DE102006031169A1 - Donor device for fixing at output opening of packaging means, has many chambers for acceptance of inlets different from each whereby chambers are coupled over inlets communicating to multi-way valve - Google Patents

Abstract

The donor device (2) has many chambers (3,4) for the acceptance of inlets which are different from each other. The chambers are coupled over inlets (7,8), communicating to a multi-way valve (6). The product quantity released by the user from the chambers by the actuation of the actuating means, can be defined by means of selector lever (10) coupled with the multi-way valve and operated from outside.

Description

The The invention relates to a dispensing device, in particular a trigger spray dispenser, with a multiway valve for the convenient selection of defined dispensing or mixing ratios from a plurality of chambers, the different preparations from each other include.

State of the art

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

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

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

Just In addition, with very aggressive cleaning preparations exists the problem that the aggressive cleaning components include the in the preparations persistent fragrances or other active substances decompose, so that they have only a low storage stability.

to solution the problem of low storage stability were among other multi-chamber containers in which the incompatible Compositions spatially stored separately from each other and only at the time of application be mixed together.

to clients, in particular large-scale and / or Foam-forming application of such cleaning preparations include dispenser in the form of trigger pumps known.

For example, this is off US 5857591 a dispensing device for the simultaneous spraying of two mutually different preparations known. This document discloses a trigger pump, which simultaneously promotes preparations of separate chambers of a bottle, the delivery to the environment can be done by two spatially separate conduit systems, so that it comes only after the product delivery to a mixture of both preparations.

In this solution, there is the disadvantage that a complex-shaped multi-chamber bottle is used. In the US 5857591 The disclosed trigger pump also has the disadvantage that no selection of the preparations to be dosed with one another can take place. Only the preparations in the two chambers can be sprayed in a certain mixing ratio to one another.

A dispenser device that can deliver a particular preparation from a multichamber container is off US 5152431 known. US 5152431 discloses a trigger pump which is rotatably mounted on the closure of a multi-chamber bottle. From an adapter plate in each case a riser extends into each of the chambers which are filled with different compositions. By rotation of the trigger pump, a suction-side supply pipe, which is connected to the pump, are communicatively coupled via the adapter plate with a riser. In this way it is possible to optionally spray a certain preparation from one of the chambers.

A disadvantage of this US 5152431 known solution is that the production of such multi-chamber bottles is relatively complicated and expensive. Furthermore, only one particular preparation can be dosed by the proposed solution.

However, it is desirable to the user of such a dispenser bottle to ver together mixing preparations, for example, so as to add the conveyed product with a particular fragrance or other additive substances.

Task of invention

It It is therefore the object of the invention to provide a dispensing device which overcomes the known disadvantages of the prior art and in one for the user convenient way of promoting different compositions allowed, wherein one of the compositions of the user from a number at possibilities selectable is. Another object of the invention is to provide the dispensing device in such a way that they, without constructive changes to make on single-chamber bottles, can be used.

These Task is achieved by a dispensing device with the features of claim 1 solved.

By the realizable with the invention spatial separation certain Active substances (fragrance, enzymes, bleach, etc.) from a preparation and their portioned arrangement in the dispenser is the in Packing product located in a simple way to assemble.

Therefore is a significant advantage of the dispenser device according to the invention therein to see that the user has a wide range of self-to-choose Fabrication options for a Can be provided in the packaging product.

Further can the dispenser device according to the invention with only one subsidy to deliver the two mutually different preparations the chambers and the packaging are operated, whereby the constructive and thus the cost can be kept low.

Multi-way valve

The Multiway valve has at least two inlets and at least one outlet wherein at least one of the inlets communicating with an additive chamber is connected.

The Multi-way valve is with a user-operable selector lever coupled in such a way that the operation of the selector lever a defined configuration of the inlet and outlet switching states of the multi-way valve causes.

Some typical switching states are listed as examples in the following table:

Of the Inflow through the inlets is by at least one corresponding actuator of the multi-way valve controllable. For example, the actuator as a horizontal Bored cylinder bores are formed, wherein the cylinder in the valve body is rotatably mounted such that the holes in a closed position prevent the flow of a fluid from an inlet to an outlet while they are in a dispensing position, the flow of a fluid from an inlet allow to an outlet.

Further The flow rate through the inlets of the multi-way valve can be controlled be. That's how it is it is possible, for example by a suitable configuration of the corresponding flow cross sections a defined mixing ratio to adjust between packaging fluid and an additive fluid.

In a further embodiment of the invention, at least one of the inlets communicatively connected to the packaging means, so that the product fluid from the packaging material and at least one additive fluid be merged from an additive chamber directly in the multi-way valve.

Of the Selector lever can, for example, as a knob, turntable, rocker or sliders be designed.

The switching states of the multiway valve are therefore not by a rotation of the Dispenser device opposite the packaging selected, but by the operation of the selection lever on the dispenser device, so that the dispenser device and the packaging need not be rotated against each other, which a much simplified seal is feasible.

funding

in the Meaning of this application is a subsidy a device coupled to the actuator and is suitable, a preparation of the packaging in the environment to promote.

Especially can the funding be designed as a pump. The pump can be mechanical or electrical be driven.

A Pump can be selected be from the group of positive displacement pumps, screw conveyors (Archimedean screw), bellows pumps, piston pumps, rotary lobe pumps, Gear pumps, diaphragm pumps, rotary vane pumps, peristaltic pumps, Toothed belt pumps, eccentric screw pumps, screw pumps, flow pumps, Centrifugal pumps, axial pumps, diagonal pumps, foam pumps or radial pumps.

In a preferred embodiment The invention can the conveyor designed as a pressurized aerosol packaging be the funding as such, by the pressurized propellant of the aerosol package is trained.

In a further embodiment is the funding designed as a preferably elastically deformable container in which the to be conveyed the preparation from the packaging necessary pressure increase in Inside of the packaging by a jerky squeezing the packaging jacket walls is effected. In this case, the conveying means and the actuating means as a device, namely the squeezable container, executed.

packaging

One Packing means in the context of this application is a device that is intended to wrap a preparation so that it is shipping, storage and / or salable.

The Packaging usually has a floor and a lateral surface on, through which a volume is formed for receiving a preparation becomes. Furthermore, the packaging regularly has an opening for dispensing the preparation from the packaging, wherein the opening by a closing means lockable is. The closing means and the dispenser device preferably be designed as a component, for example in Shape of an integrally formed on the dispenser device, with an internal thread provided lapel rings.

One Packaging can be selected in particular from the group of Bottles, containers, cans, boxes, bags etc.

to Use with trigger dispenser or donor devices, for product delivery a vertical stroke of the actuator need, It is, for example, in terms of stability or stability of a standstill such packaging means system advantageous, the packaging in particular to form as a shape or volume stable container.

In a preferred embodiment invention, the packaging is formed squeezable. The packaging may in particular be formed elastically in the way that the Packaging after a squeezing his original Take shape before bruising. Due to the squeezable shape of the packaging material it is possible sufficient pressure on the preparation in the packaging exercise, the delivery of the preparation from the packaging to the environment causes.

hereby For example, the packaging means may be the function of the actuating means and the funding.

In a further embodiment According to the invention, the packaging is designed as an aerosol packaging. Here forms a can or bottle the pressure-resistant body of the aerosol container in which a liquid, pressurized by a propellant, pasty or powdery contents on actuation an aerosol valve as a spray or foam can be removed.

The Packaging has a filling volume from 100ml-5,000ml, preferably 125ml-2,000ml, more preferably 150ml-1,500ml most preferably 175ml-1250 ml.

Especially If the packaging is a one-chamber bottle.

actuating means

Under an actuating means For the purposes of this application, a device is understood which is coupled directly or indirectly with the funding, that by operation of the actuating means the user dispensing a preparation from a packaging is effected.

The actuating means can in particular be used as a hinged lever, for example in the form of a Triggers be formed, the operation regularly by a substantially horizontal movement of the free end of the lever he follows.

It is possible, too the actuating means as a pump dispenser, which is usually a vertical Movement and actuation kinetics having.

In a further preferred embodiment invention, the packaging is formed squeezable. By the squeezable shaping of the packaging material, it is possible, a sufficient Exert pressure on the preparation contained in the packaging, the causes a release of the preparation from the packaging to the environment. In this way, the packaging means, in particular the function of the actuating means and the funding.

These initially described actuating means are sufficient known from the prior art, so that they are not discussed here in detail becomes.

additive chamber

in the For the purposes of this application, an additive chamber is one for coupling the terminal of the dispenser molded packaging for at least one an additive contained in the preparation of the preparation in the packaging is different.

The Individually packed in an additive chamber, portionable additives Product units are made by a suitable positive, non-positive or cohesive Connection firm or detachable fixed at the connection of the dispenser. Especially preferred Types of connection are snap-in connections, screwed, plugged or Press connections and adhesive bonds.

In a preferred embodiment the invention, the additive chambers are each individually through the User can be coupled to the port. It is very convenient the additive chambers which can be coupled to the port at the Dispenser or the packaging for the user removed, especially individually removable, to order. For example, you can the dispensing device or the packaging means receiving means provided be in or on which the additive chambers are releasably fixed, so that the user to use a particular additive chamber this Remove the receptacle from the dispenser or bottle and can connect to the port.

to optical control of the level can be an additive chamber over have a viewing window or made of an at least partially transparent material be.

A Additive chamber can be a filling volume comprising a single dose of the additive containing Preparation allowed. This means that by pressing the actuating element almost the entire content of the additive chamber from the packaging funded Preparation is added.

It However, it is also conceivable that an additive chamber is a filling volume having a multiple dosage of the additive containing Preparation allowed, by pressing the actuator only a part of the contents of the additive chamber of the subsidized from the packaging Preparation is added.

Around the need for manual opening of the additive chamber To prevent use by the user or mechanically expensive opening devices provided in the dispensing device, according to another embodiment in the invention, the additive chamber comprises a closure such accomplished is that by the following when operating the conveyor and by the flow at least in the suction line or pressure line resulting negative pressure a part of the preparation is dispensed from the additive chamber. For this For example, the closure may be a membrane or silicone valve be designed. Furthermore, the closure may be shaped in such a way that due to the surface tension or viscosity the preparation is prevented from running out.

A Additive chamber has a filling volume from 1 ml-300ml, preferably 2ml-175ml, more preferably 2.5 ml-100ml, most preferably 3ml-50ml.

Prefers At least two additive chambers are arranged on the dispenser device.

A coupled to the connection of the dispenser additive chamber can directly with the funding be connected, creating a precise adjustment of the pressure conditions an exact dosage of the preparation from the additive chamber is possible. Furthermore, the preparation of the additive chamber and the packaging only merged directly into or after the grant, whereby the danger of possible undesirable Effects by the reaction of the two preparations, for example in the form of deposits or gelling, which is a clogging of Could cause supply lines is reduced.

Around a simpler adaptation of the connection for additive chambers without design changes an existing subsidy However, it is also conceivable that an additive chamber indirectly, i. above one with the funding existing supply line is formed. A release of the in the Additive containing additive composition then takes place, for example due to a Venturi effect caused by the flow of a fluid in the supply line to the funding causes a negative pressure in the connection of the additive chamber.

The Additive chamber may contain a preparation that is in the packaging preparation forms an emulsion or suspension. So For example, the additive chamber may be a solid in the form of a Powders include wherein the powder acts as an abrasive, for example.

Of the Content of the additive chambers may be one or more of the same or different products or additives such as, for example, Fragrances, cleaning substances, dyes, enzymes, hygroscopic Substances and the like exist.

So would it be For example, it is conceivable substances with different scents in each separate additive chambers to order different perfumings to allow the contents of the packaging. So, for example when using a fragrance-neutral cleaning liquid, with each product delivery from the packaging a fragrance from a be added to other additive chamber. This prevents for a the olfactory adaptation to a particular scent, on the other hand Can a fragrance according to the requirements a special application room (toilet, living room, kitchen). This does not require the use of several special ones perfumed Cleaning substances, which also means environmental protection and resource conservation desirable is.

Of Furthermore, it is advantageous in the additive chambers acidic or alkaline solutions which, in particular with a substantially neutral solution in the packaging, adjusted the pH of the mixed preparation can be. So it is conceivable, for example, in one use the dispenser device according to the invention for cleaning bath surfaces of lime deposits to set a low pH while, for example at the solution of fatty deposits by selecting the appropriate ones Additive chamber a high, alkaline pH can be selected can.

preparation

For the purposes of this application, a preparation is a liquid, pasty, gelatinous or pulverulent, baitable substance or mixture of substances.

The Preparation can be a solution, Mixture, emulsion or suspension of several substances present be.

additive

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

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

fragrances

When Perfume oils or Fragrances can in the context of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, Ketones, alcohols and hydrocarbons are used. fragrance compounds the type of esters are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl-carbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and Benzylsalicylate. For example, the ethers include Benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 C-atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, α-isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly the terpenes like limonene and pinene. However, mixtures are preferred different fragrances used, which together create an appealing Create a fragrance. Such perfume oils can also natural Contain fragrance mixtures, as they are accessible from plant sources, e.g. Pine, Citrus-Jasmine, Patchouly, rose or ylang-ylang oil. Also suitable are muscatel, Sage oil, Chamomile oil, Clove oil, Balm oil, mint oil, Cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, as well as Orange blossom oil, neroliol, Orange peel oil and Sandalwood oil.

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

By means of a suitable selection of said fragrances or perfume oils, the product smell can be influenced in this way for agents according to the invention immediately upon opening the brand-new composition as well as the use fragrance, for example when used in a dishwashing machine. These fragrance impressions can of course be the same, but can also differ. For the latter Odor impression is the use of adhesive odoriferous beneficial, while more volatile fragrances can be used for Produktbeduftung. Adhesion-resistant fragrances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamot oil, Champacablütenöl, Edel fir oil, Edeltannenzapfen oil, Elemiöl, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, Guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine oil, copaia balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, Musk Grain Oil, Myrrh Oil, Clove Oil, Neroli Oil, Niaouli Oil, Olibanum Oil, Orange Oil, Origanum Oil, Palmarosa Oil, Patchouli Oil, Peru Balsam Oil, Petitgrain Oil, Pepper Oil, Peppermint Oil, Pimento Oil, Pine Oil, Rose Oil, Rosemary Oil, Sandalwood Oil, Celery Oil, Spik Oil, Star Aniseed Oil, Turpentine Oil, Thuja Oil, Thyme oil, verb ena oil, vetiver oil; Juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon oil, lemon oil, lemon oil and cypress oil.

But also the higher-boiling ones or solid odoriferous natural or of synthetic origin in the context of the present invention as adherent fragrances or Fragrance mixtures, so fragrances are used. To this Counting connections the following compounds as well as mixtures of these: 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, Heptincarbonsäuremethylester, 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-methyl acetophenone, Methylchavikol, p-methylquinoline, methyl-β-naphthylketone, methyl-n-nonylacetaldehyde, Methyl n-nonyl ketone, Muskon, β-naphthol ethyl ether, β-naphthol methyl ether, Nerol, nitrobenzene, n-nonylaldehyde, Nonyl alcohol, n-octyl aldehyde, p-oxy acetophenone, pentadecanolide, β-phenylethyl alcohol, Phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegone, safrole, salicylic acid isoamyl ester, Salicylsäuremethylesten, Salicylsäurehexylester, Salicylsäurecyclohexylester, Santalol, skatole, terpineol, thymen, thymol, γ-undelactone, vaniline, veratrum aldehyde, Cinnamaldehyde, cinnamyl alcohol, cinnamic acid, cinnamate, Zimtsäurebenzylester. To the more volatile In particular, fragrances count the lower-boiling fragrances natural or synthetic Origin, which can be used alone or in mixtures. Examples for easier volatile Fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, Linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, Phenylacetaldehyde, terpinyl acetate, citral, citronellal.

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

Other active substances

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

dyes

A 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 not have pronounced substantivity towards textile fiber, glass, plastic dishes or Have ceramic so as 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 grass-W-2201), Sandoplast Blue 2B, Fat Yellow 3G, Iragon ^® Red SRE 122 Iragon ^® Green SGR 3, Solvent Yellow 33 and Solvent Yellow 16, but other dyes may be included.

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

The Indicator effect can be achieved in several ways: on the one hand A dye can be used in the course of the application period escapes from the particles. This can be done for example by the im Dishwashing liquid contained ingredients. For this purpose, a dye used, which adheres well to the particles or only slowly diffused out of them to ensure that the discoloration does not too early, namely when the fragrance is not consumed, it is finished. on the other hand But it can also be due to a chemical reaction or thermal decomposition a color change are caused.

Antimicrobial agents, Germicides, fungicides

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

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

antioxidants

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

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

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

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

metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally in addition one or more of the o.g. Anions exist. The central atom is one the o.g. Metals in one of the above Oxidation states. The ligands are neutral molecules or anions which are monodentate or polydentate; the term "ligands" within the meaning of the invention is e.g. in "Römpp Chemie Lexicon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, Page 2507 " in a metal complex the charge of the central atom and the charge of the ligand (s) is not zero, so, depending on whether a cationic or an anionic charge excess is present, either one or more of the above. Anions or one or more Cations, z. As sodium, potassium, ammonium ions, for the charge balance. Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

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

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ and mixtures thereof, see above in that preferred agents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [ 1-hydroxyethane-1,1-diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ .

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

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

bleach

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

As important constituents of detergents or cleaners, bleaching agents and bleach activators may be present in the compositions according to the invention, among other constituents. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further usable 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-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1, 4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used.

Become the agents according to the invention used in combination with automatic dishwashing detergents, these can Bleach activators are included to assist in cleaning at temperatures of 60 ° C and including achieving an improved bleaching effect. As bleach activators can Compounds which, under perhydrolysis conditions, are aliphatic peroxycarboxylic acids preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atomic number and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

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

in which R ¹ is -H, -CH _3, a C _2-24 -alkyl or -alkenyl radical, a substituted C _2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 -alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

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

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

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

surfactants

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

When Anionic surfactants in acid form are preferred one or more substances from the group of carboxylic acids, the Schwefelsäurehalbester and the sulfonic acids, preferably from the group of fatty acids, fatty alkylsulfuric acids and the alkylanosulphonic acids, used. To have sufficient surface-active properties the said compounds should have longer hydrocarbon radicals, ie have 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 (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. are preferred in the context of the present invention Use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t Octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatrienoic acid For reasons of cost, it is preferable not to use the pure species, but technical mixtures of the individual acids, as they are accessible from lipid cleavage. Such mixtures are, for example, coconut oil fatty acid (about 6 wt .-% C ₈ , 6 wt .-% C ₁₀ , 48 wt .-% C ₁₂ , 18 wt .-% C ₁₄ , 10 wt .-% C ₁₆ , 2 wt % C ₁₈ , 8% by weight C _{18 '} , 1% by weight C _{18 "} ), palm kernel oil fatty acid (about 4% by weight C ₈ , 5% by weight C ₁₀ , 50% by weight). % C ₁₂ , 15 wt .-% C ₁₄ , 7 wt .-% C ₁₆ , 2 wt .-% C ₁₈ , 15 wt .-% C _{18 '} , 1 wt .-% C _18'' ), tallow fatty acid ( about 3 wt .-% C ₁₄ , 26 wt .-% C ₁₆ , 2 wt .-% C _{16 '} , 2 wt .-% C ₁₇ , 17 wt .-% C ₁₈ , 44 wt .-% C _{18 '} , 3 wt .-% C _18'' , 1 wt .-% C _18''' ), hardened tallow fatty acid (about 2 wt .-% C ₁₄ , 28 wt .-% C ₁₆ , 2 wt .-% C ₁₇ , 63 wt .-% C ₁₈ , 1 wt .-% C _{18 '} ), technical oleic acid (about 1 wt .-% C ₁₂ , 3 wt .-% C ₁₄ , 5 wt .-% C ₁₆ , 6% by weight C _{16 '} , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _18' , 10% by weight C _{18 "} , 0.5% by weight % C _{18 '''} ), technical palmitic / stearic acid (about 1 wt .-% C ₁₂ , 2 wt .-% C ₁₄ , 45 wt .-% C ₁₆ , 2 wt .-% C ₁₇ , 47 wt. % C ₁₈ , 1% by weight C _{18 '} ) and soybean oil fatty acid (about 2% by weight C ₁₄ , 15 wt .-% C ₁₆ , 5 wt .-% C ₁₈ , 25 wt .-% C _{18 '} , 45 wt .-% C _18'' , 7 wt .-% C _18''' ).

Sulfuric acid semi-esters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the context of the present invention. Their alkali metal salts, in particular sodium salts, the fatty alcohol sulfates are industrially available from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, sulfamic acid or sulfur dioxide to the respective alkyl sulfuric acids and subsequently neutralized. The fatty alcohols are thereby obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters. The quantitatively most important industrial process for the production of fatty alkylsulfuric acids is the sulfation of the alcohols with SO ₃ / air mixtures in special cascade, falling film or tube bundle reactors.

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

Also alkanesulfonic and olefinsulfonic acids are in the context of the present invention as anionic surfactants in acid form used. alkanesulfonic can the sulfonic acid group terminal bound (primary alkane sulfonic acids) or along the C chain (secondary alkanesulfonic acids), wherein only the secondary alkanesulfonic have commercial significance. These are by sulfochlorination or Sulfoxidation of linear hydrocarbons. In the sulfochlorination According to Reed n-paraffins with sulfur dioxide and chlorine under Irradiation with UV light converted to the corresponding sulfochlorides, on hydrolysis with alkalis directly the alkanesulfonates, upon reaction with water the alkanesulfonic acids, deliver. As in the sulfochlorination di- and Polysulfochloride as well Chlorinated hydrocarbons as by-products of the radical reaction may occur, the reaction usually becomes only up to implementation levels of 30% performed and then canceled.

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

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

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

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

Linear alkylbenzenesulfonates are prepared from linear alkylbenzenes, which in turn are accessible from linear olefins. For this purpose, large-scale petroleum fractions are separated with molecular sieves in the n-paraffins of the desired purity and dehydrogenated to the n-olefins, resulting in both α- and i-olefins. The resulting olefins are then reacted in the presence of acidic catalysts with benzene to the alkylbenzenes, the choice of the Friedel-Crafts catalyst has an influence on the isomer distribution of the resulting linear alkylbenzenes: When using aluminum trichloride, the content of the 2-phenyl isomers in the mixture with the 3-, 4-, 5- and other isomers at about 30 wt .-%, however, hydrogen fluoride is used as the catalyst, the content of 2-phenyl isomer can be 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, the product as a 97 wt .-% Al kylbenzenesulfonic acid (ABSS), which can be used in the context of the present invention as anionic surfactant.

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

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

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

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

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

When Cationic surfactants come for the agents according to the invention all usual Substances into consideration, whereby cationic surfactants with textile softening Effect are clearly preferred.

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

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

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

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

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

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

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

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

in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 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.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula XIV,

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

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

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

As already mentioned, the use of surfactants in detergents for the machine is limited dishwashing preferably on the use of nonionic surfactants in small amounts. 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 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Especially for cleaning agents for automatic dishwashing it is preferred that this one Nonionic surfactant containing a melting point above Room temperature, preferably a nonionic surfactant with a melting point above 20 ° C. Preferably used nonionic surfactants have melting points above 25 ° C, particularly preferably used Nonionic surfactants have melting points between 25 and 60 ° C, in particular between 26.6 and 43.3 ° C.

suitable nonionic surfactants, the melting or softening points in said Temperature range, for example, low-foaming nonionic Surfactants which may be solid or highly viscous at room temperature. Become used at room temperature highly viscous nonionic surfactants, it is preferred that these a viscosity above 20 Pas, preferably above 35 Pas and especially above 40 Pas. Also nonionic surfactants which are waxy at room temperature Consistency are preferred.

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

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

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

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

Further particularly preferred nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per Mole of trimethylolpropane.

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

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

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

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

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

enzymes

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

Among the proteases, those of the subtilisin type are preferable. Examples 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 Propenase ^® by the company Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ^® and protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

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

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

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

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

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

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

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

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

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

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

alternative can the enzymes for both the solid as well for the liquid Dosage form can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural polymer or in the form of capsules, for example those in which the enzymes are as in enclosed in a solidified gel or in core-shell type, in which an enzyme-containing core with a water, air and / or Chemical-impermeable Protective layer coated is. In superimposed layers additional active ingredients, For example, stabilizers, emulsifiers, pigments, bleaches or dyes be applied. Such capsules are known per se Methods, for example by shaking or rolling granulation or applied in fluid-bed processes. Advantageously Such granules, for example by applying polymeric film-forming agents, low in dust and storage-stable due to the coating.

Farther Is it possible, to assemble two or more enzymes together, making one individual granules has several enzyme activities.

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

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

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

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

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

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

Prefers For example, combinations of stabilizers are used made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing Salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing Salt. The action of peptide-aldehyde stabilizers can be achieved by the combination with boric acid and / or boric acid derivatives and polyols increased and according to the additional use of divalent cations, such as calcium ions on reinforced become.

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

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

1

Packaging System

2

donations device

3

additive Kammen

4

additive Kammen

5

packaging

6

Multi-way valve

7

supply

8th

supply

9

exit line

10

selector lever

11

pressure line

12

nozzle head

13

funding

14

suction

15

connection

16

connection

pictures

1 shows the dispensing device with vertically arranged additive chambers in a perspective view

2 shows the dispensing device with horizontally arranged additive chambers in a perspective view

1 shows the dispensing device according to the invention 2 shaped as a trigger spray bottle, wherein the trigger or actuating lever is not shown. The T-shaped donation device 2 is on the discharge opening of a bottle-shaped packaging 5 fixed. The packaging 5 includes a preparation that is not shown.

The donation device 2 has a designed as a pump conveyor 13 on. From the pump 13 extends a suction line 14 to promote preparation from the bottle 5 , The pressure side is at the pump 14 a pressure line 11 arranged, different from the pump 13 in the nozzle head 12 extends and allows a delivery of the subsidized preparation in the environment.

At the, the nozzle head 12 opposite leg of the T-shaped dispensing device 2 are a first additive chamber 3 and a second additive chamber 4 arranged. The additive chambers 3 . 4 can be fixed or detachable to the donation device 2 be fixed.

At the head of the chambers 3 . 4 are connections 15 . 16 provided in corresponding receptacles of the donation device 2 can be coupled, so that a preferably tight connection between dispensing device 2 and the additive chambers 3 . 4 is trained.

The connections 15 . 16 the additive chambers 3 . 4 are over the supply lines 7 . 8th with the inlets of the reusable valve 6 connected.

The multiway valve 6 is with a selector lever 10 coupled, so that the operation of the selector lever 10 a defined configuration of the inlet and outlet switching states of the multiway valve 6 causes.

The outlet line 9 connects the nozzle head 12 with the outlet of the returnable valve 6 ,

The release of the preparation contained in the additive chamber is then carried out at a corresponding switching state of the multi-way valve 6 for example, by a venturi effect caused by the flow of a fluid in the pressure line 11 a negative pressure in the outlet line 9 causes, whereby additive preparations from the chambers 3 and or 4 through the supply lines 8th and or 7 and the multiway valve 6 be encouraged.

2 shows a further embodiment of the dispensing device according to the invention 2 , The pressure line 11 is here directly with an inlet of the multi-way valve 6 connected. The multiway valve 6 is on a selector lever 10 coupled, which is formed as a rotary lever or knob.

Claims (7)

Donation device ( 2 ) for fixing to or on the discharge opening of a packaging ( 5 ) and for dispensing at least one preparation from the packaging material ( 5 ), comprising • at least one funding ( 13 ) for transporting at least one preparation from the packaging material ( 5 ) in the environment and • an actuating means, which with the conveyor ( 13 ) is coupled in such a way that the dispensing of at least the first preparation from the packaging material ( 5 ) is effected characterized in that • the donation device ( 2 ) a plurality of chambers ( 3 . 4 ) for receiving mutually different preparations, the chambers ( 3 . 4 ) via supply lines ( 7 . 8th ) communicating with a multiway valve ( 6 configured such that the amount of product discharged by the actuation of the actuating means from the chambers ( 3 . 4 ) by the user by means of an externally operable and with the multi-way valve ( 6 ) coupled selector lever ( 10 ) is determinable. Donation device according to one or more of the previous ones Claims, characterized in that the chambers are releasably attached to the dispensing device are arranged. Dispensing device according to one or more of the preceding claims, characterized in that the multiway valve ( 6 ) is configured such that in each case only one preparation from the packaging ( 5 ) or the chambers ( 3 . 4 ) is releasable. Dispensing device according to one or more of the preceding claims, characterized in that the multiway valve ( 6 ) is configured such that a preparation from the packaging material ( 5 ) and at least one preparation from the chambers ( 3 . 4 ) is releasable. Dispensing device according to one or more of the preceding claims, characterized in that in the packaging ( 5 ) has a substantially neutral pH. Dispensing device according to one or more of the preceding claims, characterized in that at least one chamber ( 3 . 4 ) contains a substantially acidic preparation. Dispensing device according to one or more of the preceding claims, characterized in that at least one chamber ( 3 . 4 ) contains a substantially alkaline preparation.