force of at least 0.1 N is necessary to solve a portion ratio (7) from the receiving means (4).

5. Closure according to one of the preceding claims, characterized in that the means (4) for receiving the portion containers (7) are blind holes.

6. Closure according to one of the preceding claims, characterized in that the portion containers (7) comprise predetermined breaking points (9).

7. Closure according to one of the preceding claims, characterized in that the portion containers (7) have at least one opening which can be closed with a closure means.

8. Closure according to one of the preceding claims, characterized in that the portion containers (8) contain mutually different substances (8) or substance mixtures (8) or additives.

9. Closure according to one of the preceding claims, characterized in that the portion containers (7) contain more than 1% by weight of perfumes.

10. Closure according to one of the preceding claims, characterized in that the portion containers (7) have at least one opening which cooperate with the means (4) for receiving the portion containers (7) such that the opening of a fixed in the closure portion container (7 ) is closed.

11.Verschluss according to any one of the preceding claims, characterized in that the portion containers (7) include a non-flowable substance (8).