EP1461410A2

EP1461410A2 - Shaped body containing agents with increased storage stability

Info

Publication number: EP1461410A2
Application number: EP02796694A
Authority: EP
Inventors: Michael Dreja; Wolfgang Von Rybinski; Andreas Buhl; Dieter Nickel; Matthias Sunder; Georg Meine
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2001-12-30
Filing date: 2002-12-20
Publication date: 2004-09-29
Also published as: WO2003055965A3; WO2003055965A2; DE10164137B4; DE10164137A1; AU2002361181A8; AU2002361181A1

Abstract

The present invention relates to shaped bodies containing agents with increased storage stability, characterized in that the shaped body and/or the outer coatings thereof comprises the following: at least one thermoplastic, water-soluble polymer; at least one ionic salt which does not complex said polymer; at least one compound containing at least two anionic groups whereby said compound containing at least two ionic groups reversibly complexes the water-soluble polymer; optionally, at least one carrier and/or at least one extruding agent.

Description

Shaped bodies containing agents with increased storage stability

The present invention relates to moldings containing compositions with increased storage stability, their use, in particular as washing, cleaning and / or care products, and to a process for producing the moldings containing compositions with increased storage stability.

Conventional washing, cleaning and / or care agents consist of only one liquid phase, the main part of which is mostly water, in which the active, fat-dissolving and cleaning-active surfactants and auxiliaries, such as enzymes, are present in dissolved or finely dispersed form. Such detergent, cleaning agent and / or care agent formulations, in particular liquid agents, have the disadvantage that active ingredients which are incompatible with the formulation, such as colorants, fragrances, care oils, vitamins, enzymes, antibacterial active ingredients, acids, bases, are present in them and / or oxidizing agents that are used in such formulations often lose their activity, or at least be greatly reduced, during storage and / or before their desired time of use due to chemical reactions and / or physical influences.

In particular in the case of detergents and cleaning agents containing surfactant, additional active detergents and auxiliaries active in washing and cleaning are usually incorporated into the formulation. The chemical properties of the active ingredients generally result in formulation disadvantages. Negative interactions that can occur are, in particular, destabilization of emulsions (e.g. BAC in fabric softener), decomposition of the active ingredients after prolonged storage (e.g. amino-functional silicone oils in acid detergents), general incompatibility of individual ingredients (e.g. complexation of QACs with anionic surfactants).

Numerous commercial encapsulation systems based on natural or synthetic polymers already exist. These can enclose an active ingredient or its solution and then be physically or chemically crosslinked in the shell or can be precipitated by a coacervation process with another polymer. There are also encapsulations by liposomes, for example 'nanotopes' from Ciba-Geigy or sponge-like particles such as 'microsponges' from Advanced Polymer Systems. For example, microencapsulated molded articles are used to increase the stability of pharmaceutical active ingredients, to influence taste, to target organ-specific active ingredient release and to avoid incompatibilities with other auxiliaries and active ingredients. Microcapsules are also used in adhesive technology. Also known are fragrance capsules with gelatin as wall material, from which perfume oils are released by mechanical destruction. In addition to "real" microcapsules that have a shell / core structure, there are spherical carrier particles, for example made of alginate, gelatin or polyvinyl alcohol (PVAI), in which an active substance, living cells or enzymes can be embedded. These capsules can be produced, for example, by a dropletization process. In general, microcapsules are particles with diameters of <1 mm. In addition to being encapsulated in capsules of various sizes, substances can also be adsorbed or chemically modified on suitable carrier materials.

As described above, numerous efforts have been made in the prior art to protect such active components by encapsulation, coating or the like.

It is disadvantageous that components protected in this way in the agents lose activity even during storage, in particular in liquid detergents, cleaning agents and / or care products, since the materials of the encapsulations, coatings or the like dissolve to an increased extent and thus their protective effect to lose.

In addition, migration and diffusion effects contribute to the release of substances, such as streaking in solutions, and / or to loss of activity of active ingredient components.

Furthermore, the encapsulations, coatings, carriers or the like known in the prior art have the disadvantage that the components which are protected, adsorbed or chemically modified in this way are released during storage and that release of active substances at the site of the specific application is not controlled can be.

For aesthetic reasons, it is also desirable for many agents to add components of the agent separately to the agent in a delimited form, for example in the form of capsules. be balls, drops, as a second phase or as a further phase and / or the like. In addition to aesthetic effects, such spatial delimitations, as listed above, aim to improve activity stability during storage and / or upon dilution. In particular in the case of dyes, which are often constituents of protective layers, such as coverings, coatings and the like, streaks can be formed in such agents of the prior art, even in highly concentrated solutions, when stored for a prolonged period of time, ie weeks or months - “so-called Bleed "- to observe the molded body.

In addition to the dyes, the streaking of which can already be seen by the user with the naked eye, the unwanted, premature escape of fragrances causes great problems.

EP 0 782 853 A2 and the corresponding DE 195 19 804 A1 describe bioactive capsules with a variable shell, in particular for use in living tissue or in biotechnological applications, with a core containing living cells and / or enzymes and a shell consisting of several , the core is completely enclosed individual layers, which consist of a porous network of intertwined macromolecules, at least one of the layers consisting of a material that changes or dissolves the structure as a function of an ion concentration and / or physical quantities and / or by reagents ,

WO 99/02252 describes a process for the production of high-strength capsules which have a core made of a polyanionic polysaccharide, which is coated with a polycationic polysaccharide membrane. The capsules described there are used in particular in the field of pharmacy, but also in the field of catalysis, biology, pesticides and herbicides, agriculture, cosmetics and the food industry.

US-A-4,352,883 describes a method for encapsulating living tissue, single cells, hormones, enzymes or antibodies in a semi-permeable membrane which is permeable to small molecules but is impermeable to large molecules which are potentially hazardous to health. The semipermeable membrane is applied to discrete, temporary capsules or gel droplets that retain their shape, the gel then being liquefied again. US-A-4 690 682 describes a dosing system for the controlled release of substances with a substantially constant delivery quantity. These are capsules with a semipermeable membrane, which contain a material to be released in encapsulated form. The release genetics should be controllable via the pore size of the membranes.

WO 91/15196 describes an osmotic dosing system for active pharmaceutical ingredients, which consists of an outer semipermeable membrane, an osmotically active middle layer and an inner capsule, which comprises a liquid formulation with the active pharmaceutical ingredient.

DE 197 12 978 A1 describes chitosan microspheres which are obtained by mixing chitosans and / or chitosan derivatives with oil bodies and then introducing the mixture into alkaline surfactant solutions, so that microcapsules filled with oil bodies are formed. In this way, lipophilic phases can be encapsulated and can then be incorporated as active substance depots in formulations containing surfactants.

WO 00/46337 describes a liquid cleaning composition which comprises more than 5% by weight of a surfactant and more than 10% by weight of an encapsulated active substance and a crosslinked anionic rubber material. The active ingredient is in particular a fragrance.

EP 0 280 155 B1 describes the microencapsulation of biologically active material by producing a semipermeable membrane which consists of a biocompatible, non-toxic polyacid and a polybase, the polybase being formed from a special polymer with special, defined, repeating monomer units.

Denkbas et a /., "Chitosan Microspheres and Sponges: Preparation and Characterization" in Journal of Applied Polymer Science, Volume 76, pages 1637-1643 (2000) describe studies on the formation of chitosan microcapsules and networks for various biomedical applications. Chitosan microcapsules and networks are formed in a suspension medium which contains chitosan, acetic acid, an emulsifier and a crosslinking agent, namely glutaraldehyde. Bartkowiak et al., "Alginate-Oligochitosan Microcapsules: A Mechanistic Study Relating Membrane and Capsule Properties to Reaction Conditions" in Chem. Mater. 1999, 11, pages 2486-2492 investigate the mechanism of the production of microcapsules by polyelectrolyte complexation reactions between oppositely charged polysaccharides, one of which is an oligomer. The ionic strength and the pH of the solution used in the capsule formation influence the structure of the membrane. The investigations are carried out on an alginate-oligochitosan system.

Bergbreiter, "Self-organized, semi-permeable capsules with diameters in the sub-micrometer range" in Angew. Chem. 1999, 111, No. 19, pages 3044-3046 describes the self-assembly of ions for the formation of semipermeable capsules for the design of new materials, which should be relevant to questions of catalysis, sensor design, biochemistry and materials science.

Yamamoto et al., "Polyion complex fiber and capsule formed by self-assembly of chitosan and gellan at solution interfaces" in Macromol. Chem. Phys. 201, No. 1, pages 84-92 describe the formation of polyionic complexes (PIC) by reaction of a polyelectrolyte with an oppositely charged polyelectrolyte in aqueous solution. To ensure that the encapsulated material is securely enclosed, the authors recommend subsequent coating of the microcapsule with another polymer.

Dautzenberg et al., "Polyelectrolyte complex formation at the interface of solutions" in Progr. Colloid. Polym. Be. (1996) 101: pp. 149-156, Steinkopff-Verlag, investigate the kinetics of the reaction between oppositely charged polyelectrolytes at the interface of their aqueous solutions, whereby microcapsule membranes are formed which consist of the reaction components sodium cellulose sulfate and poly (dial- lyldimetylammoniumchlorid) are formed. The authors investigate the kinetics of membrane formation.

Kokufuta, "Polyelectrolyte-coated microcapsules and their potential applications to biotechnology" in Bioseperation 7: Pages 241-252 (1999) describe polyelectrolyte-coated microcapsules which are produced by adsorption of polyions on microcapsule surfaces in aqueous solution under suitable pH values and ionic conditions become can. The authors investigate the pH-dependent control of the permeability of the capsule walls as a function of changes in the adsorbed polyion layer.

There is therefore a great need to make additional, incompatible with the formulation, diffusing, migrating and / or streaking constituents in agents, such as detergent, cleaning agent and / or care agent formulations, stable in storage. There is also a need to provide agents, such as detergent, cleaning agent and / or care agent formulations, which have their effect at a particular point in time at the place of use, for example towards the end of the wash cycle in a washing machine.

Therefore, methods or systems for the release of active ingredients when using detergents and cleaners are sought, which provide a switching mechanism for the respective protective coverings or encapsulations, with the aid of which a targeted release of the ingredients can take place.

It is therefore an object of the present invention to overcome the above-described disadvantages of the prior art and to provide moldings which have a significantly increased storage stability, in particular in aqueous liquid or gel phases, and which allow a wide range of applications. Such molded articles should be usable in particular in detergents and cleaning agents, preferably liquid detergents and cleaning agents, fabric softeners and laundry aftertreatment agents, but also in other products, such as cosmetic products and personal care products. In particular, such shaped articles in water-containing compositions at the place of use, in spite of the improved storage stability, should enable a quick, easily inducible release of the ingredients during use and should be capable of being dissolved and / or removed without residue after use.

The object of the present invention is achieved by providing a shaped body containing an agent with increased storage stability, the shaped body and / or its outer shaped body shell comprising: at least one thermoplastic, water-soluble polymer; at least one ionic salt not complexing the polymer; at least one compound containing at least two anionic groups, the compound having at least two anionic groups reversibly complexing the water-soluble polymer; and optionally at least one carrier and / or at least one extrusion aid.

It has surprisingly been found that, in particular, polyvinyl alcohol (PVAI) capsules or spheres can be and are dispersed by mixing PVAI, non-crosslinking salts and partially crosslinking dyes, which are stable in detergents and cleaning agents, preferably liquid detergents and cleaning agents dissolve when used while dispensing active ingredient. Such capsules or spheres open automatically when diluted, i.e. without shear, i.e. the switching mechanism is activated directly during application (dilution). The dyes do not diffuse from the capsules or balls and do not reach the agent or the application site prematurely.

Another object of the present invention relates to the production of PVAI coatings by mixing PVAI, non-crosslinking salts and crosslinking dyes, which enclose granular powder mixtures and disperse them stably in (liquid) detergents and cleaning agents and dissolve when used with release of active ingredient.

Shaped bodies in the sense of this invention preferably have a solid outer, layer-like covering and a shaped body core, wherein the shaped body core can be solid, liquid or gel-like. The molded body core can be partially or preferably completely encased in at least one layer-like covering.

The shaped body, the shaped body layer (s) or wrappings and / or the shaped body core can have active substances, such as washing, care and / or cleaning substances.

The shaped body can be designed onion-like, ie it comprises at least two layer-shaped coverings, of which at least one, preferably at least two layer-shaped coverings, form a complete covering surrounding the shaped body. Active substances, such as wash, care and / or cleaning substances. The shaped body can also be formed in one, two or more pieces.

The molded article or articles are preferably in the form of a solid phase (s) in a multiphase system with at least one further solid, liquid and / or gel phase, preferably with a high electrolyte content.

The agent containing the shaped body, preferably at least one phase of the agent, particularly preferably the phase in which the shaped body is contained, can have a water content> 0 to 88 88% by weight, preferably ≤ 50% by weight, more preferably 20 20% by weight. % and more preferably ≤ 12% by weight.

A preferred embodiment of the shaped body according to the invention relates to an essentially homogeneous, solid or gel-shaped shaped body which is formed, for example, from a mixture of all constituents of the shaped body, this shaped body is preferably molded in one step. Such a shaped body can be extruded, cast, pressed, foamed, dripped and / or blown.

Shaped bodies in the sense of this invention can also be particles, agglomerates, powders, drops and / or the like. For example, a shaped body according to the invention can be formed from a plurality of microparticle shaped bodies.

It is important that the active substance or substances whose storage stability is to be improved and / or whose premature release is to be prevented are surrounded by at least one thermoplastic, water-soluble polymer; at least one ionic salt not complexing the polymer; at least one compound containing at least two anionic groups, the compound having at least two anionic groups reversibly complexing the water-soluble polymer; and optionally of at least one carrier substance and / or at least one extrusion aid.

It is most preferred if the active substance (s) whose storage stability is to be improved and / or whose premature release is to be prevented is the compound which contains at least two anionic groups and which is the water-soluble one Polymer reversibly complexed. Alternatively, active substances (s) whose storage stability is to be improved and / or whose premature release is to be prevented and which usually do not have at least two anionic groups can be correspondingly derivatized by chemical processes which are well known to those skilled in the art.

Without being bound by any particular theory, it is believed that a matrix is formed from: at least one thermoplastic, water-soluble polymer; at least one ionic salt not complexing the polymer; at least one compound containing at least two anionic groups, the compound having at least two anionic groups reversibly complexing the water-soluble polymer; and optionally at least one carrier substance and / or at least one extrusion aid.

The matrix formed in this way protects the compound containing at least two anionic groups, for example an active substance such as a dye, and / or active substances encased in the matrix, for example against migration, diffusion and / or solution effects which lead to active substance release, so that improved storage stability is achieved and premature release of active substance is prevented on average.

The complex formation constant of the reversible complex formed can have a value in the range from 10 to 10 ⁶⁰ , preferably 100 to 10 ³⁰ and preferably 10 ^{3 to} 10 ¹⁵ .

In the case where the compound having at least two anionic groups, which reversibly complexes the water-soluble polymer, is an active substance, the storage stability is improved and / or its premature release is delayed or prevented on average by the active substance by the aforementioned Forms matrix as an integral part.

According to the invention, agents, in particular liquid detergents or liquid cleaners, can be made available in which molded articles are present as a further separate, spatially delimited phase. The molded body preferably has a solid shape, in particular a spherical or capsule-like shape that is visually visible and distinguishable in the first phase.

The mechanism for releasing the active substances from the shaped body can be activated by several possible parameters: time-controlled dissolution of the shaped body and / or the shaped body shell (s) when the shaped body-containing agent is diluted pH-controlled dissolving of the shaped body and / or the shaped body - Envelope (s) in the case of dilution of the agent containing temperature-controlled dissolution of the shaped body and / or the article shell (s) in the event of dilution of the agent containing the electrolyte. The dissolution of the article and / or the article shell (s) when the agent is diluted Means containing moldings.

A time-controlled dissolution of the shaped body and / or the shaped body shell (s) by means of dilution, preferably by means of dilution with an excess of water, of the agent containing the shaped body is particularly preferred.

In particular, it has been found that the storage stability of shaped bodies containing dye can be improved and / or the premature release of the dye can be significantly reduced or prevented on average if the dye has at least two anionic groups which reversibly complex the water-soluble polymer, and additionally at least one ionic salt not complexing the polymer is present.

A preferred embodiment of the above invention relates in part or in full to molded articles, such as capsules, spheres, foils or small particles, which are produced from the material mixture forming the matrix and comprise at least one thermoplastic, water-soluble polymer which, at a high electrolyte content, as described in a liquid detergent formulation ( Concentrate) is present, is insoluble, but at low ionic strength, ie after dilution with water (at the time of application), is water soluble. Polymers such as polyvinyl alcohol (PVAI) or polyvinyl alcohol copolymers are particularly preferred.

Ideally, such shaped bodies or the material mixture forming the matrix can also be crosslinked in order to further increase the stability, in order, for example, to prevent bleeding of a containing dye. In principle, this can be achieved by diffusing in or adding borates or other polyvalent salts, as are often contained in liquid detergents.

According to the invention, the molded body, molded body layer and / or molded body coating is preferably free of borates and / or other non-reversibly complexing salts.

It has surprisingly been found that when using a compound with multiple anionic charges as a matrix component, e.g. Bi-ionic dye, which has reversibly crosslinking properties and has a sufficiently high storage stability, so that no borate is necessary.

The amount of reversibly crosslinking dye is generally chosen so that the thermoplastic, water-soluble polymer is only partially crosslinked and becomes completely soluble in the application when diluted, for example with an excess of water.

Above all, it is advantageous that, owing to the partial, reversible, physical crosslinking, the multiply anionically charged compound (ie at least two anionic groups), for example a bi-ionic dye itself, does not diffuse out of the shaped body, for example spheres, which results in the formation of “comets "or streaks are suppressed.

Another preferred embodiment of the above invention relates to the use of the matrix material as a shaped body coating (coating) of granules, powders, spheres, capsules or particles, e.g. of extruded detergents. Such a coating means that the coated material becomes insoluble with a high electrolyte content, as is present in the liquid detergent formulation, but becomes water-soluble with a low ionic strength. Here too, a bi-ionic dye can be used in order to achieve a color differentiation of the molded body from the surrounding, outer liquid phase.

The shaped bodies, such as capsules or shaped body coverings, can contain substances which achieve an additional effect during the washing application. For example, the capsules can contain fragrances such as perfume oils, possibly applied to a carrier material such as Zeoiith. This leads to an increased fragrance of the laundry after washing. Alternative ingredients concern fabric softener surfactants (esterquat), soil repellent polymers, sub- punches for anti-crease effects, antibacterial substances, substances for color protection, discoloration inhibitors, vitamins, care substances, layered silicates, wash and rinse active, wash and rinse support substances and / or odor complexing substances.

Preferred ingredients or active substances (the terms ingredients, active substance and active substance are used synonymously in the description of the invention), such as detergent, care and / or cleaning substances, are selected from the group comprising anionic surfactants, cationic surfactants, amphoteric surfactants , Builder substances, bleaching agents, bleach activators, bleach stabilizers, bleaching catalysts, enzymes, polymers, cobuilders, alkalizing agents, acidifying agents, anti-deposition agents, silver protective agents, colorants, optical brighteners, UV protective substances, fabric softeners, auxiliary agents, fragrances, dirt-repellent substances, anti - Wrinkle fabrics, antibacterial fabrics, color protection agents, discoloration inhibitors, vitamins, layered silicates, odor-complexing substances and / or rinse aid.

The shaped body, the matrix-forming material of the shaped body, the shaped body layer and / or the shaped body covering can have thermoplastic properties, so that processing by means of extrusion processes is possible. It has proven to be particularly advantageous if the matrix, the molded body, the molded body layer and / or molded body covering has at least one carrier substance and / or at least one extrusion aid, more preferably at least one inert carrier substance and / or at least one extrusion aid.

Talc and / or starch are particularly suitable extrusion aids.

A particularly suitable carrier is zeolite.

The compound having at least two anionic groups is preferably selected from the group comprising Congo red, Trypan Blue (Direct Blue 14), Chicago Blue (Direct Blue 1); Macro anions, preferably montmorillonite (layered silicates), metaphosphates; and / or polyanions, preferably polystyrene sulfonate, carboxymethyl cellulose and / or polyacrylates.

The anionic groups can be selected from the group comprising O ^{2 "} , RBO ₂ ² -, RCOO ^" , RCONR-, OH ^" , NO ₃ ^" , NO ₂ ^' , NO, CO, S ^2' , RS ^" , PO ₃ ^{2 "} , PO3OR ³ -, H ₂ O, CO ₃ ² -, HCO ³ -, ROH, NRR'R", RCN, CI ^" , Bf, OCN ^" , SCN ^" , CN ^' , N3 ^" , F, I ^" , RO \ CIO ₄ ^' , SO ₄ ^{2 "} , HSO ₄ ^" , SO ₃ ^{2 "} and / or RSO ₃ ^" , and particularly preferably O ^{2 "} , RBO ^2" , RCOO ^" , OH ^" , NO ₃ ^" , NO _∑ f, NO, CO, CN ^" , S ² -, RS ^" , PO ₄ ^{3 "} , H ₂ O, CO ₃ ² -, HCO ^3" , ROH, NRR'R ", RON, CI ^" , Bf, OCN ^" , SCN ^" , N3 ^" , F, I ^" , RO ^" , CIO ₄ ^" , SO ₄ ^2" , HSO ₄ ^" , SO ₃ ^2" , RSO ₃ ^_ and / or CF ₃ SO3 ^" , and more preferably SO3N er, OH ^" , SO ₄ ^{2 "} , PO ₃ ² -, PO ₄ ^{3 '} , COO ^" , NO ₃ ^" , CO ₃ ² -, CHaCOO ^" , C ₂ O ₄ ² -, citrates and / or acetates, where R, R', R" are the same or different from one another, selected from the group comprising alkyl, alkenyl, alkoxy, alkylene, cycloalkyl, aryl, arylene or heteroaryl.

Alkyl = linear and / or branched C1-C6-alkyl;

Alkenyl = C3-C6 alkenyl;

Cycloalkyl: C6-C8 cycloalkyl;

Alkoxy = C1-C4 alkoxy;

Alkylene = is selected from the group comprising: methylene; 1,2-ethylene; 1,3-propylene; Butan-2-ol-1,4-diyl; 1,4-butylene; CycIohexan-1,1-diyl; Cyclohexane-1,2-diyl; Cyclohexane, 1,4-diyl; Cyclopentane-1,1-diyl; and / or cyclopentane-1,2-diyl;

Aryl = is selected from the group comprising: phenyl; biphenyl; naphthalenyl; Anthracenyl; and / or phenanthrenyl;

Arylene = is selected from the group consisting of: 1,2-phenylene; 1,3-phenylene; 1,4-phenylene; 1, 2-NaphtaIenyIen; 1,4-naphthalenes; 2,3-naphthalenylene and / or 1-hydroxy-2,6-phenylene;

Heteroaryl = is selected from the group comprising: pyridinyl; pyrimidinyl; quinolinyl; pyrazolyl; triazolyl; isoquinolinyl; imidazolyl; and / or oxazolidinyl, wherein the heteroaryl is linked to the compound via a ring atom of the selected heteroaryl.

The weight content of the compound containing anionic groups, based on the total weight content of the shaped body, can range from between 0.001-10% by weight, preferably 0.01-5% by weight and preferably 0.05-2% by weight.

The non-complexing salt is preferably selected from the group comprising alkali and / or alkaline earth metal salts, preferably alkali metal and / or alkaline earth metal halides. nides, more preferably alkali and / or alkaline earth metal sulfates, nitrates, phosphates, carboxylates, citrates, hydroxides, borates, acetates, phosphates, silicates, oxalates, formates, percarbonates , and / or perborates.

The weight content of the non-complexing salt, based on the total weight content of the shaped body, can be between 1-50% by weight, preferably 1-30% by weight and preferably 2-20% by weight.

The water-soluble polymer is preferably selected from the group comprising polyvinyl alcohol (PVA), acetalized polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, starch and derivatives of the abovementioned substances, and / or mixtures of the abovementioned polymers, polyvinyl alcohol being particularly preferred.

The weight content of the water-soluble polymer, based on the total weight content of the shaped body, can range from between 10-95% by weight, preferably 20-75% by weight and preferably 30-60% by weight.

Polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above polymers can additionally be added to the water-soluble polymer.

The water-soluble polymer can in particular comprise a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

The water-soluble polymer can preferably comprise a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^"1 , preferably from 11,000 to 90,000 gmol ^{" 1} , particularly preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

The shaped body and / or the outer shell of the shaped body can be water-soluble polymer in amounts of 50 50% by weight, preferably ≥ 70% by weight, particularly preferably ≥ 80 wt .-% and in particular ≥ 90 wt .-%, each based on the total weight of the molded body and / or the outer shell.

In addition, the water-soluble polymer can contain plasticizers in amounts of at least> 1% by weight, preferably ≥ 10% by weight, particularly preferably ≥ 20% by weight and in particular ≥ 30% by weight, based in each case on the total weight of the water-soluble polymer of the shaped body.

The detergent containing shaped articles can in particular be a detergent, cleaning agent, care agent, hair treatment agent, hair colorant, medicament, crop protection agent, food, cosmetic, agrochemical, fertilizer, building material, adhesive, bleaching agent, disinfectant and / or fragrance agent.

The molded articles containing the agents can have a different content and / or a different composition of substances which are active in washing, care and / or cleaning.

The reversibly complexed, water-soluble polymer-containing outer molded body shell can have a wall thickness of between 0.01 and 5 mm, preferably between 0.06 and 2 mm, preferably between 0.07 and 1.5 mm, further preferably between 0.08 - 1.2 mm, more preferably between 0.09-1 mm and most preferably between 0.1-0.6 mm.

The agent contained in the molding, in particular washing and / or cleaning agent, can be released predominantly or completely into the aqueous application liquor (excess water) within ≤ 5 min, preferably within <3 min, preferably within 1 1 min.

For the purposes of this invention, the terms “predominantly” and “essentially” refer to a quantitative indication of> 50%.

The molded article or articles can be present in a liquid medium of the agent, which is diluted with water before use, the liquid medium preferably is a solution with a water content of between 0 - 88 wt .-%, based on the total weight of the liquid medium, or a gel.

The liquid medium can have a viscosity of between 10-100000 mPas (at 100 s ^"1 ), preferably between between 100 - 50000 mPas (at 100 s ^{" 1} ) and particularly preferably between between 200 - 20000 mPas (at 100 s ^" ¹ ) ¹ ) have.

The agents according to the invention, which can be present in particular as powdery solids, in post-compacted particle form, as homogeneous solutions or suspensions, can in principle contain all known active substances which are common in such agents, hereinafter also referred to as ingredients. The agents according to the invention can contain anionic surfactants, cationic surfactants, amphoteric surfactants, builder substances, bleaching agents, bleach activators, bleach stabilizers, bleaching catalysts, enzymes, polymers, cobuilders, alkalizing agents, acidifying agents, anti-redeposition agents, silver protective agents, colorants, optical brighteners, UV protective agents, fragrance substances, softening substances, fragrance substances, dirt-repellent substances, anti-crease substances, antibacterial substances, color protection substances, discoloration inhibitors, vitamins, layered silicates, odor-complexing substances, rinse aids, foam inhibitors, foaming agents, preservatives and / or auxiliaries.

The agents according to the invention preferably have, in particular, builder substances, surface-active surfactants, organic and / or inorganic peroxygen compounds, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators, additional peroxygen activators, Dyes and fragrances.

A disinfectant according to the invention can contain conventional antimicrobial active ingredients in addition to the previously mentioned ingredients in order to enhance the disinfectant action against special germs. Such antimicrobial additives are preferably contained in the disinfectants according to the invention not more than 10% by weight, particularly preferably from 0.1% by weight to 5% by weight. Surfactant (s) which can be used in the agents (s) according to the invention include anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants in textile detergents, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants. The total surfactant content of the agent, for example in the case of detergent, care or cleaning agent compositions, is preferably below 30% by weight, based on the total agent.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and 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 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12- alcohols with 3 EO, 4 EO or 7 EO, C ₉ n-alcohols with 7 EO, C ₃ _{5 5} alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ ιβ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C ₁₂ . ₁₈ alcohol with 7 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, is preferably 12 to 18 carbon 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, in particular fatty acid methyl ester.

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 alkanol amides 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 I,

I

R-CO-N- [Z] I

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 II

R ¹ -OR ²

I

R-CO-N- [Z] II in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or is an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, with C _-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this residue.

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

The content of non-ionic surfactants preferably portioned washing, care or cleaning agent compositions according to the invention suitable for textile washing is 5 to 20% by weight, preferably 7 to 15% by weight and in particular 9 to 14% by weight, in each case based on the total funds.

Low-foaming nonionic surfactants are preferably used in automatic dishwashing detergents. Machine dishwashing detergents according to the invention particularly preferably contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents are characterized in that they contain 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.

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 highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants 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 alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex 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 solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 Kohienstoffatomen (C _16-2 alcohol), a C ₁₈ alcohol and preferably at least 12 mol, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won. Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) that consist of C ₆ . ₂ o-monohydroxyalkanols or C ₆ . ₂₀ -alkylphenols or C _16-2 o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

The nonionic surfactant preferably additionally has 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 rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain 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 which are particularly preferably used contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverse block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25 % By weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

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

A further preferred portioned washing, care or cleaning agent according to the invention contains nonionic surfactants of the formula

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

in which R ^{1 represents} 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 stands for a value of at least 15.

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

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _i 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, if x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been chosen here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

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

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

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 have} 9 to 14 carbon atoms, R ^{3 represents} H and x assumes values from 6 to 15.

If the latter statements are summarized, portioned washing, care or cleaning agents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

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

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 O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² in which x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

Anionic, cationic and / or amphoteric surfactants can also be used in conjunction with the surfactants mentioned, but because of their foaming behavior in machine dishwashing detergents they are of only minor importance and mostly only in amounts below 10% by weight, mostly even below 5 % By weight, for example from 0.01 to 2.5% by weight, in each case based on the agent. The agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.

The agents according to the invention can contain, for example, cationic compounds of the formulas III, IV or V as cationic active substances:

R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (III)

(CH ₂ ) _n -TR ²

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

R ¹ TT

I I

R ² R ²

R ¹ R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (V)

R ⁴

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

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C _9-13 alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C _12-18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products. Also suitable are alkanesulfonates, which are for example obtained from _2- Cι ι ₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. Likewise, the esters of o-sulfo fatty 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 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 become. 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.

The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁ -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, straight-chain alkyl radical which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₄ -C ₁₅ alkyl sulfates are preferred from a washing-technical point of view. 2,3-AlkylsuIfate which are prepared for example according to US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are 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 whose fatty alcohol residues 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 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated and unsaturated 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, olive oil 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.

The anionic surfactant content of preferred textile detergents according to the invention is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20% by weight, in each case based on the total composition.

In the context of the present invention, preferred agents additionally contain one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents. tel, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, swelling and anti-abrasion agents and UV. The builders that can be contained in the agents according to the invention include, in particular, phosphates, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

The use of the generally known phosphates as builder substances is possible according to the invention, provided that such use should not be avoided for ecological reasons. 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 general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{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 tissues and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1, 91, preferably ^-3 , melting point 60 °) and as a monohydrate (density 2.04, preferably ^-3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O) at 200 ° C, and at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33, preferably ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ))] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gladly ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 like ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and goes into the diphos- phat Na ₄ P ₂ O ₇ over. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Potassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62, preferably ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) a density of 2.536 gladly ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase quartz phosphate), K ₃ PO, is a white, deliquescent, granular powder with a density of 2.56, preferably ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534, preferably ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1, 836, preferably ^-3 , melting point 94 ° below) loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33, preferably ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4. Condensation of the NaH ₂ PO or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. 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 (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the manufacture of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K5P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). 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:

(NaPO ₃ ) ₃ + 2 KOH - »Na ₃ K ₂ P3θ ₁₀ + H ₂ O

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.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x +} ι H ₂ O, 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. 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 O ₅ -yH ₂ O are preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The dissolving delay compared to conventional amorphous sodium silicates can be done in different ways, for example by surface treatment, compounding, compacting / sealing. seal or caused 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 deliver 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.

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 (about 80% by weight zeolite X ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and which has the formula nNa ₂ O ^• (1-n) K ₂ O ^■ AI ₂ O ₃ ^• (2 - 2.5) SiO ₂ ^• ( 3.5 - 5.5) H ₂ O

can be described. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Other important builders are in particular the carbonates, citrates and silicates. Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicate and / or metasilicate.

Alkali carriers can be present as further constituents. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the abovementioned substances are considered to be alkali carriers, the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, 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.

In addition, other ingredients may be present, washing, care or cleaning agents according to the invention being preferred which additionally contain one or more substances from the group of the acidifying agents, chelate complexing agents or the deposit-inhibiting polymers.

Both inorganic acids and organic acids are suitable as acidifiers, provided they are compatible with the other ingredients. For reasons of consumer protection and handling safety, the solid mono-, oligo- and polycarboxylic acids in particular can be used. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. The anhydrides of these acids can also be used as acidifying agents, maleic anhydride and succinic anhydride in particular being commercially available. Organic sulfonic acids such as amidosulfonic acid can also be used. A commercially available as an acidifier in the context of the present invention also preferably be used is Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and Adipic acid (max. 33% by weight).

Another possible group of ingredients are the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, ie being at least “bidentate”. In this case, stretching is normally carried out Compounds formed into rings by complex formation via an ion The number of ligands bound depends on the coordination number of the central ion. Common chelate complex images which are preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers, that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and which generally react with suitable metal atoms to form chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3 -Dicarbonyl and crown ether residues with z. T. very specific Activities against ions of different metals. The base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.

In the context of the present invention, particular preference is given to agents, in particular washing, care and / or cleaning agents, which comprise one or more chelating agents from the groups of

(i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, (ii) nitrogen-containing mono- or polycarboxylic acids, (iii) geminal diphosphonic acids, (iv) aminophosphonic acids, (v) phosphonopolycarboxylic acids, (vi) cyclodextrins

in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the Dishwashing detergent included. All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups. The following are preferably used individually or in a mixture with one another: a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid, b) nitrogen-containing mono- or polycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, Hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserine diacetic acid, N, N-di- (β-hydroxyethyl) -glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) -glycine, N- (1, 2 -Dicarboxy-2-hydroxyethyl) -aspartic acid or nitrilotriacetic acid (NTA), c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues with up to 8 carbon atoms and those containing hydroxyl or amino groups Derivatives thereof and 1-aminoethane-1,1-diphosphonic acid, their higher homologues with up to 8 carbon atoms as well as derivatives thereof containing hydroxyl or amino groups, d) aminophosphonic acids such as Ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid), e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1, 2,4-tricarboxylic acid and f) cyclodextrins.

In the context of this patent application, polycarboxylic acids a) are understood to mean carboxylic acids - also monocarboxylic acids - in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.

Deposit-inhibiting polymers can also have cobuilder properties. Organic cobuilders which can be used in the dishwasher detergents according to the invention are, 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 adjust a lower and milder pH of the agent, such as 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 or scale inhibitors, 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 provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. the. 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 500 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1000 to 4000 g / mol, can in turn be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention. The copolymers containing sulfonic acid groups are described in detail below.

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 content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

Also particularly preferred are biodegradable polymers composed 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-alkylallylsulfonic 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. Poly- aspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures 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 processes, for example acid-catalyzed or enzyme-catalyzed. 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 owns. 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. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this connection. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. used as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition to the substances from the classes of substances mentioned, the agents according to the invention can contain other usual ingredients of washing, care or cleaning agents, bleaching agents, bleach activators, enzymes, silver protection agents, colorants and fragrances being particularly important. These substances are described below.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecadic acid.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the detergent tablets. Bleach activators which can be used are compounds which, under perhydrolysis conditions, aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbene result in zoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-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, are preferred (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, especially acylated triacid alcohols, acylated polyhydric alcohols Ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

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

Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or inhibit the transfer of color. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. examples for Such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, approximately 0.1 to 5% by weight, preferably 0.12 to approximately 2% by weight.

According to the state of the art, enzymes are primarily added to a cleaning agent preparation, in particular to a dish care product which is intended for the main wash cycle. The disadvantage here was that the optimum effect of the enzymes used restricted the choice of temperature and problems also occurred with the stability of the enzymes in a strongly alkaline environment. With the detergent or cleaning agent portions according to the invention, it is possible to introduce enzymes into a separate compartment and then also to use them in the pre-rinse cycle and thus to use the pre-rinse cycle in addition to the main rinse cycle for enzyme action on soiling of the wash ware.

According to the invention, it is particularly preferred to add enzymes to the detergent-active preparation or part portion of a detergent and / or care agent portion provided for the pre-rinse cycle, and then to prepare such a preparation — more preferably — with a material of a flexible, preferably elastic, hollow body that is water-soluble even at low temperature to include, for example, to protect the enzyme-containing preparation from a loss of activity due to environmental conditions. The enzymes are furthermore preferably optimized for use under the conditions of the pre-care program, for example in cold water.

The detergent portions according to the invention can be advantageous if the enzyme preparations are in liquid form, as are partly offered commercially, because then a quick effect can be expected, which is already in the (relatively short and carried out in cold water). Even if - as usual - the enzymes are used in solid form and they are provided with a hollow body covering made of a water-soluble material that is already soluble in cold water, the enzymes can develop their effect before the main wash or main wash cycle. The advantage of using a casing made of water-soluble material, in particular of a material soluble in cold water, is that the enzyme (s) quickly comes into effect in cold water after the casing has been dissolved. This can extend their effectiveness, which benefits the washing or rinsing result.

The cleaning agents according to the invention for machine dishwashing can contain corrosion inhibitors to protect the wash ware or the machine, silver protection agents in particular being particularly important in the area of machine 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. In addition, active chlorine-containing agents are often found in cleaner formulations, 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. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglu- cin, 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 of the 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 and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

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 manufacturing perspective, the use of NaCI or MgCI ₂ in the agents according to the invention is vorzugt. The proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.

Non-aqueous solvents that can be used in the agents according to the invention come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether , Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy -2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. Non-aqueous solvents can be used in the liquid detergents according to the invention in amounts between 0.5 and 10% by weight, but preferably below 5% by weight and in particular below 3% by weight.

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 alkalis 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 5% by weight of the total formulation.

In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable 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 compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.

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 antiredeposition 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 proportion of methoxy Groups of 15 to 30 wt .-% and of hydroxypropyl groups of 1 to 15 wt .-%, each 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 from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of 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 acids), 4,4'-distyryl-biphenylene, methylumbelliferones, coumarins, dihydroquinolinones, 1, 3-diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole systems and the pyrene derivatives usually substituted by heterocycles Quantities between 0, 05 and 0.3 wt .-%, based on the finished agent, used.

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. For this purpose, water-soluble colloids of mostly organic nature are suitable, for example 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, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, preference is given to cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof in amounts of 0.1 to 5% by weight, based on the composition, used If the agents according to the invention are packaged as agents for automatic dishwashing, further ingredients can be used. Today, machine-washed dishes are often subject to higher requirements than hand-washed dishes. For example, dishes that have been completely cleaned of food residues are not considered to be perfect if, after machine dishwashing, they still have whitish stains based on water hardness or other mineral salts, which, due to the lack of wetting agents, originate from dried water drops. To obtain crystal-clear and spotless dishes, rinse aid is used successfully today. The addition of rinse aid at the end of the wash program ensures that the water runs off the dishes as completely as possible, so that the different surfaces are residue-free and flawlessly shiny at the end of the wash program. The automatic cleaning of dishes in domestic dishwashers usually comprises a pre-wash, a main wash and a rinse cycle, which are interrupted by intermediate wash cycles. In most machines, the pre-wash cycle for heavily soiled dishes can be activated, but is only selected by the consumer in exceptional cases, so that in most machines a main wash cycle, an intermediate rinse cycle with pure water and a rinse cycle are carried out. The temperature of the main wash cycle varies between 40 and 65 ° C depending on the machine type and program level selection. In the rinse cycle, rinse aids are added from a dosing tank in the machine, which usually contain non-ionic surfactants as the main component. Such rinse aids are in liquid form and are widely described in the prior art. Your main task is to prevent limescale and deposits on the dishes.

The agents according to the invention can be formulated as “normal” detergents, which are used together with commercially available supplements (rinse aid, regeneration salt). However, with the products according to the invention, the additional dosage of rinse aid can be dispensed with. These so-called “2in1” products lead to simplification of handling and relieve the consumer of the burden of additional dosing of two different products (detergent and rinse aid).

Even when using "2in1" products, two dosing processes are required to operate a household dishwasher at intervals, since after a certain number of rinsing processes the regeneration salt has to be refilled in the water softening system of the machine. These water softening systems consist of ion-exchange polymers which are added to the machine Soften hard water and be regenerated by rinsing with salt water after the rinsing program.

However, it is also possible to provide products according to the invention which, as so-called “3in1” products, combine the conventional cleaners, rinse aids and a salt replacement function.

In the context of the present invention, unsaturated carboxylic acids of the formula VI can also be added as a monomer to the agent according to the invention,

R ¹ (R ² ) C = C (R ³ ) COOH (VI),

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.

The unsaturated carboxylic acids which can be described by formula VI include, 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.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula VII

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VII),

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

Preferred among these monomers are those of the formulas VIIa, VIIb and / or VIIc, H ₂ C = CH-X-SO ₃ H (Vlla),

H ₂ C = C (CH ₃ ) -X-SO ₃ H (VIIIb),

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (Vllc),

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X 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 (O) -NH- C (CH ₃ ) - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in the formula VIIa), 2-acrylamido-2-propanesulfonic acid (X = - C (O) NH-C (CH ₃ ) ₂ in formula VIIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula Vlla), 2-methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula VIIb), 3-methacrylamido-2-hydroxy-propanesulfonic acid (X = -C (O) NH-CH ₂ CH (OH) CH ₂ - in formula VIIb), allyl sulfonic acid sulfonic acid (X = CH ₂ in formula VIIa), methallyl sulfonic acid (X = CH ₂ in formula VIIb), Allyloxybenzol- ( X = -CH ₂ -OC ₆ H - in formula XVIIa), methallyloxybenzenesulfonic acid (X = - CH ₂ -OC ₆ H ₄ - in formula VIIIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl- 2-propenl-sulfonic acid (X = CH ₂ in formula VIII), styrene sulfonic acid (X = C ₆ H ₄ in formula VIII), vinyl sulfonic acid (X not present in formula VIIa), 3-sulfopropyl acrylate (X = - C (O) NH -CH ₂ CH ₂ CH ₂ - in formula VIII), 3-sulfopropyl methacrylate (X = -C (O) NH- CH ₂ CH ₂ CH ₂ - in formula VIIIb), sulfomethacrylamide (X = -C (O) NH- in formula VIIIb), sulfo- methyl methacrylamide (X = -C (O) NH-CH ₂ - in formula VIIIb) and water-soluble salts of the acids mentioned.

Other ionic or nonionic monomers that can be used are, in particular, ethylenically unsaturated compounds. The content of monomers of group iii) in the polymers used according to the invention 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 of i) unsaturated carboxylic acids of the formula VI.

R ¹ (R ² ) C = C (R ³ ) COOH (VI),

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, alkyl or alkenyl radicals substituted by -NH, -OH or -COOH as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or is a branched hydrocarbon radical having 1 to 12 carbon atoms,

ii) Monomers of the formula VII containing sulfonic acid groups

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VII),

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

iii) optionally further ionic or nonionic monomers

particularly preferred.

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 Vlla, Vllb and / or Vllc containing sulfonic acid groups:

H ₂ C = CH-X-SO ₃ H (Vlla),

H ₂ C = C (CH ₃ ) -X-SO ₃ H (VIIIb),

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (Vllc),

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X 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 (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) - iii) optionally further ionic or nonionic monomers.

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

For example, agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula VIII

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

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 for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, 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 in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula IX

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

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 for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, 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. Agents according to the invention which contain one or more copolymers are structural units of the formula X

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

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 for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is preferred, is also a preferred embodiment of the present invention, just as agents are preferred, which are characterized in that they contain one or more copolymers, the structural units of the formula XI

-tCH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) N-SO ₃ H] _p - (XI),

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, preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula XI

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

contain, in which m and p each represent an integer between 1 and 2000 and Y 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 -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, are preferred and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula XII - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XII),

In summary, automatic dishwashing agents according to the invention are preferred which contain, as ingredient b), one or more copolymers which have structural units of the formulas VII and / or VIII and / or IX and / or X and / or XI and / or XII

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

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

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

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] p- (X),

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

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

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 -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

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 replaced by metal ions, preferably alkali metal ions and in particular by sodium ions. Corresponding agents which are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.

The monomer distribution of the copolymers used in the agents according to the invention is preferably 5 to 95% by weight i) or ii), particularly preferably 50 to 90% by weight, in the case of copolymers which contain only monomers from groups i) and ii) .-% monomer from group i) and 10 to 50 wt .-% monomer from group ii), each based on the polymer. In the case of terpolymers, those which contain 20 to 85% 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 polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol ^"1 , preferably from 4000 to 25,000 gmol ¹ and in particular from 5000 to 15,000 gmol ^-1 .

The content of one or more copolymers in the agents according to the invention can vary depending on the intended use and the desired product performance, preferred dishwasher detergents according to the invention being characterized in that they contain the copolymer (s) in amounts of 0.25 to 50% by weight. %, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 to 15% by weight.

As already mentioned above, both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention. The polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred. Such polyacrylates are commercially available under the trade names Sokalan ^® PA15 or Sokalan ^® PA25 (BASF).

The agents according to the invention can also be packaged as fabric softeners or washing additives. Depending on the intended use, additional ingredients can be used. Fabric softener compositions for rinse bath finishing are widely described in the prior art. These compositions usually contain a cationic quaternary ammonium compound as the active substance, which is dispersed in water. Depending on the content of active substance in the finished plasticizer composition, one speaks of dilute, ready-to-use products (active substance contents below 7% by weight) or so-called concentrates (active substance contents above 7% by weight). Because of the lower volume and the reduced consumption Packing and transport costs, the textile softener concentrates have advantages from an ecological point of view and have become more and more established in the market. Due to the incorporation of cationic compounds which have only a low water solubility, conventional fabric softener compositions are in the form of dispersions, have a milky, cloudy appearance and are not translucent. For reasons of product aesthetics, however, it may also be desirable to provide the consumer with translucent, clear fabric softener that stands out visually from the known products.

As a fabric softening active substance, portioned fabric softeners according to the invention preferably contain cationic surfactants which have already been described in detail above (formulas XII, XIII and XIV). "Soft care portions" according to the invention particularly preferably contain so-called ester quats. While there are a large number of possible compounds from this class of substances, ester quats are used according to the invention with particular preference which are obtained by reacting trialkanolamines with a mixture of fatty acids and dicarboxylic acids, optionally followed by alkoxylation of the reaction product and quaternization can be produced in a manner known per se, as described in DE 195 39 846.

The esterquats produced in this way are outstandingly suitable for the production of portions according to the invention which can be used as fabric softeners. Since, depending on the choice of the trialkanolamine, the fatty acids and the dicarboxylic acids and the quaternizing agent, a large number of suitable products can be prepared and used in the agents according to the invention, a description of the ester quats to be used according to the invention via their route of manufacture is more precise than the specification of a general formula.

The components mentioned, which react with one another to give the ester quats to be used with preference, can be used in varying proportions to one another. In the context of the present invention, portioned fabric softeners are preferred in which a reaction product of trialkanolamines with a mixture of fatty acids and dicarboxylic acids in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, which optionally alkoxylates and then in was quaternized in a known manner, is present in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight. The use of triethanolamine is particularly preferred, so that further preferred portioned fabric softener of the present invention is a reaction product of triethanolamine with a mixture of fatty acids and dicarboxylic acids in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, which was optionally alkoxylated and then quaternized in a manner known per se, in amounts of 2 to 60, preferably contain 3 to 35 and in particular 5 to 30 wt .-%.

All acids obtained from vegetable or animal oils and fats can be used as fatty acids in the reaction mixture for producing the esterquats. A fatty acid that is not solid at room temperature, i.e. pasty to liquid, fatty acid can be used.

The fatty acids can be saturated or mono- to polyunsaturated regardless of their physical state. Of course, not only "pure" fatty acids can be used, but also the technical fatty acid mixtures obtained from the cleavage of fats and oils, these mixtures being clearly preferred from an economic point of view.

For example, individual species or mixtures of the following acids can be used in the reaction mixtures for producing the ester quats for the clear aqueous fabric softener according to the invention: caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-ol acid, arachic acid , Behenic acid, lignoceric acid, cerotinic acid, melissic acid, 10-undecenoic acid, petroselinic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, linolaidic acid, oc- and ß-eläosterainic acid, gadoleic acid, erucic acid, brassidic acid. Of course, the fatty acids with an odd number of carbon atoms can also be used, for example undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, henicosanoic acid, tricosanoic acid, pentacosanoic acid, heptacosanoic acid.

In the context of the present invention, the use of fatty acids of the formula XIII in the reaction mixture for the preparation of the esterquats is preferred, so that preferred portioned fabric softener is a reaction product of trialkanolamines with a mixture of fatty acids of the formula XIII,

R ¹ -CO-OH (XIII)

in which R1-CO- represents an aliphatic, linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds and dicarboxylic acids in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5 : 1, if necessary alkoxylated and then quaternized in a manner known per se, in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight in the compositions.

Suitable dicarboxylic acids which are suitable for producing the esterquats to be used in the agents according to the invention are, in particular, saturated or mono- or polyunsaturated α, β-dicarboxylic acids. Examples include the saturated species oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic and dodecanoic acid, brassylic acid, tetra- and pentadecanoic acid, thapic acid as well as hepta-, octa- and nonadecanoic acid, eicosanoic acid, eicosanoic acid and eicosanoic acid and also called phellogenic acid. Dicarboxylic acids which follow the general formula XXIII are preferably used in the reaction mixture, so that portioned agents according to the invention are preferred which are a reaction product of trialkanolamines with a mixture of fatty acids and dicarboxylic acids of the formula XIV,

HO-OC- [X] -CO-OH (XIV)

in which X represents an optionally hydroxyl-substituted alkylene group with 1 to 10 carbon atoms, in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, which was optionally alkoxylated and then quaternized in a manner known per se, in quantities from 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight in the compositions.

Of the large number of esterquats that can be prepared and used according to the invention, those in which the alkanolamine is treithanolamine and the dicarboxylic acid is adipic acid have proven particularly useful. Thus, in the context of the present invention, agents are particularly preferred which are a reaction product of triethanolamine with a mixture of fatty acids and adipic acid in a molar ratio of 1: 5 to 5: 1, preferably 1: 3 to 3: 1, which is then carried out in a manner known per se was quaternized in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30 wt .-% in the compositions

Depending on whether they are formulated as textile detergents, washing aids or fabric softeners, the agents according to the invention can also be provided with additional benefits. Here are, for example, color-transfer-inhibiting compositions, agents with an “anti-gray formula”, agents with ironing relief, agents with special fragrance release, agents with improved soil release or prevention of Resoiling, antibacterial agents, UV protection agents, color refreshing agents, etc. can be formulated. Some examples are explained below:

Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending and kinking. If pressing and squeezing across the fiber direction 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, alkyloiesters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

To combat microorganisms, the agents according to the invention can contain antimicrobial agents. Depending on the antimicrobial spectrum and 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, alkylarlylsulfonates, halogenophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely in the inventive agents.

In order to prevent undesirable changes in the 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.

Increased wearing comfort can result from the additional use of antistatic agents, 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 suitable as antistatic agents. for textiles or as an additive to detergents, with an additional finishing effect.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example silicone derivatives can be used in the agents according to the invention. 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 completely 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. The viscosities of the preferred silicones are in the range between 100 and 100,000 centistokes at 25 ° C., the silicones being used in amounts between 0.2 and 5% by weight, based on the total agent.

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.

Other conceivable additives which are preferred in special embodiments are surfactants, which in particular can influence the solubility of the water-soluble wall of the flexible, preferably elastic, hollow body or the compartmenting device, but can also control their wettability and the foam formation when dissolved, and also foam inhibitors, but also Bitter substances that can prevent children from accidentally swallowing such hollow bodies or parts of such hollow bodies.

Fragrances are added to the detergent, cleaning agent and / or care agent portions according to the invention in order to improve the overall aesthetic impression of the products and, in addition to the technical performance (fabric softener result), to the consumer to provide a sensorially typical and distinctive product. Individual fragrance compounds can be used as perfume oils or fragrances, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, pt-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexyl benzylatepylpropionate, stally. The ethers include, for example, benzyl ethyl ether. The aldehydes include e.g. B. linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lileal and bourgeonal.

The ketones include the ionones, α-isomethyl ionone and methyl cedryl ketone. Alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include terpenes such as limonene and pinene. Mixtures of different odoriferous substances are preferably used which are coordinated with one another in such a way that together they produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as are obtainable from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are nutmeg oil, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olivan oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrance content is usually in the range of up to 2% by weight of the total detergent, cleaning agent or care agent portion.

The fragrances can be incorporated directly into the wash-active, cleaning-active or care-active preparation (s); However, it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of textiles due to a slower fragrance release. Cyclodextrins, for example, have proven themselves as such carrier materials. The cyclodextrin-perfume complexes can also be coated with other auxiliaries. The agents according to the invention can be used as washing, cleaning, care, hair treatment, building materials, cosmetics, adhesives, antibacterial agents and / or disinfectants.

Depending on the intended use, the agents according to the invention can contain anionic surfactants, cationic surfactants, amphoteric surfactants, builder substances, bleaching agents, bleach activators, bleach stabilizers, bleaching catalysts, enzymes, polymers, cobuilders, alkalizing agents, acidifying agents, anti-redeposition agents, silver preservatives, colorants, optical brighteners, UV stabilizers , Fabric softener, fragrances, dirt-repellent substances, anti-crease substances, antibacterial substances, color protection substances, discoloration inhibitors, vitamins, layered silicates, odor-complexing substances, rinse aids, foam inhibitors, foaming agents, preservatives and / or auxiliaries. Depending on the composition, moldings containing moldings according to the invention can be used as detergents, cleaning agents, care products, hair treatment agents, hair colorants, pharmaceuticals, crop protection agents, foods, cosmetics, fertilizers, building materials, adhesives, bleaches, disinfectants and / or fragrances

Shaped bodies can generally be produced by mixing at least one thermoplastic, water-soluble polymer, at least one ionic salt which does not complex the polymer and at least one compound containing at least two anionic groups and in a further step shaping the shaped body from the mixture, preferably Balls, capsules, foils, particles, agglomerates and / or powders are formed, in particular by means of extrusion and / or under the action of heat.

The production of spherical / drop-shaped shaped bodies comprises the steps:

Mixing at least one thermoplastic, water-soluble polymer, at least one ionic salt not complexing the polymer and at least one compound containing at least two anionic groups, diluting the mixture with water,

Drip the mixture into an aqueous alkaline collecting bath, remove and dry the shaped bodies obtained by dripping. Films can be produced by mixing at least one thermoplastic, water-soluble polymer, at least one ionic salt which does not complex the polymer and at least one compound containing at least two anionic groups and producing a film by casting. Optionally, the film can be Manufacture moldings with any external contours, such as stars and the like.

The moldings can not only be used in liquid formulations or compositions, but the moldings, for example extruded particles, can also be added to powders and thus lead to a controlled or delayed release of ingredients in such compositions.

Table I below generally gives the concentrations of the materials forming the matrix for the production of a shaped body according to the invention, and the drying temperature and the processing temperature in the extruder.

Table I

The agents can generally be produced by adding shaped articles according to the invention to the agent.

The moldings containing agents are essentially dimensionally stable in a 20% saturated, aqueous NaCl solution at 40 ° C. after ≥ 10 days, preferably> 20 days, more preferably ≥ 30 days.

It has been shown that the moldings in the above agents in a 20% saturated, aqueous NaCl solution at room temperature of 23 ° C ≥ 1 month, preferred wise ≥ 2 months, in particular ≥ 3 months and particularly preferably ≥ 6 months are essentially dimensionally stable.

The molded article (s) containing the agent are in particular in a universal detergent gel pH 8 and a viscosity of 400 mPas, containing 44% by weight of water, 25% by weight of nonionic surfactant, 7% by weight of anionic surfactant, 8% by weight of soap, 3 % By weight of NaOH, 1% by weight of citric acid, 1% by weight of boric acid, 9% by weight of glycerin and a total of 2% by weight of enzymes, perfume, defoamer and dye, the weight data being based on the total weight of the universal detergent without Molded body is essentially dimensionally stable at 40 ° C. after ≥ 10 days, preferably ≥ 20 days, more preferably ≥ 30 days.

For the purposes of this invention, essentially dimensionally stable means that, with a test duration of 30 days and 40 ° C., a solid, spherical shaped body with a diameter of 2 mm (initial state) has a diameter of between 2 mm and 2.3 mm (final state) , The optionally slightly swollen spherical shaped body can be somewhat deformable.

The moldings containing the compositions of the present invention are particularly preferably concentrates which are diluted with water before use.

Shaped bodies containing aqueous agents are preferably present in a ≥ 10% saturated, more preferably ≥ 15% by weight, and most preferably ≥ 20% solution saturated with salt, the salt preferably being an alkali and / or alkaline earth metal Salt is.

The subject matter of the present invention is explained in more detail with reference to Examples 1 to 10 below.

Examples

example 1

An aqueous solution of 40% polyvinyl alcohol (Erkol 05/140 with a degree of saponification of approx. 87%) and 7% NaCl and 0.01% bi-ionic dye Congo red was prepared. 10 g of talc and 12 g of a mixture of 8 g of zeolite which was impregnated with 4 g of perfume oil were added to 100 g of the solution. The mass was homogenized with a mixer.

Example 2

The mixture obtained according to Example 1 was dried to a thermoplastic material and this was then processed into a strand using an extruder. The strand was cut into pellets, these were rounded. The red balls of 0.2-4 mm diameter obtained were added to the liquid detergent in a concentration of 0.3-10% by weight, based on the total weight of the liquid detergent without red balls. They are stable in storage there for months and are clearly visible. When diluted to the application concentration, they dissolve within 30 minutes at 20 ° C or 15 minutes at 40 ° C and release the included fragrance.

Example 3

The mixture obtained according to Example 1 was diluted with 100 ml of water and then added dropwise to a collecting bath which consists of an aqueous solution of 0.5% NaOH and 20% Na ₂ S0 ₄ . The red spheres obtained were dried and then added to the liquid detergent in a concentration of 0.3-10% by weight, based on the total weight of the liquid detergent without red spheres. They are stable there for months. When diluted to the application concentration, they dissolve within 30 minutes at 20 ° C or 15 minutes at 40 ° C and release the included fragrance.

Example 4

A film 2 mm thick was produced from the mixture obtained according to Example 1 by casting and asterisks were punched out therefrom. The red asterisks obtained are given in a concentration of 0.3-10% by weight, based on the total weight of the liquid detergent without red asterisks. They are stable there for months. When diluted to the application concentration, they dissolve within 30 minutes at 20 ° C or 15 minutes at 40 ° C and release the included fragrance. Examples 5 and 6

As example 1, except that instead of the Congo red dye, the bi-ionic

Trypan blue dye (Direct Blue 14) - Example 5 - or the bi-ionic Chicago Blue dye (Direct Blue 1) - Example 6 - used. After extrusion and rounding, these mixtures also provide blue-colored, spherical shaped articles with a diameter of 0.2-1 mm, which are stable in liquid detergents in a concentration of 0.3-10% by weight, based on the total weight of the liquid detergent without blue balls whose color does not bleed and which dissolve without residue in the washing application. Such moldings are stable in storage there for months and are clearly visible. When diluted to the application concentration, the spherical shaped bodies dissolve within 10 minutes at 20 ° C or 5 minutes at 40 ° C and release the enclosed material.

Example 7

An aqueous solution of 40% polyvinyl alcohol (Erkol 05/140 with a degree of saponification of approx. 87%) and 7% NaCl and 0.01% Congo red dye was prepared.

Example 8

The mixture obtained according to Example 7 was sprayed onto a granulate of soda, surfactants and granulation aids (MP-crude extrudate) located in a rotating steel barrel until a homogeneous, red-colored film had formed on the granulate. After drying the film, red-colored pellets of 0.2-4 mm in diameter were obtained, which were added in a concentration of 0.3-10% by weight, based on the total weight of the liquid detergent without red-colored pellets. The pellets are stable there for months and are clearly visible. When diluted to the application concentration, they dissolve within 10 minutes at 20 ° C or 5 minutes at 40 ° C and release the enclosed material.

Example 9

An aqueous solution of 40% polyvinyl alcohol (Erkol 05/140 with a degree of saponification of approx. 87%) and 12% urea and 0.01% Direct Blue 1 dye was prepared. 10 g of talc and 8 g of polypropylene glycol PPG-9 are added to 100 g of the solution. The mass is homogenized with a mixer.

Example 10

The mixture obtained according to Example 9 was dried to a thermoplastic material and this was then processed into a strand using an extruder. The Strand is cut into pellets, these are rounded. The blue balls of 0.2-1 mm diameter obtained are placed in a concentration of 0.3 -5% by weight, based on the total weight of the hand dishwashing detergent without red balls, in a hand dishwashing detergent. The red spheres are stable in storage for months and are clearly visible. When diluted to the application concentration, they dissolve within 8 minutes at 20 ° C or 3 minutes at 40 ° C and release the enclosed active substance.

Claims

claims

1. A molded article containing agents with increased storage stability, characterized in that the molded article and / or its outer molded article shell comprises: at least one thermoplastic, water-soluble polymer; at least one ionic salt not complexing the polymer; at least one compound containing at least two anionic groups, the compound having at least two anionic groups reversibly complexing the water-soluble polymer; and optionally at least one carrier and / or at least one extrusion aid.

2. The shaped article according to claim 1, characterized in that the shaped article or articles are present as a solid phase (s) in a multiphase system with at least one solid, liquid and / or gel phase, preferably with a high electrolyte content.

3. The molded article according to claim 1 or 2, characterized in that the molded article, preferably at least one phase of the composition, particularly preferably the phase contained in the molded article, has a water content> 0 to ≤ 88% by weight, preferably ≤ 50% by weight, more preferably ≤ 20% by weight and even more preferably ≤ 12% by weight.

4. The shaped article according to one of the preceding claims, characterized in that the shaped article in a 20% saturated, aqueous NaCl solution at 40 ° C after ≥ 10 days, preferably ≥ 20 days, more preferably ≥ 30 days, essentially is dimensionally stable.

5. The shaped article according to any one of the preceding claims, characterized in that the shaped article in a universal detergent gel pH 8 and a viscosity of 400 mPas, containing 44 wt .-% water, 25 wt .-% nonionic surfactant, 7 wt .-% anionic surfactant , 8% by weight of soap, 3% by weight of NaOH, 1% by weight of citric acid, 1% by weight of boric acid, 9% by weight of glycerol and a total of 2% by weight of enzymes, perfume, defoamer and dye, where the weight information is based on the total weight of the universal washing medium gel without moldings, is essentially dimensionally stable at 40 ° C. after ≥ 10 days, preferably ≥ 20 days, more preferably ≥ 30 days.

6. The molded article according to one of the preceding claims, characterized in that the compound having at least two anionic groups is selected from the group comprising dyes, in particular bi-ionic dyes.

7. The shaped article according to one of the preceding claims, characterized in that the compound having at least two anionic groups is selected from the group comprising Congo red, Trypan blue, Chicago blue; Macro anions, layered silicates, preferably montmorillonite, metaphosphates; and / or polyanions, preferably polystyrene sulfonate, carboxymethyl cellulose and / or polyacrylates.

8. The shaped article according to one of the preceding claims, characterized in that the at least two anionic groups are selected from the group comprising O ^{2 "} , RBO ₂ ^2" , RCOO ^" , RCONR ^" , OH ^" , NO ₃ -, NO ₂ ^" , NO, CO, S ^2" , RS ^" , PO ₃ ^{2 '} , PO ₃ OR ³ -, H ₂ O, CO ₃ ² -, HCO ³ -, ROH, NRR'R", RCN, CP, Bf, OCN ^" , SCN ^" , CN ^" , N3 ^" , F, I ^" , RO ^' , CIO ₄ ^" , SO ₄ ^2- , HSO ₄ ^" , SO ₃ ^2' and / or RSO ₃ ^" , and particularly preferably O ^{2 "} , RBO ₂ ^{2 "} , RCOO ^" , OH ^" , NO ₃ ^' , NO ₂ ^" , NO, CO, CN ^" , S ^2" , RS ^" , PO ₄ ^3" , H ₂ O, CO3 ² -, HCO ^{3 "} , ROH, NRR'R ", RCN, Cr, Br ^" , OCN ^" , SCN ^' , N3 ^" , F, I ^" , RO ^' , CI0 ₄ ^" , SO ₄ ^{2 "} , HSO ₄ ^" , SO ₃ ^{2 "} , RSO ₃ - and / or CF ₃ SO ₃ ^_ , and more preferably SO ₃ ^_ , Cl ~, OH-, SO ₄ ^2_ , PO ₃ ^2_ , PO ₄ ^3_ , COO-, NO ₃ ^_ , CO ₃ ^2_ , CH ₃ COO ^" , C ₂ O ₄ ^2_ , citrates and / or acetates, where R, R ', R" are identical or different from one another, selected from the group comprising alkyl, alkenyl, alkoxy, alkylene, Cycloalkyl, aryl, arylene or heteroaryl.

9. The shaped article according to one of the preceding claims, characterized in that the non-complexing salt is selected from the group comprising alkali and / or alkaline earth salts, preferably alkali and / or alkaline earth metal halides, more preferably alkali and / or alkaline earth metal sulfates, nitrates, phosphates, carboxylates, citrates, hydroxides, borates, acetates, phosphates, silicates, oxalates, formates, percarbonates, and / or perborates ,

10. The shaped article according to one of the preceding claims, characterized in that the weight content of the water-soluble polymer, based on the total weight content of the shaped article, is between 10-95% by weight, preferably 20-75% by weight and preferably 30- Accounts for 60% by weight.

11. The shaped article according to one of the preceding claims, characterized in that the weight content of the non-complexing salt, based on the total weight content of the shaped article, is between 1-50% by weight, preferably 1-30% by weight and preferably 2 - makes up 20% by weight.

12. The shaped article according to one of the preceding claims, characterized in that the weight content of the compound containing at least two anionic groups, based on the total weight content of the shaped article, is between 0.001-10% by weight, preferably 0.01-5% by weight. -% and preferably 0.05 - 2 wt .-%.

13-containing pressure-molded body according to any one of the preceding claims, characterized in that the complex formation constant has a value in the range of 10 - 10 and ³⁰ preferably 10 ³ - - 10 ¹⁵ is 10 ^60, preferably 100.

14. The molded article according to one of the preceding claims, characterized in that the water-soluble polymer is selected from the group comprising polyvinyl alcohol (PVA), acetalized polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, starch and derivatives of the aforementioned substances, and / or mixtures of the aforementioned polymers, polyvinyl alcohol being particularly preferred.

15. The shaped article according to one of the preceding claims, characterized in that the water-soluble polymer additionally contains polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above Polymers are added.

16. The shaped article according to one of the preceding claims, characterized in that the water-soluble polymer comprises a polyvinyl alcohol, the Degree of hydrolysis accounts for 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

17. The shaped article according to one of the preceding claims, characterized in that the water-soluble polymer comprises a polyvinyl alcohol, the molecular weight of which is in the range from 10,000 to 100,000 gmol ^"1 , preferably from 11,000 to 90,000 gmol ^{" 1} , particularly preferably from 12,000 to 80,000 gmol ^"1 and in particular from 13,000 to 70,000 gmol ^{" 1} .

18. The molded article according to one of the preceding claims, characterized in that the molded article and / or the outer shell of the molded article is water-soluble polymer in amounts of ≥ 50% by weight, preferably ≥ 70% by weight, particularly preferably> Contains 80 wt .-% and in particular ≥ 90 wt .-%, each based on the total weight of the molded body and / or the outer shell.

19. The shaped article according to any one of the preceding claims, characterized in that the water-soluble polymer plasticizer in amounts of at least ≥ 1 wt .-%, preferably ≥ 10 wt .-%, particularly preferably ≥ 20 wt .-% and in particular of ≥ 30% by weight, based in each case on the total weight of the water-soluble polymer of the shaped body.

20. The shaped article according to one of the preceding claims, characterized in that the shaped article has a spherical, capsule, film, particle, agglomerate and / or powder form.

21. The shaped article according to one of the preceding claims, characterized in that the agent is a detergent, cleaning agent, care agent, hair treatment agent, hair dye, medicament, crop protection agent, food, cosmetic, agrochemical, fertilizer, building material, adhesive, bleach, disinfectant and / or Is a fragrance.

22. The shaped article according to one of the preceding claims, characterized in that the washing, care and / or cleaning substances are selected from the group comprising anionic surfactants, cationic surfactants, ampho- tere tensides, builder substances, bleaching agents, bleach activators, bleach stabilizers, bleaching catalysts, enzymes, polymers, cobuilders, alkalizing agents, acidifying agents, anti-redeposition agents, silver protection agents, coloring agents, optical brighteners, UV protection substances, fabric softeners, auxiliaries, fragrances, anti-bacterial substances, anti-fouling substances, anti Fabrics, color protection agents, discoloration inhibitors, vitamins, layered silicates, odor-complexing substances and / or rinse aid.

23. The shaped article containing the agent according to one of the preceding claims, characterized in that the respective shaped article containing the agent has a different content and / or a different composition of washing, care and / or cleaning substances.

24. The molded article according to one of the preceding claims, characterized in that the reversibly complexed, water-soluble polymer-containing outer molded article has a wall thickness of between 0.01 and 5 mm, preferably between 0.06 and 2 mm, preferably between 0 and 07-1.5 mm, more preferably between 0.08-1.2 mm, more preferably between 0.09-1 mm and most preferably between 0.1-0.6 mm.

25. The shaped article according to one of the preceding claims, characterized in that the agent contained in the shaped article, in particular washing and / or cleaning agent, into the aqueous application liquor within ≤ 5 min, preferably within ≤ 3 min, preferably within ≤ 1 min, predominantly or completely released.

26. The shaped article according to one of the preceding claims, characterized in that the shaped article or articles are present in a liquid medium which is diluted with water before use, the liquid medium preferably being a solution with a water content of between 0 and 88% by weight .-%, based on the total weight of the liquid medium, or a gel.

27. The shaped article according to one of the preceding claims, characterized in that the liquid medium has a viscosity of between 10-100000 mPas (at 100 s ^"1 ), preferably between between 100 - 50000 mPas (at 100 s ^{" 1} ). and particularly preferably from between between 200 and 20,000 mPas (at 100 s ^"1 ).

28. Use of the shaped article according to one of the preceding claims as a detergent, cleaning agent, care agent, hair treatment agent, hair dye, medicament, crop protection agent, food, cosmetic, fertilizer, building material, adhesive, bleach, disinfectant and / or fragrance agent.

29. Use of the at least one water-soluble polymer, at least one ionic salt not complexing the polymer, and at least one compound containing at least two anionic groups according to one of the preceding claims, wherein the compound having at least two anionic groups reversibly complexes the water-soluble polymer as outer casing of a sphere, capsule, particle, agglomerate and / or powder containing agents, particularly preferably as an outer casing of extruded agents, in particular detergents.

30. A process for the production of moldings according to one of the preceding claims, characterized in that at least one thermoplastic, water-soluble polymer, at least one ionic salt which does not complex the polymer and at least one compound containing at least two anionic groups is mixed and in a further one Step forms the shaped body from the mixture, preferably balls, capsules, foils, particles, agglomerates and / or powders being formed, in particular by means of extrusion and / or under the action of heat.

31. A method for producing molded body (s) according to one of the preceding claims, comprising the steps:

Dripping the mixture into an aqueous alkaline collecting bath, removing and drying the shaped bodies obtained by dripping.

32. A process for the production of moldings according to one of the preceding claims, characterized in that at least one thermoplastic, water-soluble polymer, at least one ionic salt which does not complex the polymer and at least one compound containing at least two anionic groups is mixed and one is cast by casting Foil created.

33. A process for the production of molded article (s) according to one of the preceding claims, characterized in that at least one thermoplastic, water-soluble polymer, at least one ionic salt which does not complex the polymer and at least one compound containing at least two anionic groups is mixed and then the outer surface of spheres, capsules, foils, particles, agglomerates and / or powders containing active substance, partially or completely coated with the mixture obtained.

34. A process for the preparation of an agent by combining the molded article (s) with at least one liquid phase or solid phase.