EP1888736B1 - Detergent and cleanser dosing unit - Google Patents

Description

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 consumer's desire 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. In order to resolve this "conflict" between sufficient tablet hardness and short disintegration times, numerous technical solutions have been disclosed in the patent literature, reference being made by way of example to the use of so-called tablet disintegrating agents at this point. These disintegrants are added to the tablets in addition to the washing or cleaning-active substances, and as a rule have no washing or cleaning-active properties, and thus increase the complexity and the costs of these agents. A further disadvantage of the tabletting of mixtures of active substances, in particular mixtures containing washing or cleaning substances, is the inactivation of the active substances contained by the compaction pressure which occurs during tabletting. Inactivation of the active substances can also take place due to the increased contact area of the ingredients due to the tableting due to chemical reaction.

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 allow the preparation of liquid or powdered washing or Detergents, which are distinguished from the Kompaktaten by a better resolution and faster effectiveness.

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

Subject of the WO 01/83657 A2 (Procter & Gamble ) are, on the other hand, pouches containing, in a receiving chamber, two particulate solids each present in fixed regions and not intermixing.

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 gluing second individual chambers describes the international application WO 02/85736 A1 (Reckitt Benckiser ).

DE 10062582 A1 (Henkel ) describes filled detergent tablets with at least one cavity.

The object of the present application was to provide an optimized process for the preparation of detergents or cleaners, which enables the combined preparation of solid and liquid or flowable detergent compositions in separate areas of a compact metering unit. The final process product should be characterized by an attractive appearance. The resulting metering units should preferably be able to be marketed without additional packaging or with significantly reduced packaging costs. This object has been achieved by a method according to claim 1, wherein the water-soluble film materials used to formulate the contained flowable detergent or cleaner compositions are used simultaneously as packaging material for the entire dosing unit.

The spatial forms of the molding detergent and / or detergent premixes are advantageously adapted in their dimensions to the dispensing compartment of commercially available dishwashers or dishwashers, so that they can be metered directly into the corresponding compartments of the dispensing compartment. Alternatively, moldings according to the invention can of course also be used directly in the washing drum or the machine interior are dosed, optionally dosing can be used.

In the context of the present invention, moldings can be used in practically all designs which can be handled reasonably, for example in the form of a tablet, in bar or bar form, cube, cuboid and corresponding spatial element with flat side surfaces and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form of the actual tablet to compact cylinder pieces with a ratio of height to diameter above 1. Other preferred geometric shapes, which can be preferably produced by one of the molding methods mentioned below are in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, octagonal and octagonal prismatic, and rhombohedral shapes. Completely irregular ground surfaces such as arrow or animal shapes, trees, clouds etc. can also be realized in the shaping process. If the shaped body has corners and edges, these are preferably rounded off. As additional optical differentiation, an embodiment with rounded corners and chamfered edges is preferred.

Regardless of their geometric or structural structure, the single-phase or multiphase tablets used in the method according to the invention have a cavity. As already described for the shaped body, the shape of the cavity can also be freely selected, with moldings, in particular tablets, being preferred in which at least one cavity has a round or oval, one, two, three, four, five, six - Has seven, eight or polygonal opening area. The cavity may be bounded by concave or convex bottom surfaces and may assume cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disc, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, hexagonal, octagonal prismatic, and rhombohedral forms , Completely irregular cavity forms such as arrow or animal shapes, trees, clouds etc. can also be realized. As with the moldings, cavities with rounded corners and edges or with rounded corners and chamfered edges are preferred. In two-phase or multi-phase shaped bodies, the described cavity is not necessarily limited to the volume of space of one of the outer phases, but may in special embodiments also project beyond one or more phase boundaries into one or more further phases.

The size of the cavity compared to the entire molded body depends on the intended use of the molded body. Depending on whether and with which substances in which aggregate states the cavity is to be filled, the size of the cavity may vary. Regardless of the intended use, detergent tablets are preferred in which the volume ratio of basic tablets to cavity volumes in the range from 1: 1 to 100: 1, preferably from 2: 1 to 80: 1, particularly preferably from 3: 1 to 50: 1 and in particular from 4: 1 to 30: 1.

The absolute cavity volume is preferably between 1 and 100 ml, preferably between 1 and 50 ml, more preferably between 1 and 30 ml and in particular between 2 and 20 ml.

Similar statements can be made to the surface portions that make up the base molding or the cavity opening on the entire surface of the molding. Here, washing or cleaning agent tablets are preferred in which the surface of the cavity opening makes up 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface area of the tablet.

If, for example, the overall shaped article has dimensions of 20 × 20 × 40 mm and thus a total surface area of 40 cm ² , then cavities are preferred which have a surface area of 0.4 to 10 cm ² , preferably 0.8 to 8 cm ² , more preferably of 1.2 to 6 cm ² and in particular from 1.6 to 4 cm ² .

The cavity of the detergent tablets is limited by a bar surrounding the cavity. This web serves as a support surface for the water-soluble film applied in step b). Furthermore, as detailed below, with particular preference in the region of this web, an adhesive bond between the molded article and the water-soluble film applied in step b) and / or between the water-soluble film applied in step b) and in step d) generated. Since with increasing web width both the stability of the detergent or cleaning agent molding itself, as well as the stability of the aforementioned adhesive compounds is increased, such manufacturing methods are preferred in which the web has a width of at least 1.5 mm, preferably at least 2 mm and in particular between 2 and 10 mm.

For the production of the single-phase or multi-phase detergent tablets provided in step a), all molding methods known to those skilled in the art are suitable, in which case the tableting and / or extrusion and / or roll compaction and / or solidification and / or sintering and / or or crystallization, but especially tabletting.

The tableting of the washing and / or cleaning agent premix is, according to the above, a preferred shaping method in the context of the present invention. The tablets resulting from this process can be both single-phase and multi-phase, whereby the term multi-phase tablet includes, for example, the so-called multi-layer tablets (sandwich tablets), coated tablets (dry-coated tablets) or point tablets (bull-eye tablets).

In step b) of the method according to the invention, a water-soluble film is applied to the web extending around the cavity. The water-soluble film can be in the form of a prefabricated individual label for a single molded article or in the form of a film covering a plurality of moldings.

In a preferred process variant, the water-soluble film 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 mixtures thereof.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten."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%. , thus 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 it is preferred for the film material to comprise a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

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 ^® (Clariant). 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: description Degree of hydrolysis [%] Molecular weight [kDa] Melting point [° C] Airvol ^® 205 88 15-27 230 Vinex ^® 2019 88 15-27 170 Vinex ^® 2144 88 44 - 65 205 Vinex ^® 1025 99 15-27 170 Vinex ^® 2025 88 25 - 45 192 Gohsefimer ^® 5407 30 - 28 23,600 100 Gohsefimer ^® LL02 41 - 51 17,700 100

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, NM11Q, 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 under the name "SOLUBLON® ^®" from Syntana Handelsgesellschaft E. Harke GmbH & Co. available 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 at 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 offered 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, wherein the glucose units are linked α-glycosidically. 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. While the amylose forms long, helical, entangled chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4-position, the chain branched in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like structure 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. But also celluloses in which the hydroxy groups are functional Groups that are not bound by an oxygen atom have been replaced, can 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 hydroxypropylmethylcellulose (HPMC) having a degree of substitution (average number of methoxy groups per anhydroglucose unit of 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 is preferably transparent. For the purposes of this invention, transparency is to be understood as meaning that the permeability within the visible spectrum of the light (410 to 800 nm) is greater than 20%, preferably greater than 30%, very 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.

Preferred process variants are characterized in that at least one of the water-soluble films used in the process according to the invention has 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 has.

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 .-%.

The film applied in step b) not only covers the web but also the inner wall, more preferably the inner wall and the bottom of the cavity.

In a further preferred embodiment, the film applied in step b) has dimensions such that this film, after laying on the web and the optional covering of the inner wall, or the inner wall and the bottom of the cavity, over the web extending around the cavity protrudes and at least partially to the molding body limiting side walls and bottom surface can be created. The detergent or cleaning agent tablet is "beaten" in such a process variant in the second water-soluble film. In other words, in addition to the filled cavity and the webs extending around the cavity, the side walls of the washing or cleaning agent shaped body adjoining the web continue to be at least partly covered by this film.

The water-soluble film applied in step b) is preferably not applied solely to the web running around the cavity, but preferably also covers, at least partially, also the side surfaces of the molded body adjoining the web.

1. a) Bereitstellen eines Wasch- oder Reinigungsmittelformkörpers mit mindestens einer Kavität und einem um die Kavität umlaufenden Steg einer Breite von mindestens 1 mm;
2. b) Aufbringen eines ersten wasserlöslichen Films auf den um die Kavität umlaufenden Steg und Einformen des Films in die Kavität, wobei der in Schritt b) aufgebrachte Film die Innenwand, vorzugsweise die Innenwand und den Boden, der Kavität bedeckt;
3. c) Befüllen der Kavität;
4. d) Aufbringen eines zweiten wasserlöslichen Films über die befüllte Kavität, wobei der Wasch- oder Reinigungsmittelformkörper in den zweiten wasserlöslichen Film eingeschlagen wird und Versiegeln der in Schritt c) befüllten Kavität;

wobei der in Schritt b) aufgebrachte Film an dem Formkörper vor dem Befüllen der Kavität durch Einwirken eines Vakuums fixiert wird,
wobei der in Schritt b) aufgebrachte Film den Steg und die Seitenwand des Wasch- oder Reinigungsmittelformkörpers, bedeckt.A preferred object is therefore a production process for a washing or cleaning agent dosing unit, comprising the steps:

1. a) providing a washing or cleaning agent shaped body having at least one cavity and a circumferential around the cavity web of a width of at least 1 mm;
2. b) applying a first water-soluble film to the web circulating around the cavity and molding the film into the cavity, the film applied in step b) covering the inner wall, preferably the inner wall and the bottom, of the cavity;
3. c) filling the cavity;
4. d) applying a second water-soluble film over the filled cavity, wherein the detergent article is wrapped in the second water-soluble film and sealing the cavity filled in step c);

wherein the film applied in step b) is fixed to the shaped body before the filling of the cavity by the action of a vacuum,
wherein the film applied in step b) covers the web and the side wall of the detergent tablet.

1. a) Bereitstellen eines Wasch- oder Reinigungsmittelformkörpers mit mindestens einer Kavität und einem um die Kavität umlaufenden Steg einer Breite von mindestens 1 mm;
2. b) Aufbringen eines ersten wasserlöslichen Films auf den um die Kavität umlaufenden Steg und Einformen des Films in die Kavität, wobei der in Schritt b) aufgebrachte Film die Innenwand, vorzugsweise die Innenwand und den Boden, der Kavität bedeckt;
3. c) Befüllen der Kavität;
4. d) Aufbringen eines zweiten wasserlöslichen Films über die befüllte Kavität, wobei der Wasch- oder Reinigungsmittelformkörper in den zweiten wasserlöslichen Film eingeschlagen wird und Versiegeln der in Schritt c) befüllten Kavität;

wobei der in Schritt b) aufgebrachte Film an dem Formkörper vor dem Befüllen der Kavität durch Einwirken eines Vakuums fixiert wird,
wobei der in Schritt b) aufgebrachte Film den Steg sowie die Innenwand der Kavität, nicht jedoch deren Boden, sowie weiterhin die Seitenwand des Wasch- oder Reinigungsmittelformkörpers bedeckt.A further preferred subject matter of the present application is a production process for a washing or cleaning agent dosing unit, comprising the steps:

1. a) providing a washing or cleaning agent shaped body having at least one cavity and a circumferential around the cavity web of a width of at least 1 mm;
2. b) applying a first water-soluble film to the web circulating around the cavity and molding the film into the cavity, the film applied in step b) covering the inner wall, preferably the inner wall and the bottom, of the cavity;
3. c) filling the cavity;
4. d) applying a second water-soluble film over the filled cavity, wherein the detergent article is wrapped in the second water-soluble film and sealing the cavity filled in step c);

wherein the film applied in step b) is fixed to the shaped body before the filling of the cavity by the action of a vacuum,
wherein the film applied in step b) covers the web as well as the inner wall of the cavity, but not its bottom, and furthermore the side wall of the detergent tablet.

1. a) Bereitstellen eines Wasch- oder Reinigungsmittelformkörpers mit mindestens einer Kavität und einem um die Kavität umlaufenden Steg einer Breite von mindestens 1 mm;
2. b) Aufbringen eines ersten wasserlöslichen Films auf den um die Kavität umlaufenden Steg und Einformen des Films in die Kavität, wobei der in Schritt b) aufgebrachte Film die Innenwand, vorzugsweise die Innenwand und den Boden, der Kavität bedeckt ;
3. c) Befüllen der Kavität;
4. d) Aufbringen eines zweiten wasserlöslichen Films über die befüllte Kavität, wobei der Wasch- oder Reinigungsmittelformkörper in den zweiten wasserlöslichen Film eingeschlagen wird und Versiegeln der in Schritt c) befüllten Kavität;

wobei der in Schritt b) aufgebrachte Film an dem Formkörper vor dem Befüllen der Kavität durch Einwirken eines Vakuums fixiert wird,
wobei der in Schritt b) aufgebrachte Film den Steg sowie die Innenwand und den Boden der Kavität, sowie weiterhin die Seitenwand des Wasch- oder Reinigungsmittelformkörpers bedeckt.A preferred subject matter of the present application is furthermore a production process for a washing or cleaning agent dosing unit, comprising the steps:

1. a) providing a washing or cleaning agent shaped body having at least one cavity and a circumferential around the cavity web of a width of at least 1 mm;
2. b) applying a first water-soluble film to the web circulating around the cavity and molding the film into the cavity, the film applied in step b) covering the inner wall, preferably the inner wall and the bottom, of the cavity;
3. c) filling the cavity;
4. d) applying a second water-soluble film over the filled cavity, wherein the detergent article is wrapped in the second water-soluble film and sealing the cavity filled in step c);

wherein the film applied in step b) is fixed to the shaped body before the filling of the cavity by the action of a vacuum,
wherein the film applied in step b) covers the web as well as the inner wall and the bottom of the cavity as well as furthermore the side wall of the detergent tablet.

Since the water-soluble film applied in step b) is intended to cover not only the web, but also the inner wall, preferably the inner wall and the bottom, of the cavity, this film is molded into the cavity of the shaped body.

The molding of the water-soluble film is preferably carried out by a deep-drawing process.

In the context of the present application, the term "deep-drawing process" refers to processes in which a first film-like or film-like covering material is molded into the cavity after being introduced via a cavity by the action of pressure and / or vacuum. The pressure can be applied by a tool and / or by compressed air, which (s) presses the film into the cavity.

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 shaped body.

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.

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 the 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 in particular 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, in preferred process variants in step c), already form into the cavity of the molded article due to their own weight.

A vacuum is used to fix the water-soluble film in the course of one or more subsequent process steps on the molding. By fixing the film to the surface, the filling is facilitated and reduces the waste in the water-soluble film used. The film applied in step b) is fixed to the shaped body before the filling of the cavity by the action of a vacuum.

The film applied in step b) can be adhesively bonded to the shaped body before filling the cavity.

In step c) of the method according to the invention, the cavity is filled. Manufacturing process in which the cavity is filled with a flowable substance, are particularly preferred.

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 c). These solid or liquid flowable substances or substance mixtures are preferably applied to the Foil material poured 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. The term "liquid" therefore also comprises, in addition to liquid pure substances, also solutions, suspensions, emulsions or melts. Preference is given to using substances or mixtures of substances which are in the liquid state at 20 ° C. As a preferred constituent, the liquids contain at least one substance from the group of nonionic surfactants and / or polymers and / or organic solvents. The liquid may in turn have several phases.

With particular preference are as flowable substances or mixtures of substances liquids having a viscosity (Brookfield LVT-II at 20 rev / min and 20 ° C, spindle 3) of 500 to 100,000 mPas, preferably from 1000 to 50,000 mPas, more preferably from 1200 up to 10000 mPas and in particular from 1300 to 5000 mPas. Such viscous liquids or gels, in particular, have advantages in portioning over liquids which are highly or less viscous.

After filling the cavity in step c), a second water-soluble film is applied to the cavity in step d) and the filled cavity is sealed. The sealing preferably takes place by the formation of an adhesive bond between the water-soluble films applied in steps b) and d).

Manufacturing method, characterized in that the first and the second water-soluble film in step d) are adhesively bonded together, according to the invention are preferred.

With particular preference, the adhesive connections along a circumferential seal seam is realized. This sealed seam can be produced by a number of different procedures. 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, especially preferred are Such methods according to the invention, in which the water-soluble films applied in step b) and step d) are adhesively bonded by gluing and / or heat-sealing. Also in the case of heat sealing, a circumferential sealing seam, that is, a self-contained sealing seam is particularly preferred. A number of different tools and processes are available to the person skilled in the art for heat-sealing the water-soluble films.

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.

The adhesive connection of the two water-soluble films is preferably carried out in the region of the web surrounding the cavity. With particular preference is not only an adhesive connection between the first and the second water-soluble film, but at the same time also an adhesive connection between the first water-soluble film and the web of the molding achieved.

As already described above for the water-soluble film applied in step b), the water-soluble film applied in step d) also preferably serves not only to cover and seal the cavity filled in step c), but is also preferably used for washing - Or detergent tablets at least partially pack. For this purpose, a water-soluble film is applied to the filled cavity in step d), which protrudes due to its dimensions over the circumferential web around the cavity and at least partially applied to the molding body limiting side walls and bottom surface. The detergent or cleaning agent tablet is "beaten" in such a process variant in the second water-soluble film. In other words, in addition to the filled cavity and the webs extending around the cavity, the side walls of the washing or cleaning agent shaped body adjoining the web continue to be at least partly covered by this film.

Manufacturing method, characterized in that the washing or cleaning agent molded body is struck in step d) in the second water-soluble film, according to the invention are preferred.

1. a) Bereitstellen eines Wasch- oder Reinigungsmittelformkörpers mit mindestens einer Kavität und einem um die Kavität umlaufenden Steg einer Breite von mindestens 1 mm;
2. b) Aufbringen eines ersten wasserlöslichen Films auf den um die Kavität umlaufenden Steg und Einformen des Films in die Kavität, wobei der in Schritt b) aufgebrachte Film die Innenwand, vorzugsweise die Innenwand und den Boden, der Kavität bedeckt;
3. c) Befüllen der Kavität;
4. d) Aufbringen eines zweiten wasserlöslichen Films über die befüllte Kavität, wobei der Wasch- oder Reinigungsmittelformkörper in den zweiten wasserlöslichen Film eingeschlagen wird und Versiegeln der in Schritt c) befüllten Kavität;

wobei der in Schritt b) aufgebrachte Film an dem Formkörper vor dem Befüllen der Kavität durch Einwirken eines Vakuums fixiert wird,
wobei der Wasch- oder Reinigungsmittelformkörper in den zweiten wasserlöslichen Film eingeschlagen wird.A preferred object is therefore a production process for a washing or cleaning agent dosing unit, comprising the steps:

1. a) providing a washing or cleaning agent shaped body having at least one cavity and a circumferential around the cavity web of a width of at least 1 mm;
2. b) applying a first water-soluble film to the web circulating around the cavity and molding the film into the cavity, the film applied in step b) covering the inner wall, preferably the inner wall and the bottom, of the cavity;
3. c) filling the cavity;
4. d) applying a second water-soluble film over the filled cavity, wherein the detergent article is wrapped in the second water-soluble film and sealing the cavity filled in step c);

wherein the film applied in step b) is fixed to the shaped body before the filling of the cavity by the action of a vacuum,
wherein the detergent tablet is wrapped in the second water-soluble film.

1. a) Bereitstellen eines Wasch- oder Reinigungsmittelformkörpers mit mindestens einer Kavität und einem um die Kavität umlaufenden Steg einer Breite von mindestens 1 mm;
2. b) Aufbringen eines ersten wasserlöslichen Films auf den um die Kavität umlaufenden Steg und Einformen des Films in die Kavität; wobei
   • der in Schritt b) aufgebrachte Film den Steg sowie die Innenwand der Kavität, nicht jedoch deren Boden, sowie weiterhin die Seitenwand des Wasch- oder Reinigungsmittelformkörpers bedeckt; oder
   • der in Schritt b) aufgebrachte Film den Steg sowie die Innenwand und den Boden der Kavität, sowie weiterhin die Seitenwand des Wasch- oder Reinigungsmittelformkörpers bedeckt.
3. c) Befüllen der Kavität;
4. d) Aufbringen eines zweiten wasserlöslichen Films über die befüllte Kavität und Versiegeln der in Schritt c) befüllten Kavität,

wobei der in Schritt b) aufgebrachte Film an dem Formkörper vor dem Befüllen der Kavität durch Einwirkung eines Vakuums fixiert wird,
wobei der Wasch- oder Reinigungsmittelformkörper in den zweiten wasserlöslichen Film derart eingeschlagen wird, dass der wasserlösliche Film die Seitenwände des Formkörper bezogen auf deren Gesamtfläche zu mindestens 10 %, vorzugsweise mindestens 50 %, besonders bevorzugt zu mindestens 80 % und insbesondere vollständig bedeckt.This preferred method variant can be varied in various ways with regard to the above-mentioned embodiments. In particular, those variants of the method are preferred in which the water-soluble film applied in step b) of the method is applied to the side walls of the shaped body and covers it. A further preferred subject is therefore a production process for a washing or cleaning agent dosing unit, comprising the steps:

1. a) providing a washing or cleaning agent shaped body having at least one cavity and a circumferential around the cavity web of a width of at least 1 mm;
2. b) applying a first water-soluble film to the web surrounding the cavity and molding the film into the cavity; in which
   • the film applied in step b) covers the web and the inner wall of the cavity, but not the bottom thereof, and furthermore the side wall of the detergent tablet; or
   • the film applied in step b) covers the web as well as the inner wall and the bottom of the cavity, as well as furthermore the side wall of the washing or cleaning agent shaped body.
3. c) filling the cavity;
4. d) applying a second water-soluble film over the filled cavity and sealing the cavity filled in step c),

wherein the film applied in step b) is fixed to the shaped body prior to filling the cavity by the action of a vacuum,
wherein the washing or cleaning agent shaped body is wrapped in the second water-soluble film such that the water-soluble film covers the side walls of the shaped body with respect to their total area to at least 10%, preferably at least 50%, particularly preferably at least 80% and in particular completely.

Preference is given in particular to those processes in which the water-soluble film applied in step b) is applied to the washing or cleaning agent molding in such a way that it does not act alone the side surface but also the bottom surface, ie the side opposite the cavity opening side surface of the molding, covered. In these process variants, the water-soluble films applied in steps b) and d) overlap in the region of the side walls of the shaped body, whereby the storage stability of unpackaged shaped bodies as well as the tightness of the filled cavity can be decisively improved.

1. a) Beretistellen eines Wasch- oder Reinigungsmittelformkörpers mit mindestens einer Kavität und einem um die Kavität umlaufenden Steg einer Breite von mindestens 1 mm;
2. b) Aufbringen eines ersten wasserlöslichen Films auf den um die Kavität umlaufenden Steg und Einformen des Films in die Kavität; wobei
   • der in Schritt b) aufgebrachte Film den Steg und die Seitenwand des Wasch- oder Reinigungsmittelformkörpers, bedeckt; oder
   • der in Schritt b) aufgebrachte Film den Steg sowie die Innenwand der Kavität, nicht jedoch deren Boden, sowie weiterhin die Seitenwand des Wasch- oder Reinigungsmittelformkörpers bedeckt; oder
   • der in Schritt b) aufgebrachte Film den Steg sowie die Innenwand und den Boden der Kavität, sowie weiterhin die Seitenwand des Wasch- oder Reinigungsmittelformkörpers bedeckt;
3. c) Befüllen der Kavität;
4. d) Aufbringen eines zweiten wasserlöslichen Films über die befüllte Kavität und Versiegeln der in Schritt c) befüllten Kavität

wobei der in Schritt b) aufgebrachte Film an dem Formkörper vor dem Befüllen der Kavität durch Einwirkung eines Vakuums fixiert wird,
wobei der Wasch- oder Reinigungsmittelformkörper in den zweiten wasserlöslichen Film derart eingeschlagen wird, dass der wasserlösliche Film die sowie zusätzlich die Bodenfläche des Formkörpers vollständig bedeckt.A further preferred subject is therefore a production process for a washing or cleaning agent dosing unit, comprising the steps:

1. a) Beretistellen a detergent or cleaning product molding having at least one cavity and a circumferential around the cavity web of a width of at least 1 mm;
2. b) applying a first water-soluble film to the web surrounding the cavity and molding the film into the cavity; in which
   • the film applied in step b) covers the web and the side wall of the detergent tablet; or
   • the film applied in step b) covers the web and the inner wall of the cavity, but not the bottom thereof, and furthermore the side wall of the detergent tablet; or
   • the film applied in step b) covers the web as well as the inner wall and the bottom of the cavity, as well as further covering the side wall of the washing or cleaning agent shaped body;
3. c) filling the cavity;
4. d) applying a second water-soluble film over the filled cavity and sealing the cavity filled in step c)

wherein the film applied in step b) is fixed to the shaped body prior to filling the cavity by the action of a vacuum,
wherein the washing or cleaning agent shaped body is wrapped in the second water-soluble film such that the water-soluble film completely covers the and additionally the bottom surface of the shaped body.

In an alternative embodiment of the process according to the invention, in a further step e), a third water-soluble film can be applied to the bottom surface, ie the side of the molded article opposite the cavity opening of the molded article, in order to achieve complete encapsulation of the filled washing or cleaning agent shaped article.

1. a) Bereitstellen eines Wasch- oder Reinigungsmittelformkörpers mit mindestens einer Kavität und einem um die Kavität umlaufenden Steg einer Breite von mindestens 1 mm;
2. b) Aufbringen eines ersten wasserlöslichen Films auf den um die Kavität umlaufenden Steg und Einformen des Films in die Kavität; wobei
   1. i. der in Schritt b) aufgebrachte Film den Steg sowie die Innenwand der Kavität, nicht jedoch deren Boden, sowie weiterhin die Seitenwand des Wasch- oder Reinigungsmittelformkörpers bedeckt; oder
   2. ii. der in Schritt b) aufgebrachte Film den Steg sowie die Innenwand und den Boden der Kavität, sowie weiterhin die Seitenwand des Wasch- oder Reinigungsmittelformkörpers bedeckt.
3. c) Befüllen der Kavität;
4. d) Aufbringen eines zweiten wasserlöslichen Films über die befüllte Kavität und Versiegeln der in Schritt c) befüllten Kavität
5. e) Aufbringen einer dritten wasserlöslichen Folie auf die Bodenfläche des Formkörpers, wobei der in Schritt b) aufgebrachte Film an dem Formkörper vor dem Befüllen der Kavität durch Einwirkung eines Vakuums fixiert wird.

Preference is therefore furthermore given to production processes for a washing or cleaning agent dosing unit, comprising the steps:

1. a) providing a washing or cleaning agent shaped body having at least one cavity and a circumferential around the cavity web of a width of at least 1 mm;
2. b) applying a first water-soluble film to the web surrounding the cavity and molding the film into the cavity; in which
   1. i. the film applied in step b) covers the web and the inner wall of the cavity, but not the bottom thereof, and furthermore the side wall of the detergent tablet; or
   2. ii. the film applied in step b) covers the web as well as the inner wall and the bottom of the cavity, as well as furthermore the side wall of the washing or cleaning agent shaped body.
3. c) filling the cavity;
4. d) applying a second water-soluble film over the filled cavity and sealing the cavity filled in step c)
5. e) applying a third water-soluble film to the bottom surface of the shaped body, wherein the film applied in step b) is fixed to the shaped body before filling the cavity by the action of a vacuum.

In a preferred variant of this method, the third water-soluble film applied in step e) is dimensioned so that these films not only the bottom surface of the molded body but also the side wall of the molded body based on the total area to at least 10%, preferably at least 50%, especially preferably at least 80% and in particular completely covered. By this procedure, in turn, an overlap of water-soluble films in the region of the side walls of the molded body is achieved, which in turn improves the storage stability and the tightness of the filled cavity.

Particularly preferred are those process variants in which the third water-soluble film applied in step e) is adhesively bonded to the first and / or second water-soluble film, preferably to form a water-soluble film layer completely enveloping the washing or cleaning agent shaped article. To achieve the adhesive connection preferably the means and methods described above are used.

The four- or five-stage processes described above are suitable for producing detergent tablets which are completely wrapped or packaged in water-soluble films. As described, not only the storage stability but also the tightness of the filled cavity could be increased by this packaging. At the same time, however, the washing or cleaning agent tablets are distinguished by increasing disintegration times as the proportion of packaging in the aqueous liquor increases. These disintegration times could in turn be reduced by such process variants, in which a complete coating of the shaped body, for example by appropriate dimensioning of the water-soluble films used and / or by using perforated water-soluble films was avoided.

Production processes according to the invention are therefore particularly preferred in which the applied water-soluble film is designed in such a way and / or applied to the washing or cleaning agent shaped body that no water-soluble film layer completely enveloping the washing or cleaning agent shaped body is obtained.

The compositions according to the invention or the compositions prepared by the process according to the invention described above contain washing and cleaning substances, preferably washing and cleaning substances from the group of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids , Fragrances and perfume carriers. These preferred ingredients will be described in more detail below.

The builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

Preference is given to using crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layer-form silicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, makatite).

Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O, in which x is 2. In particular, both .beta.- and δ-sodium Na ₂ Si ₂ O ₅ · y H ₂ O, and further in particular Na-SKS-5 (α-Na ₂ Si ₂ O _5), Na-SKS-7 (.beta.-Na ₂ Si ₂ O _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3 H ₂ O, kanemite), Na-SKS-11 ( t-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

Detergents or cleaning agents preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} .yH ₂ O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular of 0.4 to 10 wt .-%, each based on the total weight of these agents.

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 preferably delayed release and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying be. In the context of this invention, the term "amorphous" is understood to mean 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 , cause.

Alternatively or in combination with the abovementioned amorphous sodium silicates, X-ray-amorphous silicates are used whose silicate particles give washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such X-ray amorphous silicates also have a dissolution delay compared to 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 alkali metal disilicates, be present in detergents or cleaners in amounts of from 3 to 60% by weight, preferably from 8 to 50 Wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the washing or cleaning agent, are included.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference of pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate) in the washing and cleaning industry have the greatest importance.

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 (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 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.

Technically particularly important phosphates are the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate). The sodium potassium tripolyphosphates are also preferably used according to the invention.

If phosphates are used as washing or cleaning substances in detergents or cleaning agents in the context of the present application, preferred agents contain 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 and in particular from 20 to 70% by weight. %, in each case based on the weight of the washing or cleaning agent.

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 cited alkali metal silicates, 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 cleaning agent 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. Particular preference is given to compositions which, based on the weight of the washing or cleaning agent, contain less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate ( e) and / or bicarbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate.

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

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or 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. The free acids have beside Their builder effect also typically 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 cleaning agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.

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 salts of acrylic acid and maleic acid as monomers and vinyl alcohol or vinyl alcohol derivatives or containing as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

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

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

Particularly preferred as sulfonic acid-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, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -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-SO 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, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -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 ) -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO 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 (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred sulfonic acid-containing monomers are 1-acrylamido-1-propane-sulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3 -Sulfopropylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.

Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds. The content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH and monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H.

• i) ungesättigten Carbonsäuren der Formel R¹(R²)C=C(R³)COOH in der R¹ bis R³ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• ii) Sulfonsäuregruppen-haltigen Monomeren der Formel R⁵(R⁶)C=C(R⁷)-X-SO₃H in der R⁵ bis R⁷ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und - C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren besonders bevorzugt.

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, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above, or -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-SO 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 with 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 with 1 to 12 carbon atoms, and X is an optionally present 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 are particularly preferred.

• i) einer oder mehreren ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln:
  
          H₂C=CH-X-SO₃H
  
          H₂C=C(CH₃)-X-SO₃H
  
          HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H,
  
  in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, - CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren.

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 H
  
  H ₂ C = C (CH ₃ ) -X-SO ₃ H
  
  HO 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 (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -
• iii) optionally further ionogenic 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 each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic 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 - o -the -NH-CH (CH ₂ CH ₃ ) - is, 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 selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein 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.

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 each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic 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 ) -, are particularly preferred, just 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 -

in which 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 substituted aromatic 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 ) - are, are preferred.

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 ) - stands, are preferred. Also preferred according to the invention are copolymers which contain structural units of the formula

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

in which 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 substituted aromatic 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 ) - are, are preferred.

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-SO 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) OY-SO ₄ H] _p -

in which 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 substituted aromatic hydrocarbon radicals having from 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 ) - are, are preferred.

In the polymers, the sulfonic acid groups may be wholly or partly in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially 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 agents are characterized in that the copolymers have molar masses 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 .

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.

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.

The group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

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

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

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

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

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

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

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can 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, washing or cleaning agents, in particular automatic dishwashing detergents, contain 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 are native Origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol is preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The indicated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Particular preference is therefore given to ethoxylated nonionic surfactants consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

With particular preference further combinations of one or more tallow fatty alcohols with 20 to 30 EO and silicone defoamers are used.

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, is / 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 nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa · s, preferably above 35 Pa · s and in particular above 40 Pa · s. Also, nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.

Nonionic surfactants from the group of alkoxylated alcohols, more preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also used with particular preference.

The nonionic surfactant solid at room temperature preferably 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 content of such nonionic surfactant molecules preferably makes up 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 Make up surfactants.

Preferably used surfactants come from the groups of 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.

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

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.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 blocks 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. Here are nichionic surfactants 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 independently stand for integers from 1 to 6.

The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula 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 unbranched, the linear radicals being selected from alcohols of natural 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. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants in which R ¹ in the above formula 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. Preferably, nonionic surfactants of the above formula in which R ² and R ³ are a radical -CH _3, w and x independently of one another for values of 3 or 4 and y and z are independently values of 1 or second

In summary, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 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.

Surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A '"O) _y - (A'" O) _z -R ² , in which R ¹ and R ^{2 is} independently a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 -alkyl or -alkenyl radical; 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 ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _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 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, wherein x stands for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Particularly preferred are surfactants 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 with 4 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.

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 (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another is 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 R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

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 x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

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

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

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 aforementioned nonionic surfactants can be used 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 ,

If anionic surfactants are used as constituents 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.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.As cationic active substances, for example, cationic compounds of the following formulas can be used:

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

In automatic dishwashing detergents, 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.

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" in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers come from the groups of 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 dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

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.

Preferred washing or cleaning agents, in particular preferred automatic dishwashing agents, are 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 ⁴ radical ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy, C _1-30 linear or branched alkyl groups, aryl, aryl substituted C _1-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups 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 in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one Aminogr uppe with a positive charge is.

bei der R¹ und R⁴ unabhängig voneinander für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen steht; R² und R³ unabhängig voneinander für eine Alkyl-, Hydroxyalkyl-, oder Aminoalkylgruppe stehen, in denen der Alkylrest linear oder verzweigt ist und zwischen 1 und 6 Kohlenstoffatomen aufweist, wobei es sich vorzugsweise um eine Methylgruppe handelt; x und y unabhängig voneinander für ganze Zahlen zwischen 1 und 3 stehen. X^□ repräsentiert ein Gegenion, vorzugsweise ein Gegenion aus der Gruppe Chlorid, Bromid, Iodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen.In the context of the present application, particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula

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), cumenesulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula 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.

Very particular preference is given to polymers which have a cationic monomer unit of the above general formula 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 unit 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, they are also referred to as DADMAC (diallyldimethylammonium chloride).

Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

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

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.

For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula 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 (methylacrylamidopropyltrimethylammonium chloride).

According to the invention, preference is given to using polymers which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units are derived, for example, from the group of the linear or branched, saturated or unsaturated carboxylates, the linear or branched, saturated or unsaturated phosphonates, the linear or branched, saturated or unsaturated sulfates or the linear or branched, saturated or unsaturated Sulfonates. Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and their derivatives, the allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.

Preferred employable amphoteric polymers are 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 / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Preferred zwitterionic polymers are 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 are from the group of the Methacrylamidoalkyl-trialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the Methacrylamidoalkyltrialkylammoniumchlorid / 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 the methacrylamidopropyltrimethylammonium chloride / dimethyl (diaflyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth ) -acrylic acid copolymers and their alkali metal and ammonium salts.

• die Verkapselung der Polymere mittels wasserlöslicher oder wasserdispergierbarer Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• die Verkapselung der Polymere mittels wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30°C;
• die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder (Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers is suitable inter alia

• the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• the encapsulation of the polymers by means of water-insoluble, meltable 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.

Detergents or cleaning agents contain the aforementioned cationic and / or amphoteric polymers preferably in amounts of between 0.01 and 10 wt .-%, each based on the total weight of the detergent or cleaning agent. In the context of the present application, however, preference is given to those detergents or cleaners in which the weight fraction of the cationic and / or amphoteric polymers 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.

The bleaching agents are a particularly preferred washing or cleaning substance. Among the compounds serving as bleaches 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 H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.

Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl. 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 [phthaliminoperoxyhexanoic acid (PAP)] , o-Carboxybenzamidoperoxycaproic acid, N-Nonenylamidoperadipic Acid and N-Nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-Diperoxycarboxylic acid, 1,9-Diperoxyazelaic acid, Diperocysebacic acid, Diperoxybrassic acid, the Diperoxyphthalic acids, 2-Decyldiperoxybutan-1,4- diacid, N, N-terephthaloyl-di (6-aminopercapronate).

As a bleaching agent and chlorine or bromine releasing substances can be used. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable. According to the invention, washing or cleaning agents, in particular automatic dishwashing agents, are preferred which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight % Bleach, preferably sodium percarbonate.

The active oxygen content of the washing or cleaning agents, in particular the automatic dishwashing agents, in each case based on the total weight of the composition, preferably between 0.4 and 10 wt .-%, particularly preferably between 0.5 and 8 wt .-% and in particular between 0.6 and 5 wt .-%. Particularly preferred compositions have an active oxygen content above 0.3 wt .-%, preferably above 0.7 wt .-%, more preferably above 0.8 wt .-% and in particular above 1.0 wt .-% to.

Bleach activators are used in laundry detergents or cleaners, for example, to achieve an improved bleaching effect 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 number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and also acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl-fructose, tetraacetyl-xylose and octaacetyl lactose as well as 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.

These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.

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

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

in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^-, oder (HOCH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^- besonders bevorzugt sind, wobei aus der Gruppe dieser Substanzen wiederum das kationische Nitril der Formel (CH₃)₃N⁽⁺⁾CH₂-CN X^-, in welcher X^- für ein Anion steht, das aus der Gruppe Chlorid, Bromid, Iodid, Hydrogensulfat, Methosulfat, p-Toluolsulfonat (Tosylat) oder Xylolsulfonat ausgewählt ist, besonders bevorzugt wird.Particularly preferred is a cationic nitrile of the formula

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , 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 (HOCH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{- are} particularly preferred, wherein from the group of these substances turn the cationic nitrile of Formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- in which X ^{- represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate , is particularly preferred.

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.

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, particularly preferably the cobalt (ammine) Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are described 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 .-%, in each case based on the total weight of the bleach activator-containing agents used. In special cases, however, more bleach activator can also be used.

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 or cleaning agents, which are preferably used accordingly. Detergents or cleaners contain enzymes preferably in total amounts of 1 × 10 × ⁶ to 5% by weight, 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 of these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae, as well as the further developments of the aforementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

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. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens . It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii .

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.

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. 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 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 several 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. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

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% by weight, and in particular from 0.4 to 4 wt .-%, each based on the total enzyme-containing agent used.

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 zinc salts and magnesium and zinc complexes.

The spectrum of the invention preferred zinc salts, preferably organic acids, particularly 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 below 0.01 have mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C. water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

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

In the context of the present invention, the content of zinc salt in detergents or cleaners is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight. , or the content of zinc in oxidized form (calculated as Zn ²⁺ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 0, 2 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.

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 triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. According to the invention, preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, these substances being particularly preferably used in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 Wt .-%, particularly preferably 0.01 to 0.04 wt .-% are 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 and succinic acid. All 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-alkyl-3-amino-1,2,4-triazoles and mixtures thereof are particularly effective 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, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds used. Also, salt and complex inorganic compounds, such as salts 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 the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can 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 are present.

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

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ , and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) _{3 are used} with particular preference ,

The inorganic redox-active substances, in particular metal salts or metal complexes, are preferably coated, ie completely coated with a water-tight 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 processes, such as, for example, sandwik melt coating processes 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 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 agent.

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. By tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients.

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 disintegrates. 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 are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants 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. % contain. 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 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. However, celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be classified as cellulose derivatives deploy. 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 a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. 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.

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.

Preferred disintegration aids, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are 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 here, which release, for example, nitrogen, oxygen or hydrogen, the bubble system used in detergents and cleaners can be selected both on the basis of economic and environmental considerations. Preferred shower systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

As Acidifizierungsmittel which release carbon dioxide from the alkali metal salts in aqueous solution, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil.

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

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 substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic tableware do not stain them.

When choosing the colorant, it must be taken into account that the colorants have a high storage stability and insensitivity to light. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 ^-2 to 10 ^-3 % by weight are typically selected. By contrast, in the case of the particularly preferred, but less readily water-soluble, pigment dyes due to their brilliance, the suitable concentration of the colorant in detergents or cleaners is typically about 10 ^-3 to 10 ^-4 % by weight.

Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable are, for example, anionic colorants, e.g. anionic nitrosofarads.

In addition to the components described in detail so far, the detergents or cleaners can contain further ingredients which further improve the performance and / or aesthetic properties of these compositions. Preferred agents contain one or more of the group of electrolytes, pH adjusters, 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 , Phobic 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 washing or cleaning agents is preferred.

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

Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials. In the context of the present application preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear polymeric silicones, which are constructed according to the scheme (R ₂ SiO) _x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1000 and 150,000 and viscosities between 10 and 1,000,000 mPa · s.

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") can be added to the detergents or cleaners to eliminate graying and yellowing of the treated textiles. These fabrics impinge on the fiber and cause whitening and bleaching by transforming invisible ultraviolet radiation into visible longer wavelength light, emitting ultraviolet light absorbed from the sunlight as faint bluish fluorescence, and pure yellow with the yellowed or yellowed wash White results. Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives.

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. For this purpose, water-soluble colloids are usually suitable organic nature, for example, the water-soluble salts 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. Also usable as graying inhibitors are cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.

Since textile fabrics, in particular of rayon, rayon, cotton and their mixtures, can tend to wrinkle because the individual fibers are sensitive to bending, buckling, pressing and crushing transversely to the fiber direction, synthetic anti-crease agents can be used. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

Phobic and impregnation processes are used to furnish textiles with substances that prevent the deposition of dirt or facilitate its leaching ability. Preferred repellents and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum u. Zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical. Antistatic agents may also be included. The antisoiling equipment with repellents and impregnating agents is often classified as an easy-care finish. The penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension. A further field of application of repellents and impregnating agents is the water-repellent finishing of textiles, tents, tarpaulins, leather, etc., in which, in contrast to waterproofing, the fabric pores are not closed, so the fabric remains breathable (hydrophobing). The water repellents used for hydrophobizing coat textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable water repellents are, for example, paraffins, waxes, metal soaps, etc. with additions of aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, tin-organic compounds and glutaric dialdehyde and perfluorinated compounds. The hydrophobized materials do not feel greasy; nevertheless, similar to greasy substances, water droplets emit from them without moistening. For example, silicone-impregnated textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juices and the like are easier to remove.

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, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, although it is entirely possible to do without these compounds.

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.

Increased comfort may result from the additional use of antistatic agents. 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.

Silicone derivatives can be used to improve water absorbency, rewettability of the treated fabrics and to facilitate ironing of the treated fabrics. These additionally improve the rinsing out of detergents or cleaning agents 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 completely 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. Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which comprise, for example, polyethylene glycols and the polyalkylene oxide-modified dimethylpolysiloxanes.

Finally, according to the invention, it is also possible to use UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers. 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. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, 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.

Protein hydrolyzates are due to their fiber-care effect further in the context of the present invention preferred active substances from the field of detergents and cleaners. Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins). According to the invention, protein hydrolysates of both vegetable and animal origin can be used. Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts. Preferred according to the invention is the use of protein hydrolysates of plant origin, e.g. Soy, almonds, rice, pea, potato and wheat protein hydrolysates. Although the use of the protein hydrolysates is preferred as such, amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyrroglutamic acid, may also be used in their place. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products.

Claims (10)

1. Manufacturing method for a detergent or cleaning agent dosing unit, comprising the following steps:

   a) providing a detergent or cleaning agent molded body having at least one cavity and a web, surrounding the cavity, which has a width of at least 1 mm;

   b) applying a first water-soluble film to the web surrounding the cavity, and molding the film into the cavity, wherein the film applied in step b) covers the inner wall, preferably the inner wall and the base, of the cavity;

   c) filling the cavity;

   d) applying a second water-soluble film over the filled cavity and sealing the cavity filled in step c),
   characterized in that the film applied in step b) is fixed to the molded body by action of a vacuum prior to filling the cavity.
2. Manufacturing method according to Claim 1, characterized in that the web has a width of at least 1.5 mm, preferably at least 2 mm, and in particular between 2 and 10 mm.
3. Manufacturing method according to one of Claims 1 or 2, characterized in that the film applied in step b) covers the web and the side wall of the detergent or cleaning agent molded body.
4. Manufacturing method according to one of Claims 1 or 2, characterized in that the film applied in step b) covers the web and the inner wall of the cavity, preferably the inner wall and the base of the cavity, and in addition covers the side wall of the detergent or cleaning agent molded body.
5. Manufacturing method according to one of Claims 1 to 4, characterized in that the cavity is filled with a flowable substance.
6. Manufacturing method according to one of Claims 1 to 5, characterized in that the first and the second water-soluble film are adhesively bonded to one another in step d).
7. Manufacturing method according to one of Claims 1 to 6, characterized in that the detergent or cleaning agent molded body is wrapped in the second water-soluble film in step d).
8. Manufacturing method according to one of Claims 1 to 7, characterized in that in a further step e), a third water-soluble film is applied to the side of the molded body opposite from the cavity opening of the molded body.
9. Manufacturing method according to Claim 8, characterized in that the third water-soluble film applied in step e) is adhesively bonded to the first and/or second water-soluble film, preferably forming a water-soluble film layer which completely envelops the detergent or cleaning agent molded body.
10. Manufacturing method according to Claims 1 to 9, characterized in that the applied water-soluble film is designed and/or placed on the detergent or cleaning agent molded body in such a way that no water-soluble film layer which completely envelops the detergent or cleaning agent molded body is obtained.