EP1740689A1

EP1740689A1 - Method for the production of detergent or cleaning agents

Info

Publication number: EP1740689A1
Application number: EP05733723A
Authority: EP
Inventors: Wolfgang Barthel; Salvatore Fileccia; Ulf Arno Timmann; Thomas Holderbaum; Sandra Behr; Dirk Gerst
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2004-04-28
Filing date: 2005-04-21
Publication date: 2007-01-10
Anticipated expiration: 2025-04-21
Also published as: EP1740689B1; ES2456016T3; WO2005105974A1; PL1740689T3; DE102004020839A1; US20080004202A1

Abstract

The invention relates to a method for production of a dosing unit for detergent or cleaning agents, comprising the steps: a) preparation of a moulded body with at least one cavity, b) application of a first film material to the moulded body surface through the opening of the cavity, c) deep-drawing of the first film material into the cavity and d) filling of a detergent or cleaning active substance onto the film material in the cavity. The above is suitable for the production of highly-active detergent or cleaning agents, in particular, for the production of pre-dosed combination products with solid and liquid phases.

Description

Process for the preparation of detergents or cleaners

The present invention is in the field of detergents or cleaners. In particular, the present invention relates to a process for the preparation of detergents or cleaners, in particular of metering units of detergents or cleaners.

Detergents or cleaners are now available to the consumer in a variety of forms. In addition to washing powders and granules, this offer also includes, for example, detergent concentrates in the form of extruded or tabletted compositions. These fixed, concentrated or compressed forms of supply are characterized by a reduced volume per dosing unit and thus reduce the costs for packaging and transport. In particular, the washing or cleaning agent tablets additionally meet the desire of the consumer for simple dosing. The corresponding means are comprehensively described in the prior art. However, in addition to the advantages listed, compacted detergents or cleaners also have a number of disadvantages. Especially tableted supply forms are characterized by their high compression often by a delayed disintegration and thus a delayed release of their ingredients. Numerous technical solutions have been disclosed in the patent literature for resolving this "conflict" between sufficient tablet hardness and short disintegration times, reference being made by way of example to the use of so-called tablet disintegrants These disintegrants are added to the tablets in addition to the washing- or cleaning-active substances Although they themselves generally do not have any washing or cleaning-active properties, in this way they increase the complexity and the costs of these agents Active substances due to the compaction pressure occurring during tabletting Inactivation of the active substances may also be due to the increased contact surfaces of the ingredients due to chemical reaction e rfolgen.

As an alternative to the particulate or compacted detergents or cleaners described above, solid or liquid detergents or cleaners which have a water-soluble or water-dispersible packaging are increasingly being described in recent years. These agents are characterized as the tablets by a simplified dosage, since they can be dosed together with the outer packaging in the washing machine or dishwasher, on the other hand, but at the same time they also allow the preparation of liquid or powder detergents or cleaning agents Compared to the compact data by a better resolution and faster effectiveness.

For example, EP 1 314 654 A2 (Unilever) discloses a dome-shaped pouch with a receiving chamber containing a liquid.

The subject of WO 01/83657 A2 (Procter & Gamble), however, are pouches which contain two particulate solids in a receiving chamber, each of which is present in fixed regions and does not mix with one another.

In addition to the packages which have only one receiving chamber, the prior art has also disclosed forms of offers which comprise more than one receiving chamber or more than one ready-made form.

Subject of the European application EP 1 256 623 A1 (Procter & Gamble) is a kit of at least two bags with different composition and optics. The bags are separate and not as a compact single product.

A method for producing multi-chamber bags by bonding second individual chambers describes the international application WO 02/85736 A1 (Reckitt Benckiser).

The object of the present application was to provide a process for the preparation of detergents or cleaners, which enables the joint preparation of solid and liquid or flowable detergent or cleaner compositions in separate areas of a compact dosing unit. The final process product should be characterized by an attractive appearance.

It has now been found that the above objects can be achieved by a method in which a washing or cleaning-active molded body is provided with a Kavitat, in which Kavitat a thermoformed body is formed, which can be filled in the connection.

Process for the preparation of a dosing unit for detergents or cleaners, comprising the steps of a) providing a shaped body having at least one cavity; b) placing a first sheet material on the molding surface over the opening of the cavity; c) deep drawing the first sheet material into the cavity; d) filling a washing or cleaning substance on the film material in the Kavitat.

In the first step of the method according to the invention, a shaped body is provided. Such moldings are obtainable, for example, by compaction methods such as tableting, by extrusion, such as extrudate extrusion, by injection molding or by casting. In the context of the present application, moldings which are produced by tabletting or by casting are particularly preferred. The moldings contain or consist of washing or cleaning-active substances or substance mixtures.

The preparation of washing or cleaning agent tablets is carried out in a manner known to those skilled in the art by compressing particulate starting substances. To prepare the tablets, the premix is compressed in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection. The tabletting is preferably carried out on so-called rotary presses.

When tableting with rotary presses, it has proven to be advantageous to carry out the tableting with the lowest possible weight fluctuations of the tablet. In this way, the hardness fluctuations of the tablet can be reduced. Small variations in weight can be achieved in the following ways:

Use of plastic inserts with small thickness tolerances Low number of revolutions of the rotor Large filling shoes Matching the filling vane speed to the speed of the rotor Filling shoe with constant powder height Decoupling of filling shoe and powder feed

To reduce Stempelanbackungen offer all known from the art non-stick coatings. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished. Preferred processes in the context of the present invention are characterized in that the pressing takes place at pressures of from 0.01 to 50 kNcm ^"2 , preferably from 0.1 to 40 kNcm ^{" 2} and especially from 1 to 25 kNcm ^"2 .

The production of preferred casting bodies according to the invention is carried out, for example, by casting a washing or cleaning-active preparation into a mold and then removing the solidified cast body to form a (mold) shaped body. Tools which have cavities which can be filled with pourable substances are preferably used as "molds." Such tools can be designed, for example, in the form of individual cavities but also in the form of plates with a plurality of cavities mounted on horizontal circulating conveyor belts, which allow a continuous or discontinuous transport of the cavities, for example along a number of different workstations (eg: casting, cooling, filling, sealing, demolding, etc.).

The washing or cleaning active preparations are potted in the preferred process and subsequently solidified to a dimensionally stable body. In the context of the present invention, "solidification" characterizes any curing mechanism which delivers a body which is solid at room temperature from a deformable, preferably flowable mixture or substance or mass, without the need for pressing or compacting forces The purpose of the present invention is therefore, for example, the curing of melts of solid substances at room temperature by cooling. "Solidification processes" in the context of the present application are also the curing of formable materials by time-delayed water binding, by evaporation of solvents, by chemical reaction, crystallization, etc. and the reactive curing of flowable powder mixtures to form stable hollow bodies.

For processing in the described method are generally all washing or cleaning active preparations that can be processed by casting techniques. With particular preference, however, washing or cleaning active preparations are used in the form of dispersions. In a particularly preferred embodiment of the present application, the washing or cleaning-active preparation poured into the receiving trough of the molding tool is a dispersion of solid particles in a dispersion medium, dispersions which, based on their total weight i) are from 10 to 85% by weight. Dispersants and ii) contain 15 to 90 wt .-% of dispersed substances, particularly preferred. As dispersion in this application a system of several phases is referred to, one of which is dispersed continuously (dispersion medium) and at least one further (dispersed substances).

Suitable dispersants in the context of the present invention are preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers. The dispersant may be both a single polymer and mixtures of various water-soluble or water-dispersible polymers. In a further preferred embodiment of the present invention, the dispersant or at least 50 wt .-% of the polymer mixture of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidone, vinylpyrrolidone / Ninylester copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.

Particular preference is given to using dispersions which contain, as dispersants, a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, the weight fraction of the poly (ethylene) glycol being based on the total weight of all dispersing agents is preferably between 10 and 90% by weight, more preferably between 30 and 80% by weight and in particular between 50 and 70% by weight. Particular preference is given to dispersions in which the dispersant contains more than 92% by weight, preferably more than 94% by weight, more preferably more than 96% by weight, very particularly preferably more than 98% by weight. and in particular to 100 wt .-% of a poly (alkylene) glycol, preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular consists poly (ethylene) glycol. Dispersing agents which also contain poly (propylene) glycol in addition to poly (ethylene) glycol preferably have a ratio of the weight proportions of poly (ethylene) glycol to poly (propylene) glycol between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, more preferably between 10: 1 and 1, 5: 1 and in particular between 7: 1 and 2: 1 on.

Further preferred dispersants are the nonionic surfactants, which are used alone, but particularly preferably in combination with a nonionic polymer. Detailed information on the usable nonionic surfactants can be found in the description of washing or cleaning-active substances below.

For the purposes of the present application, all materials which are solid at room temperature or are active in washing or cleaning, but especially washing or cleaning substances from the group of builders (builders and cobuilders), are suitable as dispersed substances washing or cleaning active polymers, bleach, bleach activators, glass corrosion inhibitors, silver protectants and / or enzymes. A more detailed description of these ingredients can be found below in the text.

Dispersions preferably used as detergent tablets according to the invention are characterized in that they are dissolved in water (40 ° C.) in less than 9 minutes, preferably less than 7 minutes, preferably less than 6 minutes, more preferably less than 5 minutes and in particular dissolve in less than 4 minutes. To determine the solubility, 20 g of the dispersion are introduced into the interior of a dishwashing machine (Miele G 646 PLUS). The main rinse of a standard rinse program (45 ° C) is started. The determination of the solubility is carried out by the measurement of the conductivity, which is recorded via a conductivity sensor. The dissolution process is completed when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau. The conductivity measurement starts with the replacement of the circulation pump in the main wash cycle. The amount of water used is 5 liters.

The moldings produced by tabletting or casting, for example, may take any geometric form, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal , pentagonal, octagonal and octagonal prismatic as well as rhombohedral forms are preferred. Even completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can be realized. If the shaped bodies according to the invention have corners and edges, these are preferably rounded off. As additional optical differentiation, an embodiment with rounded corners and bevelled ("touched") edges is preferred.

Of course, the moldings can also be produced in multiple phases. For reasons of process economy, two-layered or three-layered shaped bodies, in particular two-layered or three-layered tablets, have proven particularly useful here.

In a particularly preferred embodiment, tablets and / or compacts, for example roll compacts, and / or extrudates, and / or injection-molded bodies and / or casting bodies and / or molded articles composed of these shaped bodies are used in step a) of the process according to the invention.

To improve its shaped-body optics and / or to influence its dissolution behavior, the shaped body may have a coating. The coating can cover both the entire molded body and individual areas of the molded body. Particular preference is given to moldings which have a coating on their entire surface. Preference is furthermore given to shaped bodies in which the coating extends only to individual surfaces of the shaped body, for example the shaped body surfaces outside the cavity, or to individual corners or edges of the shaped body.

Suitable coating materials are all materials known to the person skilled in the art. Preferred coating materials in the context of the present application are the water-soluble or water-insoluble natural or synthetic organic polymers, water-soluble or water-dispersible organic polymers being particularly preferred. Also suitable for the coating of the moldings are the salts of organic or inorganic acids. Of the group of organic acids, in particular the salts of mono-, di-, tri, tetra- or polycarboxylic acids are preferred.

Preferred methods according to the invention are accordingly characterized in that the shaped body has a coating.

In the context of the present invention, the term "cavitation" identifies hollows as well as openings or holes which pass through the shaped body and which connect two sides of the shaped body, preferably opposite sides of the shaped body, for example the bottom and roof surfaces of the shaped body.

The shape of the cavity, which is preferably a well, may be chosen freely, with tablets being preferred in which at least one well is a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disc-shaped, tetrahedral, dodecahedral, octahedral , conical, pyramidal, ellipsoidal, pentagonal, hexagonal, octagonal prismatic and rhombohedral. Completely irregular shapes such as arrow or animal shapes, trees, clouds etc. can also be realized. As with the basic moldings, wells with rounded corners and edges or with rounded corners and chamfered edges are preferred. The bottom surface of the trough can be flat or inclined.

In a particularly preferred embodiment, the cavity is an opening which connects two opposite sides of the molding together. A corresponding shaped body can be referred to as a ring body. The aperture areas of the aperture in the surface of this annular body may be the same size but may differ in size. If a tablet is used as the shaped body, then the shaped body with such a breakthrough corresponds to a so-called ring tablet. Particularly preferred such shaped bodies are used with breakthrough, in which the opening areas of the opening on the opposite sides of the molding, based on the larger of the two opening surfaces by less than 80%, preferably less than 60%, preferably less than 40%, more preferably less than 20% and in particular differ less than 10%. Particularly preferred ring tablets are used, in which the opening areas of the aperture have the same size. The cross-section of the aperture may be angular or round. Cross sections with one, two, three, four, five, six or more corners can be realized, however, such shaped bodies are particularly preferred in the context of the present application, which have a breakthrough without corners, preferably a breakthrough with a round or oval cross-section. In this case, a "cross section" refers to a surface which is perpendicular to a straight connecting line between the center points of the two opposite opening surfaces of the shaped body.

Of course, the molding may have more than one cavity. Moldings having two, three, four, five, six, seven, eight, nine, ten, eleven, twelve or more cavities are particularly preferred in the present application. If the shaped body has more than one cavity, these cavities can be both the wells described above and the breakthroughs described above. Shaped bodies which have more than one cavity, wherein at least one of the cavities is a well and at least one further of the cavities is a breakthrough, are particularly preferred in the context of the present application.

The volume of the cavity is preferably between 0.1 and 20 ml, preferably between 0.2 and 15 ml, more preferably between 1 and 10 ml and in particular between 2 and 7 ml.

Before a film material is applied to the cavities of the shaped bodies provided in step a) in step b), in a preferred process variant these cavities can be filled proportionally with a solid or liquid, washing or cleaning-active substance. Such methods, in which the cavity of the molded article is filled in part with a washing or cleaning substance before applying the first film material in step b), are particularly preferred in the context of this application. With preference in the context of the present application between the steps a) and b) flowable washing and cleaning active preparations, preferably liquid (s), in particular melts, and / or gel (s) and / or powder and / or granules (e) and / or extrudate (s) and / or Kompaktat (s) used.

With particular preference, the cavity is filled prior to placing the first film material in step b) proportionally with a washing or cleaning active powder, granules or extrudate. The term "liquid" in the present application denotes substances or substance mixtures as well as solutions or suspensions which are in the liquid state of matter.

Powder is a general term for a form of division of solids and / or mixtures obtained by comminution, that is, grinding or crushing in the mortar (pulverization), grinding in mills or as a result of atomization or freeze-drying. A particularly fine division is often called atomization or micronization; the corresponding powders are called micro-powders.

After the grain size is a rough division of the powder in coarse, fine u. Very fine powder usual; A more detailed classification of powdery bulk solids is made by their bulk density and sieve analysis. In the context of the present application, however, preferred powders have lower particle sizes below 5000 .mu.m, preferably less than 3000 .mu.m, preferably less than 1000 .mu.m, very particularly preferably between 50 and 1000 .mu.m and in particular between 100 and 800 .mu.m.

Powders can be compacted and agglomerated by extrusion, pressing, rolling, briquetting, pelleting and related processes. Each of the methods known in the prior art for the agglomeration of particulate mixtures is in principle suitable for producing the solids contained in the agents according to the invention. In the context of the present invention, preferably agglomerates used as solid (s) are, in addition to the granules, the compacts and extrudates.

Granules are aggregates of granules. A granule (granule) is an asymmetric aggregate of powder particles. Granulation methods are widely described in the art. Granules can be prepared by wet granulation, by dry granulation or compaction and by melt solidification granulation.

The most common granulation technique is wet granulation, since this technique is subject to the fewest restrictions and leads most safely to granules with favorable properties. The wet granulation is carried out by moistening the powder mixtures with solvents and / or solvent mixtures and / or solutions of binders and / or solutions of adhesives and is preferably carried out in mixers, fluidized beds or spray towers, said mixer can be equipped, for example, with stirring and kneading tools. However, combinations of fluidized bed (s) and mixer (s) or combinations of different mixers can also be used for the granulation. The granulation takes place Depending on the starting material and the desired product properties under the action of low to high shear forces.

If the granulation in a spray tower so as starting materials, for example, melting (melt solidification) or, preferably aqueous, slurries (spray drying) of solid substances are used, which are sprayed at the top of a tower in a defined droplet size, solidify in free fall or dry and on Floor of the tower incurred as granules. Melt solidification is generally particularly suitable for shaping low-melting substances which are stable in the melting temperature range (eg urea, ammonium nitrate and various formulations such as enzyme concentrates, pharmaceuticals etc.), the corresponding granules are also referred to as prills. Spray drying is used especially for the production of detergents or detergent ingredients.

Further agglomeration techniques described in the prior art are extruder or perforated roll granulations in which powder mixtures optionally mixed with granulating liquid are plastically deformed during perforation by perforated disks (extrusion) or on perforated rolls. The products of extruder granulation are also referred to as extrudates.

Builders, enzymes, bleaches, bleach activators, bleach catalysts, silver protectants or glass corrosion inhibitors are particularly suitable as ingredients of the washing or cleaning-active formulations introduced into the cavities between steps a) and b). Bleaches, in particular peroxygen compounds such as percarbonates or perborates, bleach activators or silver protectants, are particularly preferably introduced. These ingredients are preferably filled as part of solid washing or cleaning active preparations between steps a) and b) in the cavity. These ingredients are described in more detail later in the text. To avoid repetition, reference is made at this point to the comments there.

A further preferred subject matter of the present application is therefore a process for the preparation of a dosing unit for detergents or cleaners, comprising the steps of a) providing a shaped body having at least one cavity; a ') Partial filling of the Kavitat with a washing or cleaning active composition, preferably a solid washing or cleaning active composition, which particularly preferably contains at least one substance from the group of builders, enzymes, bleaching agents, bleach activators, bleach catalysts, silver protectants and glass corrosion inhibitors; b) placing a first sheet material on the molding surface over the opening of the cavity; c) deep drawing the first sheet material into the cavity; d) filling a washing or cleaning substance on the film material in the Kavitat.

The volume of the substances introduced between steps a) and b) is preferably between 0.5 and 12 ml, particularly preferably between 0.5 and 8 ml, very particularly preferably between 0.5 and 6 ml and in particular between 0.5 and 4 ml. The Kavitat of the shaped body is preferably between 1 and 80 vol .-%, preferably between 5 and 60 vol .-%, especially between 10 and 50 vol .-% and in particular between 20 and 50 vol .-% filled.

In step b) of the method according to the invention, a film material is placed on the mold body surface over the opening of the cavity. In a preferred embodiment of the process according to the invention, the first film material used in step b) is a water-soluble or water-dispersible film material, preferably a polymeric water-soluble or water-dispersible film material.

In a preferred process variant, the film material in step b) comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and their mixtures.

"Polyvinyl alcohols" (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure

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

contain. Commercially available polyvinyl alcohols, which 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), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups. The polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

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

In the context of the present invention, it is preferred that the film material used in the process according to the invention at least partially comprises a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and in particular 82 to 88 mol%. In a preferred embodiment, the first film material used in the process according to the invention comprises at least 20% by weight, more preferably at least 40% by weight, very preferably at least 60% by weight and in particular at least 80% by weight. of a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and more preferably 82 to 88 mol%.

Polyvinyl alcohols having a specific molecular weight range are preferably used as the film material, wherein the film material preferably comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably 11,000 to 90,000 gmol ^-1 , particularly preferably 12,000 to 80,000 gmol ^"1 and in particular from 13,000 to 70,000 gmol ^{" 1} lies.

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500. The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Glariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

Further polyvinyl alcohols which are particularly suitable as film material are shown in the following table:

Other suitable polyvinyl alcohols are as the film material ELVANOL 51-05, 52-22, 50-42, 85- 82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX 72.5 ^®, 78 , B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A-300, AH-22, C-500, GH -20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11 Q, KZ-06 (Trademark of Nippon Gohsei KK).

The water solubility of PVAL can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols which are acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly advantageous and particularly advantageous on account of their pronounced cold water solubility. To use extremely advantageous are the reaction products of PVAL and starch.

Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values. Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Examples of suitable water PVAL films are those available under the name "SOLUBLON® ^®" from Syntana Handelsgesellschaft E. Harke GmbH & Co. PVAL films. their Solubility in water can be adjusted to the exact degree and films of this product series are available which are soluble in aqueous phase in all temperature ranges relevant for the application.

Polyvinylpyrrolidones, referred to as PVP for short, can be described by the following general formula:

PVP are prepared by radical polymerization of 1-vinylpyrrolidone. Commercially available PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and are available as white, hygroscopic powders or as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula

H- [O-CH ₂ -CH ₂ ] _n -OH

the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.

Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance.

In the context of the process according to the invention, preference is given to film materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose, and mixtures thereof.

Starch is a homoglycan in which the glucose units are glycosidically linked. Starch is composed of two components of different molecular weight: from about 20 to 30% straight-chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW about 300,000 to 2,000,000). In addition, small amounts of lipids, phosphoric acid and cations are still included. Whereas the amylose forms long, helical, entangled chains with approximately 300 to 1,200 glucose molecules as a result of the 1, 4-position bond, the amylopectin branch branches off into a branch-like structure after an average of 25 glucose building blocks by 1,6-bonding with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, starch-derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for the preparation of water-soluble coatings of the detergent, detergent and cleaner portions in the context of the present invention. Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5,000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.

Other preferred film materials are characterized by comprising hydroxypropyl methylcellulose (HPMC) having a degree of substitution (average number of methoxy groups per unit of anhydroglucose cellulose) of from 1.0 to 2.0, preferably from 1.4 to 1.9, and a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose) of from 0.1 to 0.3, preferably from 0.15 to 0.25.

Preferred methods according to the invention are characterized in that at least one of the film materials used is transparent or translucent. The film material used, for example, for deep-drawing and / or sealing is preferably transparent. For the purposes of this invention, transparency means that the transmittance within the visible spectrum of the light (410 to 800 nm) is greater than 20%, preferably greater than 30%, more preferably greater than 40% and in particular greater than 50%. Thus, once a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent within the meaning of the invention.

Preparations made according to the invention, for the production of which transparent film material has been used, may contain a stabilizing agent. Stabilizing agents in the context of the invention are materials which protect the ingredients at least partially enclosed by the film material from decomposition or deactivation by light irradiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.

Particularly suitable stabilizing agents in the context of the invention are the antioxidants. In order to prevent undesirable changes in the formulations caused by light irradiation and thus radical decomposition, the formulations may contain antioxidants. Examples of antioxidants which may be used here are sterically hindered groups, substituted phenols, bisphenols and thiobisphenols. Further examples are propyl gallate, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long chain (C8-C22) esters of gallic acid, such as dodecyl gallate. Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic acid palmitate, organosulfur compounds, such as the esters of 3,3'-thiodipropionic acid with C ^^ - alkanols, in particular C ₁₀ - ₁₈ -A kanolen, metal ion deactivators that are capable of catalyzing the auto-oxidation of metal ions such as copper to complex such as nitrilotriacetic acid and its derivatives and their mixtures. Antioxidants may be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.

Another class of preferably usable stabilizers are the UV absorbers. UV absorbers can improve the light stability of the formulation components. Below are Organic substances (sunscreen) to understand that are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg heat to give back. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. In addition, substituted benzotriazoles, such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) - 4-hydroxy-5- (methylpro-pyl) monosodium salt (Ciba Fast ^® H), 3-phenyl-substituted acrylates ( Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid. The biphenyl and especially stilbene derivatives, which are available as Tinosorb ^® FD or Tinosorb ^® FR ex Ciba commercial. Suitable UV-B absorbers are 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, eg 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably 4-

(Dimethylamino) benzoic acid 2-ethylhexyl ester, 4- (dimethylamino) benzoic acid 2-octyl ester and 4- (dimethylamino) benzoic acid amyl ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives, e.g. 2,4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine and octyl triazone or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-diones, e.g. 1- (4-tert-butylphenyl) -3- (4'-methoxy-phenyl) -propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of the 3-benzylidene camphor, e.g. 4- (2-oxo-3-bomylidenemethyl) benzenesulphonic acid and 2-methyl-5- (2-oxo-3-bomylidene) -sulfonic acid and its salts.

As a typical UV-A filter, in particular derivatives of benzoylmethane come into question, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1, 3-dione and enamine compounds. Of course, the UV-A and UV-B filters can also be used in mixtures. In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and in addition oxides of iron, zirconium, silicon, manganese, aluminum and cerium, and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments may also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Preferably, micronized zinc oxide is used.

Another preferred class of stabilizers to be used are the fluorescent dyes. They include the 4,4 ^{^{'diamino-2,2'}} -stilbendisuIfonsäuren (flavonic), 4,4'-distyrylbiphenyls, methyl umbelliferone, coumarins, dihydroquinolinones, 1, 3- diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole, and Benzimidazole systems and substituted by heterocycles pyrene derivatives. Of particular importance are the sulfonic acid salts of diaminostilbene derivatives and polymeric fluorescent substances.

Preferred process variants are characterized in that the film materials used in step b) of the process according to the invention have a thickness between 5 and 2000 .mu.m, preferably between 10 and 1000 .mu.m, more preferably between 15 and 500 .mu.m, very particularly preferably between 20 and 200 .mu.m and in particular between 25 and 100 microns have.

The films used may be single-layer or multi-layer films (laminate films). Regardless of their chemical or physical structure, the water content of the film materials is preferably below 10 wt .-%, more preferably below 7 wt .-%, most preferably below 5 wt .-% and in particular below 4 wt .-%.

In step c) of the method according to the invention, the first film material is deep-drawn into the cavity.

In a preferred process variant, the packaging film used is conditioned before molding. Such methods according to the invention are particularly preferred, in which the packaging film is pretreated before thermoforming in step c) by heating and / or solvent application. If the film material is pretreated by the action of heat before or during deep drawing into the cavity of the shaped body, this is preferably for this purpose for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and especially for 0 , 4 to 2 seconds to temperatures above 60 ° C, preferably above 80 ° C, more preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C. Such pretreated film materials form in preferred process variants in step c) already due to their own weight in the Kavitat of the molding.

Particular preference is furthermore given to those processes in which the first film material is deep-drawn into the cavity in step c), in that a negative pressure is generated in the cavity of the molded article.

To generate this negative pressure are all known in the art for this purpose pumps, particularly preferably used for a rough vacuum water jet, Flüssigkeitsdampfstrahl-, Wasserring- u. Piston pumps. However, it is also possible to use, for example, rotary slide valves, slide gate valves, trochoidal and sorption pumps as well as so-called Roots blowers and cryopumps. To set a fine vacuum, rotary vane pumps, diffusion pumps, Roots blowers, positive displacement, turbomolecular, sorption, ion getter pumps (getters) are preferred.

In a preferred embodiment of the method according to the invention, the negative pressure generated is between -100 and -1013 mbar, preferably between -200 and -1013 mbar, particularly preferably between -400 and -1013 mbar and in particular between -800 and -1013 mbar.

The negative pressure can be generated in the Kavitat by different procedures. In the simplest case, the cavity is one of the breakthroughs described above. By applying a negative pressure to one of the openings of the opening, which was not covered by a first film material in step b), the film material can be deep-drawn into the cavity.

Accordingly, in the context of the present application, a method for producing a dosing unit for detergents or cleaning agents is preferred, comprising the steps of a) providing a shaped body having at least one cavity in the form of an opening; b) placing a first sheet material on the shaped body surface via an opening of the opening; c) deep drawing the first sheet material into the aperture by applying a negative pressure to an aperture of the aperture which is not covered by the first sheet material; d) filling a washing or cleaning substance on the film material in the Kavitat.

As explained above, the shaped body with the opening is preferably a ring tablet. In a particularly preferred embodiment, the application therefore comprises, in particular, a method for producing a dosing unit for detergents or cleaners, comprising the steps of a) providing a ring tablet; b) placing a first sheet material on the shaped body surface via an opening of the ring tablet; c) deep drawing the first sheet material into the cavity of the ring tablet by applying a negative pressure to the further opening; d) filling a washing or cleaning substance on the film material in the Kavitat.

As a ring-shaped body or ring tablets such moldings are referred to having two interconnected openings in its surface. These interconnected openings form a passage penetrating the body or tablet, which preferably connects two mutually opposite sides.

If ring tablets are used in the process according to the invention for producing the washing or cleaning agent dosing units, deep drawing of the film material takes place in the opening of these ring tablets in a particularly preferred embodiment after a molding tool has been introduced into the opening of the ring tablet. This mold may be inserted into the aperture before or after the first film material is placed on the mold surface over the aperture of the ring tablet. Of course, the introduction of the mold can also be done simultaneously with the laying of the film material. The molding tool serves as a "placeholder" in this process variant and reduces the void volume of the opening into which the film material can be deep-drawn.Thus, the receiving chamber formed by the deep drawing of the film material does not become the entire opening but only that in the opening after insertion of the molding tool remaining void volume Completion. The receiving chamber formed from the film material thus fills the breakthrough only partially.

A preferred subject of the present application is therefore a process for the preparation of a dosing unit for detergents or cleaners, comprising the steps of a) providing a ring-shaped body, preferably a ring tablet; b) introducing a molding tool through a first opening of the annular tablet breakthrough in this opening; c) placing a first, preferably water-soluble film material on the molding surface via the second opening of the opening; d) deep drawing of the first sheet material in the breakthrough of the ring tablet to form a receiving chamber which fills the breakthrough only partially; e) filling a washing or cleaning-active substance in the receiving chamber formed in step d).

As already stated, the method steps b) and c) in this preferred variant of the method can be carried out in the reverse order or at the same time.

By introducing the mold into the breakthrough of the ring tablet this breakthrough partially but not completely filled. Particularly preferred are those processes in which the mold between 5 and 95 vol .-%, preferably between 10 and 90 vol .-%, preferably between 15 and 85 vol .-% and in particular between 20 and 80 vol .-% of the opening the ring tablet fills out.

Suitable materials for the production of molds are in particular metals or metal alloys and, preferably, polymers. Alternatively, of course, metallic molds with, preferably polymeric, coatings can be used. Such coatings are suitable, for example, for increasing the chemical or physical stability of the molds, for example against corrosion or mechanical stress. Furthermore, polymeric coatings are suitable for preventing adhesion to the surface of the mold.

In preferred methods, the mold introduced into the aperture of the ring tablet is adapted, in terms of its spatial shape, to the spatial shape of the aperture of the ring tablet. Thus, the mold is preferably close to the inner wall of the ring tablet, that is, on the wall of the opening to. Particularly preferred are those methods in which the distance between the introduced in the breakthrough mold and the inner wall of the Ring tablet is less than 10 mm, preferably less than 5 mm, preferably less than 3 mm and in particular between 0.1 and 2 mm.

The molding tool preferably has a rotationally symmetrical horizontal cross section. Particularly preferred molds are characterized by a triangular or quadrangular, preferably square, horizontal cross-section. The corners of these molds are preferably rounded. In an alternative, likewise preferred embodiment, the horizontal cross section of the body introduced into the ring mold is oval or circular.

The upper side of the molding tool, that is to say the side of the molding tool facing the first film material placed on the opening of the ring tablet, can be designed in different ways. Since the in step c) applied to the opening of the Ringtablette sheet material in step d) of this preferred embodiment is deep drawn in the at least partially filled with the molding breakthrough, preferably deep-drawn so that this film material fits tightly against the top of the mold, can by the spatial configuration of the upper side of the molded body is also directly influenced by the spatial configuration of the bottom surface of the receiving chamber produced by the deep-drawing process. Thus results from the use of a mold with a flat top a, taking into account the naturally occurring in thermoforming shrinkage shrinkage of the deep-drawn sheet material, substantially flat bottom surface of the receiving chamber.

With particular preference in this process variant molds with a flat, concave or convex top, but in particular molds are used with a concave top. In a particularly preferred variant, the upper side of the molding tool has both planar and curved sections, as concave and / or convex sections. Very particular preference is given to molds having a peripheral, planar edge region and a concave inner part enclosed by this planar edge region, that is to say a depression surrounded by this planar edge region.

With particular preference, the introduced in the breakthrough of the ring tablet mold is designed such that by applying a negative pressure to the mold, the gas space between the mold and the applied to the opening of the ring tablet film material can be evacuated. Therefore, preferred molding tools have notches, grooves or holes, by means of which by applying a negative pressure, the gas space between the mold and the first placed on the opening of the ring tablets first Foil material at least partially evacuated and in this way the film material can be deep-drawn into the opening.

If after the introduction of the mold into the opening of the ring tablet in step d) of this preferred process variant, the sheet material deep-drawn into the opening of the ring tablet, the receiving chamber formed by the deep drawing of the sheet material can naturally fill the space in the breakthrough, which does not by the Mold is taken. By filling a washing or cleaning-active substance in this receiving chamber in the subsequent step e), the breakthrough of the ring tablets is therefore also only partially filled. The deep drawing is preferably carried out by applying a negative pressure, but can for example also be effected by the action of a punch.

The receiving chamber formed by the deep drawing of the first film material is preferably filled with a flowable substance. The flowable substances may be solids or liquids, with particular preference liquid (s) and / or gel (s) and / or powder and / or granules (e) and / or extrudate (s) and / or Kompaktat (e) are used. A more detailed description of these flowable substances is given below in the text.

After filling the receiving chamber with the washing or cleaning active substance, this receiving chamber is preferably sealed. Suitable sealing materials are, for example, solidifying melts or liquids or, preferably, precisely fitting shaped bodies. With particular preference, however, water-soluble film materials are used as sealing materials.

A further preferred subject matter of the present application is thus a process for the production of a dosing unit for detergents or cleaners, comprising the steps of a) providing a ring molding, preferably a ring tablet; b) introducing a molding tool through a first opening of the annular tablet breakthrough in this opening; c) placing a first, preferably water-soluble film material on the molding surface via the second opening of the opening; d) deep drawing of the first sheet material in the breakthrough of the ring tablet to form a receiving chamber which fills the breakthrough only partially; e) filling a washing or cleaning-active substance in the receiving chamber formed in step d); f) sealing the filled receiving chamber.

For example, solvents and / or adhesives can be used for sealing and adhering the first film material with the further water-soluble film material. With particular preference, however, the sealing takes place by means of heat, preferably by laser welding or heat sealing.

The sealing can be carried out in principle in the region of the shaped body of the ring tablet itself and / or in the region of the opening. In the first case, the metering units have a, preferably circumferential, sealing seam, which is in direct contact with the shaped body; in the second case, the, preferably circumferential, sealing seam lies in the region of the opening and does not touch the shaped body.

As already stated above, in this preferred variant of the method molds are used with particular advantage, the upper side of which has a peripheral, planar edge region and a concave inner part, that is to say a hollow enclosed by this flat edge region. With particular preference, the sealing of the thermoformed first sheet material with the used for sealing further water-soluble sheet material by means of heat sealing, wherein the receiving chamber occluding, preferably circumferential sealing seam, with particular preference, the shaped body is not affected, that is generated for example in the region of the opening.

A further preferred subject matter of the present application is thus a process for the production of a dosing unit for detergents or cleaners, comprising the steps of a) providing a ring molding, preferably a ring tablet; b) introducing a molding tool, the upper side of which has a peripheral, planar edge region, through a first opening of the annular tablet breakthrough into this opening; c) placing a first, preferably water-soluble film material on the molding surface via the second opening of the opening; d) deep drawing of the first sheet material in the breakthrough of the ring tablet to form a receiving chamber which fills the breakthrough only partially; e) filling a washing or cleaning-active substance in the receiving chamber formed in d); f) sealing the filled receiving chamber by applying a water-soluble film material to the filled receiving chamber and Heat-sealing the first film material with the water-soluble film material in the planar edge region of the molding tool.

By sealing the two film materials forming the receiving chamber in the region of the planar edge region of the molding tool, the tightness of the sealed receiving chambers can be significantly increased in comparison to conventional methods. With particular preference in this process variant metallic molds are used. With particular preference, the molds used are heated.

After completion of the seal resulting detergent or Reinigungsmitteldosiereinheiten comprising a ring tablet and the breakthrough of the ring tablet partially fills, filled, preferably water-soluble receiving chamber. Ring tablet and filled receiving chamber are preferably adhesively bonded together. This adhesive connection can be made, for example, by gluing the ring tablet to the first film material placed over the opening of the ring tablet in step c) or by heat-sealing the first film material to the surface of the ring tablet. The breakthrough of the ring tablet is not filled below the water-soluble receiving chamber.

In a preferred embodiment of the method variant described above, the mold is removed after completion of the seal from the opening and the cavity located in the opening below the filled receiving chamber filled with another, preferably flowable, washing or cleaning-active substance. For this purpose, the partially filled ring tablet is preferably first turned over. After filling, the second opening of the opening is preferably also sealed, with the sealing materials mentioned above, in particular water-soluble film materials, being used with particular preference.

A further preferred subject matter of the present application is thus a process for the production of a dosing unit for detergents or cleaners, comprising the steps of a) providing a ring molding, preferably a ring tablet; b) introducing a mold, the top of which preferably has a circumferential planar edge region, through a first opening of the opening of the annular tablet in this opening; c) placing a first, preferably water-soluble film material on the molding surface via the second opening of the opening; d) deep drawing of the first sheet material in the breakthrough of the ring tablet to the top of the mold to form a receiving chamber which fills the breakthrough only partially; e) filling a washing or cleaning-active substance in the receiving chamber formed in d); f) sealing the filled receiving chamber by applying a water-soluble film material to the filled receiving chamber and heat-sealing the first, preferably water-soluble film material with this water-soluble film material, wherein the sealing preferably takes place in the planar edge region of the mold; g) removing the molding tool through the first opening from the opening of the annular tablet and filling another washing or cleaning substance in the previously occupied by the mold portion of the opening; h) sealing the first opening of the filled opening with a, preferably water-soluble, film material.

Process variants are particularly preferred in which a washing or cleaning-active liquid or a washing or cleaning-active gel is introduced into at least one of the process steps e) or h). Very particular preference is given to processes in which a washing or cleaning-active liquid or a washing or cleaning-active gel is introduced in step e), while in step h) a flowable, washing or cleaning-active solid, preferably a powder or granules or a Extrudate, is filled.

Regardless of the nature of the process variant, the first film material in step c) or in step d) of the process according to the invention is preferably deep-drawn by applying a negative pressure. In a further preferred variant of the method, the negative pressure in the cavity is created by applying a negative pressure to a hole or notch which connects the cavity to the part of the surface of the shaped body (outside the cavity) which does not extend through the first foil material Step b) is covered. Such a hole may, for example, be a bore which connects the cavity to a side surface or the underside of the shaped body. Such a bore preferably has a diameter below 5 mm, preferably below 3 mm and in particular below 2 mm. Of course, the cavity can also be connected by more than one hole with one or more outer sides, the shaped body also have more than one bore. Alternatively or additionally, the shaped body can furthermore have notches. These notches or grooves open into the opening of the cavity opening and lead from there preferably to a side surface of the molding. The width of these notches is preferably less than 10 mm, preferably less than 7 mm, more preferably less than 4 mm and in particular less than 2 mm. The depth of the notches is preferably in the range between 1 and 15 mm, preferably between 1 and 10 mm and in particular between 1 and 5 mm.

In a further variant of the method according to the invention, the first film material is applied by applying a negative pressure to a hole or a notch which connects the cavity to the part of the surface of the molded article (outside the cavity), not through the first film material from step b) is deep-drawn into the cavity.

A further preferred subject matter of this application is therefore a process for the production of a dosing unit for detergents or cleaners, which accordingly comprises the steps of a) providing a shaped body having at least one cavity in the form of a trough; a ') Optional partial filling of the well with a washing or cleaning active composition, preferably a solid washing or cleaning active composition, particularly preferably at least one substance from the group of builders, enzymes, bleach, bleach activators, bleach catalysts, silver protectants and glass corrosion inhibitors; b) placing a first sheet material on the molding surface over the opening of the well; c) deep drawing the first sheet material into the trough by applying a negative pressure to a hole or indentation which connects the trough to that part of the surface of the shaped body (outside the trough) that is not penetrated by the first sheet material from step b ) is covered; d) filling a washing or cleaning-active substance on the film material in the trough.

If the shaped body has sufficient porosity, the negative pressure in the cavity can be generated by applying a negative pressure to the shaped body surface (outside the cavity). Surprisingly, it has been found that the abovementioned washing or cleaning agent tablets are suitable for such a process. By compacting, preferably tabletting, particulate starting mixtures can thus be produced moldings which have sufficient porosity to generate by applying a negative pressure at the surface of the shaped body, which is not covered by the film material within the Kavitat sufficient negative pressure to the Deep opening of the cavitate covering film material in this Kavitat deep draw. A further preferred variant of the method according to the invention, the first sheet material is produced by applying a negative pressure to the part of the surface of the shaped body (outside the cavity), which is not covered by the sheet material from step b) deep drawn into the Kavitat.

A further subject of this application is therefore a process for the preparation of a dosing unit for detergents or cleaners, thus comprising the steps of a) providing a shaped body having at least one cavity in the form of a trough; a ') Optional fractional filling of the Kavitat with a washing or cleaning active composition, preferably a solid washing or cleaning active composition, particularly preferably at least one substance from the group of builders, enzymes, bleach, bleach activators, bleach catalysts, silver protectants and glass corrosion inhibitors; b) applying a first foil material to the shaped body surface via an opening of the cavity; c) drawing the first sheet material into the cavity by applying a negative pressure to that part of the surface of the shaped body (outside the cavity) which is not covered by the sheet material of step b); d) filling a washing or cleaning substance on the film material in the Kavitat.

In the preferred method variants described so far, the negative pressure in the cavity is produced by the air in the cavity below the film material applied in step b) "through the tablet", that is to say by applying a negative pressure to holes specially provided for this purpose, Notches or holes, or by utilizing the tablets porosity was removed from this Kavitat.In another particularly preferred variant of the method, the negative pressure in the Kavitat is generated by the air in Kavitat below the laid down in step b) air through holes in this Foil material is removed from the cavity.

Process for the preparation of a dosing unit for detergents or cleaners, comprising the steps of a) providing a shaped body having at least one cavity; a ') Optionally proportionate filling of Kavitat with a washing or cleaning active composition, preferably a solid wash or cleaning-active composition, which particularly preferably contains at least one substance from the group of builders, enzymes, bleaching agents, bleach activators, bleach catalysts, silver protectants and glass corrosion inhibitors; b) placing a first sheet material on the molding surface over the opening of the cavity; c) deep-drawing the first film material into the cavity by creating a negative pressure in the cavity in that the air in the cavity below the film escapes at least partially through openings in the film material applied in step b); d) filling a washing or cleaning substance on the film material in the Kavitat; are particularly preferred in the context of this application.

Particular preference is given to processes according to the invention in which the negative pressure is generated both in the cavity, ie below the film material applied in step b), and also outside the cavity above the film material applied in step b). Such a particularly advantageous process procedure can be realized, for example, by the fact that the molded body covered with the film material is brought into a vacuum chamber. Due to the openings in the film material, when a vacuum is applied to the vacuum chamber both in the cavity of the molded body, ie below the film material applied in step b), and outside the molded body, above the film material applied in step b) is produced the air located below the film material applied in step b) passes through these openings into the space above the film material applied in step b) and is removed therefrom by the applied vacuum from the vacuum chamber. In a subsequent process step, the film web applied in step b) is sealed with the filled container in such a way that the container is closed on all sides and in particular no air can pass through the openings of the film web applied in step c) into the container. If the sealed container is then removed from the vacuum chamber, the atmospheric pressure acting on the container from outside causes the outer walls of the container, in particular the film web applied in step b), to fit tightly against the molded body into the cavity.

Process for the preparation of a dosing unit for detergents or cleaners, comprising the steps of a) providing a shaped body having at least one cavity; a ^' ) optional fractional filling of the Kavitat with a washing or cleaning active composition, preferably a solid washing or cleaning active composition, particularly preferably at least one substance from the group of builders, enzymes, bleach, bleach activators, bleach catalysts, silver protectants and glass corrosion inhibitors; b) placing a first sheet material on the molding surface over the opening of the cavity; c) deep drawing of the first film material in the cavity by the covered with the film web moldings is placed in a vacuum chamber and in this chamber a negative pressure is generated, whereby in the Kavitat thereby a negative pressure is generated, that in Kavitat located below the film Air escapes at least partially through openings in the film material applied in step b); d) filling a washing or cleaning substance on the film material in the Kavitat. are also particularly preferred in the context of this application.

By deep-drawing of the film material into the cavity in step c) of the method according to the invention, the film material is molded into the cavity to form a receiving trough. This receiving trough is then filled in the subsequent step d) with a washing or cleaning-active substance. The shape and the volume of the receiving trough will of course depend on the shape and the volume of the cavity of the molding on which the process is based. Preference is given in particular to those processes in which the volume of the receiving trough formed by the film material is at least 40% by volume, preferably at least 60% by volume, very particularly preferably at least 80% by volume, in particular at least 90% by volume and particularly preferably at least 95% by volume of the volume of the cavity of the shaped body in step a) or in step a ').

For the spatial fixation of shaped bodies and foil material before the subsequent filling in step d), the shaped body and the foil material are adhesively bonded together in a preferred embodiment of the method according to the invention. The adhering connection preferably takes place in spatial proximity to the opening of the cavity into which the film material was deep-drawn in step c). Particularly preferred is the adhesive compounds along a circumferential sealed seam. This sealed seam can be realized by a number of different procedures. However, preference is given to those processes in which the adhesive compound is formed by the action of adhesives and / or solvents and / or compressive or squeezing forces. However, particularly preferred are those inventive Method in which the molded body before, simultaneously with or after the deep drawing of the first film material in step c) is adhesively bonded to this first film material by a bond and / or a heat seal. Also in the case of heat sealing, a circumferential sealing seam, that is, a self-contained sealing seam is particularly preferred. For heat sealing of molded articles and film material, a number of different tools and processes are available to the person skilled in the art.

In a first preferred embodiment, the heat seal is effected by the action of heated sealing tools.

In a second preferred embodiment, the heat seal is effected by the action of a laser beam.

In a third preferred embodiment, the heat seal is effected by the action of hot air.

In step d) of the process according to the invention, a washing or cleaning-active substance is filled onto the film material in the cavity. As washing or cleaning substances are suitable solids as well as liquids. The washing or cleaning-active substance can be filled onto the film material in the cavity by any metering method known to those skilled in the art.

In a first preferred embodiment, in step d) prefabricated molded bodies, for example cast bodies, tablets or extrudates are placed on the film material in the cavity. If a trough tablet or a ring tablet is used as the shaped body in step a), the end product of this preferred variant of the method corresponds to a core tablet or a "bullet-tablet", in which the cavity of step a ) is filled with a cast body, another tablet or an extrudate, wherein the tablet and the inserted core are separated from each other by the in step c) deep-drawn in the cavity film material.

The washing or cleaning-active substance filled in step d) preferably has a density above 1.0 g / cm 3, preferably above 1.1 g / cm 3, more preferably above 1.2 g / cm 3, very particularly preferably above 1.3 g / cm3 and especially above 1.4 g / cm3. The volume ratio of the shaped body provided in step a) to the volume of substance introduced into the cavity in step d) is preferably between 1: 1 and 20: 1 and in particular between 3: 1 and 15: 1. In the context of the present application, particular preference is given in particular to those processes in which a flowable detergent or cleaning substance is introduced in step d). These solid or liquid flowable substances or substance mixtures are preferably poured onto the film material in the cavity. Liquid (s) and / or gel (s) and / or powder and / or granules (e) and / or extrudate (s) and / or compact (e) are preferably used as flowable substances.

If particulate substances, for example powders, granules or extrudates, are used as solid flowable substances or substance mixtures, these particulate substances or substance mixtures have an average particle size below 5000 μm, preferably less than 3000 μm, preferably less than 1000 μm, very particularly preferably between 50 and 1000 μm and in particular between 100 and 800 μm.

In a further preferred embodiment, the flowable washing or cleaning substance is a liquid. In this context, substances or mixtures of substances in their liquid state of aggregation are referred to as liquid. Accordingly, in addition to liquid pure substances, the term "liquid" furthermore also includes solutions, suspensions, emulsions or melts.Preferably used are those substances or substance mixtures which are in the liquid state at 20 ° C. As a preferred constituent, the liquids contain at least one substance from the group the nonionic surfactants and / or the polymers and / or the organic solvents The liquid may itself have several phases.

As flowable washing or cleaning-active substances, it is also possible to use molten substances or substance mixtures.

Preference is therefore given in particular to those processes according to the invention for producing a dosing unit for detergents or cleaners, comprising the steps of a) providing a shaped body having at least one cavity; a ') Optional partial filling of the cavity with a washing or cleaning active composition, preferably a solid washing or cleaning active composition; b) placing a first sheet material on the molding surface over the opening of the cavity; c) deep drawing the first sheet material into the cavity; d) filling a second washing or cleaning active substance, preferably a liquid washing or cleaning substance, on the film material in the cavity. In step d), the cavity is preferably filled with a liquid. This liquid-filled cavity is then preferably sealed. In a particularly preferred embodiment, in addition to the liquid, a gas or gas mixture is additionally enclosed during the sealing in the cavity. This gas or gas mixture may be, for example, an inert gas (eg argon or nitrogen) a reactive gas such as carbon dioxide but also, for example, the natural ambient air. Processes according to the invention in which the cavity is filled with a liquid in step d) and subsequently sealed with the inclusion of a gas bubble are particularly preferred. The volume of the gas bubble is preferably between 1 and 25% by volume, preferably between 2 and 20% by volume and in particular between 4 and 10% by volume of the volume of the sealed cavity.

In a further preferred embodiment, the shaped bodies provided in step a) have a coating of a water-soluble or water-dispersible material, preferably an envelope of a water-soluble or water-dispersible film material, more preferably of a water-soluble or water-dispersible polymer-based film material. Particularly preferred film materials are the materials described above from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof. This enclosure may include the shaped body completely or only partially. Particularly preferred are processes in which the shaped body in step a) is partially surrounded by a water-soluble or water-dispersible film material. Such a partial coating can be realized, for example, by deforming a first water-soluble or water-dispersible film material, for example by deep drawing to form a receiving chamber and the shaped body is moved in step a) in this resulting receiving chamber. Alternatively, the water-soluble or water-dispersible receiving chamber may also be made by injection molding a water-soluble or water-dispersible material. After the shaped body has been moved into this receiving chamber in step a), the remaining steps of the method according to the invention are carried out as described above, with the difference that in this variant of the method, the shell material of the shaped body from step a) in the course of the process with the first or second preferably water-soluble film material from steps b) or e) to connect adhesively and in this way to achieve a complete enclosure of the provided in step a), a ^' ) and d) washing or cleaning-active substances. The resulting final process product is not only distinguished by the separation of the active substances introduced in steps a) and a ^' ) or d), but also makes possible the Preparation of readily soluble and thus highly active active substances in powder form or in the form of liquid compositions in a prefabricated dosing unit.

Preference is thus further given to a process for the preparation of a dosing unit for detergents or cleaners, comprising the steps of a) providing a shaped body in a water-soluble or water-dispersible receiving chamber, wherein the shaped body has at least one cavity; a ^' ) Optional partial filling of the cavity with a washing or cleaning active composition, preferably a solid washing or cleaning active composition; b) placing a first sheet material on the molding surface over the opening of the cavity; c) deep drawing the first sheet material into the cavity; d) filling a second washing or cleaning active substance, preferably a liquid washing or cleaning substance, on the film material in the cavity.

The water-soluble or water-dispersible receiving chamber is preferably adhesively bonded in a further process step with the first film material from step b). The adhesive connection is preferably carried out subsequent to the deep-drawing of the first film material in step c), but can also be carried out with preference in the connection to the steps b) or d).

As mentioned above, the cavity can be a depression or a breakthrough. With particular preference, the latter method variant is carried out with a shaped body which has a breakthrough as a cavity. The process product of this process variant is then a ring-core tablet ("bull-eye tablet"), the breakthrough is closed on both sides by means of a water-soluble or water-dispersible material, the breakthrough itself by another water-soluble or water-dispersible Material, which may be identical to the aforementioned water-soluble or water-dispersible material, but may also differ from this material, is divided into two separate chambers, which preferably have a different filling.

A further subject of the present application is therefore a process for the preparation of a dosing unit for detergents or cleaners, comprising the steps a) providing a shaped body in a water-soluble or water-dispersible receiving chamber, wherein the shaped body has at least one breakthrough; a ^' ) Partial filling of the opening with a first washing or cleaning active composition, preferably a solid washing or cleaning active composition; b) placing a first sheet material on the molding surface over the opening of the opening; c) deep drawing the first sheet material into the aperture; d) filling a second washing or cleaning active substance, preferably a liquid washing or cleaning substance, on the film material in the cavity.

In the methods described above, it is preferred to seal the cavity opening following step d) in a further step e). In a preferred variant of the method, this sealing takes place by applying a second film material to the cavity opening and subsequent heat sealing and / or ultrasonic sealing and / or high-frequency sealing. This second film material may be the same or a different film material from the first film material used in step b). The second film material may differ from the first film material, for example, by its thickness and / or its composition. Of course, the sealing of the second film material via the cavity opening can also take place by gluing the second film material to the first film material or to the shaped article. In addition to adhesives known to the person skilled in the art, in particular solvents, particularly preferably water or aqueous solutions, are suitable for sealing the cavity opening of the bonding.

The sealed cavity preferably has an overpressure. Such a crowning can be achieved, for example, by adding gas-releasing components to the washing or cleaning-active substances filled in step d). As a result of the release of gas after the cavity has been sealed in step e), the film material used for the sealing bulges and forms a visually appealing, convex curvature.

It is preferred that the molded article is adhesively bonded to the first film material and / or to the second film material by the heat-sealing and / or ultrasonic sealing and / or high-frequency sealing and / or gluing.

According to the invention, preference is furthermore given to a process for the production of a dosing unit for detergents or cleaners, comprising the steps a) providing a shaped body having at least one cavity; a ') Optional partial filling of the cavity with a washing or cleaning active composition, preferably a solid washing or cleaning active composition; b) placing a first sheet material on the molding surface over the opening of the cavity; c) deep drawing the first sheet material into the cavity; d) filling a second washing or cleaning active substance, preferably a liquid washing or cleaning substance, on the film material in the cavity; e) sealing the cavity filled in step d), preferably by applying a second film material and adhesive bonding of the second film material to the shaped article from step a) and / or the first film material from step b).

Preference is thus furthermore given to a process according to the invention for producing a dosing unit for detergents or cleaners, comprising the steps of a) providing a shaped body in a water-soluble or water-dispersible receiving chamber, wherein the shaped body has at least one cavity; a ') Optional partial filling of the cavity with a washing or cleaning active composition, preferably a solid washing or cleaning active composition; b) placing a first sheet material on the molding surface over the opening of the cavity; c) deep drawing the first sheet material into the cavity; d) filling a second washing or cleaning active substance, preferably a liquid washing or cleaning substance, on the film material in the cavity; e) sealing the cavity filled in step d), preferably by applying a second film material and adhesive bonding of the second film material to the shaped article from step a) and / or the first film material from step b); wherein the water-soluble or water-dispersible receiving chamber is adhesively bonded in a further process step with the first film material from step b) and / or the second film material from step e). The adhesive connection preferably takes place together with the sealing of the cavity filled in step d) in step e). The subject of this application is thus further a shaped body with a breakthrough (ring-core tablet or "bull-eye tablet"), the breakthrough is closed on both sides by means of a water-soluble or water-dispersible material, the breakthrough itself by another water-soluble or water-dispersible material is subdivided into two separate chambers, which preferably have a different filling, Particular preference is given to those shaped bodies, one of the chambers being a solid washing or cleaning substance, particularly preferably a solid washing or cleaning substance in the form of a powder, Granules or extrudates, while the second compartment contains a liquid detergent or cleaning substance, the water-soluble or water-dispersible materials which seal the opening on either side or divide the opening into two separate compartments i However, they can also differ from each other.

The volume of the chambers located in the breakthrough is preferably between 0.5 and 15 ml, preferably between 0.5 and 12 ml, more preferably between 0.5 and 8 ml and in particular between 0.5 and 6 ml Chambers to each other is preferably between 10: 1 and 1:10, preferably between 8: 1 and 1: 8, more preferably between 6: 1 and 1: 6 and in particular between 4: 1 and 1: 4.

The shaped bodies with filled breakthrough described above enable the combined formulation of solid and liquid washing and cleaning substances using minimal amounts of packaging materials. By using water-soluble or water-dispersible packaging materials, these means are also suitable for direct metering into the metering chamber or the interior of a dishwasher or washing machine. The shaped bodies of this particular embodiment according to the invention are distinguished by at least three phases (shaped body, first washing or cleaning substance in chamber 1, second detergent or cleaning substance in chamber 2) and thus allows the visualization complex drug combinations (eg "2in1" - or "3in1" automatic dishwashing or combination products of a laundry detergent and conditioner such as a softener, a dye transfer inhibitor or a crease inhibitor.

Following the process according to the invention, the process end products are preferably separated and compounded. If, for example, a film web is used as first or second film material, which film is processed to more than one of the metering units according to the invention, then this film material is cut into shape during or after completion of the process. Inventive method, characterized in that the first or second sheet material in the course of the process, preferably after a Sealing step is severed by a mechanical and / or thermal process to form a cutting line, wherein the cutting line preferably extends circumferentially on the surface of the molding, are particularly preferred.

The process according to the invention may also be followed by packaging of the process end products in "flow packs", stand-up pouches or cardboard packaging.

In the method according to the invention, a film material, preferably a water-soluble or water-dispersible film material, is thermoformed to form a receiving chamber in the cavities of detergent tablets or detergent tablets. The present application therefore furthermore relates to metering units for detergents or cleaners, comprising a shaped body having at least one cavity, a film material deep-drawn into the cavity to form a receiving chamber, and a washing or cleaning substance located on the film material in the cavity. By the deep-drawing process, the film material is applied tightly against the inner walls of the cavity. This method is thus distinguished from alternative approaches, such as the pressing or inserting of a film material through an optimized use of space.

As described above, the shaped body is preferably a tablet, a compact, an extrudate, an injection molding or a casting. With regard to the preferred manufacturing method of these moldings and their preferred spatial forms, reference is made at this point to avoid repetition of the statements above in the description.

According to the invention, preference is given to those metering units which have a cavity or an opening as a cavity. The volume of the cavity is preferably between 0.1 and 20 ml, preferably between 0.2 and 15 ml, more preferably between 1 and 10 ml and in particular between 2 and 7 ml.

The dosing units according to the invention comprise, in addition to a shaped body, a receiving trough filled with washing or cleaning-active ingredients and preferably made of a water-soluble or water-dispersible foil material. In the case of a simple, single-phase molded body, the dosing unit thus has two phases separated from one another. These separate phases allow, for example, the separation of incompatible ingredients or the joint dosage of detergents or cleaning agents with different states of aggregation or Konfektionsformen. In a particularly preferred embodiment of the compositions according to the invention, the dosing unit is characterized in that the receiving chamber formed from the thermoformed sheet material with a flowable, preferably a liquid washing or cleaning substance, more preferably with one or more active substance (s) from the group of Group of nonionic surfactants and / or polymers and / or organic solvents, is filled.

The flowable washing or cleaning substances may be solid or liquid. Liquid (s) and / or gel (s) and / or powder and / or granules (e) and / or extrudate (s) and / or compact (e) are preferably used as flowable substances.

In a further preferred embodiment, the flowable washing or cleaning substance is a liquid. In this context, substances or mixtures of substances in their liquid state of aggregation are referred to as liquid. Accordingly, in addition to liquid pure substances, the term "liquid" furthermore also includes solutions, suspensions, emulsions or melts.Preferably used are those substances or substance mixtures which are in the liquid state at 20 ° C. As a preferred constituent, the liquids contain at least one substance from the group the nonionic surfactants and / or the polymers and / or the organic solvents.

The number of these phases of metering units according to the invention can be increased by increasing the number of phases of the shaped body and / or the number of phases filled into the cavity.

In a preferred embodiment, therefore, the shaped body has two, three, four or more phases. In a further preferred embodiment, the washing or cleaning active material filled in the cavity has two, three, four or more phases. For example, a plurality of different washing or cleaning-active substances or substance mixtures can be filled into the one receiving chamber formed from the thermoformed sheet material. An example of such a preferred embodiment is a dosing unit according to the invention, in which the receiving chamber formed from the thermoformed sheet material is filled with a two- or multi-phase liquid phase. Alternatively, a multi-phase filling of this receiving chamber can also be realized, for example, by filling two or more or above-mentioned flowable, solid washing or cleaning-active substances in layers in the receiving chamber.

A dosing unit, characterized in that the cavity additionally in part with a washing or cleaning active substance, preferably a substance from the group Builders, enzymes, bleach, bleach activators, bleach catalysts, silver protectants or glass corrosion inhibitors is filled, which is not in the formed from the thermoformed sheet material receiving chamber is particularly preferred.

Particularly preferred is an embodiment of the dosing unit according to the invention, in which the cavity below the thermoformed sheet material is partially filled with a washing or cleaning active substance, preferably a solid washing or cleaning active substance. The resulting dosing unit then comprises a mono- or multiphase shaped body with a cavity, a washing or cleaning substance filled into the cavity, which only partially fills the cavity, and a receiving chamber made of film material filled with a further detergent or cleaning substance Partially filled cavity was deep-drawn. If the cavity is a well, the washing or cleaning active substance filled in the cavity is enclosed between the bottom of the well and the receiving chamber formed from the thermoformed sheet material, and, if the filled receiving chamber is not at least partially transparent, in usually not visible from the outside. On the other hand, if the cavity is an opening with two openings facing one another, then the washing or cleaning-active substance filled in the cavity is through one of the openings filled with the washing or cleaning-active substance filled in the receiving chamber of deep-drawn sheet material visible.

It is preferred that the washing- or cleaning-active substances which are filled into the cavity of the shaped body outside the receiving chamber on deep-drawn sheet material are selected from the group of builders, enzymes, bleaches, bleach activators, bleach catalysts, silver protectants or glass corrosion inhibitors. Bleaches, in particular peroxygen compounds such as percarbonates or perborates, bleach activators or silver protectants, are particularly preferably introduced. These ingredients are preferably filled into the cavity as part of solid washing or cleaning active preparations between steps a) and b). These ingredients are described in more detail later in the text. To avoid repetition, reference is made at this point to the comments there.

In order to prevent that the washing or cleaning-active substances filled in the receiving chamber formed from the thermoformed Folienmateriai, in particular the pourable washing or cleaning-active substances do not fall out of this receiving chamber, these substances are preferably fixed in the receiving chamber. This fixation can be done for example by adhesion promoters. However, a preferred Dosing unit according to the invention, in which the receiving chamber filled with the washing or cleaning active substance and formed from the thermoformed sheet material is sealed. Suitable sealing materials are, for example, melts of organic polymers or sugar melts. Preferably, however, the receiving chamber formed by the deep-drawn sheet material and filled with the washing or cleaning substance is sealed with another sheet material. As before, this sheet material is preferably a water-soluble or water-dispersible sheet material. In the case of shaped bodies which have a breakthrough as a cavity, preferably both opening surfaces of the opening are sealed. The sealing material may partially cover the shaped body surface, for example, in the targeted sealing of individual cavity openings with a water-soluble or water-dispersible sheet material. However, the sealing material can also be used to completely encase the molded body.

Dosing units according to the invention are therefore particularly preferred, comprising a molding having at least one cavity, a film material deep-drawn into the cavity to form a receiving chamber, and a washing or cleaning substance present on the film material in the cavity, the molding additionally comprising a coating of a water-soluble or water-soluble material having water-dispersible material. Such a water-soluble or water-dispersible coating may comprise, for example, a deep-drawn or injection-molded packaging.

In a further preferred embodiment, the shaped body is adhesively bonded to the film material deep-drawn in the cavity and / or to the further film material used for sealing the thermoformed sheet material by means of heat sealing and / or ultrasonic sealing and / or high-frequency sealing.

Unlike conventional multiphase detergents or cleaning agents, for example the marketed mortar tablets with molding or casting core, the ingredients of the detergent or cleaning product according to the invention are spatially separated from the ingredients contained in the receiving chamber formed from the sheet material. The resulting dosing unit is thus distinguished, in addition to the advantageous multiphase product appearance, by increased product and storage stability.

The detergents or cleaners according to the invention can be used for textile cleaning as well as for cleaning hard surfaces or dishes.

In addition to the abovementioned substances which are active in washing or cleaning, the detergents or cleaners prepared according to the invention preferably contain further washing and cleaning agents cleaning-active substances, in particular washing and cleaning-active substances from the group of bleaches, bleach activators, builders, surfactants, enzymes, polymers, disintegration aids, electrolytes, pH adjusters, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, corrosion inhibitors and glass corrosion inhibitors. These preferred ingredients will be described in more detail below.

builders

In the context of the present application, the builders include, in particular, the zeolites, silicates, carbonates, organic co-builders and-where there are no ecological prejudices against their use-also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x 0 _{2x +} ι Η ₂ 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ß- and δ-sodium disilicates Na ₂ Si ₂ 0 ₅ 'yH ₂ 0 are preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared with the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

In the context of the present invention, it is preferred that these silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous Alkalidisilikate, in washing or Detergents in amounts of 10 to 60 wt .-%, preferably from 15 to 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the washing or cleaning agent, are included.

When the silicates are used as part of automatic dishwashing agents, these compositions preferably comprise at least one crystalline, layered silicate of the general formula NaMSi _x 0 _{2x + 1} ^'y H ₂ 0 wherein M is sodium or hydrogen, x is a number from 1, 9 to 22 , preferably from 1, 9 to 4, and y is a number from 0 to 33. The crystalline layer-form silicates of the formula NaMSi _x 0 _{2x + 1} ^' y H ₂ O are sold, for example, by Glariant GmbH (Germany) under the trade name Na-SKS, eg Na-SKS-1

(Na ₂ Si ₂₂ O ₄₅ - ^χ H ₂ O, kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O _2g- H ₂ 0, magadiite), Na-SKS-3 (Na ₂ Si ₈ O _{1 7} - 2H ₂ 0) or Na-SKS-4 (Na ₂ Si ₄ Og-χH ₂ 0, makatite).

Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula (I) in which x is 2. Of these, especially Na-SKS-5 (-Na ₂ Si ₂ O ₅ ), Na are suitable.

SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ 0 ₅ Η ₂ 0), Na-SKS-10 (NaHSi ₂ O ₅ -3H ₂ O, kanemite), Na -SKS-11 (t-Na ₂ Si ₂ 0 ₅ ) and Na-SKS-13 (NaHSi ₂ 0 ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ 0 ₅ ).

When the silicates are used as a constituent of machine dishwashing detergents, such funds included in the present application, a proportion by weight of the crystalline layered silicate of the formula NaMSi _x 0 _{2x +} ι ^'y H ₂ 0 of 0.1 to 20 wt .-%, preferably from 0 , 2 to 15 wt .-% and in particular from 0.4 to 10 wt .-%, each based on the total weight of these agents. It is particularly preferred in particular if such automatic dishwashing agents have a total silicate content of less than 7% by weight, preferably less than 6% by weight, preferably less than 5% by weight, more preferably less than 4% by weight, most preferably less than 3% by weight % and in particular below 2.5 wt .-%, wherein it is in this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt .-% and in particular to At least 90 wt .-% of silicate of the general formula NaMSi _x 0 _{2x + 1} 'y H ₂ 0 is.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and preferred in the context of the present invention used is, for example, a co-crystallizate of zeolite X and zeolite A (ca. 80 wt .-% zeolite X) which is marketed by CONDEA Augusta SpA under the trade name VEGOBOND AX ^® and by the formula n Na ₂ 0 ^■ ( 1-n) K ₂ O ^• Al ₂ O ₃ ^• (2 - 2.5) Si0 ₂ "(3.5-5.5) H ₂ 0

can be described. The zeolite can be used both as a builder in a granular compound, as well as to a kind of "powdering" of the entire mixture to be pressed, wherein usually both ways for incorporating the zeolite are used in the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. This applies in particular to the use of agents according to the invention as automatic dishwasher detergents, which is particularly preferred in the context of the present application. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric H ₃ P0 in addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Suitable phosphates are, for example, the sodium dihydrogen phosphate, NaH ₂ PO ₄ , in the form of the dihydrate (density 1, 91 like ^"3 , melting point 60 °) or in the form of the monohydrate (density 2.04 like ^{" 3} ), the disodium hydrogen phosphate (secondary sodium phosphate) , Na ₂ HP0 ₄ , which is anhydrous or with 2 moles (density 2.066 like ^"3 , water loss at 95 °), 7 moles (density 1, 68 like ^{" 3} , melting point 48 ° with loss of 5 H ₂ 0) and 12 mol. Water (density 1, 52 like ^"3 , melting point 35 ° with loss of 5 H ₂ 0) can be used, in particular however the Trisatriumphosphat (tertiary sodium phosphate) Na ₃ P0, which as Dodecahydrat, as Decahydrat (according to 19- 20% P ₂ 0 ₅ ) and in anhydrous form (corresponding to 39-40% P ₂ 0 ₅ ) can be used. Another preferred phosphate is the tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ P0 ₄ . Also preferred are the tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , which in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1, 815-1, 836 like ^{" 3} , melting point 94 ° with loss of water), and the corresponding potassium salt potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ 0 ₇ .

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ 0 crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] _n -Na with n = 3. The corresponding potassium salt Pentakaliumtriphosphat, K5P3O (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ 0 ₅ , 25% K ₂ 0) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH - Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

If phosphates are used as detergents or cleaning agents in the context of the present application, preferred agents comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate). , in amounts of from 5 to 80% by weight, preferably from 15 to 75% by weight, in particular from 20 to 70% by weight, in each case based on the weight of the washing or cleaning agent.

In particular, it is preferred to use potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1: 1, preferably more than 2: 1, preferably more than 5: 1, more preferably more than 10: 1 and in particular more than 20: 1. It is particularly preferred to use exclusively potassium tripolyphosphate without admixtures of other phosphates. Further builders are the alkali carriers. Suitable alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metal silicates, and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention. Particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. Because of their low chemical compatibility with the other ingredients of detergents or cleaners compared with other builders, the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or Reinigugnsmittels used. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2 to 50 wt .-%, preferably from 5 to 40 wt .-% and in particular from 7.5 to 30 wt .-%, each based on the weight of the washing or cleaning agent. Particularly preferred are agents which, based on the weight of the washing or cleaning agent (ie the total weight of the combined product without packaging) less than 20 wt .-%, preferably less than 17 wt .-%, preferably less than 13 wt .-% and in particular less than 9% by weight of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonates, particularly preferably sodium carbonate.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

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

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of detergents or cleaners to (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%. To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-AlkylaIlylsulfonsäure and sugar derivatives ,

Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particularly preferred are polyaspartic acids or their salts and.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

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

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as builders.

surfactants

In addition to the nonionic surfactants described at the outset, the anionic, cationic and amphoteric surfactants are also counted among the group of surfactants.

In the context of the present application, all nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants. Preference is given to alkoxylated, advantageously ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used in which the alcohol radical may be linear or methyl branched preferably in the 2-position or linear and methyl-branched radicals may be present in the mixture 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 ethoxylated alcohols include, for example, C _12th _14- alcohols with 3 EO or 4 EO, Cg-n-alcohol with 7 EO, Ci ₃ -i- ₅ 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 . _1- 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, 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 an arbitrary 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.

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

Further suitable surfactants are polyhydroxy fatty acid amides of the formula (V), R ¹ I

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

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

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

R ¹ -0-R ²

R-CO-N- [Z] 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, wherein C ^ alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives thereof residue.

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

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, the machine dishwashing detergents according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. 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 ethoxylated alcohols include, for example, C _12th ₁₄ alcohols with 3 EO or 4 EO, n-alcohol with 7 EO, Cι ₃ .i ₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C _{_12-18} alcohols containing 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ . ₁₄ -alcohol with 3 EO and C ₂ . _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.

Particular preference is further claimed in particular those automatic dishwashing detergents which contain as surfactant (s) one or more tallow fatty alcohols with 20 to 30 EO in combination with a silicone defoamer. Nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-nonionic surfactants, are used with particular preference in the context of the present application.

Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, are particularly preferred.

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 highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.

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

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

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms _(C16. _2, o--alcohol), a C preferably ₁₈ 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.

With particular preference, therefore ethoxylated nonionic surfactants, which are from C ₆ . ₂₀ - monohydroxyalkanols or C ₆ . _20- alkylphenols or C ₁₆ . ₂₀ fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide were obtained per mole of alcohol used.

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. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants are included.

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

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

Another preferred dishwashing detergent according to the invention contains nonionic surfactant (s) of 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 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for 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. When the value of x is> 2, each R ³ may be different in the above formula. 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, 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 last-mentioned 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.

Summarizing the latter statements, dishwashing agents according to the invention are preferred, 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

included, are 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, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO-BIöcken are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Machine dishwashing agents according to the invention which are preferred as nonionic surfactant (s) of the general formula

R ¹ -O- (CH ₂ -CH ₂ -O) _w - (CH ₂ -CH-O) _x - (CH ₂ -CH ₂ -O) _y - (CH ₂ -CH-O) HIIR ² R ³

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently of one another are integers from 1 to 6.

The preferred nonionic surfactants of formula II can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in formula II above may vary depending on the origin of the alcohol. When native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually undisplayed, the linear radicals being selected from alcohols of native origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Regardless of the nature of the preparation according to the invention in Automated dishwashing agents according to the invention which are used in the compositions containing nonionic surfactants are preferred in which R in formula VII is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from - CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are suitable. Preferred automatic dishwashing agents are characterized in that R ² and R ³ are each a residue -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.

In summary, especially nonionic surfactants are preferred for use in the inventive compositions comprising a C ₈ - ₁₅ of L include alkyl having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed of L to 4 ethylene oxide followed to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x R ²

in which R ^{1 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably between 1 and have 5 hydroxy groups and are preferably further functionalized with an ether group, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2- ButyIrest stands, x for values between 1 and 40.

Automatic dishwashing detergents containing nonionic surfactant (s) of the general formula

R 0 [CH ₂ CH (R ³ ) 0] _x R ²

contains, in which R ^{1 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{2 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and are preferably further functionalized with an ether group, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical and x is between 1 and 40 are also preferred.

In a particularly preferred embodiment of the present application, R ³ in the abovementioned general formula is H. From the group of the resulting end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH ₂ O] _x R ²

In particular those nonionic surfactants are preferred in which R ^{1 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, R ^{2 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.

In particular, those end-capped poly (oxyalkylated) nonionic surfactants are preferred, which according to the formula R ¹ 0 [CH ₂ CH ₂ 0] _x CH ₂ CH (OH) R ²

in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical with 1 have up to 30 carbon atoms R ² , which is a monohydroxylated intermediate group - CH ₂ CH (OH) - adjacent. x in this formula stands for values between 1 and 90.

In particular, in the context of the present application, preference is given to those automatic dishwashing agents which contain nonionic surfactant (s) of the general formula

R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ²

which in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 carbon atoms R ² , which is adjacent to a monohydroxylated intermediate group -CH ₂ CH (OH) - and in which x stands for values between 1 and 90.

With particular preference, the present application claims such automatic dishwashing detergents which nonionic (s) surfactant (s) of the general formula

R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ²

containing, in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic Hydrocarbon radical R ² having 1 to 30 carbon atoms, preferably 2 to 22 carbon atoms, which is a monohydroxylated intermediate group - CH ₂ CH (OH) - adjacent and in which x stands for values between 40 and 80, preferably for values between 40 and 60 ,

The corresponding end-capped poly (oxyalkylated) nonionic surfactants of the above formula can be obtained, for example, by reacting a terminal epoxide of the formula R ² CH (O) CH ₂ with an ethoxylated alcohol of the formula R 1 CH ₂ CH ₂ CH ₂ O 3 CH ₂ CH ₂ OH.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (CH ₃ ) O] _y CH ₂ CH (OH) R ²

in which R ¹ and R ² independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with values for x from 15 to 32 and y of 0.5 and 1.5 are most preferred.

Automatic dishwashing detergents containing nonionic surfactant (s) of the general formula R ¹ 0 [CH ₂ CH ₂ O] _x [CH ₂ CHO] _y CH ₂ CH (OH) R ² IR ³

embedded image in which R ¹ and R ² independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , - CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ , but preferably is -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with values for x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred, within the scope of the present application are constituents of preferred agents according to the invention.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.

Of course, the dishwasher detergents according to the invention may contain the aforementioned nonionic surfactants not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,

In the context of this application, preference is given in particular to machine dishwashing agents comprising from 0.5 to 12% by weight of a surfactant system from a) at least one nonionic surfactant F of the general formula

R ^{1 is} -CH (OH) CH ₂ O- (AO) _w - (AO) _x - (A "O) _y - (A"'O) _z -R ² in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical; R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; - A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) - CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z for values between 0.5 and 25, where x, y and / or z can also be 0; and b) at least one nonionic surfactant G of the general formula

R ¹ -O- (AO) _w - (A'0) _x - (A "0) _y - (A '" 0) _z -R ² in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical; R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'" independently of one another are radicals from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH, -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ - CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z are values between 0.5 and 25 where y and / or z can also be 0; wherein the surfactant system comprises the nonionic surfactants F and G in a weight ratio of F: G between 1: 4 and 100: 1.

In the context of this application, particular preference is given to those automatic dishwashing detergents which comprise a surfactant system which comprises a nonionic surfactant F of the general formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in which R ¹ , R ^{2 represents} a saturated, linear hydrocarbon radical having 8 to 12 carbon atoms, preferably having 8 hydrocarbon radicals, and in which x is between 14 and 14 26, preferably represents values of 20 to 24, which with a nichionic surfactant G of the general formula

R ¹ -O- (CH ₂ -CH ₂ -O) _w - (CH ₂ -CH-O) _x - (CH ₂ -CH ₂ -O) _y - (CH ₂ -CH-O) _z -HIR ² R ³

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z are independently of one another integers from 1 to 6, is combined. In the context of this application, further preference is given to those automatic dishwashing detergents which have a surfactant system which comprises a nonionic surfactant F of the general 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 saturated, unbranched aliphatic hydrocarbon radical having 8 to 12 carbon atoms, preferably having 8 to 10 carbon atoms, further R ^{2 is} a saturated, linear hydrocarbon radical having 8 to 12 carbon atoms, preferably 8 Hydrocarbon radicals, and in which x stands for values of 1 or 2, while y stands for values between 18 and 24, preferably for values of 20 to 24, which with a nichionic surfactant G of the general formula

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z are independently of one another integers from 1 to 6, is combined.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C ₉ . _13- AlkylbenzoIsul- fonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are for example from C ₂ . ₁₈ mononefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C ₁₂ .ι ₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of sulfo fatty acids (ester sulfonates), for example the sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical having an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ - alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which can be obtained as commercial products of Shell Oil Company under the name DAN ^® , are suitable anionic surfactants.

Also, the sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 moles of ethylene oxide. ₂₁ -alcohols, such as 2-methyl-branched Cg- _T i-alcohols having an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ -ι ₈ -fatty alcohols having 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -ι ₈ fatty alcohol radicals or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the Al k (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or triethanolamine, available. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

If the anionic surfactants are part of automatic dishwasher detergents, their content, based on the total weight of the compositions, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Machine dishwashing detergents which do not contain anionic surfactants are particularly preferred.

Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants.

As cationic active substances, it is possible, for example, to use cationic compounds of the formulas III, IV or V:

R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (H

(CH ₂ ) _n -TR ²

R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -CH-CH ₂ (IV)

R ¹ TT

FT R

R '

R? 3_-MN ( ⁺ ) ^; - (CH ₂ ) _n -TR (V)

R ⁴

wherein each group R ^{1 is} independently selected from C 1-6 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 automatic dishwashing detergent, the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %. Automatic dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.

polymers

The group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.

"Cationic polymers" for the purposes of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride Copolymers, the quaternized polyvinyl alcohols or specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Poiyquaternium 27 polymers.

For the purposes of the present invention, "amphoteric polymers" further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

Washing or cleaning preparations, in particular automatic dishwashing detergents, characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ in which each R ¹ , R ² , R ³ , R is ^{4 is} independently selected from hydrogen, derivatized hydroxy, C1 to C30 linear or branched alkyl groups, aryl, aryl substituted C 1-0 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group having a positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one R, R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized nitrogen atom or at least one amino group having a positive charge, are particularly preferred in the context of the present application.

In the context of the present application, particularly preferred cationic or amphoteric polymers comprise as monomer unit a compound of the general formula (I)

R ¹ R ² R ⁴ IIIH ₂ C = C- (CH ₂ ) _x -N ⁺ - (CH ₂ ) _y -C = CH ₂ X ^- (I), IR ³

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X ^" represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula (VII) are selected from -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 , and - (CH ₂ CH ₂ -O) _n H.

For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the general formula (I) in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer units of the formula

H ₂ C = CH- (CH ₂ ) -N ⁺ (CH ₃ ) ₂ - (CH ₂ ) -CH = CH ₂ X ^"

in the case of X ^" = chloride also referred to as DADMAC (diallyldimethylammonium chloride). Further cationic or amphoteric polymers which are particularly preferred for the purposes of the present application comprise a monomer unit of the general formula (II)

R ¹ HC = CR ² -C (O) -NH- (CH ₂ ) _x -N ⁺ R ³ R ⁴ R ⁵ X ^" (II)

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another are a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -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 , and - (CH ₂ CH ₂ -O) _n H and x is an integer between 1 and 6.

In the context of the present application, very particular preference is given to polymers which have a cationic monomer unit of the general formula (II) in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

H ₂ C = C (CH ₃ ) -C (O) -NH- (CH ₂ ) _x -N ⁺ (CH ₃ ) ₃ X ^"

In the case of X- = chloride also referred to as MAPTAC (Methyacrylamidopropyl- trimethylammonium chloride).

Detergents or cleaning agents which are preferred according to the invention, in particular automatic dishwasher detergents, are characterized in that the polymer a) contains, as monomer units, diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups. Such anionic Monomereinheinheiten originate for example from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth) acrylic acids, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids. Preferred usable amphoteric polymers are selected from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the

Alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the

Alkylacrylamide / MethyImethacrylsäure / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / alkymethacrylate / Alkylaminoethylmethacrylat / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.

Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.

Also preferred are amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.

Particularly preferred amphoteric polymers come from the group of Methacrylamidoalkyl- triaikylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the

Methacrylic amidoaIkyltriaIkylammoniumchlorid / dimethyl (diallyI) ammonium chloride / methacrylic acid

Copolymers and the

MethacrylamidoalkyltrialkylammoniumchIorid / dimethyl (diallyl) ammonium chloride / alkyl

(meth) acrylic acid copolymers and their alkali metal and ammonium salts.

Particular preference is given to amphoteric polymers from the group of

Methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammoniumchIorid / acrylic acid

Copolymers, the Methacrylamidopropyltrimethylammoniumchlorid / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.

In a particularly preferred embodiment of the present invention, the polymers contained in the agents according to the invention have a molecular weight of 2000 μmol ^"1 or more in prefabricated form For the preparation of the polymers, the encapsulation of the polymers by means of water-soluble or water-dispersible coating agents is preferred by means of water-soluble or water-dispersible natural or synthetic polymers; the encapsulation of the polymers by means of water-insoluble, fusible coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C; the co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing- or cleaning-active substances, more preferably from the group of builders or cobuilders.

The inventively preferred compositions have a weight fraction of the aforementioned polymers between 0.01 and 10 wt .-%, each based on the total weight of the detergent or cleaner on. In the context of the present application, however, preference is given to those detergents or cleaners in which the weight fraction of the polymer a) is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing agent is.

Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.

Particularly preferred as Suldonsäuregruppen-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.

In the context of the present invention are as unsaturated monomer carboxylic acids of the formula

R ¹ (R ² ) C = C (R ³ ) COOH

in which R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with --NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is - COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the above formula are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) is preferred. In the sulfonic acid-containing monomers are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H

in which R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with --NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is - COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional Spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ HH ₂ C = C (CH ₃ ) -X-SO ₃ H H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacryamido-2-hydroxypropanesulfonic acid, allylsulfonic acid (X = CH ₂ in formula VIIa), methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen-1-sulfonic acid, styrenesulfonic acid,

Vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.

Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The content of the polymers used in monomers of group iii) is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of groups i) and ii). In summary, copolymers are made of

i) unsaturated carboxylic acids of the formula

R ¹ (R ² ) C = C (R ³ ) COOH

in the R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,

ii) sulfonic acid group-containing monomers of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H

in the R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers

particularly preferred.

Further particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid ii) one or more sulfonic acid group-containing monomers of the formulas: H ₂ C = CH-X-SO ₃ HH ₂ C = C (CH ₃ ) -X-SO ₃ H H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (0) -NH-CH (CH ₂ CH ₃ ) - iii) optionally further ionic or nonionic monomers.

The copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii). Particularly preferred polymers have certain structural units, which are described below.

For example, copolymers which are structural units of the formula are preferred

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

in which m and p are in each case an integer between 1 and 2000 and Y is a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. When the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred. The corresponding copolymers contain the structural units of the formula

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2000 and Y is a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y is -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH- CH (CH ₂ CH ₃ ) -, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, copolymers which are structural units of the formula

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p -

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, as preferred as copolymers, the structural units of the formula

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p -

where m and p are each an integer between 1 and 2,000, and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals containing from 1 to 24 carbon atoms, wherein: Y is -O - (CH ₂ ) _n - where n = 0 to 4, -Ö- (C ₆ H ₄ ) -, -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - ,

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are preferred and to inventively preferred copolymers, the structural units of the formula - [HOOCCH-CHCOOH] _rn - [CH ₂ -C (CH ₃ ) C (O) O-Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2000 and Y is a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ )- stands.

In summary, such copolymers are preferred according to the invention, the structural units of the formulas

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y -S0 ₃ H] _p - - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) O-Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer. In the case of terpolymers, particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred washing or cleaning compositions are characterized in that the copolymers have molecular weights of 2000 to 200,000 gmol ^"1 , preferably from 4000 to 25,000 gmol ^{" 1} and in particular from 5000 to 15,000 gmol ^"1 .

bleach

A preferred ingredient of the compositions of the invention is the bleaching agent. Among the compounds which serve as bleaches and deliver in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which yield H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. 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,

Diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyidiperoxybutane-1, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in the compositions according to the invention. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichlorocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or

Dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable. Compositions according to the invention, in particular automatic dishwashing agents, characterized in that it contains 1 to 35% by weight, preferably 2.5 to 30% by weight, more preferably 3.5 to 20% by weight and in particular 5 to 15% by weight. % Bleach, preferably sodium percarbonate, are particularly preferred in the context of the present application.

The active oxygen content of the compositions according to the invention, in particular automatic dishwashing agents, in each case based on the total weight of the dishwashing agent, is preferably between 0.4 and 10% by weight, more preferably between 0.5 and 8% by weight and in particular between 0.6 and 5% by weight. Particularly preferred dishwashing detergents have an active oxygen content above 0.3% by weight, preferably above 0.7% by weight, more preferably above 0.8% by weight and in particular above 1.0% by weight.

Bleach activators

Bleach activators are used, for example, in detergents or cleaners to achieve improved bleaching performance when cleaned 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 and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylene diamines, 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, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- diacetoxy-2,5-dihydrofuran. 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

R ² -N ⁽⁺⁾ - (CH ₂ ) -CN X ^(" >,

R ³

in the R ¹ for -H, -CH ₃ , a C ₂ . ₂₄ alkyl or alkenyl, a substituted C ₂ . _2- alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN, a Aikyl- or alkenylaryl radical having a C ^ alkyl group, or is a substituted alkyl or Alkenylarylrest having a C ^ 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 _a , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH ( OH) -CH ₃ , -CH ₂ - CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O ) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

Particularly preferred is a cationic nitrile of the formula

R ⁴

R ⁵ -N ⁽⁺⁾ - (CH ₂ ) -CN X (-)

R

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 , wherein R ⁴ additionally also -H may be 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 ^" , in which X ^{" is} an anion selected from the group chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-ToluolsuIfonat (tosylate) or xylenesulfonate is particularly preferred.

Other suitable bleach activators are 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 alkylene diamines, 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, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5- Diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA) and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular Pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose, and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

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

If, in addition to the nitrile quats, further bleach activators are to be used, preference is given to bleach activators from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (US Pat. N- or iso-NOBS), n-methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, each based on the total weight of the bleach activator-containing agents used.

Bleach-enhancing transition metal complexes, in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts. and / or complexes, more preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are in conventional amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total weight of the bleach activator-containing Medium, used. But in special cases, more bleach activator can be used.

Glass corrosion inhibitors

Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes. A preferred class of compounds that can be used to prevent glass corrosion are insoluble zinc salts.

Insoluble zinc salts in the context of this preferred embodiment are zinc salts which have a solubility of a maximum of 10 grams of zinc salt per liter of water at 20 ° C. Examples of particularly preferred insoluble zinc salts according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn ₂ (OH) ₂ CO ₃ ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (PO ₄ ) ₂ ), and zinc pyrophosphate (Zn ₂ (P ₂ 0 ₇ )).

The zinc compounds mentioned are preferably used 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 % By weight, based in each case on the entire glass corrosion inhibitor-containing agent. The exact content of the agent on the zinc salt or zinc salts is naturally dependent on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration should be in the funds.

Since the insoluble zinc salts remain largely unchanged during the Geschirreinigungsvorgangs, the particle size of the salts is a criterion to be observed, so that the salts do not adhere to glassware or machine parts. Here are preferred agents in which the insoluble zinc salts have a particle size below 1, 7 millimeters.

If the maximum particle size of the insoluble zinc salts is below 1.7 mm, insoluble residues in the dishwasher are not to be feared. Preferably, the insoluble zinc salt has an average particle size which is significantly below this value in order to further minimize the risk of insoluble residues, for example an average particle size of less than 250 μm. Again, this is even more true the less the zinc salt is soluble. In addition, the glass corrosion inhibiting effectiveness increases with decreasing particle size. For very poorly soluble zinc salts, the average particle size is preferably below 100 microns. For still less soluble salts, it may be even lower; For example, average particle sizes below 100 μm are preferred for the very poorly soluble zinc oxide.

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 all magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be used, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred.

The spectrum of the inventively preferred zinc salts of organic acids, preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / L, preferably below 10 mg / L, in particular have no solubility, to such Salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature). The first group of zinc salts includes, for example, the zinc nitrate, the zinc oleate and the zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

With particular preference is used as a glass corrosion inhibitor at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or Zinkeitrat used. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

In the context of the present invention, the content of cleaning agents to zinc salt is preferably between 0.1 to 5 wt .-%, preferably between 0.2 to 4 wt .-% and in particular between 0.4 to 3 wt .-%, or the content of zinc in oxidized form (calculated as Zn ²⁺ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight. -%, in each case based on the total weight of the glass corrosion inhibitor-containing agent.

corrosion inhibitors

Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants 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 the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. As examples of the preferred 3-amino-5-alkyl 1,2,4-triazoles may be mentioned: 5-propyl, -butyl, -pentyl, -heptyl, -octyl, -nonyl, -decyl, -nedecyl, -dodecyl-, Isononyl, -Versatic-10-alkyl, -phenyl, -p-tolyl, - (4-tert-butylphenyl) -, - (4-methoxyphenyl) -, - (2-, -3-, - 4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5-oxo-2-pyrrolidinyl) -, 3-amino-1, 2,4-triazole , In dishwashing agents, the alkylamino-1, 2,4-triazoles or their physiologically acceptable salts in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 wt .-%, particularly preferably 0.01 to 0.04 wt .-% used. Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid. Especially effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-alkyl-3-amino-1, 2,4-triazoles and mixtures of these substances.

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. 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 complexes, more 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, redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, wherein the metals preferably in one of the oxidation states II, III , IV, V or VI.

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

Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally additionally one or more of the abovementioned anions. The central atom is one of the above-mentioned metals in one of the abovementioned oxidation states. The Ligands are neutral molecules or anions that are monodentate or polydentate; The term "ligands" in the context of the invention is explained in more detail, for example, in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507". If, in a metal complex, the charge of the central atom and the charge of the ligand (s) are not zero, either one or more of the abovementioned anions or one or more cations, depending on whether there is a cationic or anionic charge surplus, e.g. As sodium, potassium, ammonium ions, for the charge balance. Suitable complexing agents are, for example, 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 MnS0 ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V ₂ 0 ₅ , V ₂ 0 ₄ , V0 ₂ , TiOS0 ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ and mixtures thereof. so that preferred automatic dishwasher detergents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group MnS0 ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxy-ethane

1, 1-diphosphonate], V ₂ 0 ₅ , V ₂ 0 ₄ , V0 ₂ , TiOS0 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. For example, this is from the S0 ₃ -Herstellung

(Contact method) known mixture of pentavalent and tetravalent vanadium (V Og, V0 ₂ , V ₂ 0) suitable, as well as the resulting by diluting a Ti (S0 ₄ ) ₂ solution titanyisulfate,

TiOS0 ₄ .

The inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, ie completely coated with a waterproof material which is readily soluble in the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage. Preferred coating materials, which are applied by known methods, such as Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids. The coating material which is solid at room temperature is applied in the molten state to the material to be coated, for example by adding finely divided material coating material is spun in continuous stream through a likewise continuously generated spray zone of the molten coating material. The melting point must be chosen so that the coating material easily dissolves or melts during the silver treatment. The melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C.

The metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total corrosion inhibitor-containing agent.

enzymes

To increase the washing or cleaning performance of detergents or cleaners enzymes can be used. 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 weight-percent based on active protein The protein concentration can be determined by known methods, for example the BCA method 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, Bagsveerd, 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, from β. amyloliquefaciens or from ß. stearothermophilus and their improved for use in detergents and cleaners further developments. The enzyme from ß. 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 of β. amyloliquefaciens is sold by Novozymes under the name BAN ^®, and derived variants from the α- amylase from ß. 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 cyclodextrin glucanotransferase (CGTase) from β. agaradherens (DSM 9948).

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® .

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting 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. From the company 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 sold by the company Meito Sangyo KK, Japan under the name Mentioned Lipase MY-30 ^® , Lipase OF ^® and Lipase PL ^® marketed enzymes, and the product Lumafast ^® from Genencor.

Furthermore, enzymes can be used, which are summarized by 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 from ß. subtilis .beta.-glucanase obtained is available under the name Cereflo ^® from Novozymes.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. 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 originate, for example, either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.

The purification of the relevant enzymes is preferably 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 enzymes can be used 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 may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Compositions according to the invention may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

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

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders are additionally capable of stabilizing a contained enzyme. Lower aliphatic alcohols, but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers. Also used are calcium salts, such as calcium acetate or calcium formate, and magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or 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 as enzyme stabilizers. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds also act as enzyme stabilizers.

Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation. A sulfur-containing reducing agent is, for example, sodium sulfite.

Preferably, combinatons of stabilizers are used, for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is enhanced by the combination with boric acid and / or boric acid derivatives and polyols and further enhanced by the additional use of divalent cations, such as calcium ions.

Preference is given to one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, in amounts of from 0.1 to 5% by weight, preferably from 0.2 to 4.5 and in particular from 0, 4 to 4 wt .-%, each based on the total enzyme-containing agent used.

disintegration aid

In order to facilitate the disintegration of preformed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times. According to Römpp (9th edition, Vol. 6, p. 4440) and Voigt "Textbook of Pharmaceutical Technology" (6th edition, 1987, pp. 182-184), excipients are understood to mean excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form. These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles decays. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.

Preferred disintegrating agents used in the present invention are cellulose-based disintegrating agents, so that preferred washing and cleaning compositions comprise such a cellulose-based disintegrating agent in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) π and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The cellulose used as disintegration aid is preferably not used in finely divided form, but before admixing with the premixes to be compressed in a coarser form converted, for example, granulated or compacted. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention.

As a further disintegrating agent based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 μm and can be compacted, for example, into granules having an average particle size of 200 μm.

Disintegration auxiliaries preferred in the context of the present invention, preferably a cellulose-based disintegration assistant, preferably in granular, cogranulated or compacted form, are present in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight. and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrating agent-containing agent.

Furthermore, according to the invention, gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries. The gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water. Usually, however, the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas. While a variety of systems are conceivable and executable that release, for example, nitrogen, oxygen or hydrogen, the effervescent system used in the detergent and cleaner compositions according to the invention can be selected both on the basis of economic and ecological considerations. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course you have to not the respective pure alkali metal carbonates or bicarbonates are used; Rather, mixtures of different carbonates and bicarbonates may be preferred.

Preference is given as effervescent 2 to 20 wt .-%, preferably 3 to 15 wt .-% and in particular 5 to 10 wt .-% of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and especially 3 to 10 wt. % of an acidifying agent, in each case based on the total weight of the agent used.

Acidifying agents that release carbon dioxide from the alkali salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates,

Alkali metal dihydrogen phosphates and other inorganic salts. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. However, it is also possible in particular to use the other solid mono-, oligo- and polycarboxylic acids. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group. Organic sulfonic acids such as sulfamic acid are also usable. A commercially available as an acidifier in the context of the present invention also preferably be used is Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and adipic acid ( at most 33% by weight).

Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred within the scope of the present invention.

fragrances

As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate,

Allyl cyclohexyl 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 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, α-lsomethylionon and Methylcedrylketon to 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 can also be natural fragrance mixtures as available from plant sources, eg, pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

The fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

dyes

Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the dye-containing agents to be treated substrates such as glass, ceramic or plastic tableware, not these to stain.

In addition to the components described in detail so far, the detergents and cleaners according to the invention may contain further ingredients which further improve the performance and / or aesthetic properties of these compositions. In the context of the present invention, preferred agents comprise one or more substances from the group of electrolytes, pH regulators, fluorescers, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides. Antioxidants, antistatic agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents and UV absorbers.

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 agents according to the invention is preferred.

In order to bring the pH of the agents according to the invention in the desired range, the use of pH adjusting agents may be indicated. Can be used here are all known acids or alkalis, unless their use of application or environmental Reasons or for reasons of consumer protection. Usually, the amount of these adjusting agents does not exceed 1% by weight of the total formulation.

Suitable foam inhibitors which can be used in the compositions according to the invention are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials. Suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.

Optical brighteners (so-called "whiteners") may be added to the compositions of the present invention to eliminate graying and yellowing of the treated fabrics, which will attract the fiber and cause lightening and fake bleaching by converting invisible ultraviolet radiation into visible longer wavelength light. wherein the absorbed from sunlight ultraviolet light is radiated as pale bluish fluorescence and pure for the yellow shade of the grayed or yellowed laundry White results. Suitable compounds originate, for example 2,2 ^{'-stiibendisulfonsäuren} from the substance classes of 4,4'-diamino ( flavonic), 4,4 ^{'-Distyryl-biphenyIen,} Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, benzisoxazole, and benzimidazole systems, and pyrene derivatives substituted by heterocycles.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches etc. Polyvinylpyrrolidone is also useful. Cellulosic ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, can also be used as graying inhibitors Methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.

Since textiie fabrics, especially from rayon, rayon, cotton and their blends, may tend to wrinkle, because the individual fibers against sagging, kinking. Pressing and squeezing transverse to the fiber direction are sensitive, the compositions of the invention may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, -alkylolestem, - alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

Antimicrobial agents can be used to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, and the compounds according to the invention can be completely dispensed with.

To prevent undesirable changes to the detergents and cleaners and / or the treated fabrics caused by exposure to oxygen and other oxidative processes, the compositions may contain anti-oxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

An increased wearing comfort can result from the additional use of antistatic agents which are additionally added to the compositions according to the invention. Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges. External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, wherein additionally a softening effect is achieved.

To care for the textiles and to improve the textile properties such as a softer "feel" (avivage) and reduced electrostatic charge (increased wearing comfort), the compositions according to the invention can contain fabric softeners "Esterquats", quaternary ammonium compounds having two hydrophobic groups, such as disteraryldimethylammonium chloride, which, however, due to its insufficient biodegradability, are increasingly being replaced by quaternary ammonium compounds which contain in their hydrophobic groups ester groups as breaking points for biodegradation.

To improve the Wasserabsorptioηsvermögens, the rewettability of the treated textiles and to ease the Bügeins the treated textiles, for example, silicone derivatives can be used in the inventive compositions. These additionally improve the rinsing out of the compositions according to the invention by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are fully or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds

Finally, the agents according to the invention may also contain UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds which are active by radiationless deactivation and derivatives of benzophenone having substituents in the 2- and / or 4-position. Furthermore, substituted benzotriazoles, in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in 2-StelIung, salicylates, organic Ni complexes and natural products such as umbelliferone and the body's own urocanic acid are suitable.

Claims

claims

1. A method for producing a dosing unit for detergents or cleaners, comprising the steps of a) providing a shaped body having at least one cavity; b) placing a first sheet material on the molding surface over the opening of the cavity; c) deep drawing the first sheet material into the cavity; d) filling a washing or cleaning active substance on the film material in the cavity.

2. The method according to claim 1, characterized in that it is in the shaped body to a tablet, a Kompaktat, an extrudate, an injection molded body, a casting or a composite of these moldings shaped body.

3. The method according to any one of claims 1 or 2, characterized in that the shaped body has a coating.

4. The method according to any one of claims 1 to 3, characterized in that the ratio of molding volume to in step d) filled into the cavity volume of the substance between 1: 1 and 20: 1, preferably between 3: 1 and 15: 1.

5. The method according to any one of claims 1 to 4, characterized in that the cavity of the shaped body prior to placing the first sheet material in step b) is partially filled with a washing or cleaning active substance.

6. The method according to claim 5, characterized in that it is the washing or cleaning-active substance is a washing or cleaning-active powder, granules or extrudate, which preferably one or more active ingredients from the group builders, enzymes, bleach, bleach activators, Bleaching catalysts, silver protectants or glass corrosion inhibitors.

7. The method according to any one of claims 1 to 6, characterized in that the first film material in step b) a water-soluble or water-dispersible film material, preferably a polymeric water-soluble or water-dispersible film material is used.

8. The method according to any one of claims 1 to 7, characterized in that the first sheet material in step c) is deep drawn into the cavity by a negative pressure is generated in the cavity of the shaped body.

9. The method according to claim 8, characterized in that the negative pressure in the cavity of the shaped body by applying a negative pressure to the part of the surface of the shaped body (outside the cavity) is generated, which is not covered by the film material from step b).

10. The method according to any one of claims 8 or 9, characterized in that the negative pressure in the cavity of the shaped body by applying a negative pressure to a hole or a notch takes place, which (s) the cavity with the part of the surface of the shaped body (outside the Cavity) not covered by the first sheet material of step b).

11. The method according to any one of claims 1 to 10, characterized in that the molded body prior to, simultaneously with or after thermoforming of the first sheet material in step c) is adhesively bonded to this first sheet material by a bond and / or a heat seal.

12. The method according to any one of claims 1 to 11, characterized in that in step d) a flowable washing or cleaning substance is introduced.

13. The method according to claim 12, characterized in that in step d) a liquid is introduced, which preferably contains one or more active substances from the group consisting of the group of nonionic surfactants and / or polymers and / or organic solvents.

14. The method according to any one of claims 1 to 13, characterized in that the cavity opening is sealed after step d) in a further step e).

15. The method according to claim 14, characterized in that the sealing of the cavity opening by placing a second film material on the cavity opening and subsequent heat sealing and / or ultrasonic sealing and / or high-frequency sealing takes place.

16. The method according to claim 15, characterized in that is adhesively connected by the heat seal and / or ultrasonic sealing and / or high frequency sealing of the molded body with the first sheet material and / or with the second sheet material.

17. The method according to any one of claims 1 to 16, characterized in that the first or second sheet material is severed in the course of the process, preferably after a sealing step by a mechanical and / or a thermal process to form a cutting line, wherein the cutting line preferably circulating runs on the surface of the molding.

18. A process for the preparation of a dosing unit for detergents or cleaners, comprising the steps of a) providing a ring tablet; b) introducing a molding tool through a first opening of the annular tablet breakthrough in this opening; c) placing a first, preferably water-soluble film material on the molding surface via the second opening of the opening; d) deep drawing of the first sheet material in the breakthrough of the ring tablet to form a receiving chamber which fills the breakthrough only partially; e) filling a washing or cleaning-active substance in the receiving chamber formed in d).

19. The method according to claim 18, characterized in that the mold has on its upper side a peripheral planar edge region.

20. The method according to any one of claims 18 or 19, characterized in that the filled receiving chamber is sealed in a further step f), wherein the sealing is preferably carried out by heat sealing of the first film material with the water-soluble film material in the planar edge region of the mold.

21. The method according to any one of claims 18 to 20, characterized in that the mold is removed after sealing in step f) in a further step g) from the first opening of the opening and in the previously occupied by the mold portion of the opening the ring tablet is filled with another washing or cleaning substance.

22. The method according to any one of claims 18 to 21, characterized in that the first opening of the opening in a further step g) is sealed.

23. Dosing unit for detergents or cleaners, comprising a molding having at least one cavity, a deep-drawn into the cavity to form a receiving chamber film material and a washing or cleaning substance on the film material in the cavity.

24. Dosing unit according to claim 23, characterized in that it is the tablet is a tablet, a compact, an extrudate, an injection molding or a casting.

25. Dosing unit according to one of claims 23 or 24, characterized in that it is the cavity to a trough or a breakthrough.

26. Dosing unit according to one of claims 23 or 24, characterized in that the cavity is additionally partially filled with a washing or cleaning active substance, preferably a substance from the group of builders, enzymes, bleach, bleach activators, bleach catalysts, silver protectants or glass corrosion inhibitors, which is not in the formed from the thermoformed sheet material receiving chamber.

27. Dosing unit according to one of claims 23 to 26, characterized in that the receiving chamber formed from the thermoformed sheet material with a flowable, preferably a liquid detergent or cleaning substance, more preferably with one or more active substance (s) from the group of Group of nonionic surfactants and / or polymers and / or organic solvents, is filled.

28. Dosing unit according to one of claims 23 to 27, characterized in that the filled with the washing or cleaning substance filled from the thermoformed sheet material receiving chamber is sealed.

29. Dosing unit according to claim 28, characterized in that the filled with the washing or cleaning substance filled from the thermoformed sheet material receiving chamber is sealed with another film material.

0. Dosing unit according to claim 23, characterized in that the shaped body with the film material thermoformed in the cavity and / or with the further film material used for sealing the thermoformed sheet material by means of a heat seal and / or ultrasonic sealing and / or high frequency sealing is attached.