EP1740690A1

EP1740690A1 - Method for producing detergent or cleaning products

Info

Publication number: EP1740690A1
Application number: EP05733100A
Authority: EP
Inventors: Thomas Holderbaum; Arno DÜFFELS
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2004-04-28
Filing date: 2005-04-20
Publication date: 2007-01-10
Anticipated expiration: 2025-04-20
Also published as: US20080248989A1; JP2007534808A; DE102004020720A1; EP1740690B1; WO2005105975A1; PL1740690T5; PL1740690T3; EP1740690B2

Abstract

The invention concerns detergent or cleaning products comprising at least one detergent or cleaning moulded body and at least one water-soluble or water-dispersible film-like material, and are characterized in that the detergent or cleaning moulded body and the film-like material are assembled together by adhesion through a heat-seal. The inventive products are characterized by the stable seals and are suitable for combined preparation of solid and liquid or flowable detergent or cleaning compositions in separate areas of a compact metering unit.

Description

Process for the production of washing or cleaning agents

The present invention is in the field of detergents or cleaning agents. In particular, the present invention relates to a method for producing detergents or cleaning agents, in particular dosing units of detergents or cleaning agents.

Detergents or cleaning agents are now available to consumers in a wide variety of forms. In addition to washing powders and granules, this range also includes cleaning agent concentrates in the form of extruded or tableted compositions. These solid, concentrated or compacted offer forms are characterized by a reduced volume per dosing unit and thus lower the costs for packaging and transport. The detergent or cleaning agent tablets in particular also meet the consumer's desire for simple dosing. The corresponding agents are described in detail in the prior art. In addition to the advantages mentioned, compacted washing or cleaning agents also have a number of disadvantages. In particular, tableted forms of offer are often characterized by a delayed disintegration and thus a delayed release of their ingredients due to their high compression. 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 here to the use of so-called tablet disintegrants. This disintegration accelerator is added to the tablets in addition to the washing or cleaning substances , which generally have no washing or cleaning-active properties, and thus increase the complexity and the cost of these agents. Another disadvantage of tableting active substance mixtures, in particular mixtures containing washing or cleaning active substances, is the inactivation of the contents Inactive substances can also be inactivated due to the increased contact areas of the ingredients due to the chemical reaction e rfolgen.

As an alternative to the particulate or compact detergents or cleaning agents described above, solid or liquid detergents or cleaning agents which have water-soluble or water-dispersible packaging have been increasingly described in recent years. Like the tablets, these agents are characterized by a simplified dosage, since they can be dosed together with the outer packaging in the washing machine or dishwasher, but on the other hand they also enable the packaging of liquid or powder detergents or cleaning agents, which distinguish themselves from the compact specimens by better resolution and faster effectiveness.

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

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

In addition to the packaging, which has only one receiving chamber, the prior art also disclosed forms of offer which comprise more than one receiving chamber or more than one form of confection.

The subject of European application EP 1 256 623 A1 (Procter & Gamble) is a kit consisting of at least two bags with different compositions and different looks. The bags are separate from each other and not as a compact single product.

The international application WO 02/85736 A1 (Reckitt Benckiser) describes a method for producing multi-chamber bags by gluing two individual chambers.

The object of the present application was to provide a process for the production of detergents or cleaning agents with water-soluble or water-dispersible packaging, by means of which the amounts of the water-soluble or water-dispersible material used can be minimized, the water-soluble or water-dispersible packaging also being used without the use of conventional adhesives or Adhesion promoter should have stable sealed seams. The resulting process products should also enable the joint assembly of solid and liquid or flowable detergent or cleaning agent compositions in separate areas of a compact dosing unit. The end product of the process should be characterized by an attractive appearance.

These tasks were solved by a washing or cleaning agent, in which a washing or cleaning agent shaped body and the water-soluble or water-dispersible packaging material are adhesively bonded to one another by a heat seal seam.

A first subject of the present application is therefore a detergent or cleaning agent comprising at least one shaped detergent or cleaning agent and at least one Water-soluble or water-dispersible film material, characterized in that the detergent tablet and the film material are adhesively bonded to one another by a heat seal seam.

In contrast to conventional cleaning agents, the sealing seam in the cleaning agents according to the invention does not connect two film materials, for example for sealing a bag or pouch in which there is a detergent or cleaning agent, but rather connects the film material directly to the washing or cleaning agent. The adhesive connection of the film material and the shaped detergent body preferably leads to the formation of a cavity delimited by this film material and this shaped body, which in turn can now be filled, preferably with another detergent or cleaning agent. In such an embodiment, it is preferred that the composition of the shaped detergent or cleaning agent differs from the composition of the detergent or cleaning agent filled in the cavity.

The heat seal seam of the agents according to the invention preferably has the shape of a circumferential seal seam, that is to say a self-contained seal seam. The thickness of the sealed seam is preferably between 0.1 and 5 mm, preferably between 0.5 and 3 mm and particularly preferably between 1 and 2 mm. The heat seal seam is formed by bringing the film material and the molded body into contact with one another and then heating them in a spatially defined area.

The heat sealing is preferably carried out at a temperature above 40 ° C., particularly preferably above 60 ° C., very particularly preferably above 80 ° C. and in particular above 100 ° C. The film material and the adjoining region of the shaped body are preferably at temperatures above 60 ° C., preferably for a maximum of 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 heated above 80 ° C, particularly preferably between 100 and 120 ° C and in particular to temperatures between 105 and 115 ° C.

The heat sealing of the detergent tablet with the water-soluble or water-dispersible film material can be carried out not only by the action of hot air or the action of a laser beam, but also by means of heated sealing tools. When sealing using sealing tools (“sealing jaws”), the film material and the shaped body are heated in the area of the subsequent sealing seam. The sealing tool can be guided up to the surface of the shaped body and support the sealing process by applying additional pressure. Preferred detergents or cleaning agents are out this Basically characterized in that the molded body has a breaking pressure above 1 bar, preferably above 2.5 bar and in particular above 4 bar.

The breaking pressure is determined by inserting the molded body between two plane-parallel surfaces and moving them towards each other. The pressing force of the plates acts orthogonal to the level of the heat seal seam. The breaking pressure then results from the force at which the shaped body breaks, taking into account the area of the plates used.

A first component of the agents according to the invention is a detergent tablet. Shaped bodies of this type can be obtained, for example, by compacting processes such as tableting, by extrusion, such as strand extrusion or by casting processes. Moldings which are produced by tableting or by casting processes are particularly preferred in the context of the present application. The moldings contain or consist of washing or cleaning-active substances or substance mixtures.

Washing or cleaning agent tablets are produced in a manner known to those skilled in the art by pressing particulate starting substances. To produce the tablets, the premix is compacted in a so-called die between two punches to form a solid compressed product. This process, which is briefly referred to below as tableting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection. The tableting is preferably carried out on so-called rotary presses.

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

Use of plastic inserts with low thickness tolerances Low speed of rotation of the rotor Large filling shoes Adjustment of the filling shoe wing speed to the speed of the rotor filling shoe with constant powder height Decoupling of the filling shoe and powder feed To reduce stamp caking, all non-stick coatings known from the art are available. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotating punches have also proven to be advantageous, with the upper and lower punches being designed to be rotatable if possible. In the case of rotating punches, a plastic insert can generally be dispensed with. The stamp surfaces should be electropolished here.

Processes preferred in the context of the present invention are characterized in that the pressing is carried out at pressures of from 0.01 to 50 kNcm ^"2 , preferably from 0.1 to 40 kNcm ^{" 2} and in particular from 1 to 25 kNcm ^"2 .

Preferred casting bodies according to the invention are produced, for example, by pouring a washing or cleaning-active preparation into a mold and then demolding the solidified cast body to form a (trough) shaped body. Tools which have cavities which can be filled with pourable substances are preferably used as the “mold”. Such tools can be designed, for example, in the form of individual cavities or in the form of plates with several cavities. The individual cavities or cavity plates are preferably in industrial processes horizontally rotating conveyor belts are installed, which enable the cavities to be transported continuously or discontinuously, for example, along a number of different work stations (for example: pouring, cooling, filling, sealing, demolding, etc.).

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

In general, all active washing or cleaning preparations that can be processed by casting techniques are suitable for processing. However, washing or cleaning preparations in the form of dispersions are used with particular preference. In one particularly In a preferred embodiment of the present application, the washing or cleaning-active preparation poured into the receiving cavity of the molding tool is a dispersion of solid particles in a dispersing agent, dispersions which, based on their total weight i), 10 to 85% by weight of dispersing agent and ii ) Contain 15 to 90 wt .-% dispersed substances, are particularly preferred.

In this application, dispersion is a system consisting of several phases, one of which is continuous (dispersant) and at least one other is finely divided (dispersed substances).

Suitable dispersants in the context of the present invention are preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers. The dispersant can be either a single polymer or a mixture of different water-soluble or water-dispersible polymers. In a further preferred embodiment of the present invention, the dispersant or at least 50% by weight of the polymer mixture consists of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidones, vinylpyrrolidone / vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.

Dispersions are particularly preferably used which contain a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, the proportion by weight of the poly (ethylene) glycol in the total weight of all dispersants is preferably between 10 and 90% by weight, particularly preferably between 30 and 80% by weight and in particular between 50 and 70% by weight. Dispersions in which the dispersant is more than 92% by weight, preferably more than 94% by weight, particularly preferably more than 96% by weight, very particularly preferably more than 98% by weight are particularly preferred. and in particular 100% by weight of a poly (alkylene) glycol, preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular poly (ethylene) glycol. Dispersing agents which, in addition to poly (ethylene) glycol, also contain poly (propylene) glycol, preferably have a ratio by weight of poly (ethylene) glycol to poly (propylene) glycol of between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, particularly preferably between 10: 1 and 1, 5: 1 and in particular between 7: 1 and 2: 1. Other preferred dispersants are the nonionic surfactants, which are used both alone, but particularly preferably in combination with a nonionic polymer. Detailed information on the nonionic surfactants that can be used can be found below in the description of detergent or cleaning substances.

Suitable dispersed substances in the context of the present application are all substances which are active in washing or cleaning at room temperature, but in particular substances which are active in washing or cleaning from the group of builders (builders and cobuilders), active polymers for washing or cleaning, bleaching agents and bleach activators , the glass corrosion protection agent, the silver protection agent and / or the enzymes. A more detailed description of these ingredients can be found below in the text.

Dispersions preferably used as detergent tablets according to the invention are distinguished in that they disperse in water (40 ° C.) in less than 9 minutes, preferably less than 7 minutes, preferably in less than 6 minutes, particularly preferably in less than 5 minutes and especially dissolve in less than 4 minutes. To determine the solubility, 20 g of the dispersion are introduced into the interior of a dishwasher (Miele G 646 PLUS). The main wash cycle of a standard wash program (45 ° C) is started. The solubility is determined by measuring the conductivity, which is recorded by a conductivity sensor. The dissolving process ends when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau. The conductivity measurement begins with the insertion of the circulation pump in the main wash cycle. The amount of water used is 5 liters.

The shaped bodies produced, for example, by tableting or casting, can assume any geometrical shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, elliptical , pentagonal, hexagonal and octagonal prismatic and rhombohedral shapes are preferred. Completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. can also be realized. If the shaped bodies according to the invention have corners and edges, they are preferably rounded. As an additional optical differentiation, an embodiment with rounded corners and beveled (“gripped”) edges is preferred.

Of course, the moldings can also be produced in multiple phases. For reasons of process economy, two-layer or three-layer tablets, in particular two-layer or three-layer tablets, have proven particularly useful here. In the context of the present application, detergents or cleaning agents according to the invention are particularly preferred in which the detergent tablets are a single- or multi-phase detergent or cleaning tablet.

In a particularly preferred embodiment, tablets and / or compactates, for example compacted rollers, and / or extrudate and / or castings are used as shaped bodies in step a) of the process according to the invention.

The detergent tablets according to the invention can be completely or partially encased in the water-soluble or water-dispersible film material. The film material, which is adhesively bonded to the shaped body by a heat seal seam, can therefore cover both the entire shaped body and individual areas of the shaped body. Particularly preferred are detergent tablets according to the invention which are covered with a film material on their entire surface. Shaped bodies in which the film material covers only parts of the surface of the shaped body, for example individual side faces, in particular such side faces with a cavity, are further preferred.

In order to improve its molded body appearance and / or to influence its dissolution behavior, the molded body can have a coating. The coating can cover both the entire molded body and individual areas of the molded body. Moldings which have a coating on their entire surface are particularly preferred. Shaped bodies in which the coating extends only to individual surfaces of the shaped body, for example the shaped body surfaces outside the cavity, or to individual corners or edges of the shaped body are further preferred.

All materials known to the person skilled in the art for this purpose are suitable as coating materials. Preferred coating materials in the context of the present application are the water-soluble or non-water-soluble natural or synthetic organic polymers, water-soluble or water-dispersible organic polymers being particularly preferred. The salts of organic or inorganic acids are also suitable for coating the moldings. From the group of organic acids, the salts of mono-, di-, tri, tetra- or polycarboxylic acids are particularly preferred.

Suitable coating materials or as a component of the coating, for example as binders in combination with salts, preferably inorganic salts in particular polymers or polymer mixtures, the polymer or at least 50% by weight of the polymer mixture being selected from a) water-soluble nonionic polymers from the group of a1) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers b) water-soluble amphoteric polymers from the group of b1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic Copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers from b8i) unsaturated carboxylic acids bδii) cationically derivatized unsaturated or ionic ionic mono en c) water-soluble zwitterionic polymers from the group of d) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethylbetaine / methacrylate water-soluble copolymers from anion Group of d1) vinyl acetate / crotonic acid copolymers d2) vinyl pyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers d4) graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, copolymerized or methacrylic acid with polyalkylene oxides and / or polykalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the nonionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinking agent d6) copolymers obtained by copolymerization of at least one monomer of each of the three following groups: d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, dδiii) esters of long chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group dδii) with saturated or unsaturated, linear or branched C _{_8-18} Alcohol d7) terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester d8) tetra- and pentapolymers of d8i) crotonic acid or allyloxyacetic acid dδii) vinyl acetate or vinyl propionate dδiii) branched allyl or methallyl esters or vinyl or allyl methyladlyl or vinylidyl vinyl ether ylesters d9) crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts d10) terpolymers from vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position

e) water-soluble cationic polymers from the group of e1) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone derivatives with quaternary acid of the dialkylamino acrylate and methacrylate e6) vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol eδ) under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27. Water-soluble polymers in the sense of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature.

The moldings are preferably coated with a polymer or polymer mixture, the polymer (and accordingly the entire coating) or at least 50% by weight of the polymer mixture (and thus at least 50% of the coating) being selected from certain polymers. The coating consists entirely or at least 50% of its weight of water-soluble polymers from the group of nonionic, amphoteric, zwitterionic, anionic and / or cationic polymers. In a further preferred embodiment, the coating of the shaped body consists of a further inorganic salt which contains one of the polymers mentioned as a binder. Preferred polymers from these groups have been listed above and are described in more detail below.

Water-soluble polymers preferred according to the invention are nonionic. Suitable nonionic polymers are for example:

Polyvinylpyrrolidones, as, for example, sold under the name Luviskol ^® (BASF). Polyvinylpyrrolidones are preferred nonionic polymers in the context of the invention. Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula

which are prepared by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol, which are characterized by the specification of the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinylpyrrolidones are readily soluble in Water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

VinylpyrrolidonΛ / inylester copolymers, such as those sold under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / inyl acetate copolymers, are particularly preferred nonionic polymers. The vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula

- CH, - CH- O ^ O R

as a characteristic basic building block of macromolecules. Of these, the

Vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates as by far the most important representatives are of greatest technical importance.

The vinyl esters are polymerized by free radicals using various processes

(Solution polymerization, suspension polymerization, emulsion polymerization,

Bulk polymerization.).

Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and

Methylhydroxypropylcellulose, such as are for example sold under the trademark Culminal® ^® and Benecel ^® (AQUALON). Cellulose ethers can be described by the general formula

in R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in the above formula is -CH CH ₂ CH ₂ -OH or - CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose with the Have reacted etherification reagent or how many moles of the etherification reagent were added to an anhydroglucose unit on average. Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Further polymers preferred according to the invention are water-soluble amphopolymers. Ampho-polymers are amphoteric polymers, ie polymers that contain both free amino groups and free -COOH or S0 ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - Contain COO ^" - or -S0 ₃ ^" groups, and summarized those polymers which contain -COOH or S0 ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3- tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Methacrylic acid and its simple esters. Also preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyl-trimethyl-ammonium chloride) and optionally other ionic or non-ionic monomers, such as in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be seen. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat ^® 2001 N, are particularly preferred amphopolymers according to the invention. Other suitable amphoteric polymers are, for example, / 2-hydroxypropyl methacrylate copolymers of the octylacrylamide / methyl tert-butylaminoethyl methacrylate available under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL).

Suitable zwitterionic polymers are, for example, acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts. Further suitable zwitterionic polymers methacroylethylbetaine / methacrylate copoly- mers are obtainable under the name Amersette® ^® (AMERCHOL).

Anionic polymers suitable according to the invention include: Vinyl acetate / crotonic acid copolymers, such as are commercially available for example under the names Resyn ^® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF). These polymers have monomer units of the general formula

[-CH (CH ₃ ) -CH (COOH) -] _n .

Vinyl pyrrolidone / vinyl acrylate copolymers available, for example, under the trademark

Luviflex ^® (BASF). A preferred polymer is that under the name Luviflex ^® VBM-35

(BASF) available vinyl pyrrolidone / acrylate terpolymers.

Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, for example, under the

Name Ultrahold ^® strong (BASF) are sold.

Graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid, alone or in

Mixture copolymerized with crotonic acid, acrylic acid or methacrylic acid

Polyalkylene oxides and / or polyalkylene glycols

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture with other copolymerizable compounds

Polyalkylene glycols are obtained by heat polymerization in a homogeneous phase by converting the polyalkylene glycols into the monomers of the vinyl esters, esters of

Acrylic acid or methacrylic acid, stirred in the presence of radical formers.

Suitable vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate,

Vinyl benzoate and as esters of acrylic acid or methacrylic acid, those which are associated with low molecular weight aliphatic alcohols, in particular ethanol,

Propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-

Pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are available.

Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols

Consideration. Polymers of ethylene glycol, of the general formula

H- (0-CH ₂ -CH ₂ ) _n -OH

are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and a number immediately after the hyphen follows the number n in the above formula V corresponds. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-δ, PEG-9 , PEG-10, PEG-12, PEG-14 and PEG-16 can be used. Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone -Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers. Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula

H- (0-CH-CH ₂ ) _n -OH

CH, are sufficient, where n can have values between 1 (propylene glycol) and several thousand. Technically important here are in particular di-, tri- and tetrapropylene glycol, i.e. the representatives with n = 2, 3 and 4 in the above formula. In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used. grafted and crosslinked copolymers from the copolymerization of i) at least one monomer of the nonionic type, ii) at least one monomer of the ionic type, iii) of polyethylene glycol and iv) a crosslinker

The polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000. The nonionic monomers can be of very different types and the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene. The ionic monomers can likewise be of very different types, of which crotonic acid, allyloxyacetic acid, vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are particularly preferably contained in the graft polymers. Ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule of saccharin are preferably used as crosslinkers. The grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 65% by weight of at least one monomer of the nonionic type, ii) 3 to 30% by weight of at least one monomer of the ionic type, iii) 2 to 50% by weight, preferably 5 to 30% by weight, of polyethylene glycol and iv) 0.1 to δ% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii) is. Copolymers obtained by copolymerizing at least one monomer from each of the following three groups: i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, ii) unsaturated carboxylic acids, iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C ₈ -i ₈ alcohol Short-chain carboxylic acids or alcohols are to be understood as those having 1 to δ carbon atoms, the carbon chains of these compounds being optionally by double-bonded hetero groups such as - O-, -NH-, -S_ can be interrupted.

Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester

In addition to further monomer units, these terpolymers contain monomer units of one or more allyl or methallyesters of the formula

R ¹ R ³ IIR ² -CC (0) -0-CH ₂ - C = CH ₂

CH ₃

wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight-chain or branched Ci-β-alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2. The above-mentioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 66% by weight, preferably 71 to 63% by weight of vinyl acetate and δ to 20% by weight, preferably 10 to 17% by weight .-% allyl or methallyl esters of the above formula. Tetra and pentapolymers i) crotonic acid or allyloxyacetic acid ii) vinyl acetate or vinyl propionate iii) branched allyl or methallyl esters iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinyl methyl ether, salamides and their amide Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the D position.

Other polymers which can preferably be used as part of the coating are cationic polymers. The permanent cationic polymers are preferred among the cationic polymers. According to the invention, polymers which have a cationic group irrespective of the pH of the composition (ie both the coating and the shaped body) are referred to as “permanently cationic”. These are generally polymers which have a quaternary nitrogen atom, for example in the form of a Preferred cationic polymers are, for example, quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose Derivatives: Polysiloxanes with quaternary groups, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone) ), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer eller: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; di-quaternary polydimethylsiloxanes, quaternium-δO), cationic guar derivatives, such as, in particular, the products marketed under the trade names Cosmedia ^® Guar and Jaguar ^® , polymers of dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers. Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755. Vinylpyrrolidone-methoimidazolinium chloride copolymers, as are offered under the name Luviquat ^® . quaternized polyvinyl alcohol and the polymers known under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 with quaternary nitrogen atoms in the main polymer chain. The polymers mentioned are named according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which express reference is made here becomes.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiailylammonium salts and their copolymers. Cationic cellulose derivatives, in particular the commercial product Polymer ^® JR 400, are very particularly preferred cationic polymers.

A particularly preferred coating material for moldings in the context of the present application is polyvinyl alcohol (PVA). With regard to the degree of hydrolysis and the molecular weight of the polyvinyl alcohols preferably used for the coating, the information given below in the description of the preferred container materials applies, to which reference is made here to avoid repetition.

A second group of coating materials preferred according to the invention are the water-insoluble coating materials, in particular the coating materials from the group of fats, triglycerides and waxes.

Fat (s) or triglyceride (s) is the name for compounds of glycerol in which the three hydroxyl groups of the glycerol are esterified by carboxylic acids. The naturally occurring fats are triglycerides, which usually contain different fatty acids in the same glycerin molecule. By saponification of the fats and subsequent esterification or reaction with acyl chlorides, however, synthetic triglycerides in which only one fatty acid is bound are also accessible (eg tripalmitin, triolein or tristearin). Natural and / or synthetic fats and / or mixtures of the two are preferred as coating material in the context of the present invention. Aliphatic saturated or unsaturated, carboxylic acids with branched or unbranched carbon chain are referred to as fatty acids in the present application. A large number of production methods exist for the production of the fatty acids. While the lower fatty acids are mostly based on oxidative processes based on alcohols and / or aldehydes as well as aliphatic or acyclic hydrocarbons, the higher homologues are mostly still most easily accessible today by saponification of natural fats. Advances in the field of transgenic plants mean that there are almost unlimited possibilities for varying the fatty acid spectrum in the storage fats of oil plants. In the context of the present invention, preferred fatty acids have a melting point which allows these fats to be processed as a material or as a component of a casting. Fatty acids which have a melting point above 25 ° C. have proven particularly advantageous. Preferred matrix materials and / or constituents are therefore capric acid and / or undecanoic acid and / or lauric acid and / or tridecanoic acid and / or myristic acid and / or pentadecanoic acid and / or palmitic acid and / or margaric acid and / or stearic acid and / or nonadecanoic acid and / or arachic acid and / or erucic acid and / or elaeosteraric acid. But fatty acids with a melting point below 25 ° C can also be part of the coating.

Fatty alcohol is a collective name for the linear, saturated or unsaturated primary alcohols with 6 to 22 carbon atoms that can be obtained by reducing the triglycerides, fatty acids or fatty acid esters. The fatty alcohols can be saturated or unsaturated depending on the manufacturing process. Myristyl alcohol and / or 1-pentadecanol and / or cetyl alcohol and / or 1-heptadecanl and / or stearyl alcohol and / or erucyl alcohol and / or 1-nonadecanol and / or arachidyl alcohol and / or 1-heneicosanol and / or behenyl alcohol and / or erucyl alcohol and / or brassidyl alcohol are preferred components of the coatings.

It has also proven to be advantageous if the coating materials contain waxes. Preferred waxes have a melting range that is between approximately 45 ° C. and approximately 75 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. Waxes with such a melting range are on the one hand dimensionally stable at room temperature, but melt at temperatures of 30 ° C. to 90 ° C. which are typical for machine dishwashing and are therefore more readily water-dispersible at these temperatures.

"Waxing" is understood to mean a number of natural or artificially obtained substances which, as a rule, melt above 40 ° C. without decomposition and are relatively low-viscosity and not stringy just above the melting point. They have a strongly temperature-dependent consistency and solubility. The waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.

The natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

The chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated softening point requirements can also be used as meltable or softenable substances for the masses hardening by cooling. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or semi-synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin ^® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances. Shellac, for example shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used according to the invention as a coating material.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ^® (Pamentier & Co). In a further preferred embodiment, the majority of the moldings have paraffin wax as the coating material. This means that at least 50% by weight of the coating material, preferably more, consists of paraffin wax. Paraffin wax contents (based on the total weight of the coating materials) of about 60% by weight, about 70% by weight or about δO% by weight are particularly suitable, with even higher proportions of, for example, more than 90% by weight being particularly preferred , In a particular embodiment of the invention, the total amount of the coating material consists of paraffin wax.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C.

Preferred solid particles have at least one paraffin wax with a melting range of 40 ° C. to 60 ° C. as coating material or as part of the coating.

Further advantageous constituents of the coating of moldings are wax alcohols, ie fatty alcohols with approx. 24-36 carbon atoms, which are the main constituent of many natural waxes in the form of wax esters of higher molecular weight fatty acids (wax acids). Examples of preferred wax alcohols are lignoceryl alcohol, ceryl alcohol, myricyl alcohol or melissyl alcohol.

It is preferred in the context of the present invention that the amount of the coating substance (s), based on the total weight of the coated shaped body, is between 0.5 and 15% by weight, preferably between 1 and 12% by weight and in particular between 2 and δ% by weight is / are.

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

The detergent tablets can have a cavity. In the context of the present invention, the term “cavity” denotes both troughs and openings or holes which pass through the shaped body and which connect two sides of the shaped body, preferably opposite sides of the shaped body, for example the bottom and roof surfaces of the shaped body.

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

The trough opening area can be planar. With such a trough opening, all boundary points of the trough opening lie in one plane. In a preferred embodiment, the surface forming the trough opening is not planar. Such an embodiment can be implemented, for example, by a shaped body with an uneven surface. Alternatively, a shaped body can be provided, the trough opening of which extends over at least two boundary surfaces of a shaped body.

In a further preferred embodiment, the cavity is an opening which connects two opposite sides of the molded body to one another. If a tablet is used as the shaped body, the shaped body with such a breakthrough corresponds to a so-called ring tablet. Particularly preferred are shaped bodies with an opening in which the opening areas of the opening on the opposite sides of the shaped body are less than 80%, preferably less than 60%, preferably less than 40%, based on the larger of the two opening areas. particularly preferably differ by less than 20% and in particular by less than 10%. The cross section of the opening can be square or round. Cross sections with one, two, three, four, five, six or more corners can be realized, but in the context of the present application, shaped bodies are particularly preferred which have an opening without corners, preferably an opening with a round or oval cross section. A “cross section” is a surface that is perpendicular to a straight connecting line between the centers of the two opposite opening surfaces of the molded body.

Of course, the molded body can have more than one cavity. Shaped bodies with two, three, four, five, six, seven, eight, nine, ten, eleven twelve or more cavities are particularly preferred in the context of the present application. If the molded body has more than one cavity, these cavities can be both the troughs described above and the openings described above. Moldings which have more than one cavity, at least one of the cavities being a depression and at least one further of the cavities being an opening, are particularly preferred in the context of the present application. The volume of the cavity is preferably between 2 and 20 ml, preferably between 2 and 15 ml, particularly preferably between 2 and 10 ml and in particular between 2 and 7 ml.

In the context of the present application, detergent tablets having a cavity are particularly preferred. Such washing or cleaning agents according to the invention are very particularly preferred in which the shaped body has a cavity which is at least partially closed by the film material which is adhesively connected to the shaped body by a heat seal seam.

In a particularly preferred embodiment of the present invention, the cavity of the shaped detergent or cleaning product is filled. Flowable, washable and cleaning-active preparations, preferably liquid (s), in particular melts, and / or gel (s) and / or powder and / or granulate (s) and / or extrudate (s) and / or compact (e ) filled into the cavity of the detergent tablet.

In the present application, the term “liquid” denotes substances or substance mixtures as well as solutions or suspensions which are in the liquid state.

Powder is a general term for a form of separation of solid substances and / or mixtures of substances which is obtained by comminution, i.e. grinding or crushing in the grinding bowl (pulverization), grinding in mills or as a result of atomization or freeze drying. A particularly fine division is often called atomization or micronization; the corresponding powders are called micro powders.

According to the grain size, the powders are roughly divided into coarse, fine and. Very fine powder common; A more precise classification of powdered bulk goods is based on their bulk density and by sieve analysis. However, powders preferred in the context of the present application have lower particle sizes 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.

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

Accumulations of granules are referred to as granules. A Granulatkom (Granalie) is an asymmetrical aggregate of powder particles. Granulation processes are widely described in the prior art. Granules can be produced by wet granulation, by dry granulation or compacting and by melt solidification granulation.

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

If the granulation takes place in a spray tower, the starting materials used can be, for example, melts (melt solidification) or, preferably aqueous, slurries (spray drying) solid substances which are sprayed at the top of a tower in a defined droplet size, freeze or dry in free fall, and on Bottom of the tower accumulate as granules. Melt solidification is generally particularly suitable for shaping low-melting substances that are stable in the melting temperature range (e.g. urea, ammonium nitrate and various formulations such as enzyme concentrates, pharmaceuticals, etc.), the corresponding granules are also referred to as prills. Spray drying is used particularly for the production of detergents or detergent components.

Further agglomeration techniques described in the prior art are extruder or perforated roller granulation, in which powder mixtures optionally mixed with granulating liquid are plastically deformed when pressed by perforated disks (extrusion) or on perforated rollers. The products of extruder granulation are also called extrudates.

Enzymes, bleaches, in particular are suitable as ingredients of the washing or cleaning-active preparations filled into the cavity of the detergent tablet. Bleach activators, bleach catalysts, silver preservatives or glass corrosion inhibitors. Bleaching agents, in particular peroxygen compounds such as percarbonates or perborates, bleach activators or silver protection agents, are introduced with particular preference. These ingredients are preferably filled into the cavity as a constituent of solid washing or cleaning-active preparations between steps a) and b). These ingredients are described in more detail below in the text. To avoid repetition, reference is made here to the explanations given there.

Another preferred subject of the present application is therefore a detergent or cleaning agent comprising at least one detergent or cleaning agent shaped body and at least one water-soluble or water-dispersible film material, characterized in that the detergent or cleaning agent shaped body has a cavity in the form of a trough, which has a washing or cleaning-active substance is filled and sealed with a film material, the film material being adhesively bonded to the detergent tablet by a heat seal seam.

Of course, the molded body can also have an opening instead of a trough, with molded bodies in the form of a ring tablet being used with particular preference. In addition to the tabletting described above, moldings of this type can also be produced, for example, by casting processes or by extrusion. The present application therefore also relates to a detergent or cleaning agent comprising at least one detergent or cleaning agent tablet in the form of a ring tablet and at least one water-soluble or water-dispersible film material, characterized in that the cavity of the detergent or cleaning agent tablet contains a detergent or cleaning agent is filled, the film material being adhesively bonded to the shaped detergent or detergent body by a heat seal seam and preferably sealing at least one, particularly preferably both, openings in the cavity of the shaped body.

In the previously described embodiments of agents according to the invention, a detergent tablet was adhesively bonded to a water-soluble or water-dispersible film material by means of a heat-seal seam, the water-soluble or water-dispersible film material being used in the form of a commercially available film. In a further preferred embodiment, the water-soluble or water-dispersible film material is shaped into a hollow body, which is an injection molded and / or blow molded and / or deep-drawn part.

In the context of the present application, “deep-drawn parts” refer to containers which are obtained by deep-drawing a first film-like wrapping material. The deep-drawing is preferably carried out by moving the wrapping material over a receiving trough located in a die forming the deep-drawing plane and molding the wrapping material into this receiving trough by the action of pressure and / or vacuum. The casing material can be pretreated before or during the molding in by the action of heat and / or solvent and / or conditioning by means of relative atmospheric humidity and / or temperature changes compared to ambient conditions. The pressure can be exerted by two parts of a tool, which behave like positive and negative to each other and deform a film placed between these tools when pressed together. However, the action of compressed air and / or the weight of the film and / or the weight of an active substance placed on the top of the film are also suitable as pressure forces.

After deep-drawing, the deep-drawn envelope materials are preferably fixed by using a vacuum within the receiving troughs and in the spatial shape achieved by the deep-drawing process. The vacuum is preferably applied continuously from deep drawing to filling, preferably to sealing and in particular until the receiving chambers are separated. With comparable success, however, it is also possible to use a discontinuous vacuum, for example for deep-drawing the receiving chambers and (after an interruption) before and during the filling of the receiving chambers. The strength of the continuous or discontinuous vacuum can also vary and, for example, assume higher values at the beginning of the process (when thermoforming the film) than at the end (when filling or sealing or separating).

As already mentioned, the wrapping material can be pretreated by the action of heat before or during molding into the receiving troughs of the dies. The coating material, preferably a water-soluble or water-dispersible polymer film, is at temperatures above 60 ° 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 C, preferably above δ0 ° C, particularly preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C. In order to dissipate this heat, but in particular also to dissipate the heat introduced by the means filled into the deep-drawn receiving chambers (eg melting), it is preferred to cool the dies used and the receiving troughs located in these dies. The cooling is preferably carried out at temperatures below 20 ° C., preferably below 15 ° C., particularly preferably at temperatures between 2 and 14 ° C. and in particular at temperatures between 4 and 12 ° C. The cooling is preferably carried out continuously from the start of the deep-drawing process to the sealing and separation of the receiving chambers. Are particularly suitable for cooling Cooling liquids, preferably water, which are circulated in special cooling lines within the die.

This cooling, like the continuous or discontinuous application of a vacuum described above, has the advantage of preventing the deep-drawn containers from shrinking back after deep-drawing, which not only improves the appearance of the process product, but at the same time also escapes the agents filled into the receiving chambers the edge of the receiving chamber, for example in the sealing areas of the chamber, is avoided. This prevents problems with the sealing of the filled chambers.

In the deep-drawing process, a distinction can be made between processes in which the wrapping material is fed horizontally into a molding station and from there in a horizontal manner for filling and / or sealing and / or singling, and processes in which the wrapping material is fed via a continuously rotating die-forming roller (optionally with a counter-rotating male mold roll, which guides the shaping upper punches to the cavities of the female mold roll). The first-mentioned process variant of the flatbed process is to be operated both continuously and discontinuously; the process variant using a shaping roller is generally carried out continuously. All of the deep-drawing processes mentioned are suitable for producing the agents preferred according to the invention. The receiving guides located in the matrices can be arranged “in series” or offset.

The deep-drawn bodies can have one, two, three or more receiving chambers. These receiving chambers can be arranged next to one another and / or one above the other in the deep-drawn part. In a preferred embodiment of the present application, the agent according to the invention, in particular machine dishwashing detergent, is packaged in a water-soluble or water-dispersible deep-drawing body which, in addition to the solid washing and / or cleaning agent according to the invention, in particular machine dishwashing agent, also contains a liquid or gel detergent in a separate receiving chamber Contains detergent mixture.

The water-soluble or water-dispersible containers can also be produced by injection molding in addition to deep drawing. Injection molding refers to the shaping of a molding compound in such a way that the mass contained in a mass cylinder for more than one injection molding process plastically softens under the action of heat and flows under pressure through a nozzle into the cavity of a previously closed tool. The process is mainly used for non-hardenable molding compounds that solidify in the mold by cooling. Injection molding is a very economical, modern process for producing without cutting shaped objects and is particularly suitable for automated mass production. In practical operation, the thermoplastic molding materials (powder, granules, cubes, pastes, etc.) are heated to liquefaction (up to 1δ0 ° C) and then injected under high pressure (up to 140 MPa) into closed, two-part, that is, from dies (formerly Matrix) and core (formerly patrix), preferably water-cooled hollow molds, where they cool and solidify. Piston and screw injection molding machines can be used. Suitable molding compounds (injection molding compounds) are water-soluble polymers such as, for example, the above-mentioned cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.

Detergent tablets and hollow molds are preferably adhesively bonded to one another along a circumferential sealing seam. Alternatively, the adhesive connection can of course also take place along a simple sealing seam, which is not self-contained and makes it possible to fold the molded body and the hollow shape along this sealing seam. Such particularly preferred embodiments of agents according to the invention are notable for their advantageous optics and high flexibility in metering, in particular metering via the induction chamber or metering chambers of washing machines or dishwashers.

Finally, the molded body and the hollow body can also be adhesively connected to one another along two or more sealed seams which are separated from one another.

In a further embodiment, however, the detergent tablet has a cavity which at least partially encompasses the hollow body. Troughs are again suitable as cavities, as are openings, in other words detergent tablets in the form of a tray tablet are suitable, as are detergent tablets in the form of a ring tablet. The water-soluble or water-dispersible hollow bodies, which are adhesively connected to the molded body by a heat seal seam, are at least partially in the cavity. The hollow bodies can, for example, be inserted into the cavity, but can also be fastened in this cavity by an additional adhesive, latching or snap connection. In order to minimize the total volume of the washing or cleaning agent according to the invention, it is preferred that the hollow body has at least 50% by volume, preferably at least 70% by volume, particularly preferably at least δO% by volume and in particular to the cavity fills at least 90 vol .-%. The hollow body preferably has a filling, particularly preferably a liquid filling. Those liquid fillings are very particularly preferred which, based in each case on the total weight of the liquid filling, contain at least 10% by weight, preferably at least 20% by weight, particularly preferably at least 40% by weight and in particular at least δO% by weight have several surfactants.

It has been found that the stability and quality of the heat seal seam, which connects the detergent tablet with the water-soluble or water-dispersible film material, can be influenced by the composition of the detergent tablet. It has proven to be advantageous if the shaped body or the shaped body phase, which is adhesively bonded to the water-soluble or water-dispersible film material by a heat seal seam, has a surfactant content below 20% by weight, preferably below 16% by weight, preferably below 12% by weight, particularly preferably below δ% by weight and in particular below 4% by weight.

Just like the surfactant content, the enzyme content, the bleaching agent content and the bleach activator content in the molded body or the molded body phase, which is adhesively bonded to the water-soluble or water-dispersible film material by the heat seal seam, are kept within narrow limits.

Washing or cleaning agents are preferred, characterized in that the molded body or the molded body phase, which is adhesively bonded to the water-soluble or water-dispersible film material by a heat seal seam, has an enzyme content below 6% by weight, preferably below 4.5% by weight. -%, preferably below 3.0% by weight and in particular below 1.0% by weight.

Also preferred are detergents or cleaning agents, characterized in that the molded body or the molded body phase, which is adhesively bonded to the liquid-filled hollow body by a heat seal seam, has a bleach content below 15% by weight, preferably below 12% by weight, preferably below 9% by weight, particularly preferably below 6% by weight and in particular below 3% by weight.

Finally, detergents or cleaning agents are also particularly advantageous, characterized in that the molded body or the molded body phase, which is adhesively bonded to the water-soluble or water-dispersible film material by a heat seal seam, has a bleach activator content below 5% by weight, preferably below 3%. 5% by weight, particularly preferably below 2.0% by weight and in particular below 1.0% by weight. It has also been found that the quality and stability of the heat seal seam between the washing or cleaning agent shaped body and the water-soluble or water-dispersible film material can be increased by increasing the builder content and / or the polymer content of the shaped body or the shaped body phase which has the heat sealing seam.

Preference is therefore given to detergents or cleaning agents according to the invention in which the shaped body or the shaped body phase, which is adhesively bonded to the liquid-filled hollow body by a heat seal seam, has a builder content above 10% by weight, preferably above 15% by weight, preferably above 20% by weight, particularly preferably above 25% by weight and in particular above 30% by weight.

Detergents or cleaning agents have also proven to be advantageous, characterized in that the shaped body or the shaped body phase, which is adhesively bonded to the liquid-filled hollow body by a heat seal seam, has a polymer content above 0.5% by weight, preferably above 1 , 0% by weight, particularly preferably above 2.0% by weight and in particular above 4% by weight.

Another object of the present application is a process for the production of detergents or cleaning agents according to the invention, comprising at least one detergent or cleaning agent tablet and at least one water-soluble or water-dispersible film material, characterized by the steps a) production of detergent or cleaning agent tablets; b) providing a water-soluble or water-dispersible film material; c) Adhesive connection of at least one product from step a) with the water-soluble or water-dispersible film material from step b) by a heat seal seam.

A number of different tools and methods are available to the person skilled in the art for heat sealing the shaped body and film material.

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

In a second preferred embodiment, the heat sealing is carried out by the action of a laser beam. In a third preferred embodiment, the heat sealing is carried out by the action of hot air.

The heat sealing is preferably carried out at a temperature above 40 ° C, particularly preferably above 60 ° C, very particularly preferably above δO ° C and in particular above 100 ° C.

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 at temperatures above 60 ° C., preferably above δ0 ° C., particularly preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C.

It is preferred that the detergent tablet has a coating. It is further preferred that the water-soluble or water-dispersible film material provided in step b) is shaped into a hollow body which is an injection molding and / or blow molding and / or deep-drawn part.

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

In addition to the aforementioned washing or cleaning substances, the washing or cleaning agents according to the invention preferably contain further washing and cleaning substances, in particular washing and cleaning substances from the group of bleaching agents, bleach activators, builders, surfactants, enzymes, polymers, disintegration aids, electrolytes, pH -Positioning agents, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, corrosion inhibitors and glass corrosion inhibitors. These preferred ingredients are described in more detail below.

builders

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

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x 0 _{2x +} ι ^' H ₂ 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ 0 ₅ 'yH ₂ 0 are preferred. Amorphous sodium silicates with a Na ₂ 0: Si0 ₂ modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.6 and in particular 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

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

If the silicates are used as a component of automatic dishwashing detergents, these detergents preferably contain at least one crystalline layered silicate of the general formula NaMSi _x 0 _{2x +} ι 'y H ₂ 0, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, is preferably from 1.9 to 4 and y is a number from 0 to 33. The crystalline layered silicates of the formula NaMSi _x 0 _{2x +} ι ^' y H ₂ 0 are sold, for example, by Clariant GmbH (Germany) under the trade name Na-SKS, for example Na-SKS-1

(Na ₂ Si ₂₂ 0 ₄₅ -χH ₂ 0, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ 0 ₂ g-χH ₂ 0, magadiite), Na-SKS-3 (Na ₂ Si ₈ 0 _{1 7} - χH ₂ 0) or Na-SKS-4 (Na ₂ Si ₄ 0g-χH ₂ 0, makatite).

For the purposes of the present invention, crystalline sheet silicates of the formula (I) in which x is 2 are particularly suitable. Of these, Na-SKS-5 (α-Na ₂ Si ₂ 0 ₅ ), Na- SKS-7 (ß-Na ₂ Si ₂ 0 ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ 0 ₅ Η ₂ 0), Na-SKS-10 (NaHSi ₂ 0 ₅ -3H ₂ 0, kanemite), Na -SKS-11 (t-Na ₂ Si ₂ 0 ₅ ) and Na-SKS-13 (NaHSi ₂ 0 ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ 0 ₅ ).

If the silicates are used as a component of automatic dishwashing detergents, these detergents contain, in the context of the present application, a proportion _by weight of the crystalline layered silicate of the formula NaMSi _x 0 _{2x +} ι ^' y H ₂ 0 of 0.1 to 20% by weight, preferably of 0 , 2 to 15 wt .-% and in particular from 0.4 to 10 wt .-%, each based on the total weight of these agents. It is particularly preferred if such automatic dishwashing detergents have a total silicate content below 7% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably below 4% by weight, very particularly preferably below 3% by weight .-% and in particular below 2.5 wt .-%, with this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 60 wt .-% and in particular at least 90 wt .-% is silicate of the general formula NaMSi _x 0 _{2x +} ι ^' y H ₂ 0.

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

can be described. The zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 13 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. This applies in particular to the use of agents according to the invention as mechanical ones Dishwashing detergent, which is particularly preferred in the context of the present application. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the summary name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ P0 _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.

Suitable phosphates are, for example, sodium dihydrogen phosphate, NaH ₂ PO ₄ , in the form of the dihydrate (density 1.91, preferably ^"3 , melting point 60 °) or in the form of the monohydrate (density 2.04, preferably ^{" 3} ), the disodium hydrogen phosphate (secondary sodium phosphate) , Na ₂ HP0 ₄ , which is anhydrous or with 2 mol. (Density 2.066 like ^"3 , water loss at 95 °), 7 mol. (Density 1, 63 like ^{" 3} , melting point 4δ ° with loss of 5 H ₂ 0) and 12 mol. Water (density 1, 52 like ^"3 , melting point 35 ° with loss of 5 H ₂ 0) can be used, but especially the trisodium phosphate (tertiary sodium phosphate) Na ₃ P0 ₄ , which as dodecahydrate, as decahydrate (corresponding to 19 -20% P ₂ 0 ₅ ) and in anhydrous form (corresponding to 39-40% P ₂ 0 ₅ ) can be used.

Another preferred phosphate is tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ P0. Also preferred are the tetrasodium diphosphate (sodium pyrophosphate), Na P ₂ 0 ₇ , which in anhydrous form (density 2.534 like ^"3 , melting point 9δδ °, also given δδ0 °) and as decahydrate (density 1, 815-1, 836 like ^{" 3} , Melting point 94 ° with water loss) exists, as well as the corresponding potassium salt potassium diphosphate (potassium pyrophosphate), KP ₂ 0 ₇ .

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] _n that crystallizes with 6 H ₂ 0 -Na with n = 3. The corresponding potassium salt, pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 0 ₅ , 25% K ₂ 0). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaP0 ₃ ) ₃ + 2 KOH -> Na ₃ K ₂ P ₃ O ₁₀ + H ₂ 0

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

If, in the context of the present application, phosphates are used as washing or cleaning-active substances in washing or cleaning agents, preferred agents contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) , in amounts of 5 to 80 wt .-%, preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the detergent or cleaning agent.

It is particularly preferred to use potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1: 1, preferably more than 2: 1, preferably more than 5: 1, particularly preferably more than 10: 1 and in particular more than 20: 1. It is particularly preferred to use exclusively potassium tripolyphosphate without admixtures of other phosphates.

Other builders are the alkali carriers. Examples of alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metal silicates, and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicate, preferably being used for the purposes of this invention. A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred. A builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred. Because of their low chemical compatibility with the other ingredients of detergents or cleaning agents compared to other builder substances, the alkali metal hydroxides are preferably used only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or cleaning agent used. Agents which contain less than 0.5% by weight and in particular no alkali metal hydroxides, based on their total weight, are particularly preferred. It is particularly preferred to use carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonate (s), particularly preferably sodium carbonate, in amounts of 2 to 50% by weight, preferably 5 to 40% by weight and in particular from 7.5 to 30% by weight, based in each case on the weight of the detergent or cleaning agent. Agents which, based on the weight of the washing or cleaning agent (ie the total weight of the combination product without packaging) are less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and contain in particular less than 9% by weight of carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate.

Organic cobuilders include, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights 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 is realistic due to its structural relationship to the polymers investigated Provides molecular weight values. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given 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 from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn 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 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The (co) polymeric polycarboxylate content of washing or cleaning agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

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

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

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and are particularly preferred.

Further suitable builder substances are polyacetals, which are obtained by reacting dialdehydes with polyolcarboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained. 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.

Other 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. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. 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 customary measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

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 further suitable cobuilders. Ethylenediamine-N, N ^'- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be 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 that are able to form complexes with alkaline earth metal ions can be used as builders.

surfactants

In addition to the nonionic surfactants described at the beginning, the anionic, cationic and amphoteric surfactants are also included in the group of surfactants. All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants in the context of the present application. Alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol are used, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and may contain methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to δ EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ . ₁₄ -alcohols with 3 EO or 4 EO, Cg-n-alcohol with 7 EO, C ₁₃ -i ₅ -alcohols with 3 EO, 5 EO, 7 EO or δ EO, C ₁₂ -ι ₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -ι alcohol with 3 EO and C _{_12-18} alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxyiates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 3 to 22, preferably 12 to 1δ C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which are 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 with 1 to 4 carbon atoms in the alkyl chain.

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

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

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

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

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

R ¹ -0-R ² I R-CO-N- [Z]

in which 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 is 2 to δ carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to δ carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives thereof residue.

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

Low-foaming nonionic surfactants are used as preferred surfactants. The cleaning agents according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. Preferred nonionic surfactants are alkoxylated, advantageous tally ethoxylated, especially primary alcohols with preferably δ to 1δ C atoms and an average of 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 Can contain mixture, as they are usually present in oxo alcohol residues. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 1δ C atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to δ EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ . ₁₄ -alcohols with 3 EO or 4 EO, C ₉ . _ι alcohol with 7 EO, Cι ₃ -i ₅ alcohols with 3 EO, 5 EO, 7 EO or 3 EO, C ₁₂ . ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Cι. ₂ ₁₄ alcohol with 3 EO and C _{_12-18} alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In particular, machine dishwashing detergents which contain one or more taig fat alcohols with 20 to 30 EO in combination with a silicone defoamer as surfactant (s) are particularly preferred.

Nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO nonionic surfactants, are used with particular preference in the context of the present application.

Nonionic surfactants which have a melting point above room temperature are particularly preferred. Nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C., are particularly preferred.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. , If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred. Preferred nonionic surfactants to be used at room temperature originate from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.

A particularly preferred nonionic surfactant which is solid at room temperature is made from a straight-chain fatty alcohol having 16 to 20 carbon atoms (-C ₆ - ₂ alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide won. Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred.

Therefore, ethoxylated nonionic surfactants derived from C ₆ . ₂₀ - monohydroxyalkanols or C ₆ . ₂₀ -alkylphenols or C _{_16-2} o-fatty alcohols and more than 12 mol, preferably more than 15 mol, and were recovered in particular more than 20 moles of ethylene oxide per mole of alcohol.

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass 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% by weight, preferably up to 20% by weight and in particular up to 15% by weight, of the total molecular weight of the nonionic Make up surfactants.

Other nonionic surfactants with melting points above room temperature that are particularly preferably used contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene Block polymer blends containing 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 Moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-13 from Olin Chemicals.

Another preferred dishwashing detergent according to the invention contains nonionic surfactant (s) of the formula

R ¹ 0 [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y CH ₂ CH (OH) R ²

in which R ^{1 stands} for a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is at least 15.

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

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula can 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, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or - CH ₂ CH _{3 are} particularly preferred for the radical R ³ . 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 can be different if x ≥ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, when x is 3, the R ³ group can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units that are joined together in any order can, 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 chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

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

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly bbeevvoorrzzuuggtt ssiinndd TTeennssiiddee ,, bbeeii ddeenneenn ddiiee F residues R ¹ and R ^{2 have} 9 to 14 C atoms, R ³ stands for H and x assumes values from 6 to 15.

If the latter statements are summarized, dishwashing detergents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

contain, in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

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

In the context of the present invention, weakly foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants. Among these, surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups being bonded to one another before a block from the other groups follows. Here, automatic dishwashing agents according to the invention are preferred which act as nonionic surfactant (s) of the general formula

R ¹ -0- (CH ₂ -CH ₂ -0) _w - (CH ₂ -CH-0) _x - (CH ₂ -CH ₂ -0) _y - (CH ₂ -CH-0) -, - HIIR ² R ³

contain 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 represent 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 can vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is generally not shown, the linear radicals being of alcohols of native origin with 12 to 18 carbon atoms, for example coconut, palm, tallow or Oleyl alcohol are preferred. Alcohols accessible from synthetic sources are, for example, Guerbet alcohols or residues which are methyl-branched in the 2-position or linear and methyl-branched residues in a mixture, as are usually present in oxo alcohol residues. Regardless of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, preferred dishwasher detergents according to the invention are those in which R ¹ in the above formula for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. But also other alkylene oxides in which R ² and R ³ are selected independently of one another from -

CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are suitable. Preferred automatic dishwashing agents are characterized in that R ² or R ³ for a radical -CH ₃ , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

In summary, nonionic surfactants which have a C ₉ . ₁₅ - alkyl having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by i to 4 ethylene oxide units, followed by i to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used with particular preference according to the invention. Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x R ²

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

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

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x R ²

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

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

R ¹ 0 [CH ₂ CH ₂ 0] _x R ²

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

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

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

In the context of the present application, particular preference is given to machine dishwashing detergents which are nonionic surfactant (s) of the general formula

R ¹ 0 [CH ₂ CH ₂ 0] _x CH ₂ CH (OH) R ²

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

The present application particularly claims those automatic dishwashing detergents which contain nonionic surfactant (s) of the general formula

R ¹ 0 [CH ₂ CH ₂ 0] _x CH ₂ CH (OH) R ²

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

The corresponding end-capped poly (oxyalkylated) nonionic surfactants of the above formula can be obtained, for example, by reacting a terminal epoxide of the formula R ² CH (0) CH ₂ with an ethoxylated alcohol of the formula R ¹ 0 [CH ₂ CH ₂ 0] _x . ₁ CH ₂ CH ₂ OH obtained.

End-capped poly (oxyalkylated) nonionic surfactants of the formula are also particularly preferred

R ¹ 0 [CH ₂ CH ₂ 0] _x [CH ₂ CH (CH ₃ ) 0] _y CH ₂ CH (OH) R ²

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

R ¹ 0 [CH ₂ CH ₂ 0] _x [CH ₂ CHO] _y CH ₂ CH (OH) R ² IR ³

contain, in which R ¹ and R ² independently of one another represent 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 represents -CH ₃ , and x and y independently of one another have values between 1 and 32, nonionic surfactants having values for x from 15 to 32 and y from 0.5 and 1.5 are very particularly preferred, are part of preferred agents according to the invention in the context of the present application.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the above-mentioned nonionic surfactants represent statistical mean values which can be an integer or a fraction for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but rather from mixtures, which can result in averages and the resulting fractional numbers both for the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation.

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

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

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

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

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

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

In the context of this application, particularly preferred dishwashing detergents are those which have a surfactant system which comprises a nonionic surfactant F of the general formula R ¹ 0 [CH ₂ CH ₂ 0] _x CH ₂ CH (OH) R ² , in which R ¹ , represents a saturated, unbranched aliphatic hydrocarbon radicals having 8 to 12 carbon atoms, preferably having 10 carbon atoms, furthermore R ^{2 is} a saturated, linear hydrocarbon radical having δ to 12 carbon atoms, preferably having 8 hydrocarbon radicals, and in which x is from 14 to 26, preferably for values from 20 to 24, which with a nonionic surfactant G of the general formula

R ¹ -0- (CH ₂ -CH ₂ -0) _w - (CH ₂ -CH-0) _x - (CH ₂ -CH ₂ -0) _y - (CH ₂ -CH-0) _z -HIIR ² R ³

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

In the context of this application, preference is also given to machine dishwashing agents which have a surfactant system which comprises a nonionic surfactant F of the general formula R ¹ 0 [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y CH ₂ CH ( OH) R ² , in which R ^{1 represents} a saturated, unbranched aliphatic hydrocarbon radicals having 8 to 12 carbon atoms, preferably having 8 to 10 carbon atoms, furthermore R ^{2 is} a saturated, linear hydrocarbon radical having 8 to 12 carbon atoms, preferably δ Hydrocarbon radicals, and in which x stands for values of 1 or 2, while y stands for values between 1 δ and 24, preferably for values from 20 to 24, which with a nonionic surfactant G of the general formula

R ¹ -0- (CH ₂ -CH ₂ -0) _w - (CH ₂ -CH-0) _x - (CH ₂ -CH ₂ -0) _y - (CH ₂ -CH-0) _z -HIIR ² R ³ , in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ -alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently of one another are integers from 1 to 6, is combined.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C ₉ . ₁₃ -Alkylbenzolsul- sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C ₂ - ₁₈ receives monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation into consideration. Also suitable are alkanesulfonates, from C _{_12-18} alkanes are obtained for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. From the washing, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ are - as well as alkyl _sulfates, preferably C ₁₄ -C ₁₅ alkyl sulfates. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Also, the Schwefelsäuremonoester with 1 to 6 moles of ethylene ethoxylated straight-chain or branched C _{_7-21} alcohols, such as 2-methyl-branched Cg-n-alcohols containing on average 3.5 Moles of ethylene oxide (EO) or C _{_12-18} fatty alcohols with 1 to 4 EO, are also suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ . ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably δ to 1δ carbon atoms in the alk (en) ylette or salts thereof.

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

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

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

Instead of the surfactants mentioned or in conjunction with them, cationic and / or amphoteric surfactants can also be used.

Cationic compounds of the formulas, for example, can be used as cationic active substances: R ¹ R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² I (CH ₂ ) _n -TR ²

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

R ² R ²

R ¹

R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ²

R *

wherein each R ^{1 group is} independently selected from Ci-β-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 that do not contain cationic or amphoteric surfactants are particularly preferred.

polymers

The group of polymers includes in particular the wash- or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, in addition to nonionic polymers, cationic, anionic and amphoteric polymers can also be used in washing or cleaning agents. “Cationic polymers” in the sense of the present invention are polymers which carry a positive charge in the polymer molecule. This can be achieved, 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 ninylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylimidlolidonate, methacrylimidlolidonate, methacrylidonyl methacrylate Copolymers, the quaternized polyvinyl alcohols or the polymers specified under the IΝCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 1 δ and Polyquaternium 27.

“Amphorere polymers” in the sense of the present invention also have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups can be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

Detergents or cleaning agents, in particular machine dishwashing detergents, characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C = CR ³ R ⁴ , in which each radical R ¹ , R ² , R ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy group, C1 to C30 linear or branched alkyl groups, aryl, aryl-substituted C-. ₃₀ linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups with at least one positive charge without charged nitrogen, at least one quaternized Ν atom or at least one amino group with a positive charge in the partial range of the pH range from 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 with at least one positive charge without charged nitrogen, at least one quaternized Ν atom or at least one amino group with a positive charge are in Particularly preferred within the scope of the present application.

Cationic or amphoteric polymers which are particularly preferred in the context of the present application contain a compound of the general formula as monomer unit

R ¹ R ² R ⁴ I 1 1 1 1 1 H ₂ C = C- - (CH ₂ ) _X -Ν ⁺ - - (CH ₂ ) _y - -C = CH ₂ X ^" 1 R ³ in which R ¹ and R ⁴ independently of one another represent H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ³ independently of one another represent an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl radical is linear or branched and has between 1 and 6 carbon atoms, it preferably being a methyl group; x and y independently represent integers between 1 and 3. X ^~ represents a counter ion, preferably a counter ion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylene sulfonate, 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 -0) _n H.

In the context 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 and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer units of the formula

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

are also referred to as DADMAC (diallyldimethylammonium chloride) in the case of X ^" = chloride.

Further cationic or amphoteric polymers which are particularly preferred in the context of the present application contain a monomer unit of the general formula

R ¹ HC = CR ² -C (0) -NH- (CH ₂ ) _x -N ⁺ R ³ RR ⁵ X ^"

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another for a linear or branched, saturated or unsaturated alkyl, or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably for 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 -0) _n H and x represents an integer between 1 and 6.

In the context of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹ represent H and R ² , R ³ , R ⁴ and R ^{5 represent} methyl and x represents 3. The corresponding monomer units of the formula H ₂ C = C (CH ₃ ) -C (0) -NH- (CH ₂ ) _x -N ⁺ (CH ₃ ) ₃ X ^"

In the case of X ^" = chloride are also referred to as MAPTAC (methyacrylamidopropyl trimethylammonium chloride).

Washing or cleaning agents preferred in accordance with the invention, in particular machine dishwashing agents, are characterized in that the polymer a) contains 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 come, 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 acids, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinyl acetic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.

Preferred amphoteric polymers that can be used come from the group of alkyl acrylamide / acrylic acid copolymers, alkyl acrylamide / methacrylic acid copolymers, alkyl acrylamide / methyl methacrylic acid copolymers, alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers

Alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the

Alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers as well as the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Zwitterionic polymers that can be used preferably come from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts, acrylamidoalkyltriaikylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts and methacroylethylbetaine / methacrylate copolymers. Also preferred are amphoteric polymers which, in addition to one or more anionic monomers, comprise methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) ammonium chloride as cationic monomers.

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

Methacrylic amidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / methacrylic acid

Copolymers and the

Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / alkyl

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

Amphoteric polymers from the group of are particularly preferred

Methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid

Copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyI (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyI) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

In a particularly preferred embodiment of the present invention, the polymers contained in the agents according to the invention are in a pre-assembled form with a molecular weight of 2000 gmol ^"1 or above. For the assembly of the polymers, encapsulation of the polymers by means of water-soluble or water-dispersible coating agents is suitable, 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 agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins with a melting point above 30 ° C; the cogranulation of the polymers with inert carrier materials, preferably with carrier materials the group of active washing or cleaning substances, particularly preferably from the group of builders (builders) or cobuilders.

The agents preferred according to the invention have a weight fraction of the abovementioned polymers of between 0.01 and 10% by weight, in each case based on the total weight of the washing or cleaning agent. In the context of the present application, however, preference is given to washing or cleaning agents in which the proportion by weight of polymer a) is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight, particularly preferably between 0.01 and 2% by weight and in particular between 0.01 and 1% by weight, in each case based on the total weight of the dishwasher detergent. Polymers effective as softeners are, for example, the polymers containing sulfonic acid groups, which are used with particular preference.

Copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionic monomers can be used particularly preferably as polymers containing sulphonic acid groups.

In the context of the present invention, unsaturated carboxylic acids of the formula are monomers

R ¹ (R ² ) C = C (R ³ ) COOH

preferably in which R to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with - NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or stands for - COOH or -COOR ⁴ , where 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) preferred.

The monomers containing sulfonic acid groups are of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H

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

Preferred among these monomers are those of the formulas H ₂ C = CH-X-S0 ₃ HH ₂ C = C (CH ₃ ) -X-S0 ₃ H H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H

in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _π - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (0) -NH- CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenlsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and water-soluble salts of the acids mentioned.

Other suitable ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The group iii) monomer content of the polymers used is preferably less than 20% by weight, based on the polymer. Polymers to be used with particular preference consist only of monomers of groups i) and ii).

In summary, copolymers are made of

i) unsaturated carboxylic acids of the formula

R ¹ (R ² ) C = C (R ³ ) COOH

in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -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) Monomers of the formula containing sulfonic acid groups R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H

in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents 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 (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers

particularly preferred.

Further particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid ii) one or more monomers of the formulas containing sulfonic acid groups:

H ₂ C = CH-X-S0 ₃ HH ₂ C = C (CH ₃ ) -X-S0 ₃ H H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H

in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents 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 (0) -NH-C (CH ₃ ) ₂ - and - C (0) -NH-CH (CH ₂ CH ₃ ) - iii) optionally further ionic or nonionic monomers.

The copolymers can contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) being combined with all representatives from group ii) and all representatives from group iii) can. Particularly preferred polymers have certain structural units, which are described below.

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

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p -

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

These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which is also preferred. The corresponding copolymers contain the structural units of the formula

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p -

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

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

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p -

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

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p -

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

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, copolymers preferred according to the invention are obtained, the structural units of the formula

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p -

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

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p -

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

In summary, preferred copolymers according to the invention are those structural units of the formulas - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - - [CH ₂ -C (CH ₃ ) C00H] _m - [CH ₂ -CHC (0) -Y -S0 ₃ H] _p - - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p -

contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _π - 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.

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

The monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer, in the case of copolymers which contain only monomers from groups i) and ii) from group i) and 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

In the case of terpolymers, those which contain 20 to δ5% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred ,

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 intended use. Preferred detergent or cleaning agent compositions are characterized in that the copolymers have molecular weights of 2,000 to 200,000 gmol ^"1 , preferably 4,000 to 25,000 gmol ^{" 1} and in particular 5,000 to 15,000 gmol ^"1 .

bleach

A preferred component of the agents according to the invention is the bleaching agent. Among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ 0 ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. 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-phthalimidanoic acid paprooxyacrylic acid , 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,

Diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (δ-aminopercaproic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in the agents according to the invention. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or

Dichloroisocyanuric acid (DICA) and / or its salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Agents according to the invention, in particular machine dishwashing agents, characterized in that they contain 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 20% by weight and in particular 5 to 15% by weight. % Bleach, preferably sodium percarbonate, are particularly preferred in the context of the present application.

The active oxygen content of the detergents according to the invention, in particular machine dishwashing detergents, is in each case based on the total weight of the dishwashing detergent preferably between 0.4 and 10% by weight, particularly preferably between 0.5 and δ% by weight and in particular between 0.6 and 5% by weight. Particularly preferred dishwashing detergents have an active oxygen content above 0.3% by weight, preferably above 0.7% by weight, particularly preferably above 0.3% by weight and in particular above 1.0% by weight.

Bleach activators Bleach activators are used in detergents or cleaning agents, for example, to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C and below. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, ethylene glycol, diacetoxy-2,5-dihydrofuran. Further bleach activators which are preferably used in the context of the present application are compounds from the group of the cationic nitriles, in particular cationic nitriles of the formula

R ¹ R ² -N ⁽⁺⁾ - (CH ₂ ) -CN X ^H ,

R ³

in R ¹ for -H, -CH ₃ , a C ₂ . ₂ alkyl or alkenyl radical, a substituted C ₂ . ₂ -alkyl or -alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a C 1-4 alkyl group, or for a substituted alkyl or alkenylaryl radical with a C ₂ 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 -0) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

A cationic nitrile of the formula is particularly preferred R ⁴

R ⁵ -N ⁽⁺⁾ - (CH ₂ ) -CN X (-)

R ⁶

in which R ⁴ , R ⁵ and R ⁶ are selected independently of one another from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , where R ⁴ additionally can also be -H and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ( CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{" are} particularly preferred, the cationic in turn from the group of these substances Nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , in which X ^{" represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or the like for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes, and also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod - Ligands as well as Co, Fe, Cu and Ru amine complexes are as lead ch catalysts can be used.

If further bleach activators are to be used in addition to the nitrile quats, bleach activators from the group of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyloxy- or isononosulfonates, are preferred. n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to δ% by weight, particularly 2 to δ% by weight and particularly preferably 2 to 6% by weight, in each case based on the total weight of the agents containing bleach activator.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru xylene sulfonate, is particularly preferred.

As bleach activators it is also possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyI-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso- NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholine, n Acetonitrile methyl sulfate (MMA) and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated or acylactyl and gluconyl and gluconyl Lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are also preferably used. Combinations of conventional bleach activators can also be used.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be used. These substances are bleach-enhancing transition metal salts or transition metal complexes, 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 used in customary amounts, preferably in an amount up to 5% by weight, in particular from 0.0025% by weight to 1% by weight, and particularly preferred from 0.01% by weight to 0.25% by weight, based in each case on the total weight of the bleach activator-containing agents. But in special cases, more bleach activator can be used.

Glass corrosion inhibitors

Glass corrosion inhibitors prevent the appearance of cloudiness, streaks and scratches but also the iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes.

A preferred class of compounds that can be used to prevent glass corrosion are insoluble zinc salts.

Insoluble zinc salts in the sense of this preferred embodiment are zinc salts which have a solubility of at most 10 grams of zinc salt per liter of water at 20 ° C. Examples of insoluble zinc salts which are particularly preferred according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn ₂ (OH) ₂ C0 ₃ ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (P0 ₄ ) ₂ ), and zinc pyrophosphate (Zn ₂ (P ₂ 0 ₇ )). The zinc compounds mentioned are preferably used in amounts which have a zinc ion content of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0 % By weight, in each case based on the total glass corrosion inhibitor-containing agent. The exact content of the zinc salt or zinc salts in the agents naturally depends on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration in the agents.

Since the insoluble zinc salts remain largely unchanged during the dishwashing process, the particle size of the salts is a criterion to be observed so that the salts do not adhere to glassware or machine parts. Means are preferred in which the insoluble zinc salts have a particle size below 1.7 millimeters.

If the maximum particle size of the insoluble zinc salts is below 1.7 mm, there is no fear of insoluble residues in the dishwasher. The insoluble zinc salt preferably has an average particle size which is significantly below this value in order to further minimize the risk of insoluble residues, for example an average particle size of less than 250 μm. This, in turn, is all the more the less the zinc salt is soluble. In addition, the glass corrosion inhibiting effectiveness increases with decreasing particle size. In the case of very poorly soluble zinc salts, the average particle size is preferably below 100 μm. For even more poorly soluble salts, it can be even lower; For example, average particle sizes below 100 μm are preferred for the very poorly soluble zinc oxide.

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

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

The spectrum of the zinc salts of organic acids, preferably organic carboxylic acids preferred according to the invention, extends from salts which are sparingly or not soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility, up to those salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, particularly preferably above 1 g / L and especially have 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.

It is particularly preferred to use at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate, as the glass corrosion inhibitor. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

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

corrosion inhibitors

Corrosion inhibitors serve to protect the items to be washed or the machine, with silver protection agents in particular being particularly important in the area of automatic dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. The following may be mentioned as examples of the 3-amino-5-alkyl-1, 2,4-triazoles which are preferably to be used according to the invention: 5, -propyl, butyl, pentyl, heptyl, octyl, nonyl -, - Decyl-, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-acid alkyl-, -Phenyl-, -p-Tolyl-, - (4-tert.butylphenyl) -, - (4- Methoxyphenyl) -, - (2-, -3-, -4-pyridyi) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5- oxo-2-pyrrolidinyl) -, -3-amino-1, 2,4-triazole. In dishwashing detergents, the alkylamino-1, 2,4-triazoles or their physiologically tolerable salts are used in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04 wt .-% used. Preferred acids for the salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulfurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid. 5-Pentyl-, 5-heptyl-, 5-nonyl-, 5-undecyl-, 5-isononyl-, 5-Versatic-10-acid-alkyl-3-amino-1, 2,4-triazoles and mixtures are very particularly effective of these substances. In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding 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. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the CobaIt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

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

The metal salts or metal complexes used are said to be at least partially soluble in water. The counterions suitable for salt formation include all customary one, two or three times negatively charged inorganic anions, e.g. B. oxide, sulfate, nitrate, fluoride, but also organic anions such. B. stearate.

For the purposes of the invention, metal complexes are compounds which consist of a central atom and one or more ligands and, if appropriate, additionally one or more of the abovementioned anions. The central atom is one of the metals mentioned in one of the oxidation states mentioned above. The ligands are neutral molecules or anions that are monodentate or multidentate; the term “ligands” in the sense of the invention is explained in more detail, for example, in “Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507”. If the charge of the central atom and the charge of the ligand (s) do not add up to zero in a metal complex, then depending on whether there is a cationic or an anionic excess of charge, either one or more of the above anions or one or more cations, e.g. B. sodium, potassium, ammonium ions for charge balance. Suitable complexing agents are, for example, citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate. The common definition for "oxidation level" in chemistry is given, for example, in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 316δ".

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 0 ₅ , V ₂ 0 ₄ , V0 ₂ , TiOS0 ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoS0 ₄ , Co (N0 ₃ ) ₂ , Ce (N0 ₃ ) ₃ and mixtures thereof., so that preferred automatic dishwashing agents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxy-ethane

1, 1 -diphosphonate], V ₂ 0 ₅ , V ₂ 0 ₄ , V0 ₂ , TiOS0 ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoS0 ₄ , Co (N0 ₃ ) ₂ , Ce (N0 ₃ ) ₃ .

These metal salts or metal complexes are generally commercially available substances which can be used in the agents according to the invention for the purpose of protecting against silver corrosion without prior cleaning. For example, that's from S0 ₃ production

(Contact method) known mixture of pentavalent and tetravalent vanadium (V ₂ θ5, V0 ₂ , V ₂ 0 ₄ ) are suitable, as is the titanyl sulfate formed by diluting a Ti (S0 ₄ ) ₂ solution,

TiOS0 ₄ .

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

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

Enzymes can be used to increase the washing or cleaning performance of washing or cleaning agents. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Agents according to the invention preferably contain enzymes in total amounts of 1 x 10 ^"6 to 5 percent by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and that which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ^® from Novozymes A / S, Bagsvasrd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. The variants listed under the name BLAP ^{® are} derived from the protease from Bacillus lentus DSM 54δ3.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, which is sold under the trade name Protosol ^® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ^® by Wuxi Snyder Bioproducts Ltd., China, and in the trade name Proleather ^® and Protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

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

Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12366) and the cyclodextrin glucanotransferase (CGTase) from ß. to highlight agaradherens (DSM 9943).

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

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

Furthermore, enzymes can be used, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and ß-glucanases. Suitable mannanases, for example, under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, USA available. The from ß. subtilis .beta.-glucanase obtained is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenoloxidases, polyphenol oxidases) can be used according to the invention. Suitable commercial products are Denilite ^® 1 and 2 from Novozymes. Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of greatly different redox potentials between the oxidizing enzymes and the soiling.

The enzymes originate, for example, either originally from microorganisms, for example of the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.

The enzymes in question are preferably purified by methods which are established per se, for example by means of precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.

The enzymes can be used in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzyme is enclosed in a solidified gel are or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers. Capsules of this type are produced by methods known per se, for example by shaking or roll granulation or in fluid-bed processes applied. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.

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

A protein and / or enzyme can be protected against damage, such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage. When the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Agents according to the invention can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.

A group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters. Ovomucoid and leupeptin may be mentioned as peptide protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.

Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C ₂ , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders can additionally stabilize an enzyme contained.

Lower aliphatic alcohols, but above all polyols, such as, for example, glycerol, ethylene glycol, propylene glycol or sorbitol are further frequently used enzyme stabilizers. Calcium salts, such as calcium acetate or calcium formate, and magnesium salts are also used.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, among other things, against physical influences or pH fluctuations. Polymers containing polyamine-N-oxide act as enzyme stabilizers. Other polymeric stabilizers are the linear C ₈ -C ₈ polyoxyalkylenes. Alkyl polyglycosides can be the enzymatic components stabilize the agent according to the invention and even increase its performance. Crosslinked N-containing compounds also act as enzyme stabilizers.

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

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

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

disintegration aid

In order to facilitate the disintegration of prefabricated moldings, disintegration aids, so-called tablet disintegrants, can be incorporated into these agents in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1967, p. 1δ2-1 δ4), tablet disintegrants or disintegration accelerators are understood as auxiliary substances which are suitable for the rapid Disintegration of tablets in water or gastric juice and release of the pharmaceuticals in an absorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks 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 products such as cellulose and starch and their derivatives, alginates or casein derivatives. Disintegration aids are preferably used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, based in each case on the total weight of the agent containing disintegration aids.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and cleaning agent compositions contain such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, from a formal point of view, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention. Microcrystalline cellulose can be used as another cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. Subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

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

According to the invention, gas-developing effervescent systems can also preferably be used as tablet disintegration aids. The gas-developing shower system can consist of a single substance which releases a gas when it comes into contact with water. Among these compounds, magnesium peroxide should be mentioned in particular, which releases oxygen on contact with water. Usually, however, the gas-releasing bubble system itself consists of at least two components that react with one another to form gas. While a large number of systems are conceivable and executable here, which release nitrogen, oxygen or hydrogen, for example, the effervescent system used in the detergent and cleaning agent compositions according to the invention can be selected on the basis of both economic and ecological aspects. Preferred effervescent systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

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

The preferred shower system is 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight. -% of an acidifying agent, based in each case on the total weight of the agent. Examples of acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are boric acid and alkali metal bisulfates,

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

In the context of the present invention, preference is given to acidifying agents in the effervescent system from the group of the organic di-, tri- and oligocarboxylic acids or mixtures.

fragrances

As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate,

Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with δ-1δ C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, α-isomethylionon and methylcedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, gaibanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers by a slower fragrance release for long-lasting fragrance to care. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

dyes

Preferred dyes, the selection of which is not difficult for the person skilled in the art, 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 glass, ceramics or plastic tableware, to say nothing of them to stain.

In addition to the components described in detail so far, the washing and cleaning agents according to the invention can contain further ingredients which further improve the application technology and / or aesthetic properties of these agents. In the context of the present invention, preferred agents contain one or more substances from the group of electrolytes, pH regulators, fluorescent agents, hydrotopes, foam inhibitors, silicone oils, anti-reposition agents, optical brighteners, graying inhibitors, anti-wrinkle inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides Antioxidants, antistatic agents, ironing aids, phobing and impregnating agents, swelling and anti-slip agents as well as UV absorbers.

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

In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or bases can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 1% by weight of the total formulation.

Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials. Suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a methoxy group content of 15 up to 30% by weight and of hydroxypropyl groups from 1 to 15% by weight, in each case based on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid known from the prior art or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and results in pure white with the yellow tone of the grayed or yellowed laundry. Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2 ^' -stilbene disulfonic acids ( flavonic), ^{4,4'-biphenylene} -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, benzisoxazole, and benzimidazole systems, and pyrene derivatives substituted by heterocycles.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Also usable as graying inhibitors are cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as

Methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.

Since textile fabrics, in particular made from rayon, rayon, cotton and their mixtures, can tend to crease because the individual fibers prevent bending, kinking. If pressing and squeezing across the grain are sensitive, the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

Antimicrobial agents can be used to control microorganisms. Depending on the antimicrobial spectrum and the mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylariyl sulfonates, halophenols and phenol mercuric acetate, whereby these compounds can also be dispensed with entirely in the agents according to the invention.

In order to prevent undesirable changes in the detergents and cleaning agents and / or the treated textiles caused by the action of oxygen and other oxidative processes, the agents can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

An increased wearing comfort can result from the additional use of antstatics, which are additionally added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided 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, with an additional finishing effect.

To care for the textiles and to improve the textile properties such as a softer "handle" (finish) and reduced electrostatic charging (increased wearing comfort), the agents according to the invention can contain fabric softeners. The active ingredients in fabric softener formulations are "esterquats", quaternary ammonium compounds with two hydrophobic residues, such as, for example, disteraryldimethylammonium chloride, which, however, due to its insufficient biodegradability, is increasingly being replaced by quaternary ammonium compounds which contain ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, the agents according to the invention, for example silicone derivatives. These additionally improve the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are wholly or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds

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

Claims

claims:

1. washing or cleaning agent, comprising at least one washing or cleaning agent shaped body and at least one water-soluble or water-dispersible film material, characterized in that the washing or cleaning agent shaped body and the film material are adhesively bonded to one another by a heat seal seam.

2. Detergent or cleaning agent according to claim 1, characterized in that the molded body has a cavity which is at least partially closed by the film material.

3. washing or cleaning agent according to claim 2, characterized in that the cavity of the shaped body is filled.

4. Detergent or cleaning agent according to one of claims 1 to 3, characterized in that the water-soluble or water-dispersible film material is formed into a hollow body, which is an injection molding and / or blow molding and / or deep-drawn part.

5. Washing or cleaning agent according to claim 4, characterized in that the washing or cleaning agent shaped body has a cavity which at least partially comprises the hollow body.

6. Detergent or cleaning agent according to one of claims 1 to 5, characterized in that the detergent or cleaning agent tablet is a single or multi-phase detergent or cleaning agent tablets.

7. Detergent or cleaning agent according to one of claims 4 to 6, characterized in that the hollow body has a filling, preferably a liquid filling.

δ. Detergent or cleaning agent according to one of claims 1 to 7, characterized in that the molded body or the molded body phase, which is adhesively bonded to the water-soluble or water-dispersible film material by a heat seal seam, has a surfactant content below 20% by weight, preferably below 16% by weight, preferably below 12% by weight, particularly preferably below δ% by weight and in particular below 4% by weight.

9. washing or cleaning agent according to one of claims 1 to δ, characterized in that the molded body or the molded body phase, which (r) is adhesively bonded to the water-soluble or water-dispersible film material by a heat seal seam, has an enzyme content below 6% by weight, preferably below 4.5% by weight, preferably below 3.0% by weight and in particular below 1.0% by weight.

10. Detergent or cleaning agent according to one of claims 1 to 9, characterized in that the molded body or the molded body phase, which (r) is adhesively bonded to the liquid-filled hollow body by a heat seal, has a bleach content below 15% by weight, preferably below 12% by weight, preferably below 9% by weight, particularly preferably below 6% by weight and in particular below 3% by weight.

11. Detergent or cleaning agent according to one of claims 1 to 10, characterized in that the molded body or the molded body phase, which (r) is adhesively bonded to the water-soluble or water-dispersible film material by a heat seal seam, has a bleach activator content below 5% by weight, preferably below 3.5% by weight, particularly preferably below 2.0% by weight and in particular below 1.0% by weight.

12. Detergent or cleaning agent according to one of claims 1 to 11, characterized in that the molded body or the molded body phase, which (r) is adhesively bonded to the liquid-filled hollow body by a heat seal seam, has a builder content above 10% by weight, preferably above 15% by weight, preferably above 20% by weight, particularly preferably above 25% by weight and in particular above 30% by weight.

13. washing or cleaning agent according to one of claims 1 to 12, characterized in that the molded body or the molded body phase, which (r) is adhesively bonded to the liquid-filled hollow body by a heat seal seam, a polymer content above 0.5 wt .-%, preferably above 1.0% by weight, particularly preferably above 2.0% by weight and in particular above 4% by weight.

14. Washing or cleaning agent according to one of claims 1 to 13, characterized in that the molded body and the hollow body are adhesively connected to one another along a circumferential sealing seam.

15. Detergent or cleaning agent according to one of claims 1 to 14, characterized in that the shaped body and the hollow body are adhesively connected to one another along two or more separate sealing seams.

16. Washing or cleaning agent according to one of claims 1 to 15, characterized in that the molded body has a breaking pressure above 1 bar, preferably above 2.5 bar and in particular above 4 bar.

17. A process for the production of a detergent or cleaning agent from at least one detergent or cleaning product tablet and at least one water-soluble or water-dispersible film material, characterized by the steps a) production of washing or cleaning product tablets; b) providing a water-soluble or water-dispersible film material; c) Adhesive connection of at least one product from step a) with the water-soluble or water-dispersible film material from step b) by a heat seal seam.

18. The method according to claim 17, characterized in that the washing or cleaning agent shaped body has a coating.