WO2004085599A1 - Portion de produit nettoyant a stabilite de forme - Google Patents

Portion de produit nettoyant a stabilite de forme Download PDF

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Publication number
WO2004085599A1
WO2004085599A1 PCT/EP2004/002717 EP2004002717W WO2004085599A1 WO 2004085599 A1 WO2004085599 A1 WO 2004085599A1 EP 2004002717 W EP2004002717 W EP 2004002717W WO 2004085599 A1 WO2004085599 A1 WO 2004085599A1
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WO
WIPO (PCT)
Prior art keywords
weight
acid
water
preferred
agents
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PCT/EP2004/002717
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German (de)
English (en)
Inventor
Maren Jekel
Arno DÜFFELS
Matthias Reimann
Wolfgang Barthel
Salvatore Fileccia
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO2004085599A1 publication Critical patent/WO2004085599A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions

Definitions

  • This application concerns detergents or cleaning agents.
  • this application relates to detergents or cleaning agents which have a water-soluble or water-dispersible packaging.
  • Detergents or cleaning agents are now available to consumers in a wide variety of forms.
  • this offer also includes, for example, cleaning agent concentrates in the form of extruded or tableted compositions.
  • These solid, concentrated or compacted offer forms are characterized by a reduced volume per dosing unit and thus lower the costs for packaging and transport.
  • the detergent or cleaning agent tablets in particular also meet the consumer's desire for simple dosing. The corresponding agents are described in detail in the prior art.
  • detergents or cleaning agents can also be packaged as gels or pastes.
  • the granted European patent EP 331 370 discloses a process for producing stable, viscous liquid compositions for use in automatic dishwashers.
  • European patent EP 797 656 (Unilever) relates to non-aqueous liquid detergent compositions which contain polymeric hydrotropes.
  • water-soluble or water-dispersible films are particularly suitable for packaging solid or liquid detergents or cleaning agents.
  • the detergents packaged in this way to form individual dosing units can be simply put in one or more bags directly into the washing machine or dishwasher or in the washing-in chamber, or by throwing them into a predetermined amount of water, for example in a bucket or in a hand-washing or Sink, to be dosed.
  • Packaged detergents and cleaning agents of this type have been the subject of numerous publications.
  • the application WO 02/16222 discloses water-soluble packaging for aqueous detergent compositions, the free water content of which is at least 3% by weight.
  • WO 02/16541 (Reckitt-Benckiser) are liquid detergent compositions with a water content of between 20 and 50% by weight, which are packaged in a water-soluble or water-dispersible material, have at least one polyphosphate builder and, through a certain ratio of those in the Potassium and sodium ions contained in the agent are labeled.
  • a first object of the present invention was to improve the cleaning performance of detergents or cleaning agents. In doing so, both the removal of soiling should be improved and the effect of additives such as glass or silver protection agents should be increased.
  • Another object of the present invention was to provide a high-density washing or cleaning agent which at the same time has a high solubility.
  • Solid detergents or cleaning agents should continue to have high dimensional stability and a low tendency to break.
  • Such highly compressed detergents or cleaning agents take up a reduced volume in relation to a metering unit and are therefore compatible with a larger number of metering chambers of commercially available washing machines or dishwashers.
  • a ready-made form for detergents or cleaning agents should be provided, which can be processed in a simple manner to give shape.
  • detergent or cleaning agent dispersions which are water-soluble or water-dispersible Have packaging and which contain at least part of the active washing or cleaning substances in the form of a dispersion.
  • the resulting washing or cleaning agents are distinguished from conventional agents by an improved cleaning performance.
  • This application therefore relates to detergent or cleaning agent dispersions in water-soluble or water-dispersible packaging and to processes for their preparation.
  • a first subject of the present application is therefore a method for producing packaged detergents or cleaning agents, comprising the steps: i) shaping processing of a first wrapping material with formation of a
  • Container with at least one receiving chamber; ii) Filling at least one receiving chamber with one or more substances or substance mixtures, characterized in that at least one of the substances or substance mixtures in step ii) comprises a dispersion of solid particles in a dispersing agent which, based on their total weight, a) 10 to 65 wt .-% dispersant and b) 30 to 90 wt .-% dispersed substances.
  • a dispersing agent which, based on their total weight, a) 10 to 65 wt .-% dispersant and b) 30 to 90 wt .-% dispersed substances.
  • Thermoforming processes, injection molding processes or casting processes are suitable as shaping processes for processing the wrapping materials, that is to say for producing the water-soluble or water-dispersible packaging.
  • deep-drawing processes refer to processes in which a first film-like wrapping material is deformed after being brought into contact with a receiving trough located in a die forming the deep-drawing plane and the shaping of the wrapping material into this receiving trough by the action of pressure and / or vacuum
  • the casing material can be pretreated before or during the molding in by the action of heat and / or solvent and / or conditioning by means of relative atmospheric humidity and / or temperature changes in relation to ambient conditions.
  • the pressure can be applied by two parts of a tool, which can be like Behave positively and negatively to one another and deform a film placed between these tools when compressed, but the pressure forces are also the action of compressed air and / or the weight of the film and / or the weight of one on the top of the film Foil spent active ingredient.
  • the deep-drawn envelope materials are preferably fixed by using a vacuum within the receiving troughs and in the spatial shape achieved by the deep-drawing process.
  • the vacuum is preferably applied continuously from deep drawing to filling, preferably to sealing and in particular to the separation of the receiving chambers.
  • a discontinuous vacuum for example for deep-drawing the receiving chambers and (after an interruption) before and during the filling of the receiving chambers.
  • the strength of the continuous or discontinuous vacuum can also vary and, for example, assume higher values at the beginning of the process (when deep-drawing the film) than at the end (when filling or sealing or separating).
  • the wrapping material can be pretreated by the action of heat before or during molding into the receiving troughs of the dies.
  • the coating material preferably a water-soluble or water-dispersible polymer film, is kept at temperatures above 60 ° C. for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0.4 to 2 seconds. preferably heated above 80 ° C, particularly preferably between 100 and 120 ° C and in particular to temperatures between 105 and 115 ° C. In order to dissipate this heat, but in particular also to dissipate the heat (e.g.
  • the cooling is preferably carried out at temperatures below 20 ° C., preferably below 15 ° C., particularly preferably at temperatures between 2 and 14 ° C. and in particular at temperatures between 4 and 12 ° C.
  • the cooling is preferably carried out continuously from the start of the deep-drawing process to the sealing and separation of the receiving chambers. Cooling liquids, preferably water, which are circulated in special cooling lines within the die are particularly suitable for cooling.
  • This cooling like the continuous or discontinuous application of a vacuum described above, has the advantage of preventing the deep-drawn containers from shrinking back after deep-drawing, which not only improves the appearance of the process product, but at the same time also escapes the agents filled into the receiving chambers the edge of the receiving chamber, for example in the sealing areas of the chamber, is avoided. This prevents problems with the sealing of the filled chambers.
  • the deep-drawing process can be between processes in which the wrapping material is guided horizontally into a molding station and from there in a horizontal manner for filling and / or sealing and / or separating and processes in which the wrapping material is continuously over a distinguish between the peripheral die-forming roller (optionally with a counter-rotating male-forming roller, which guides the shaping upper punches to the cavities of the die-forming roller).
  • the first-mentioned process variant of the flatbed process is to be operated both continuously and discontinuously; the process variant using a shaping roller is generally carried out continuously. All of the deep-drawing processes mentioned are suitable for producing the agents preferred according to the invention.
  • the receiving troughs located in the matrices can be arranged “in series” or offset.
  • injection molding refers to the shaping of a Formin asse such that the mass contained in a mass cylinder for more than one injection molding process plastically softens under the influence of heat and flows under pressure through a nozzle into the cavity of a previously closed tool.
  • the process is mainly used for non-hardenable molding compounds that solidify in the mold by cooling.
  • Injection molding is a very economical, modern process for the production of non-cutting shaped objects and is particularly suitable for automated mass production.
  • thermoplastic molding materials are heated to liquefaction (up to 180 ° C) and then sprayed under high pressure (up to 140 MPa) into closed, two-part, that is, out Die (formerly die) and core (formerly patrix) existing, preferably water-cooled hollow molds, where they cool and solidify.
  • Piston and screw injection molding machines can be used.
  • Suitable molding compounds are water-soluble polymers such as, for example, the above-mentioned cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.
  • the shell materials can also be cast into hollow molds.
  • the hollow form of the resulting water-soluble or water-dispersible packaging preferred according to the invention comprises at least one solidified melt.
  • This melt can be a melted pure substance or a mixture of several substances. It is of course possible to mix the individual substances of a multi-substance melt before melting or to produce separate melts which are then combined. Melting from mixtures of substances can e.g. be of advantage if eutectic mixtures are formed which melt significantly lower and thus lower the process costs.
  • the enveloping material cast into the hollow form comprises, at least in part, an inventive washing or Cleaning supplies.
  • inventive washing or Cleaning supplies The production of cast hollow molds which consist entirely of a washing or cleaning agent according to the invention is particularly preferred.
  • Preferred agents according to the invention are characterized in that the hollow mold consists of at least one material or material mixture whose melting point is in the range from 40 to 1000 ° C, preferably from 42.5 to 500 ° C, particularly preferably from 45 to 20O ° C and in particular from 50 to 160 ° C.
  • the material of the melt preferably has a high water solubility, for example above 100 g / l, with solubilities above 200 g / l in distilled water at 20 ° C. being particularly preferred.
  • Such substances come from a wide variety of substance groups.
  • melts which consist of the groups of carboxylic acids, carboxylic acid anhydrides, dicarboxylic acids, dicarboxylic acid anhydrides, hydrogen carbonates, hydrogen sulfates, have proven to be particularly suitable as material for the hollow mold.
  • Polyethylene glycols, polypropylene glycols, sodium acetate trihydrate and / or urea are particularly preferred in which the material of the hollow form contains one or more substances from the groups of carboxylic acids, carboxylic anhydrides, dicarboxylic acids, dicarboxylic anhydrides, hydrogen carbonates, hydrogen sulfates,
  • carboxylic acids and their salts are also suitable as materials for the production of the open hollow form.
  • citric acid and trisodium citrate as well as salicylic acid and glycolic acid have proven to be particularly suitable. It is also particularly advantageous to use fatty acids, preferably those with more than 10 carbon atoms, and their salts as material for the open hollow form.
  • Carboxylic acids which can be used in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (oenanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid etc.
  • fatty acids such as Dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotinic acid) and meltsiacetic acid (9) Hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t- Octadecenoic acid ((elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 1 2
  • coconut oil fatty acid (about 6 wt .-% C 8, 6 wt .-% C 10 48 wt .-% C ⁇ 2, 18% Gewv.- C 14, 10 wt .-% C 16, 2 wt .-% C18, 8 wt .-% C 18 - 1 wt .-% C 18 -), palm kernel oil fatty acid (approx 4 wt .-% C 8.
  • the above-mentioned carboxylic acids are largely obtained industrially from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), today only water is used on an industrial scale that splits the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage.
  • the alkali metal salts of the abovementioned carboxylic acids or carboxylic acid mixtures can also be used for the preparation of the open hollow mold, if appropriate in a mixture with other materials. Salicylic acid and / or acetysalicylic acid or their salts, preferably their alkali metal salts, can also be used, for example.
  • suitable materials that can be processed into open hollow molds via the state of the melt are hydrogen carbonates, in particular the alkali metal hydrogen carbonates, especially sodium and potassium hydrogen carbonate, and the hydrogen sulfates, in particular alkali metal hydrogen sulfates, especially potassium hydrogen sulfate and / or sodium hydrogen sulfate.
  • the eutectic mixture of potassium hydrogen sulfate and sodium hydrogen sulfate has also proven to be particularly suitable, which consists of 60% by weight of NaHS0 and 40% by weight of KHS0 4 .
  • sugars are also suitable materials for the melt.
  • agents which are characterized in that the material of the hollow form contains one or more substances from the group of sugars and / or sugar acids and / or sugar alcohols, preferably from the group of sugars, particularly preferably from the group of oligosaccharides, Oligosaccharide derivatives, monosaccharides, disaccharides,
  • Monosaccharide derivatives and disaccharide derivatives and mixtures thereof, particularly from the group of glucose and / or fructose and / or ribose and / or maltose and / or lactose and / or sucrose and / or maltodextrin and / or isomalt comprises ®.
  • Sugar, sugar acids and sugar alcohols have proven to be particularly suitable materials for the melt in the context of the present invention. These substances are generally not only sufficiently soluble, but are also characterized by low costs and good processability.
  • sugar and sugar derivatives in particular the mono- and disaccharides and their derivatives, can be processed, for example, in the form of their melts, these melts having good solubility both for dyes and for many active washing and cleaning substances.
  • the solid bodies resulting from the solidification of the sugar melts are also distinguished by a smooth surface and an advantageous appearance, such as a high surface brilliance or transparent appearance.
  • the group of preferred as the material for the melt in the context of the present application include sugar from the group of mono- and disaccharides, and derivatives of mono- and disaccharides in particular glucose, fructose, ribose, maltose, lactose, sucrose, maltodextrin, and isomalt, and mixtures ® of two, three, four or more mono- and / or disaccharides and / or the derivatives of mono- and / or disaccharides.
  • Isomalt ® and glucose, Isomalt ® and lactose, Isomalt ® and fructose, Isomalt ® and ribose, Isomalt ® and maltose, glucose and sucrose, Isomalt ® and maltodextrin or Isomalt ® and sucrose are particularly preferred as materials for the melt.
  • the weight fraction of Isomalt® in the total weight of the aforementioned mixtures is preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight.
  • maltodextrin and glucose are also particularly preferred as the material for the melt.
  • the proportion by weight of maltodextrin in the total weight of the aforementioned mixtures is preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight.
  • maltodextrin refers to water-soluble carbohydrates (dextrose equivalents, DE 3-20) obtained by enzymatic degradation of starch with a chain length of 5-10 anhydroglucose units and a high proportion of maltose.
  • Maltodextrin are foods to improve theological and. added caloric properties, taste little sweet u. do not tend to retrogradate.
  • Commercial products, for example from Cerestar are generally offered as spray-dried, free-flowing powders and have a water content of 3 to 5% by weight.
  • isomalt ® in the context of the present application, a mixture of 6-O- ⁇ -D-glucopyranosyl-D-sorbitol (1, 6-GPS) and 1-O- ⁇ -D-glucopyranosyl-D-mannitol (1, 1 -GPM).
  • the weight fraction of the 1, 6 GPS is Total weight of the mixture less than 57% by weight.
  • Mixtures of this type can be prepared industrially, for example, by enzymatic rearrangement of sucrose into isomaltose and subsequent catalytic hydrogenation of the isomaltose obtained to form an odorless, colorless and crystalline solid.
  • the present invention relates to a washing or cleaning agent in the form of a dispersion, which is at least partially comprised of a water-soluble or water-dispersible hollow form comprising at least one solidified melt.
  • Hollow molds which comprise at least one further solid body are particularly preferred, the at least one further solid body being cast at least partially in the wall of the hollow mold.
  • the term “hollow shape” denotes a shape enclosing at least one space, wherein the enclosed space can be filled or can be.
  • the hollow shape can have further enclosed spaces and / or spaces that are not completely enclosed.
  • the hollow shape does not have to consist of a uniform wall material, but can also be composed of several different materials.
  • the inclusion of at least one solid in the wall of the hollow mold is possible, for example, by producing a hollow shell from a solidified melt, which at least partially encloses at least one solid. This hollow shell can then be filled and closed, for example by a melt with a different composition. The two solidified melts together form the hollow form of the agent preferred according to the invention.
  • At least one solid can also be incorporated at least partially into the melt, which closes the hollow shell from solidified melt.
  • the hollow shell made of solidified melt and the solidified melt that forms the “lid” together form the hollow form of the agents according to the invention.
  • the hollow shell can at least partially enclose at least one solid (then the hollow form contains at least two solids), it can but also be completely free of a solid, because the solid, at least partially enclosed by the sealing melt, is at least partially cast into the wall of the hollow mold.
  • the portioned agents preferred according to the invention comprise a hollow form.
  • This can be a hollow shell, for example, which is suitable for holding the dispersion according to the invention and can be closed if necessary.
  • “solid” means that the body or bodies do not melt at the melting temperature of the melt and do not dissolve in the melt either.
  • Preferred methods according to the invention are characterized in that the shaping processing of the wrapping material in step i) takes place at least in part by deep drawing or injection molding or casting, the wrapping material being shaped in step i) in a further preferred embodiment of the method according to the invention being a water-soluble one or water-dispersible wrapping material.
  • the container filled in step ii) is sealed in a further step with at least one closure part.
  • at least one receiving chamber of the container and / or at least one closure part has a wall thickness below 200 ⁇ m, preferably below 120 ⁇ m, particularly preferably below 90 ⁇ m and in particular below 70 ⁇ m.
  • closure parts described above can be applied to the water-soluble or water-dispersible container, in particular the deep-drawn body, the injection-molded body or the melting body, by different methods.
  • those agents are particularly preferred whose water-soluble or water-dispersible container is connected to the water-soluble or water-dispersible closure part by means of an adhesive.
  • adhesives all substances or mixtures of substances known to the person skilled in the art for this purpose can be used as adhesives.
  • Particularly suitable and particularly preferred in the context of the present application are water-soluble or water-dispersible polymers or their mixtures or solutions, in particular aqueous solutions, of these water-soluble or water-dispersible polymers or solutions, in particular aqueous solutions of these mixtures.
  • Aqueous solutions of polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxides, gelatin or polymers from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose, are particularly preferred.
  • water-soluble hotmelt adhesives in particular hotmelt adhesives, which a) 40 to 70% by weight of at least one homo- or copolymer with free carboxylic acid groups based on ethylenically unsaturated monomers (component A), b) 15 to 45% by weight of at least one water-soluble or water-dispersible polyurethane (component B) and c) 10 to 45% by weight of at least one inorganic or organic base (component C), d) and 0 to 20% by weight of further additives, the sum of the components being 100% by weight. -% results.
  • hotmelt adhesives which a) 40 to 70% by weight of at least one homo- or copolymer with free carboxylic acid groups based on ethylenically unsaturated monomers (component A), b) 15 to 45% by weight of at least one water-soluble or water-dispersible polyurethane (component B) and c) 10 to 45% by weight of at least one inorganic or organic base
  • the process for gluing the deep-drawn body, injection molded body or melting body can be varied over a wide range depending on the production requirements.
  • a particularly preferred method for bonding water-soluble or water-dispersible receptacles, in particular water-soluble or water-dispersible thermoformed bodies, injection molded articles or melting bodies, with water-soluble or water-dispersible closure parts will be described below.
  • the adhesive is applied in step b) by means of a roller, a rotating conveyor belt, a spraying device or a stamp.
  • closure parts made of water-soluble or water-dispersible polymers are used as closure parts in step c), it being possible, for example, to use film webs or prefabricated closure labels as closure parts.
  • closure part made of water-soluble or water-dispersible polymers, in particular in the form of film webs or prefabricated closure labels, are also preferably used here.
  • closure parts are used in the methods described above that do not close the corresponding body precisely (e.g. film webs), these closure parts must be cut to their final size after the adhesive bonding. Knives and / or punches and / or lasers are preferably used for this process step in the context of the present application.
  • a method for producing packaged detergents or cleaning agents comprising the steps: i) shaping processing of a first wrapping material with formation of a container with at least one receiving chamber; ii) filling at least one receiving chamber with one or more substances or
  • Substance mixtures characterized in that at least one of the substances or substance mixtures in step ii) comprises a dispersion of solid particles in a dispersing agent which, based on their total weight, comprises a) 10 to 65% by weight of dispersing agent and b) 30 to 90% by weight. -% dispersed substances.
  • a dispersing agent which, based on their total weight, comprises a) 10 to 65% by weight of dispersing agent and b) 30 to 90% by weight. -% dispersed substances.
  • closing the receiving chamber by means of an adhesive and a water-soluble or water-dispersible closure part; d) the corresponding adhesive was previously applied to the container and / or the closure part by means of a roller, a rotating conveyor belt, a spraying device or a stamp.
  • the dispersion contains the dispersant in amounts of 12 to 62% by weight, preferably 17 to 49% by weight and in particular 23 to 38% by weight
  • Dispersing agent is a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a polypropylene glycol, and the weight fraction of the poly (ethylene) glycol in the total weight of the dispersing agent is preferably between 10 and 90, particularly preferably between 30 and 80,% by weight. % and in particular between 50 and 70% by weight.
  • the average relative molecular weight of at least one of the dispersants contained in the dispersion is preferably between 200 and 36,000, preferably between 200 and 6000 and particularly preferably between 300 and 5000.
  • both solid and liquid substances can be used as dispersants (the state of matter refers to 20 ° C).
  • the state of matter refers to 20 ° C.
  • the dispersion contains at least one dispersant with a melting point above 25 ° C., preferably above 35 ° C. and in particular above 40 ° C.
  • processes in which the dispersant has a melting point below 15 ° C., preferably below 10 ° C. and in particular below 5 ° C. can also have advantages and are likewise preferred according to the invention.
  • the density of the dispersion used in a preferred embodiment of the process according to the invention is above 1.1 g / cm 3 , preferably above 1.2 g / cm 3 , particularly preferably above 1.3 g / cm 3 and in particular above 1.4 g / cm 3 cm 3 .
  • the dispersed solid particles preferably contain, based on their total weight Embodiment of the method at least 20% by weight, preferably between 30 and 80% by weight, particularly preferably between 40 and 70% by weight and in particular between 50 and 60% by weight of builders and / or bleaching agents and / or bleach activators and / or polymers.
  • the proportion by weight of the polymer (s) in a preferred embodiment of the process, based on the total weight of the dispersion, is preferably 0.1 to 50% by weight, preferably between 0.2 and 40% by weight, particularly preferably between 0.4 and 35% by weight and in particular between 0.6 and 31% by weight.
  • polymers containing sulfonic acid groups preferably copolymers of i) unsaturated carboxylic acids ii) sulfonic acid group-containing monomers iii) optionally further ionic or nonionic monomers as a constituent of the dispersed substances.
  • polymers which are used with particular preference as a constituent of the dispersed solid particles comprise the polymers with a molecular weight above 2000, which have at least one positive charge.
  • the content of silver dispersants and / or glass protectants and / or enzymes in the dispersed solid particles, based on the total weight of the dispersion, is between 0.04 and 18% by weight, preferably between 0.08 and 16% by weight, in a preferred embodiment of the process according to the invention .- o and in particular between 0.2 and 14 wt .-%.
  • the present application also relates to the detergents or cleaning agents described below, which can also be produced by other processes in addition to the process according to the invention.
  • Another claim of the present application is therefore directed to washing or cleaning agents, comprising i) a water-soluble or water-dispersible packaging with at least one
  • dispersion is a system consisting of several phases, one of which is continuous (dispersant) and at least one other is finely divided (dispersed substances).
  • washing or cleaning agents are characterized in that the dispersions contain the dispersing agent in amounts above 11% by weight, preferably above 13% by weight, particularly preferably above 15% by weight, very particularly preferably above 17% by weight. % and in particular above 19% by weight, in each case based on the total weight of the dispersion.
  • agents according to the invention which have a dispersion with a weight fraction of dispersion medium above 20% by weight, preferably above 21% by weight and in particular above 22% by weight, in each case based on the total weight of the dispersion .
  • the maximum content of dispersions in preferred dispersions according to the invention, based on the total weight of the dispersion, is preferably less than 63% by weight, preferably less than 57% by weight, particularly preferably less than 52% by weight, very particularly preferably less than 47 % By weight and in particular less than 37% by weight.
  • detergents or cleaning agents are particularly preferred in which the dispersion, based on the total weight of the dispersion, contains 12 to 62% by weight, preferably 17 to 49% by weight, of the dispersion contains in particular from 23 to 38% by weight.
  • the dispersing agents used are preferably water-soluble or water-dispersible.
  • the solubility of these dispersions at 25 ° C. is preferably more than 200 g / l, preferably more than 300 g / l, particularly preferably more than 400 g / l, very particularly preferably between 430 and 620 g / l and in particular between 470 and 580 g / l.
  • the water-soluble or water-dispersible polymers in particular the water-soluble or water-dispersible nonionic polymers, are preferably suitable as dispersing agents.
  • the dispersion medium can be either a single polymer or a mixture of different water-soluble or water-dispersible polymers.
  • the dispersant or at least 50% by weight of the polymer mixture consists of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidones, vinylpyrrolidone / vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.
  • Polyvinylpyrrolidones are preferred dispersants in the context of the invention.
  • Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (I)
  • polyvinylpyrrolidones which are produced by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators.
  • the ionic polymerization of the monomer only provides products with low molecular weights.
  • Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol, which are characterized by the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).
  • Vinylester vinyl pyrrolidone copolymers as are marketed, for example under the trademark Luviskol ® (BASF).
  • Luviskol ® VA 64 and Luviskol ® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.
  • the vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (II)
  • the vinyl esters are polymerized by free radicals using various processes (solution polymerization, suspension polymerization, emulsion polymerization,
  • Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (I) and (II)
  • Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and
  • Methylhydroxypropylcellulose such as are for example sold under the trademark Culminal® ® and Benecel ® (AQUALON).
  • Cellulose ethers can be described by the following general formula
  • R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical.
  • at least one R in the formula is -CH 2 CH 2 CH 2 -OH or -CH 2 CH 2 -OH.
  • Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average.
  • Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish white, odorless and tasteless powders in widely differing degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition. Polyvinyl alcohols, abbreviated as PVAL, are polymers of the general structure
  • polyvinyl alcohols are prepared in solution via polymer-analogous reactions by hydrolysis, but technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol). These technical processes also make PVAL accessible which contain a predeterminable residual proportion of acetate groups.
  • PVAL eg Mowiol ® types from Hoechst
  • PVAL eg Mowiol ® types from Hoechst
  • Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols.
  • Polymers of ethylene glycol which have the general formula III
  • n can take values between 1 (ethylene glycol) and several thousand.
  • polyethylene glycols There are various nomenclatures for polyethylene glycols that can lead to confusion.
  • the specification of the average relative molecular weight following the specification "PEG” is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210.
  • a different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula VII mentioned above.
  • polyethylene glycols are, for example, under the trade name Carbowax ® PEG 200 (Union Carbide), Emkapol ® 200 (ICI Americas), Lipoxol ® 200 MED (Huls America), polyglycol ® E-200 (Dow Chemical), Alkapol ® PEG 300 (Rhone - Poulenc), Lutrol E300 (BASF) and the corresponding trade names with higher numbers.
  • the average relative molecular weight of the dispersants contained in the dispersions, in particular the poly (alkylene) glycols used, is preferably between 200 and 36,000, preferably between 200 and 6000 and particularly preferably between 300 and 5000.
  • Polypropylene glycols are polymers of propylene glycol that have the general formula IV
  • n can take values between 1 (propylene glycol) and several thousand.
  • the dispersion comprises as dispersion medium a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a polypropylene glycol, the proportion by weight of the poly (ethylene) glycol in the total weight of the dispersion medium is preferably between 10 and 90, particularly preferably between 30 and 80% by weight and in particular between 50 and 70% by weight.
  • washing or cleaning agents according to the invention are particularly preferred in which the dispersant comprises more than 92% by weight, preferably more than 94% by weight, particularly preferably more than 96% by weight, very particularly preferably more than 98% %
  • the dispersant comprises more than 92% by weight, preferably more than 94% by weight, particularly preferably more than 96% by weight, very particularly preferably more than 98% %
  • a poly (alkylene) glycol preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular poly (ethylene) glycol.
  • Dispersing agents which, in addition to poly (ethylene) glycol, also contain poly (propylene) glycol, preferably have a ratio by weight of poly (ethylene) glycol to poly (propylene) glycol of between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, particularly preferably between 10: 1 and 1, 5: 1 and in particular between 7: 1 and 2: 1.
  • nonionic surfactants which are used both alone, but particularly preferably in combination with a nonionic polymer.
  • 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 is linear or preferred can be methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 C atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • ethoxylated alcohols Ex ielsweise C 12-14 - alcohols with 3 EO or 4 EO, C9-11 alcohol containing 7 EO, C 13- ⁇ 5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO , C 12-18 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12- ⁇ 4 alcohol containing 3 EO and C 12- ⁇ 8 alcohol containing 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (V),
  • R-CO-N- [Z] (V) in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula
  • R 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
  • R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms
  • C 1-4 -alkyl or phenyl radicals being preferred
  • [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 remainder.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the cleaning agents according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols.
  • 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 residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear alcohol residues are native Origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9- ⁇ alcohol with 7 EO, C 13- i 5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 . 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 alcohol with 3 EO and C 12 ⁇ 8 alcohol! with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactant which has a melting point above room temperature
  • preferred dishwashing detergents are characterized in that they have 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 nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature originate from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.
  • a particularly preferred nonionic surfactant which is solid at room temperature is made from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 6 or 2 o-alcohol), preferably a C 18 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide won.
  • the so-called “narrow ranks ethoxylates" are particularly preferred.
  • the / preferred dishwashing detergent according to the invention ethoxylated (s) nonionic surfactant selected from C 6- C 0 monohydroxyalkanols or 6- 0 -alkylphenols or C 16-2 o- fatty alcohols and more than 12 mol, preferably more than 15 Mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was obtained.
  • ethoxylated (s) nonionic surfactant selected from C 6- C 0 monohydroxyalkanols or 6- 0 -alkylphenols or C 16-2 o- fatty alcohols and more than 12 mol, preferably more than 15 Mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was obtained.
  • the nonionic surfactant which is solid at room temperature, preferably has additional propylene oxide units in the molecule.
  • Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants.
  • Preferred dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Make up surfactants.
  • nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight.
  • 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 dishwashing detergent according to the invention contains nonionic surfactants of the formula (VI)
  • R 1 0 [CH 2 CH (CH 3 ) 0] x [CH 2 CH 2 0] y [CH 2 CH (OH) R 2 ], (VI) 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.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • 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, iso-propyl, n -Butyl, 2-butyl or 2-methyl-2-butyl
  • 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.
  • each R 3 in the above formula can be different if x> 2.
  • the value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 O [CH 2 CH (R 3 ) 0] x CH 2 CH (OH) CH 2 OR 2 simplified.
  • R 1 , R 2 and R 3 are as defined above and x represents 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 has 9 to 14 C atoms, R 3 represents H and x assumes values from 6 to 15.
  • dishwashing detergents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n -Butyl, 2-butyl or 2-methyl-2-butyl
  • 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
  • x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • weakly foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants.
  • surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups.
  • Machine dishwashing detergents according to the invention which contain surfactants of the general formula VII as nonionic surfactant (s) are preferred here
  • R 1 represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently represent integers from 1 to 6.
  • the preferred nonionic surfactants of the formula VII can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula X can vary depending on the origin of the alcohol.
  • the radical R 1 has an even number of carbon atoms and is generally not shown, the linear radicals being of alcohols of native origin with 12 to 18 carbon atoms, for example coconut, palm, tallow or Oleyl alcohol are preferred.
  • Alcohols accessible from synthetic sources are, for example, Guerbet alcohols or residues which are methyl-branched in the 2-position or linear and methyl-branched residues in a mixture, as are usually present in oxo alcohol residues.
  • preferred dishwasher detergents according to the invention are those in which R 1 in formula VII for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 is up to 11 carbon atoms.
  • butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit.
  • R 2 or R 3 are selected independently of one another from - CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 are also suitable.
  • Preferred automatic dishwashing agents are characterized in that R 2 or R 3 for a radical -CH 3 , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.
  • non-ionic surfactants which have a 9- of L ⁇ C 5 alkyl group having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed of L to 4 ethylene oxide followed to 4 propylene oxide units.
  • These surfactants have the required low viscosity in aqueous solution and can be used with particular preference according to the invention.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula (VIII)
  • R 1 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 2 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which is preferably between 1 and 5 have hydroxyl groups and are preferably further functionalized with an ether group
  • R 3 is H or a methyl, Ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical
  • x stands for values between 1 and 40.
  • R 1 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms
  • R 2 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.
  • R 1 which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical
  • R 2 which is a monohydroxylated intermediate group - CH 2 CH (OH) - adjacent.
  • x stands for values between 1 and 40.
  • Such end-capped poly (oxyalkylated) nonionic surfactants can be obtained, for example, by reacting a terminal epoxide of the formula R 2 CH (0) CH 2 with an ethoxylated alcohol of the formula R 1 0 [CH 2 CH 2 0] x-1 CH 2 CH 2 OH obtained.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the above-mentioned nonionic surfactants represent statistical mean values which can be an integer or a fraction for a specific product. Due to the manufacturing process, best commercial products of the formulas mentioned mostly do not come from an individual representative, but from mixtures, which can result in mean values for both the C chain lengths and for the degrees of ethoxylation or alkoxylation and, consequently, broken numbers.
  • washing or cleaning agents according to the invention contain at least one nonionic surfactant, preferably at least one end-capped poly (oxyalkylated) nonionic surfactant, the weight fraction of the nonionic surfactant in the total weight of all dispersing agents preferably being between 1 and 60% by weight, particularly preferably between 2 and 50% by weight and in particular between 3 and 40% by weight.
  • Washing or cleaning agents according to the invention are particularly preferred, in which the total weight of the nonionic surfactant (s) in relation to the total weight of the agent according to the invention is between 0.5 and 40% by weight, preferably between 1 and 30% by weight, particularly preferably is preferably between 2 and 25 and in particular between 2.5 and 23% by weight.
  • Preferred washing or cleaning agents according to the invention are characterized in that the dispersion contains at least one dispersing agent with a melting point above 25 ° C, preferably above 35 ° C and in particular above 40 ° C.
  • Such agents can, for example, be a dispersant with a melting point above 26 ° C or above 27 ° C or above 28 ° C or above 29 ° C or above 30 ° C or above 31 ° C.
  • dispersing agents with a melting point or melting range between 30 and 80 ° C, preferably between 35 and 75 ° C, more preferably between 40 and 70 ° C and in particular between 45 and 65 C C, said dispersion medium, based on the total weight of the dispersants used, a weight fraction above 10% by weight, preferably above 40% by weight, particularly preferably above 70% by weight and in particular between 80 and 100% by weight.
  • the washing or cleaning agents according to the invention contain at least one dispersing agent which has a melting point below 15 ° C., preferably below 10 ° C. and in particular below 5 ° C.
  • Particularly preferred dispersants have a melting range between 2 and 14 ° C., in particular between 4 and 10 ° C.
  • Dispersions preferably used according to the invention are dimensionally stable at temperatures of 20 ° C.
  • Agents according to the invention are considered to be dimensionally stable if they have an inherent shape stability which enables them to assume a non-disintegrating spatial shape under the usual conditions of manufacture, storage, transport and handling by the consumer, this spatial shape also under longer conditions under the conditions mentioned Time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, not changed, i.e. under the usual conditions of manufacture, storage, transport and handling by the consumer in the spatial-geometric shape resulting from the manufacture, that persists means not to melt away.
  • Such dimensionally stable dispersions give the water-soluble or water-dispersible packaging of the agents according to the invention increased stability since, unlike gels, liquids or powders, for example, they retain their spatial shape even when exposed to external forces and thus give the packaged product a stable spatial structure. This advantage is particularly important in the case of deep-drawn or injection-molded water-soluble or water-dispersible packaging.
  • Suitable dispersed substances in the context of the present application are all substances which are active in washing or cleaning at room temperature, but in particular substances which are active in washing or cleaning from the group of builders (builders and cobuilders), detergents or cleaning polymers, bleaching agents and bleach activators , the glass corrosion protection agent, the silver protection agent and / or the enzymes.
  • the builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x ⁇ 2 ⁇ +1 ⁇ 2 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 0 5 "yH 2 0 are preferred.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • 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.
  • it can very well lead to particularly good builder properties if the Silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments.
  • This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • Detergents and cleaning agents preferred in the context of the present invention are characterized in that these silicate (s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in amounts of 10 to 60% by weight, preferably 15 to 50% by weight. % and in particular from 20 to 40 wt .-%, each based on the weight of the detergent or cleaning agent.
  • silicate preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in amounts of 10 to 60% by weight, preferably 15 to 50% by weight. % and in particular from 20 to 40 wt .-%, each based on the weight of the detergent or cleaning agent.
  • these agents preferably contain at least one crystalline layered silicate of the general formula NaMSi x 0 2x + ⁇ 'y H 2 0, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, is preferably from 1.9 to 4 and y is a number from 0 to 33.
  • the crystalline layered silicates of the formula (I) are, for example, from Clariant Gm bH
  • Na-SKS e.g. Na-SKS-1 (Na2Si 22 0 45 - ⁇ H 2 0, Kenyait), Na-SKS-2 (Na 2 Si 14 0 2 g- ⁇ H 2 0, magadiite) , Na-SKS-3 (Na 2 SigO 17 - ⁇ H 2 0) or Na-SKS-4 (Na 2 Si 4 O g - ⁇ H 2 0, makatite).
  • Na-SKS-5 ( ⁇ -Na 2 Si 2 0 5 ), Na-SKS-7 (ß-Na 2 Si 2 0 5 , natrosilite), Na-SKS-9 (NaHSi 2 0 5 ⁇ 2 0), Na -
  • preferred automatic dishwashing agents or automatic dishwashing aids have a weight fraction of the crystalline layered silicate of the formula (I) of 0.1 to 20% by weight, preferably 0.2 to 15% by weight and in particular 0 4 to 10 wt .-%, based in each case on the total weight of these agents.
  • Particularly preferred are dishwasher detergents which have a total silicate content below 7% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably below 4% by weight, very particularly preferably below 3% by weight.
  • this silicate based on the total weight of the silicate contained, preferably being at least 70% by weight, preferably at least 80% by weight and in particular at least 90 wt .-% is silicate of the general formula NaMSi x 0 2x + 1 'y H 2 0.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • 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 of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • the zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
  • the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphates is the summary name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 3 ) n and orthophosphoric acid H 3 P0 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They work As an alkali carrier, prevent limescale deposits on machine parts or scale incrustations in fabrics and also contribute to cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 P0 4 exists as a dihydrate (density 1.91 like “3 , melting point 60 °) and as a monohydrate (density 2.04 like “ 3 ). Both salts are white powders, which are very easily soluble in water, lose the water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 0 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 0 9 ) and Maddrell's salt (see below).
  • NaH 2 P0 4 is acidic; it arises 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 P0 is a white salt with a density of 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 3 ) ⁇ ] and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HP0 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 0) and 12 mol. Water ( Density 1, 52 like “3 , melting point 35 ° with loss of 5 H 2 0), becomes anhydrous at 100 ° and changes to diphosphate Na P 2 0 7 when heated.
  • Disodium hydrogenphosphate is used by neutralizing phosphoric acid with soda solution made from phenolphthalein as an indicator
  • Dipotassium hydrogen phosphate secondary or dibasic potassium phosphate
  • K 2 HP0 4 is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 P0 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 "3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 0 5 ) have a melting point of 100 ° C. and, in anhydrous form (corresponding to 39-40% P 2 0 5 ), a density of 2.536 ′′ 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 three-base potassium phosphate), K 3 P0 4 , is a white, deliquescent, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred in the cleaning agent industry over corresponding sodium compounds.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 ⁇ 7 , exists in anhydrous form (density 2.534 like “3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836 like " 3 , melting point 94 ° with water loss). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na 4 P 2 0 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering 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 0 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.
  • the condensation of the NaH 2 P0 4 or the KH 2 P0 4 produces higher temperatures.
  • 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.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • the technically important pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] that crystallizes with 6 H 2 0.
  • n -Na with n 3.
  • About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 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.
  • pentasodium triphosphate In the production 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, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P 2 0 5 , 25% K 2 0). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:
  • these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; also 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 be used according to the invention.
  • Agents preferred in the context of the present invention are characterized in that these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or.
  • Pentapotassium triphosphate sodium or potassium tripolyphosphate
  • these phosphate preferably alkali metal phosphate (s), particularly preferably pentasodium or.
  • Pentapotassium triphosphate sodium or potassium tripolyphosphate
  • Agents according to the invention are particularly preferred in which the weight ratio of potassium tripolyphosphate to sodium tripolyphosphate contained in the agent is more than 1: 1, preferably more than 2: 1, preferably more than 5: 1, particularly preferably more than 10: 1 and in particular more than Is 20: 1.
  • Those dispersions according to the invention which contain exclusively potassium tripolyphosphate are particularly preferred.
  • Washing or cleaning agents which are particularly preferred in the context of the present application are characterized in that the dispersed solid particles, based on their total weight, are at least 20% by weight, preferably between 30 and 80% by weight, particularly preferably between 40 and 70% by weight. % and in particular between 50 and 60% by weight of builders, preferably from the group of the phosphates, preferably from the group of the alkali metal phosphate (s), particularly preferably from the group of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
  • the group of the phosphates preferably from the group of the alkali metal phosphate (s), particularly preferably from the group of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
  • alkali carriers include alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metal silicates and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquic acid 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.
  • Particularly preferred washing and cleaning agents contain carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate, in amounts of 2 to 50% by weight, preferably 5 to 40% by weight and in particular 7.5 up to 30% by weight, each based on the weight of the detergent or cleaning agent.
  • Organic cobuilders which can be used in the washing and cleaning agents 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.
  • 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.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • 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.
  • GPC gel permeation chromatography
  • 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 molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of> maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • biodegradable polymers composed of more than two different monomer units, for example those containing the salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or the monomeric salts of acrylic acid and 2-alkylalylsulfonic acid and sugar derivatives contain.
  • copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and are particularly preferred.
  • 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 mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE Dextrose equivalent
  • 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.
  • Ethylenediamine-N, N '- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral sodium salts, e.g. B.
  • 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.
  • all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.
  • Washing or cleaning agent compositions according to the invention can furthermore contain, as dispersed substances, washing or cleaning-active polymers.
  • the group of these polymers includes, for example, the rinse aid polymers and / or polymers which act as softeners.
  • Washing or cleaning agents preferred according to the invention are characterized in that the dispersed solid particles, based on their total weight, 0.1 to 50% by weight, preferably between 0.2 and 40% by weight, particularly preferably between 0.4 and 35 wt .-% and in particular between 0.6 and 31 wt .-% of a polymer, preferably at least one polymer from the group of cationic, anionic or amphoteric polymers.
  • Polymers which act as softeners are, for example, the polymers containing sulfonic acid groups, which are used with particular preference in the agents according to the invention.
  • Copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers can be used with particular preference as polymers containing sulphonic acid groups.
  • unsaturated carboxylic acids of the formula XI are preferred as the monomer
  • 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, 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.
  • Preferred among these monomers are those of the formulas Xlla, Xllb and / or Xllc,
  • H 2 C CH-X-S0 3 H (Xlla),
  • H 2 C C (CH 3 ) -X-S0 3 H (Xllb),
  • ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds.
  • the content of the invention is preferably polymers used on monomers of group iii) 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).
  • copolymers are made of
  • 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,
  • 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
  • H 2 C CH-X-S0 3 H (Xlla),
  • H 2 C C (CH 3 ) -X-S0 3 H (Xllb),
  • the copolymers can contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii).
  • Particularly preferred polymers have certain structural units, which are described below.
  • detergent or cleaning agent compositions according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula XIII
  • 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 inventive washing or cleaning agent compositions are also preferred, and is characterized in that the preferred washing or cleaning agent compositions containing a • or more copolymers which contain structural units of the formula XIV
  • acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. So washing or
  • maleic acid can also be used as a particularly preferred monomer from group i).
  • washing or cleaning agent compositions which are preferred according to the invention and which are characterized in that they contain one or more copolymers which have structural units of the formula XVII
  • detergent or cleaning agent compositions according to the invention which contain one or more copolymers which have structural units of the formulas XIII and / or XIV and / or XV and / or XVI and / or XVII and / or XVIII
  • All or part of the sulfonic acid groups in the polymers can be 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 detergent or cleaning agent compositions 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 washing or cleaning agent compositions according to the invention is preferably 5 to 95% by weight i) or ii), particularly preferably 50 to 90, for copolymers which only contain monomers from groups i) and ii) % By weight of monomer from group i) and 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • 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 sulfo copolymers described above used in the washing or cleaning agent compositions according to the invention can be varied in order to adapt the properties of the polymers to the intended use.
  • Preferred detergent or cleaning agent compositions 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 .
  • washing or cleaning agents are characterized in that the dispersed solid particles comprise at least one polymer containing sulfonic acid groups, preferably a copolymer of i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iii) optionally further ionic or nonionic monomers.
  • Preferred agents according to the invention can furthermore improve the rinse aid result as dispersed substances Contain amphoteric or cationic polymers.
  • These particularly preferred polymers are characterized in that they have at least one positive charge.
  • Such polymers are preferably water-soluble or water-dispersible, that is to say they have a solubility in water at 25 ° C. above 10 mg / ml.
  • Washing or cleaning agents which are particularly preferred in the context of the present application are characterized in that the dispersed solid particles comprise at least one polymer with a molecular weight above 2000 which has at least one positive charge.
  • Cationic or amphoteric polymers particularly preferably contain at least one ethylenically unsaturated monomer unit of the general formula
  • R 1 to R 4 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, a heteroatomic group with at least one positively ended group, a quaternized nitrogen atom or at least one amine group with a positive charge in the pH range between 2 and 11 or for -COOH or -COOR 5 , where R 5 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • Unsaturated carboxylic acids of the general formula are particularly preferred as a constituent of the amphoteric polymers
  • 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 for - COOH or -COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • amphoteric polymers contain derivatives of diallylamine, especially dimethyldiallylammonium salt and / or as monomer units
  • Methacrylamidopropyl (trimethyl) ammonium salt preferably in the form of the chloride, bromide, iodide, hydroxide, phosphate, sulfate, hydrosulfate, ethyl sulffasts, methyl sulfate, mesylate, tosylate, formate or acetate in combination with monomer units from the group of the ethylenically unsaturated carboxylic acids.
  • the dispersions according to the invention can also contain bleaching agents as dispersed substances.
  • bleaching agents include sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other bleaching agents that can be used are, for example, peroxypyrophosphates, citrate perhydrates and H 2 0 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino-persic acid or
  • Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents.
  • Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid
  • PAP Phthaloiminoperoxyhexanoic acid
  • o-carboxybenzamidoperoxycaproic acid N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate
  • aliphatic and araliphatic peroxydicarboxylic acids such as 1, 12-diperoxycarboxylic acid, 1,9-diperoxyacetic acid diperoxyacid, diperoxyacid, diperoxyacid, diperoxyacid, diperoxyacid, D ecyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in the dispersions according to the invention.
  • Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribroisocyanuric acid, dibromoisocyanuric acid and / or
  • DICA Dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • Preferred dispersions according to the invention contain bleaching agents in amounts of 1 to 40% by weight, preferably 2.5 to 30% by weight and in particular 5 to 20% by weight, in each case based on the total dispersion.
  • the agents according to the invention are used as automatic dishwashing agents, they can also contain bleach activators as dispersed substances in order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C. and below.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU) , N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, especially triacetin, and triacetine diacetoxy-2,5-dihydrofuran.
  • TAED tetraacetylethylene di
  • bleach activators which are preferably used in the context of the present application are compounds from the group of the cationic nitriles, in particular cationic nitrile of the formula
  • R 1 represents -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2-24 alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical with a C 1-24 alkyl group, or for a substituted alkyl or alkenylaryl radical with a C 1-4 alkyl group and at least one further substituent on the aromatic ring
  • R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH , -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 - CH 2 -CH 2 -OH, -CH 2
  • bleach activators it is also possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to -4 carbon atoms, and / or optionally substituted perbenzoic acid.
  • Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU) , N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, especially triacetin, -Diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-
  • Hydrophilically substituted acylacetals and acyllactams are also preferably used.
  • Combinations of conventional bleach activators can also be used.
  • the bleach activators are usually used in machine dishwashing detergents in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight and in particular 1 to 10% by weight, based in each case on the detergent. in the In the context of the present invention, the proportions mentioned relate to the weight of the composition without the water-soluble or water-dispersible container.
  • bleach catalysts can also be incorporated into the agents.
  • 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 N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • bleach activators from the group of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyloyloxy- or isobenzononoyloxonyl or n-nonanoyloylonyloxy (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 up to 8% by weight and particularly preferably 2 to 6% by weight, based on the total weight of the dispersion.
  • TAED tetraacetylethylenediamine
  • N-acylimides especially N-nonanoylsuccinimide (NOSI)
  • NOSI N-
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group consisting of manganese and or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes , the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular 0.0025% by weight. % to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, in each case based on the total composition. But in special cases, more bleach activator can be used.
  • Another important criterion for assessing a machine dishwashing detergent is, in addition to its cleaning performance, the visual appearance of the dry dishes after cleaning. Possible calcium carbonate deposits on crockery or in the machine interior can, for example, affect customer satisfaction and thus have a causal influence on the economic success of such a cleaning agent.
  • Another long-standing problem with machine dishwashing is the corrosion of glassware, which can usually manifest itself through the appearance of cloudiness, streaks and scratches, but also through iridescence of the glass surface. The observed effects are essentially based on two processes, the emergence of alkali and alkaline earth ions from the glass in connection with hydrolysis of the silicate network, and on the other hand in the depositing of silicate compounds on the glass surface.
  • Preferred agents according to the invention therefore further contain glass corrosion protection agents, preferably from the group of the magnesium and / or zinc salts and / or magnesium and / or zinc complexes, as the dispersed substance.
  • a preferred class of compounds which can be added to the agents according to the invention to prevent glass corrosion are insoluble zinc salts. These can accumulate on the glass surface during the dishwashing process and prevent metal ions from the glass network from dissolving and the hydrolysis of the silicates. In addition, these insoluble zinc salts also prevent silicate from being deposited on the glass surface, so that the glass is protected from the consequences described above.
  • Insoluble zinc salts in the sense of this preferred embodiment are zinc salts which have a solubility of at most 10 grams of zinc salt per liter of water at 20 ° C.
  • Examples of insoluble zinc salts which are particularly preferred according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn 2 (0H) 2 CO 3 ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn 3 (PO 4 ) 2 ), and zinc pyrophosphate (Zn 2 (P. 2 0 7 )).
  • the zinc compounds mentioned are preferably used in the agents according to the invention in amounts which contain zinc ions between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0% by weight, based in each case on the agent.
  • the exact content of the agents in the .zalzalz or the zinc salts is naturally dependent on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration in the agents according to the invention.
  • the particle size of the salts is a criterion to be observed so that the salts do not adhere to glassware or machine parts.
  • Liquid aqueous dishwasher detergents according to the invention in which the insoluble zinc salts have a particle size below 1.7 millimeters are preferred here.
  • the insoluble zinc salt preferably has an average particle size which is significantly below this value in order to further minimize the risk of insoluble residues, for example an average particle size less than 250 ⁇ m. This, in turn, is all the more the less the zinc salt is soluble. In addition, the glass corrosion inhibiting effectiveness increases with decreasing particle size.
  • the average particle size is preferably below 100 ⁇ m. For even more poorly soluble salts, it can be even lower; For example, average particle sizes below 100 ⁇ m are preferred for the very poorly soluble zinc oxide.
  • Another preferred class of compounds are magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid. These have the effect that even with repeated use the surfaces of glassware do not change corrosively, in particular no clouding, streaks or scratches but also no iridescence of the glass surfaces.
  • magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be present in the claimed agents, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids are obtained from the Groups of the unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred.
  • the acids mentioned below are again preferred within these groups:
  • methanoic acid formic acid
  • ethanoic acid acetic acid
  • propanoic acid propanoic acid
  • pentanoic acid valeric acid
  • hexanoic acid caproic acid
  • heptanoic acid enanthic acid
  • octanoic acid caprylic acid
  • nonanoic acid pelargonic acid
  • decanoic acid capric acid
  • undecanoic dodecanoic (lauric)
  • tridecanoic tetradecanoic
  • myristic pentadecanoic, hexadecanoic (palmitic acid
  • heptadecanoic acid margaric
  • octadecanoic acid stearic acid
  • eicosanoic acid arachidic acid
  • docosanoic acid behenic acid
  • tetracosanoic acid lignoceric acid
  • benzoic acid 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3.5 -Dicar- boxybenzoic acid (trimesionic acid).
  • sugar acids galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid, alginic acid.
  • hydroxy acids From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), hydroxy succinic acid (malic acid), 2,3-dihydroxy-butanedioic acid (tartaric acid), 2-hydroxy-1, 2,3-propanetricarboxylic acid (citric acid) .
  • Ascorbic acid 2-hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).
  • oxo acids 2-oxopropionic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).
  • amino acids From the group of amino acids: alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine, histidine.
  • polyacrylic acid polymethacrylic acid
  • alkyl acrylamide / acrylic acid copolymers alkyl acrylamide / methacrylic acid copolymers
  • Alkyl acrylamide / methyl methacrylic acid copolymers copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers.
  • the spectrum of the zinc salts of organic acids, preferably organic carboxylic acids preferred according to the invention, extends from salts which are sparingly or not soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility, up to those salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, particularly preferably above 1 g / L and especially have above 5 g / L (all solubilities at 20 ° C water temperature).
  • the first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate
  • the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate:
  • the dispersions according to the invention contain at least one zinc salt, but no magnesium salt of an organic acid, it preferably being at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate and zinc acetate , Zinc lactate and / or zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • a preferred agent in the context of the present invention contains zinc salt in amounts of 0.1 to 5% by weight, preferably 0.2 to 4% by weight and in particular 0.4 to 3% by weight, or zinc in oxidized form (calculated as Zn 2+ ) in amounts from 0.01 to 1% by weight, preferably from 0.02 to 0.5% by weight and in particular from 0.04 to 0.2% by weight , each based on the total weight of the dispersion.
  • dispersions according to the invention are used as dishwashing detergents
  • these detergents to protect the washware or the machine can contain corrosion inhibitors as dispersed substances, silver protection agents in particular being particularly important in the field of automatic dishwashing.
  • the known substances of the prior art can be used.
  • 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.
  • 3-amino-5-alkyl-1, 2,4-triazoles which are preferably to be used according to the invention: 5, - -propyl-, -Butyl-, -Pentyl-, -Heptyl-, -Octyl-, - Nonyl-, -Decyl-, -Undecyl-, -Dodecyl-, - Isononyl-, -Versatic-10-acid alkyl-, -Phenyl-, -p-Tolyl-, - (4-tert.butylphenyl) -, - (4th -MethoxyphenyI) -, - (2-, -3-, -4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5-oxo-2-pyrrolidinyl ) -, -3
  • the alkylamino-1, 2,4-triazoles or their physiologically tolerable salts are used in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04 wt .-% used.
  • Preferred acids for the salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulfurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid.
  • detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface.
  • agents containing active chlorine which can significantly reduce the corroding of the silver surface.
  • oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds.
  • Salt and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used.
  • transition metal salts which are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the 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.
  • redox-active substances can be used in the dispersions according to the invention. These substances are preferably inorganic redox-active substances from the group of the manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, the metals preferably in one of the oxidation states II, III , IV, V or VI are present.
  • the metal salts or metal complexes used are said to be at least partially soluble in water.
  • the counterions suitable for salt formation include all customary one, two or three times negatively charged inorganic anions, e.g. B. oxide, sulfate, nitrate, fluoride, but also organic anions such. B. stearate.
  • metal complexes are compounds which consist of a central atom and one or more ligands and, if appropriate, additionally one or more of the abovementioned anions.
  • the central atom is one of the metals mentioned in one of the oxidation states mentioned above.
  • the ligands are neutral molecules or anions that are monodentate or multidentate; the term “ligands” in the sense of the invention is explained in more detail, for example, in “Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507”.
  • Suitable complexing agents are, for example, gitrate, acetylacetonate or 1-hydroxyethane-1, 1-diphosphonate.
  • oxidation level in chemistry is given, for example, in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3168".
  • metal salts and / or metal complexes are selected from the group MnS0 4 , IVln (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V 2 0 5 , V 2 0 4 , V0 2 , TiOS0 4 , K 2 TiF 6 , K 2 ZrF 6 , CoS0 4 , Co (N0 3 ) 2 , Ce (N0 3 ) 3 and mixtures thereof., so that preferred automatic dishwashing agents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxy-ethane
  • metal salts or metal complexes are generally commercially available substances which can be used in the agents according to the invention for the purpose of protecting against silver corrosion without prior cleaning. For example, that's from S0 3 production
  • the inorganic redox-active substances are preferably coated, i.e. completely covered with a waterproof material that is easily soluble at cleaning temperatures to prevent their premature decomposition or oxidation during storage.
  • a waterproof material that is easily soluble at cleaning temperatures to prevent their premature decomposition or oxidation during storage.
  • Preferred coating materials which are applied by known processes are paraffins, micro waxes, waxes of natural origin such as carnauba wax, candella wax, beeswax, higher-melting alcohols such as hexadecanol, soaps or fatty acids.
  • the coating material which is solid at room temperature, is applied in a molten state to the material to be coated, e.g.
  • the melting point must be selected so that the coating material easily dissolves or melts quickly during the silver treatment.
  • the melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C.
  • the metal salts and / or metal complexes mentioned are preferably present in the dispersions according to the invention, in particular machine dishwashing detergents, in an amount of Contain 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, based on the total weight of the dispersion.
  • Agents according to the invention can contain enzymes as dispersed substances to increase the washing or cleaning performance, it being possible in principle for all enzymes established in the prior art to be used for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Agents according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 "s to 5 percent by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferred.
  • subtilisins BPN 'and Carlsberg the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes Therm ⁇ tase, Proteinase K and that which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7.
  • Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ® from Novozymes A / S, Bagsv ⁇ erd, Denmark.
  • subtilisins 147 and 309 are marketed by Novozymes under the trade names E ⁇ sperase ® and Savinase ® , respectively.
  • the variants listed under the name BLAP ® are derived from the protease from Bacillus lentus DSM 5483.
  • proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes * ®, from Novozymes, which from under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® Genencor, sold under the trade name Protosol ® by Advanced Biochemicals Ltd., Thane, India, sold under the trade name Wuxi ® by Wuxi Snyder Bioproducts Ltd., China, sold under the trade names Proleather ® and Protease P ® by Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermo jhilus and their further developments which are improved for use in detergents and cleaning agents.
  • the enzyme out ß. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar ® ST.
  • ⁇ - amylase Development products of this ⁇ - amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
  • the ⁇ -amylase from ß. amyloiiquefaciens is marketed by Novozymes under the name BAN ® , and derived variants from the ⁇ -amylase from ß. stearothermophilus under the names BSG ® and Novamyl ® , also from Novozymes.
  • ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • Agents according to the invention can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors.
  • lipases or cutinases include, for example, the lipases originally obtainable from H micola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ® , Lipolase ® Ultra, LipoPrime ® , Lipozyme ® and Lipex ® .
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens.
  • lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase ® , Lipase AP ® , Lipase M-AP ® and Lipase AML ® available.
  • the Genencor company can use the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Suitable mannanases are available, for example under the name Gamanase ® and Pektinex AR ® from Novozymes, under th e name Rohapec ® B1 from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, USA , The from ß. subtilis .beta.-glucanase obtained is available under the name Cereflo ® from Novozymes.
  • washing and cleaning agent compositions according to the invention can use oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, Polyphenol oxidases).
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, Polyphenol oxidases).
  • Suitable commercial products are Denilite ® 1 and 2 from Novozymes.
  • organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) when the RLedox potentials between the oxidizing enzymes and the soiling differ greatly.
  • the enzymes used in agents according to the invention either originate from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.
  • the enzymes in question are advantageously purified by methods which are in themselves established, for example by means of precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
  • Agents according to the invention can be added to the enzymes in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers.
  • the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzyme is enclosed in a solidified gel are or those of the core-shell type in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.
  • Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers.
  • Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.
  • a protein and / or enzyme contained in an agent according to the invention can be protected, particularly during storage, against damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage.
  • the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases.
  • Agents according to the invention can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.
  • a group of stabilizers are reversible protease inhibitors.
  • Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters.
  • Ovomucoid and leupeptin may be mentioned as peptide protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.
  • Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders can additionally stabilize an enzyme contained.
  • polyols such as, for example, glycerol, ethylene glycol, propylene glycol or sorbitol are further frequently used enzyme stabilizers.
  • Calcium salts such as calcium acetate or calcium formate, and magnesium salts are also used.
  • Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, among other things, against physical influences or pH fluctuations.
  • Polymers containing polyamine-N-oxide act as enzyme stabilizers.
  • Other polymeric stabilizers are the linear C 8 -C 18 polyoxyalkylenes.
  • Alkyl polyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance.
  • Crosslinked N-containing compounds also act as enzyme stabilizers.
  • a sulfur-containing reducing agent is, for example, sodium sulfite.
  • Combinations of stabilizers are preferably used, for example made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
  • the effect of peptide-aldehyde stabilizers is increased by the combination with boric acid and / or boric acid derivatives and polyols and is further enhanced by the additional use of divalent cations, such as calcium ions.
  • Preferred dispersions according to the invention are characterized in that they additionally contain one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, in amounts from 0.1 to 5% by weight, preferably from 0.2 to 4.5 and in particular from 0.4 to 4 wt .-%, each based on the total agent.
  • enzymes and / or enzyme preparations preferably solid protease preparations and / or amylase preparations
  • Agents preferred according to the invention are characterized in that the dispersed substances, based on their total weight, are at least 20% by weight, preferably at least 30% by weight, particularly preferably at least 40% by weight and in particular at least 50% by weight of builders and / or contain bleaching agents and / or bleach activators and / or polymers that are active in washing or cleaning and / or glass corrosion protection agents and / or silver protection agents and / or enzymes.
  • Particularly preferred agents according to the invention consist of at least 90% by weight, preferably at least 92% by weight, preferably at least 94% by weight, particularly preferably at least 96% by weight, particularly preferably at least 98% by weight and Most preferably at least 99.5% by weight in addition to the abovementioned preferred dispersants, furthermore exclusively from builders and / or bleaching agents and / or bleach activators and / or polymers which are active in washing or cleaning and / or glass corrosion protection agents and / or silver protection agents and / or enzymes , Washing or cleaning agents according to the invention are particularly preferred in which the dispersed solid particles, based on their total weight, are between 0.04 and 18% by weight, preferably between 0.08 and 16% by weight and in particular between 0.2 and 14% by weight of one or more substances from the group of silver protection, glass protection or enzymes.
  • the dispersions according to the invention can of course contain further ingredients.
  • these ingredients are preferably one or more substances from the group of the anionic, cationic or amphoteric surfactants, the disintegrants, the acidifying agents, the disintegration aids, the hydrotopes, the pH adjusting agents, the dyes, the fragrance, the optical brighteners, the foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors and color transfer inhibitors.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • surfactants of the sulfonate type preference is given to C 9-13 -alkylberol-sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates of the type obtained, for example, from C 12-18 monoolefins with an end or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained, with subsequent hydrolysis or neutralization of C 12 . ⁇ 8 alkanes idation for example by sulfochlorination or Sulfox.
  • the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohol le and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulfates and C 2 -C 15 alkyl sulfates and C 14 -C 5 alkyl sulfates are preferred for washing technology reasons.
  • 2,3-alkyl sulfates which can be obtained as commercial products from Shell OH 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 with an average of 3.5 moles 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.
  • 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.
  • 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).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants 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.
  • agents according to the invention are used as automatic dishwashing agents, their anionic surfactant content is preferably less than 4% by weight, preferably less than 2% % By weight and very particularly preferably less than 1% by weight. Automatic dishwashing detergents that do not contain anionic surfactants are particularly preferred.
  • cationic and / or amphoteric surfactants can also be used.
  • the agents according to the invention can contain, for example, cationic compounds of the formulas XIX, XX or XXI as cationic active substances:
  • each group R 1 is independently selected from C ⁇ -Alky! -, -Alkenyl- or
  • each R group is independently selected from C 8-28 alkyl or alkenyl groups;
  • R 3 R or (CH 2 ) n -TR 2 ;
  • R 4 R 1 or R 2 or (CU 2 ) n -TR 2 ;
  • T -CH 2 -, -O- CO- or -CO-O- and n is an integer from 0 to 5.
  • agents according to the invention are used as automatic dishwashing agents, their content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. Automatic dishwashing detergents that do not contain cationic or amphoteric surfactants are particularly preferred.
  • Both inorganic acids and organic acids are suitable as acidifiers, provided that these are compatible with the other ingredients.
  • the solid mono-, oligo- and polycarboxylic acids can be used in particular for reasons of consumer protection and handling safety. 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 BAS F), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and adipic acid (max. 33% by weight).
  • disintegration aids so-called tablet disintegrants
  • tablet disintegrants or accelerators of disintegration are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in resorbable form.
  • Preferred agents according to the invention contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration aids, in each case based on the weight of the agents.
  • Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and Detergent compositions contain such a cellulose-based disintegrant in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
  • the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
  • the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be compressed.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • the above and described in more detail in the documents cited coarser disintegration aids are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier available in the present invention.
  • Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
  • Subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses which have primary particle sizes of approx. 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
  • Agents preferred in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the total weight of the composition.
  • a disintegration aid preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the total weight of the composition.
  • the agents according to the invention can also contain a gas-developing shower system.
  • the gas-developing shower system can consist of a single substance which releases a gas when it comes into contact with water.
  • magnesium peroxide should be mentioned in particular, which releases oxygen on contact with water.
  • the gas-releasing bubble system itself consists of at least two components that react with one another to form gas. While a large number of systems are conceivable and executable here, which release nitrogen, oxygen or hydrogen, for example, this will be reflected in the washing and
  • Preferred effervescent systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.
  • the alkali metal carbonates or bicarbonates the sodium and potassium salts are clearly preferred over the other salts for reasons of cost.
  • the pure alkali metal carbonates or bicarbonates in question do not have to be used; rather, mixtures of different carbonates and hydrogen carbonates may be preferred.
  • 2 to 20% by weight preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 and in particular 3 to, are used as the effervescent system 10% by weight of an acidifying agent, based in each case on the total weight of the agent according to the invention, is used.
  • Alkali metal dihydrogen phosphates and other inorganic salts can be used.
  • organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent.
  • the other fixed ones can also be used in particular Mono-, oligo- and polycarboxylic acids. Tartaric acid, succinic acid, malonic acid, adipic acid, IVlaleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred from this group.
  • Organic sulfonic acids such as amidosulfonic acid can also be used.
  • a commercially available Acidaimss edium in 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).
  • agents in which a substance from the group of the organic di-, tri- and oligocarboxylic acids or mixtures thereof are used as acidifying agents in the effervescent system.
  • Dyes and fragrances can be added to the agents according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensorially "typical and unmistakable" product.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
  • Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate,
  • the ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g.
  • perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, ol ⁇ banum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which ensure a long-lasting fragrance due to a slower fragrance release.
  • carrier materials have become
  • cyclodextrins have proven successful, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • the agents according to the invention 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 to the substrates to be treated with the compositions, such as glass, ceramics or plastic dishes, so as not to stain them.
  • the dispersions according to the invention can also contain non-aqueous organic solvents and / or thickeners in addition to the above-described active ingredients for washing or cleaning.
  • the agent according to the invention is the dispersion of a solid in a dispersing agent (suspension), which i.a. can also contain non-aqueous solvents.
  • a dispersing agent i.a. can also contain non-aqueous solvents.
  • solid suspension does not exclude that the solid substances contained in the agents according to the invention are at least partially in solution. Independently of these dissolved portions, however, the agents according to the invention have a portion of suspended solids.
  • the above-mentioned non-aqueous solvents are derived, for example, from the groups of the mono-alcohols, diols, triols or polyols, the ethers, esters and / or amides.
  • Non-aqueous solvents which are water-soluble are particularly preferred, "water-soluble" solvents being solvents in the sense of the present application, which at room temperature with water completely, ie without a miscibility gap.
  • Non-aqueous solvents which can be used in the agents according to the invention preferably come 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, etheylene glycol mononon-butyl ether, diethylene glycol methyl ether -ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxytrigly
  • a dispersion according to the invention which is particularly preferred in the context of the present invention is characterized in that it contains non-aqueous solvents in amounts of ⁇ , 1 to 15% by weight, preferably 0.2 to 12% by weight, particularly preferably 0 to 8 wt .-%, most preferably from 0.8 to 6 wt .-% and especially from 1 to 4 wt ⁇ yo, based in each case on the total dispersion, containing 4, with preferred (s) non-aqueous ( s) the solvent is / are selected from the group of nonionic surfactants which are liquid at room temperature, the polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, triacetin, ethylene glycol, propylene glycol, propylene carbonate, hexylene glycol, ethanol and n-propanol and / or iso-propanol.
  • non-aqueous solvents in amounts of ⁇ , 1 to 15% by weight,
  • the dispersions for viscosity control according to the invention can also contain further ingredients, the use of which can be used, for example, to control the settling behavior or the pourability or flowability in a targeted manner.
  • Combinations of structuring agents and thickeners have proven particularly useful in non-aqueous systems.
  • Dispersions according to the invention which are preferred in the context of the present invention further comprise a) 0.1 to 1.0% by weight of one or more structuring agents, preferably from the group of the bentonites and / or at least partially etherified sorbitols and / or b) 0, 1 to 1.0% by weight of one or more thickeners, preferably from the group of the amorphous or crystalline disilicates, in particular from the group of the pyrogenic silicas.
  • the structuring agent a) comes from the group of bentonites and / or at least partially etherified sorbitols. These substances are used to ensure the physical stability of the agents and to adjust the viscosity.
  • Bentonites are contaminated clays that are formed by weathering volcanic tuffs. Due to their high montmorillonite content, bentonites have valuable properties such as swellability, ion exchange capacity and thixotropy. It is possible to modify the properties of the bentonites according to the intended use. Bentonites are a common clay component in tropical soils and are mined as sodium bentonite, for example in Wyoming / USA. Sodium bentonite has the most favorable application properties (swellability), so that its use is preferred in the context of the present invention. Naturally occurring calcium bentonites originate, for example, from Mississippi / USA or Texas / USA or from Landshut / D.
  • the naturally obtained Ca bentonites are artificially converted into the more swellable Na bentonites by exchanging Ca for Na.
  • the main constituents of the bentonites are so-called montmorillonites, which can also be used in pure form in the context of the present invention.
  • Montmorillonites are phyllosilicates and here clay minerals belonging to the dioctahedral sectectites, which crystallize monoclinic-pseudohexagonal. Montmorillonite predominantly form white, gray-white to yellowish, completely amorphous appearing, easily friable, swelling in the water, but not becoming plastic, by the general formulas
  • Preferred dispersions according to the invention are characterized in that montmorillonites are used as structure donors.
  • Montmorillonites have a three-layer structure, which consists of two tetrahedral layers that are electrostatically cross-linked via the cations of an intermediate octahedral layer. The layers are not rigidly connected, but can swell by reversible incorporation of water (in 2-7 times the amount) and other substances such as alcohols, glycols, pyridine, ⁇ -picoline, ammonium compounds, hydroxy-aluminosilicate ions etc.
  • the above. Formulas are only approximate formulas since montmorillonites have a large ion exchange capacity.
  • So AI can be exchanged for Mg, Fe 2+ , Fe 3+ , Zn, Cr, Cu and other ions. Avis consequence of such a substitution results in a negative charge of the layers, which is balanced by other cations, especially Na + and Ca 2+ .
  • At least partially etherified sorbitols can be used as structure donors.
  • Sorbitol is a hexavalent alcohol (sugar alcohol) that is relatively easy to split off one or two moles of water intramolecularly and forms cyclic ethers (for example sorbitan and sorbide). Splitting off of water is also possible intermolecularly, noncyclic ethers being formed from sorbitol and the alcohols concerned. The formation of monoethers and bisethers is also possible here, although higher degrees of etherification such as 3 and 4 can also occur.
  • At least partially etherified sorbitols to be preferably used in the context of the present invention are double etherified sorbitols, of which dibenzylidene sorbitol is particularly preferred.
  • Machine dishwashing detergents are preferred here, which contain doubly etherified sorbitols, in particular dibenzylidene sorbitol, as structure donors.
  • the agents according to the invention can contain the structuring agents in amounts of 0.1 to 1.0% by weight, based on the total agent and on the active substance of the structuring agents.
  • Preferred compositions contain the texturing agent in amounts of 0.2 to 0.9 by weight ⁇ >, preferably in amounts from 0.25 to 0.75 wt .-% and in particular in amounts of from 0.3 to 0.5 wt. -%, each based on the total mean.
  • Pyrogenic silicic acids are preferably used as thickeners.
  • the preferred agents according to the invention contain the thickeners in amounts of 0.2 to 1.3% by weight, preferably in amounts of 0.25 to 1.15% by weight, preferably in amounts of 0.3 to 1.05% by weight .-% and in particular in amounts of 0.35 to 0.95 wt .-%, each based on the total agent.
  • thickeners are methyl and ethyl celluloses, polyurethanes and polyacrylates.
  • the water content of dispersions according to the invention is preferably less than 30% by weight, preferably less than 23% by weight, preferably less than 19% by weight, particularly preferably less than 15% by weight and in particular less than 12% by weight.
  • Washing or cleaning agents preferred according to the invention are low in water or anhydrous.
  • Particularly preferred washing or cleaning agents according to the invention are characterized in that the dispersion, based on its total weight, has a free water content below 10% by weight, preferably below 7% by weight, particularly preferably below 3% by weight and in particular below 1% by weight.
  • the agents according to the invention are distinguished by a density above 1.040 g / cm 3 .
  • This high density not only reduces the total volume of the washing or cleaning agents according to the invention.
  • Particularly preferred washing or cleaning agents according to the invention are therefore characterized in that the dispersion has a density above 1 1,050 g / cm 3 , preferably above 1,060 g / cm 3 , or above 1, 070 g / cm 3 , or above 1, 080 g / cm 3 , or above 1.090 g / cm 3 , or above 1.100 g / cm 3 , or above 1, 110 g / cm 3rd or above 1.120 g / cm 3 , or above 1.130 g / cm 3 , or above 1, 140 g / cm 3 , or above 1, 150 g / cm 3 , or above 1, 160 g / cm 3 , or above 1, 170 g / cm 3 , or above 1.180 g / cm 3 , or above 1, 190
  • dispersions which have a density in the range between 040 and 1, 700 g / cm -1, preferably between 1, 050 and 1, 700 g / cm : preferably between 060 and 1, 700 g / cm, preferably between 1, 070 and 1, 700 g / cm preferably between 080 and 1, 700 g / cm preferably between 1, 090 and 1, 700 g / cm preferably between 100 and 1, 700 g / cm preferably between 1, 110 and 1, 700 g / cm preferably between 120 and 1, 700 g / cm preferably between 1, 130 and 1, 700 g / cm preferably between 140 and 1, 700 g / cm preferably between 1, 150 and 1, 700 g / cm preferably between 160 and 1 , 700 g / cm preferably between 1, 170 and 1, 700 g / cm preferably between 180 and 1, 700 g / cm preferably between 1, 190 and 1, 700 g / cm preferably between 200 and 1, 700 g / cm preferably between 1,210 and 1,700 g /
  • Dispersions according to the invention with a density between 1,040 and 1,670 g / cm 3 , preferably between 1, 120 and 1, 610 g / cm 3 , particularly preferably between 1, 210 and 1,570 g / cm 3 are very particularly preferred between 1, 290 and 1, 510 g / cm 3 , and in particular between 1, 340 and 1, 480 g / cm 3 .
  • the information on density relates in each case to the densities of the agents according to the invention at 20 ° C.
  • the density of the dispersants used at 20 ° C. is preferably between 0.8 and 1.4 g / cm 3 .
  • Detergents or cleaning agents preferred according to the invention are characterized in that the dispersion in water (40 ° C.) takes less than 12 minutes, preferably less than 10 minutes, preferably less than 9 minutes, particularly preferably less than 8 minutes and especially in less than 7 minutes.
  • 20 g of the dispersion are introduced into the interior of a dishwasher (Miele G 646 PLUS).
  • the main wash cycle of a standard wash program (45 ° C) is started.
  • the solubility is determined by measuring the conductivity, which is recorded using a conductivity sensor.
  • the dissolving process ends when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau.
  • the conductivity measurement begins with the insertion of the circulation pump in the main wash cycle.
  • the amount of water used is 5 liters.
  • washing or cleaning agents according to the invention are distinguished by a water-soluble or water-dispersible packaging.
  • Some particularly preferred water-soluble or water-dispersible packaging materials are listed below:
  • Polyquaternium 18 and Polyquaternium 27 indicated polymers.
  • Water-soluble polymers in the sense of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature.
  • Preferred coating materials preferably comprise at least partially a substance from the group (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin.
  • Polyvinyl alcohols (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure
  • polyvinyl alcohols which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2500 (molar masses from approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups.
  • the manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.
  • polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
  • Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable.
  • the water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
  • the polyvinyl alcohol coatings are largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • an agent according to the invention has at least one packaging or wrapping material which at least partially comprises 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 8 ⁇ mol%.
  • the at least one wrapping material consists of at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least 80% by weight, of a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 69 mol% and in particular 82 to 8 ⁇ mol%.
  • the entire envelope material used preferably consists of at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least 80% by weight, of a polyvinyl alcohol whose degree of hydrolysis is 70 is up to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • Polyvinyl alcohols of a certain molecular weight range are preferably used as the coating materials, it being preferred according to the invention that the coating material comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol "1 , preferably from 11,000 to 90,000 gmol " 1 , particularly preferably from 12,000 to 80,000 gmol "1 and in particular from 13,000 to 70,000 gmol " 1 .
  • the degree of polymerization of such preferred polyvinyl alcohols is between approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to approximately 1680 and in particular between approximately 260 to approximately 1500.
  • Packaging are characterized in that the water-soluble or water-dispersible packaging material comprises polyvinyl alcohols and / or PVAL copolymers whose average degree of polymerization is between 80 and 700, preferably between 150 and 400, particularly preferably between 1 ⁇ 0 to 300 and / or their molecular weight ratio MG (50% ) to MG (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.
  • the water-soluble or water-dispersible packaging material comprises polyvinyl alcohols and / or PVAL copolymers whose average degree of polymerization is between 80 and 700, preferably between 150 and 400, particularly preferably between 1 ⁇ 0 to 300 and / or their molecular weight ratio MG (50% ) to MG (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant). Particularly suitable in the context of the present invention, polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-8 ⁇ , Mowiol ® 8-8 ⁇ and L64 ⁇ , L734, Mowiflex LPTC 221 ex KSE as well as the compounds of Texas polymer such as Vinex 2034.
  • ELVANOL ® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90- 50 ( Trademark of Du Pont)
  • ALCOTEX ® 72.5, 78, B72, F ⁇ 0 / 40, FS8 / 4, F88 / 26, F8 ⁇ / 40, F88 / 47 (trademark of Harlow Chemical Co.)
  • Gohsenol ® NK-05, A- 3O0, AH-22, C-500, GH- 20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11 Q, KZ -06 (trademark of Nippon Gohsei KK).
  • the water content preferably PVAL packaging materials is preferably less than 10 wt .-%, preferably less than 8 wt .-%, more preferably less than 6 wt. ⁇ % And especially less than 4 wt .-%.
  • the water solubility of PVAL can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • aldehydes acetalization
  • ketones ketalization
  • Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water.
  • the reaction products made of RVAL and starch are to be used extremely advantageously.
  • the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus adjusted to the desired values.
  • Films made of PVAL are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVAL films examples include the PVAL films available from Syntana bottlesgesellschaft E. Harke GmbH & Co. under the name "SOLUBLON ® ". Their solubility in water can be adjusted to the exact degree, and films of this product series are available which are soluble in all the temperature ranges relevant to the application in the aqueous phase.
  • Preferred washing or cleaning agents according to the invention with a water-soluble or water-dispersible packaging are characterized in that the water-soluble or water-dispersible packaging comprises hydroxypropylmethyl cellulose (HPMC) which has a degree of substitution (average number of methoxy groups per anhydroglucose unit of cellulose) of 1.0 to 2 , 0, preferably from 1.4 to 1.9, and a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of the cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25.
  • HPMC hydroxypropylmethyl cellulose
  • PVP Polyvinylpyrrolidones
  • PVP are produced by radical polymerization of 1-vinyl pyrrolidone.
  • Commercial PVPs have molar masses in the range from approx. 2,500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.
  • Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula
  • Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as a water-soluble coating material is extremely widespread, particularly in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a small extent because of its high price compared to the polymers mentioned above.
  • wrapping materials which comprise a polymer from the group of starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.
  • Starch is a homoglycan, with the glucose units linked ⁇ -glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% straight-chain amylose (MW. Approx. 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW. Approx. 300,000 to 2,000,000). It also contains small amounts of lipids, phosphoric acid and cations.
  • amylose forms 1, 4-position long, helical, intertwined chains with about 300 to 1,200 G of glucose molecules due to the binding in the 1,4-position
  • the chain in the amylopectin branches after an average of 25 glucose units through 1,6-binding to a knot-like one Formations with about 1,500 to 12,000 molecules of glucose.
  • starch derivatives are also used to produce water-soluble coatings for the detergent, dishwashing and cleaning agent portions within the scope of the present invention suitable, which can be obtained by polymer-analogous reactions from starch.
  • Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.
  • Pure cellulose has the formal gross composition (C 6 H ⁇ o0 5 ) ⁇ and formally represents a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approx. 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • the washing or cleaning agents according to the invention comprise a water-soluble or water-dispersible packaging with at least one receiving chamber.
  • water-soluble packaging which has two, three, four or five receiving chambers is particularly preferred in the context of the present invention.
  • Each of these receiving chambers can also have a closure part.
  • detergents or cleaning agents are preferred whose water-soluble or water-dispersible packaging has at least one closure part.
  • two or more receiving chambers can also be sealed with a single closing part, but it is also possible for several receiving chambers to be provided with their own closing part.
  • films, moldings or injection moldings are suitable as the closure part. Foils are used with particular preference.
  • the dissolution behavior of the water-soluble or water-dispersible packaging can, in addition to the chemical composition of the wrapping materials used, also be influenced, for example, by the thickness of the container walls or the closure parts.
  • Preferred agents are characterized in the context of the present application in that the container and / or the closure part (s) have a thickness of 5 to 2000 ⁇ m, preferably from 6 to 1000 ⁇ m, particularly preferably from 7 to 500 ⁇ m, very particularly preferably from 8 to 200 ⁇ m and in particular from 10 to 100 ⁇ m. It is particularly preferred to use containers and closure parts of different thicknesses, such means are advantageous whose closure parts have a smaller wall thickness compared to the associated containers.
  • the water-soluble packaging of particularly preferred washing or cleaning agents comprises at least one water-soluble or water-dispersible Aufnhamehunt and / or at least one water-soluble or water-dispersible closure part, wherein at least one receiving chamber and / or at least one closure part have a wall thickness below 200 ⁇ m, preferably below 120 ⁇ m, particularly preferably below 90 ⁇ m and in particular below 70 ⁇ m.
  • both the water-soluble or water-dispersible container and the water-soluble or water-dispersible closure part have a wall thickness below 200 ⁇ m, preferably below 120 ⁇ m, particularly preferably below 90 ⁇ m and in particular below 70 ⁇ m.
  • Preferred agents according to the invention are characterized in that the water-soluble or water-dispersible packaging is at least partially transparent or translucent.
  • the packaging used is preferably transparent.
  • transparency is understood to mean that the transmittance within the visible spectrum of light (410 to 800 nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular greater than 50%.
  • a wavelength of the visible spectrum of light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention.
  • the wrapping material used consists, for example, of a receptacle and a closure part
  • at least the receptacle or the closure part is preferably transparent or translucent.
  • packaging from the receptacle and the closure part are particularly preferred when both the receptacle and the closure part are transparent or translucent.
  • Agents preferred according to the invention can contain stabilizing agents.
  • Stabilizing agent in the sense of Invention are materials which protect the ingredients located in the receiving chambers and / or the interstices from decomposition or deactivation by exposure to light. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
  • Particularly suitable stabilizers in the sense of the invention are the antioxidants.
  • the formulations can contain antioxidants.
  • Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants.
  • Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C3-C22) esters of gallic acid, such as dodecyl gallate.
  • aromatic amines preferably secondary aromatic amines and substituted p-phenylenediamines
  • phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites
  • citric acids and citric acid derivatives such as isopropyl citrate
  • compounds containing endiol groups so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic acid palmitate
  • organosulfur compounds such as the esters of 3,3 'thiodipropionic acid with C ⁇ - 8 alkanols, especially C 10-18 alkanols
  • metal ion deactivators that are capable of catalyzing the auto-oxidation of metal ions such as copper, to complex, such as nitrilotriacetic acid and its derivatives and their mixtures.
  • Antioxidants can be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular
  • UV absorbers can improve the lightfastness of the recipe components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, eg heat. 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 such as, for example, the water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast ® H), are also 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. Of particular importance are biphenyl and especially stilbene derivatives, which are commercially available as Tinosorb ® FD or Tinosorb ® FR ex Ciba.
  • UV-B absorbers are mentioned 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably 4-
  • esters of cinnamic acid preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene);
  • Esters of salicylic acid preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester;
  • benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
  • Sulfonic acid derivatives of 3-benzylidene camphor e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.
  • UV-A filters -4'-meth-oxydibenzoylmethane (Parsol 17 ⁇ 9), 1-phenyl-3- (4'-isopropylphenyl) propane-1, 3-dione and enamine compounds.
  • the UV-A and UV-B filters can of course also be used in mixtures.
  • insoluble light-protection pigments namely finely dispersed, preferably nanoized metal oxides or salts, are also suitable for this purpose.
  • suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • Silicates (talc), barium sulfate or zinc stearate can be used as salts.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs in some other way from the spherical shape.
  • the pigments can also be surface-treated, ie hydrophilized or hydrophobized.
  • Typical examples are coated titanium dioxides, such as titanium dioxide T ⁇ 05 (Degussa) or Eusolex® T2000 (Merck).
  • silicones are used as the hydrophobic coating agent, and specifically Trialkoxyoctylsilane or Simethicone in question.
  • Micronized zinc oxide is preferably used.
  • UV absorbers can be used in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight, in each case based on the total weight of a contained in a receiving chamber or a space mixture of substances.
  • fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, benzoxazole and benzisoxazole and Benzimidazole systems as well as the pyrene derivatives substituted by heterocycles.
  • fluorescent acids 4,4'-diamino-2,2'-stilbenedisulfonic acids
  • 4,4'-distyrylbiphenyls 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, benzoxazole and benzisoxazole and Benzimidazole systems as well as the
  • Fluorescent substances based on the total weight of a substance mixture located in a receiving chamber or in an intermediate space, in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0, 03 to 0.1 wt .-% be included.
  • the aforementioned stabilizing agents are used in any mixtures. Based on the total weight of a substance mixture in a receiving chamber, the stabilizing agents are used in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 up to 5 wt .-% used.
  • agents according to the invention are preferred which, in their container part, but preferably in their closure part, enable a device for pressure compensation between the interior of the container and the surrounding atmosphere.
  • Such pressure equalization is particularly preferred for agents according to the invention whose container interior is filled with such liquid or solid active substances which tend to release gas in the course of storage after the container interior has been sealed with a closure member.
  • Chemical reactions, in particular, are usually the cause of such gas release
  • Reactions between the agents located in the interior of the container and substances (eg water) or diffused from the outside through the covering material into the interior of the container Reactions of the agents in the interior of the container with one another or decomposition reactions of individual agents in the interior of the container caused by light or heat.
  • the active substances which tend to release gas after one of the reactions described include in particular the bleaching agents described below, for example the percarbonates and perborates.
  • valves in particular, however, microholes, tDer preferred microholes with a diameter between 0.1 and 2 mm, particularly preferably between 0.2 and 1.5 mm and in particular between 0.5 and 1 mm are designated as devices for pressure compensation .
  • the design of these microholes can be automated, for example, by perforators, which “pierce” the packaging or the wrapping material, this “perforation” being able to be carried out both before filling or sealing the packaging and after sealing.
  • the piercing of the wrapping material is preferably carried out from the inside of the wrapping material, that is to say the side which is after the sealing on the inside of the container, to the outside of the wrapping material.
  • Microchannels or the use of permeable covering materials to achieve pressure equalization are also suitable for microholes.
  • the dispersions according to the invention can contain a complete detergent or cleaning agent formulation, but can be used with particular advantage in combination with further washing or cleaning agent ingredients, in particular with ingredients or ingredient mixtures which have a different form of confection.
  • These alternative forms of assembly include, for example, solids such as powders, granules, extrudates, compactates such as tablets, castings or dimensionally stable gels.
  • the solid or liquid detergents or cleaning agents which are used in combination with the dispersions according to the invention can of course have all the constituents contained in the detergent or cleaning agent sector, but their composition preferably differs from the composition of the agents according to the invention.
  • ingredients for the solid or liquid detergents or cleaning agents are in particular the builders, surfactants, bleaching agents, bleach activators, polymers, enzymes, glass corrosion protection agents, silver protection agents, dyes, fragrances, pH adjusting agents and disintegrants. To avoid repetition, reference is made to the previous paragraphs for a more detailed description of these ingredients.
  • the dispersions according to the invention are combined with further solid or liquid washing or cleaning agents to form an end product, for example by using a water-soluble or water-dispersible packaging with one, two, three or more Storage chambers, it is preferred according to the invention that the dispersion (s) according to the invention, based on the total composition of the combination product, at least 20% by weight, preferably at least 50% by weight, particularly preferably at least 70% by weight and in particular at least 90% by weight. -% of the in
  • Combination product contained anionic and / or cationic and / or amphoteric
  • polymers and / or at least 20% by weight, preferably at least 40% by weight, particularly preferably at least 60% by weight and in particular at least 60% by weight of that in the
  • Combination product containing nonionic surfactants and / or at least 10% by weight, preferably between 20 and 90% by weight, particularly preferably between 30 and 35% by weight and in particular between 40 and ⁇ O% by weight of that in the
  • Combination product contained builder, preferably of phosphate or citrate.
  • the agents according to the invention are packaged in water-soluble or water-dispersible packaging, which packaging can consist, for example, of a container with one, two, three, four or more receiving chambers.
  • packaging can consist, for example, of a container with one, two, three, four or more receiving chambers.
  • other liquids and solids such as powders, granules, extrudates, compactates, castings or dimensionally stable gels are also suitable as ingredients for the receiving chambers.
  • flowable liquids or flowable gels or flowable dispersions for example emulsions or suspensions, can be used as liquids.
  • Active substances or combinations of active substances are considered to be flowable if they have no inherent dimensional stability which enables them to assume a non-disintegrating spatial form under the usual conditions of manufacture, storage, transport and handling by the consumer, this spatial form under the conditions mentioned also not changed over a longer period of time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, that is under the usual conditions of manufacture, storage, transport and handling by the consumer in the spatial conditions caused by the manufacture. geometric shape persists, that is, does not melt away.
  • the determination of the flowability relates in particular to the conditions customary for storage and transport, that is to say in particular to temperatures below 50 ° C., preferably below 40 ° C. Liquids are therefore in particular active substances or combinations of active substances with a melting point below 25 ° C., preferably below 20 ° C., particularly preferably below 15 ° C.
  • the receiving chambers filled with liquid, powder or granules preferably have a seal.
  • the sealing is optional, but is preferred.
  • the dispersions are packaged alone or in combination with one or more solids (e.g. powders, granules, extrudates, compactates, castings, dimensionally stable gels) or liquids (e.g. liquids, flowable gels or dispersions), preferably with one or more powders in a receiving chamber, the filling of the receiving chamber can take place both simultaneously and in chronological order.
  • the step-by-step filling of the receiving chamber with the dispersion according to the invention and one or more powders is particularly preferred, since in this way fixed layer structures can be produced in a simple manner, the multiphase nature of which can be optically emphasized, for example, by adding appropriate dyes.
  • Such multilayer receiving chambers can have two, three, four, five or more individual layers.
  • the resulting water-soluble packaged multi-layer detergents or cleaning agents are notable for a density comparable to the densities of detergent or cleaning agent tablets, owing to the high density of the dispersions according to the invention, but on the other hand are soluble much more quickly, since no pressure was used to produce them.
  • the following table shows some examples of particularly preferred embodiments of these multiphase receiving chambers with up to five layers:
  • the weight fraction of the dispersion (s) is based on the total weight of the resulting washing or Cleaning agents (without taking into account the water-soluble packaging) preferably between 5 and 95% by weight, preferably between 7 and 80% by weight, particularly preferably between 9 and 65% by weight and in particular between 11 and 53% by weight.
  • dispersions are made up in combination with a further liquid or solid washing or cleaning agent, then in the context of the present application, preference is given to those combination products in which the liquid or solid washing or cleaning agent dissolves faster than the dispersion.
  • Solid detergents or cleaning agents are in particular the powders, granules, extrudates, compactates or castings already mentioned above.
  • % particularly preferably at least 80% by weight and in particular at least 90% by weight of all nonionic surfactants and / or cationic polymers and / or amphoteric polymers contained in this combination product.
  • solubility 20 g of the respective substance (dispersion or solid or liquid) are placed in the interior of a dishwasher (Miele G 646 PLUS). The main wash cycle of a standard wash program (45 ° C) is started. The solubility is determined by measuring the conductivity, which is recorded by a conductivity sensor. The dissolving process ends when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau. The conductivity measurement begins with the insertion of the circulation pump in the main wash cycle. The amount of water used is 5 liters.
  • the dispersions according to the invention are preferably less than 5% by weight, preferably less than 3% by weight, particularly preferably less than 1% by weight and in particular no waxes and / or fat (s) and / or triglyceride (s) and / or fatty acids and / or fatty alcohols or other high-melting, water-insoluble ingredients.
  • Fat (s) and / or tricglyceride (s) is the name for compounds of glycerol in which the three hydroxyl groups of the glycerol are esterified by carboxylic acids.
  • the naturally occurring fats are triglycerides, which usually contain different fatty acids in the same glycerin molecule.
  • synthetic triglycerides in which only one fatty acid is bound are also accessible (e.g. tripalmitin, triolein or tristearin).
  • Most of the dispersions according to the invention contain no natural and / or synthetic fats and / or mixtures of the two.
  • the weight fraction of fats in the total weight of dispersions according to the invention is preferably less than 4% by weight, preferably less than 3% by weight, particularly preferably less than 2% by weight, very particularly preferably less than 1% by weight and in particular less than 0.5% by weight. Dispersions according to the invention which contain no fats are particularly preferred.
  • fatty acids refer to aliphatic saturated or unsaturated, carboric acids with a branched or unbranched carbon chain.
  • Pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, erucic acid, elaeosteraric acid are examples of such fatty acids.
  • Fatty alcohol is a collective name for the linear, saturated or unsaturated primary alcohols with 6 to 22 carbon atoms that can be obtained by reducing the triglycerides, fatty acids or fatty acid esters. The fatty alcohols can be saturated or unsaturated depending on the manufacturing process.
  • Myristyl alcohol, 1-pentadecanol, cetyl alcohol, 1-heptadecanl, stearyl alcohol, erucyl alcohol, 1-nonadecanol, arachidyl alcohol, 1-heneicosanol, behenyl alcohol, erucyl alcohol, brassidyl alcohol are examples of such fatty alcohols.
  • dispersions according to the invention contain no fatty acids and / or fatty alcohols and / or mixtures of the two.
  • the weight fraction of fatty acids and / or fatty alcohols in the total weight of dispersions according to the invention is preferably less than 4% by weight, preferably less than 3% by weight, particularly preferably less than 2% by weight, very particularly preferably less than 1% by weight. % and in particular less than 0.5% by weight.
  • Dispersions according to the invention which contain no fatty acids and / or fatty alcohols are particularly preferred.
  • Waxing is understood to mean a number of natural or artificially obtained substances which usually melt above 40 ° C without decomposition and which are relatively low-viscosity and non-stringy just above the melting point. They have a strongly temperature-dependent consistency and solubility. According to their origin one divides the waxes into three groups, the natural waxes, chemically modified waxes and the synthetic waxes.
  • the natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.
  • vegetable waxes such as candelilla wax, carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax
  • animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or
  • the chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
  • Synthetic waxes are, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll ® 66 (Bayer AG), as well as the waxes synthetically produced from lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea) is available, understood.
  • synthetic or semi-synthetic esters from lower alcohols with fatty acids from native sources also fall into the group of synthetic waxes. It falls into this class of substances for example Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate or shellac, for example shellac-KPS-Dreiring-SP (Kalkhoff GmbH).
  • wax alcohols are also included in the waxes in the context of the present invention, for example.
  • Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms.
  • the wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes.
  • wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
  • Most of the dispersions according to the invention contain no waxes as dispersants.
  • the weight fraction of waxes in the total weight of dispersions according to the invention is preferably less than 4% by weight, preferably less than 3% by weight, particularly preferably less than 2% by weight, very particularly preferably less than 1% by weight and in particular less than 0.5% by weight. Dispersions according to the invention which contain no waxes are particularly preferred.
  • the dispersions according to the invention predominantly contain no paraffin wax (parrafins) as a dispersing agent.
  • Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and cycloalkanes.
  • the weight fraction of paraffin waxes in the total weight of dispersions according to the invention is preferably less than 4% by weight, preferably less than 3% by weight, particularly preferably less than 2% by weight, very particularly preferably less than 1% by weight and in particular less than 0.5% by weight.
  • Dispersions according to the invention which contain no paraffin waxes are particularly preferred.
  • the substances dispersed in the dispersions are used as finely as possible. This is particularly advantageous for polymers, builders, inorganic thickeners and bleaches.
  • automatic dishwashing agents according to the invention are preferred in which the mean particle size of polymers, builders, thickeners or bleaching agents is less than 75 ⁇ m, preferably less than 50 ⁇ m and in particular less than 25 ⁇ m.
  • Agents according to the invention in which at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight of the dispersed polymers and / or builders and / or bleaches are particularly preferred Particle size below 90 microns, preferably below 80 microns, preferably below 70 microns, particularly preferably below 60 microns and in particular below 50 microns.
  • the dispersed substances or the dispersions can be ground, for example. Both dry and wet grinding are suitable for grinding. Dry grinding can be carried out in all mills known in the prior art, pin mills, impact mills and air jet mills being listed as suitable apparatuses only by way of example.
  • the grinding is particularly preferably carried out in an impact mill or air jet mill. All grinding plants known in the prior art can also be used for the particularly preferred wet grinding, with examples being annular gap ball mills, rolling mills, colloid mills and inline dispersing mixers.
  • the wet grinding is particularly preferably carried out in a rolling mill.
  • preferred deep-drawn or injection-molded or casting bodies for the dispersions according to the invention or the closure parts for the deep-drawing, injection-molding or casting bodies are water-soluble or water-dispersible.
  • agents are therefore preferred in which the corresponding body or the corresponding closure parts has / have at least one water-soluble or water-dispersible covering material.
  • Agents according to the invention are particularly preferred in which the shell materials used comprise a water-soluble or water-dispersible polymer.
  • Particularly preferred agents are distinguished by the fact that they comprise at least two different shell materials with different dissolution behavior, these preferably differing in their chemical composition.
  • the dissolving behavior of the deep-drawn, injection-molded or casting body and the closure part, which is used to seal the body can, in addition to the chemical composition of the shell materials used, for example, also by the thickness of the walls of the deep-drawing, injection-molding or casting body or the walls of the Closure parts are affected.
  • Preferred deep-drawn or injection molded articles are characterized in the context of the present application in that the side walls of the receiving chambers, which are made of the first shell material, have a thickness of 5 to 2000 ⁇ m, preferably 10 to 1000 ⁇ m, particularly preferably 15 to 500 ⁇ m, very particularly preferably 20 up to 200 ⁇ m and in particular from 25 to 100 ⁇ m.
  • Preferred casting bodies are characterized in that the wall thickness of the casting bodies, provided they have a receiving chamber, is between 0.1 and 25 mm, preferably between 0.5 and 20 mm and in particular between 1 and 15 mm.
  • the closure part used for sealing preferably has a thickness of 5 to 100 ⁇ m, particularly preferably 6 to 80 ⁇ m and in particular 7 to 50 ⁇ m.
  • deep-drawn, injection-molded or casting bodies and closure parts have different thicknesses, whereby those deep-drawing, injection-molded or casting bodies are advantageous whose wall thickness is greater than the wall thickness of the corresponding closure part.
  • these preferred agents according to the invention are particularly suitable for the controlled release of the active substances contained, in particular the active substances from the group of washing or cleaning agents.
  • thermoformed, injection-molded or cast body can be at least partially detached in the cleaning liquor under precisely defined conditions, and thus in accordance with the requirements, within a practically relevant short time - as a non-limiting example, a few seconds to 5 minutes the wrapped content, d. H. the active cleaning material or several materials into the fleet. This release can only be controlled or controlled in different ways.
  • the water-soluble deep-drawing, injection-molded or casting body comprises areas which are less or not water-soluble at all or water-soluble only at a higher temperature and areas which are readily water-soluble or water-soluble at a low temperature.
  • the body does not consist of a uniform material that has the same water solubility in all areas, but of materials with different water solubility. Areas of good water solubility are to be distinguished on the one hand from areas with less good water solubility, with poor or no water solubility or from areas in which water solubility is only at a higher temperature or at a different pH value or only at a changed electrolyte concentration Value reached, on the other hand.
  • thermoformed, injection-molded or cast body becomes detached when used as intended under adjustable conditions, while other areas remain intact.
  • a body with pores or holes is formed, into which water and / or liquor penetrate, detach active, rinse-active or cleaning-active ingredients and can discharge them from the body.
  • systems in the form of multi-chamber deep-drawing, injection molding or casting bodies or in the form of bodies arranged one inside the other (“onion system”) can also be provided. In this way, systems with controlled release of the wash-active, rinse-active or cleaning-active ingredients can be manufactured.
  • the invention is not subject to any restrictions on the formation of such systems.
  • containers can be provided in which a uniform polymer material comprises small areas of incorporated compounds (for example salts) which are more water-soluble than the polymer material.
  • incorporated compounds for example salts
  • several polymer materials with different water solubility can also be mixed (polymer blend), so that the more rapidly soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the more slowly soluble one.
  • water-soluble areas of the thermoformed, injection-molded bodies are areas made of a material which chemically essentially corresponds to that of the readily water-soluble areas or at a lower level Temperature corresponds to water-soluble areas, but has a higher layer thickness and / or a changed degree of polymerization of the same polymer and / or a higher degree of crosslinking of the same polymer structure and / or a higher degree of acetalization (in the case of PVAL, for example with saccharides, polysaccharides, such as starch) and / or has a content of water-insoluble salt components and / or has a content of a water-insoluble polymer.
  • PVAL for example with saccharides, polysaccharides, such as starch
  • portioned detergent or cleaning agent compositions according to the invention can be provided which have advantageous properties in the release of active substances, in particular of active substances from the group of detergents or cleaning agents into the have respective fleets.
  • Possible “switches” which influence the dissolution behavior of the active substances enclosed in the deep-drawing, injection-molded or casting body according to the invention are, in particularly preferred embodiments, physicochemical parameters. Examples include, but should not be construed as a limitation
  • the mechanical stability for example of an optionally used capsule, coating or an optionally used compacted shaped body such as a tablet, which - in Dependence on time, temperature or other parameters - one that
  • Disintegration can be a determining factor; the solubility of optionally used capsules or coatings or matrices in
  • the thermoforming, injection molding or casting body according to the invention comprises at least one active substance or active substance preparation, the release of which is delayed.
  • the delayed release is preferably carried out by using at least one of the agents described above, but in particular by using different packaging materials and / or the use of selected coating materials, it being particularly preferred that this delayed release when using active substances or mixtures of active substances from the G
  • the detergents or cleaning agents are carried out at the earliest 5 minutes, preferably at the earliest 7 minutes, particularly preferably at the earliest 10 minutes, most preferably at the earliest 15 minutes and in particular at the earliest 20 minutes after the start of the cleaning or washing process.
  • the use of meltable coating materials from the group of waxes or paraffins is particularly preferred.
  • Active substances that are released with particular delay are the fragrances, the polymers, the surfactants, the bleaching agents and the bleach activators.
  • fragrances and / or surfactants are particularly preferably released with a delay.
  • washing or cleaning agents are particularly preferred, comprising i) a water-soluble or water-dispersible packaging with at least one
  • nonionic surfactants preferably nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, are used.
  • R 1 0 [CH 2 CH (CH 3 ) 0] x [CH 2 CH 2 0] y [CH 2 CH (OH) R 2 ], in which R represents a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures from this, R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1, 5 and y stands for a value of at least 15; End-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 is H or a methyl, ethyl, n-propyl, 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
  • x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • R 1 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 20 carbon atoms, x stands for values between 2 and 30, y for values between 0 and 30 and z for values between 1 and 30; nonionic surfactants of the general formula
  • R 1 stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms
  • R 2 stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, which 1 to 5, preferably have 1 hydroxyl group
  • 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.
  • Further preferred ingredients d) are the waxes and / or fat (s) and / or triglyceride (s) and / or fatty acids and / or fatty alcohols described above.
  • the water solubility of ingredient b) at 20 ° C. is preferably less than 15 g / l, preferably less than 10 g / l, particularly preferably less than 5 g / l and in particular less than 2 g / l.
  • the previously described casting bodies with filled receiving chamber or trough can, for example, have the appearance of the two-phase or multi-phase core tablets known to the person skilled in the art or of the two-phase or multi-phase ring tablets without actually being subjected to tableting.
  • Another object of the present application is the use of an agent according to the invention as a cleaning agent in a dishwasher. Examples:
  • Two cleaning agents of the compositions V1 and E1 were produced.
  • the components of the cleaning agent V1 were pressed into tablets.
  • the cleaning agent E1 part of the STTP, the non-ionic surfactant, the bleach activator, the polyacrylate, the glass corrosion protection agent, the silver protection agent and the dispersing agent were kneaded into a dispersion, and the other constituents were mixed into a powder. Together with the dispersion, this powder forms the agent E1 according to the invention.
  • the density of the dispersion was 1.37 g / cm 3 .
  • Standardized dishes milk, baked minced meat, egg yolk, starch
  • a cleaning cycle at 4-0 ° C in an automatic dishwasher (Bosch 5302).
  • 25 g of the cleaning agents V1 or E1 were dosed into the dosing box of the dishwashers (due to its weight fraction of PEG, the agent E1 according to the invention contains less detergent or cleaning substances than agent V1 for the same dosage amount). After cleaning was finished, the cleaning success was checked.
  • the agent E1 according to the invention has a cleaning performance which is improved compared to the conventional agent V1, despite a reduced consumption of washing or cleaning-active substances.
  • the formulations V1 and E1 were evaluated at 45 ° C and 21 ° d with standardized ballast soiling with regard to their rinse aid performance.
  • 25 g of the cleaning agents V1 or E1 were dosed into the dosing box of the dishwashers (due to its weight fraction of PEG, the agent E1 according to the invention contains less washing or cleaning-active ingredients than the agent V1 for the same dosage amount).
  • the rinse aid was checked.
  • Table 3 shows that the detergent E1 according to the invention has an improved rinse aid result compared to the conventional detergent V1 despite a reduced consumption of detergent or cleaning agents.
  • the two dishwasher detergents V1 and E1 containing manganese sulfate were tested with regard to their silver corrosion protection properties.
  • Silver cutlery was washed in a continuously operated dishwasher with a water hardness of 0-1 ° dH.
  • 25 g of cleaning agent V1 were metered in for each cleaning cycle; in example E1 according to the invention, 25 g of agent E1.
  • the rinsing process was repeated 50 times under the conditions described above.
  • the overall appearance of the wash ware was assessed using the rating scale below.
  • Table 4 shows that the agent E1 according to the invention, which contains the silver corrosion protection agent in the dispersion according to the invention, has significantly better silver corrosion properties than the conventional dishwashing agent under the conditions mentioned.

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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un procédé servant à produire des produits nettoyants ou détergents conditionnés et comprenant les étapes suivantes : i) façonnage d'un premier matériau enveloppant avec formation d'un contenant ayant au moins une chambre de réception ; ii) remplissage d'au moins une chambre de réception avec une ou plusieurs substances ou un ou plusieurs mélanges de substances. Le procédé selon l'invention est caractérisé en ce qu'au moins une des substances ou un des mélanges de substances de l'étape ii) comprend une dispersion de particules solides dans un agent dispersant, cette dispersion contenant, par rapport à son poids total, a) 10 à 65 % en poids d'agent dispersant et b) 30 à 90 % en poids de substances dispersées.
PCT/EP2004/002717 2003-03-25 2004-03-17 Portion de produit nettoyant a stabilite de forme WO2004085599A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10312456 2003-03-25
DE10312456.5 2003-03-25

Publications (1)

Publication Number Publication Date
WO2004085599A1 true WO2004085599A1 (fr) 2004-10-07

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WO (1) WO2004085599A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013120550A1 (fr) * 2012-02-14 2013-08-22 Henkel Ag & Co. Kgaa Produit de nettoyage liquide contenant un polymère sulfonique et présentant une faible teneur en eau

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6228825B1 (en) * 2000-10-13 2001-05-08 Colgate Palmolive Company Automatic dishwashing cleaning system
WO2002006438A1 (fr) * 2000-07-19 2002-01-24 The Procter & Gamble Company Compositions se presentant sous forme de gel pour lave-vaisselle automatique, leurs procedes de preparation et d'utilisation
WO2002042400A2 (fr) * 2000-11-27 2002-05-30 The Procter & Gamble Company Procede de lavage de vaisselle
WO2003006593A2 (fr) * 2001-07-07 2003-01-23 Henkel Kommanditgesellschaft Auf Aktien Detergents non aqueux '3 en 1' pour lave-vaisselle

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002006438A1 (fr) * 2000-07-19 2002-01-24 The Procter & Gamble Company Compositions se presentant sous forme de gel pour lave-vaisselle automatique, leurs procedes de preparation et d'utilisation
US6228825B1 (en) * 2000-10-13 2001-05-08 Colgate Palmolive Company Automatic dishwashing cleaning system
WO2002042400A2 (fr) * 2000-11-27 2002-05-30 The Procter & Gamble Company Procede de lavage de vaisselle
WO2003006593A2 (fr) * 2001-07-07 2003-01-23 Henkel Kommanditgesellschaft Auf Aktien Detergents non aqueux '3 en 1' pour lave-vaisselle

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013120550A1 (fr) * 2012-02-14 2013-08-22 Henkel Ag & Co. Kgaa Produit de nettoyage liquide contenant un polymère sulfonique et présentant une faible teneur en eau

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