EP1657295B1 - Composé comprenant un sel de zinc et silicate cristallin à structure en couches - Google Patents

Composé comprenant un sel de zinc et silicate cristallin à structure en couches Download PDF

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Publication number
EP1657295B1
EP1657295B1 EP05027033A EP05027033A EP1657295B1 EP 1657295 B1 EP1657295 B1 EP 1657295B1 EP 05027033 A EP05027033 A EP 05027033A EP 05027033 A EP05027033 A EP 05027033A EP 1657295 B1 EP1657295 B1 EP 1657295B1
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EP
European Patent Office
Prior art keywords
acid
preferred
water
salts
agents
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP05027033A
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German (de)
English (en)
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EP1657295A1 (fr
Inventor
Arnd Kessler
Ulrich Dr. Pegelow
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP1657295A1 publication Critical patent/EP1657295A1/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • the present invention is in the field of automatic dishwashing detergents.
  • the present invention relates to automatic dishwashing detergents containing zinc salts and certain silicates.
  • the so-called lower alkaline cleaners required for automatic dishwashing frequently contain mixtures of sodium disilicate and soda as alkali carriers, builders such as citric acid, for example in conjunction with polycarboxylates, and preferably low-foaming nonionic surfactants. Furthermore, bleaching agents, bleach activators, silver and corrosion inhibitors and, to enhance the cleaning power, enzymes may be included.
  • the dishes set in baskets are cleaned by intensive contact with the aqueous detergent solution at about 65 ° C and pH values between 9 and 11 and then rinsed clear.
  • the European Patent Application EP 0 383 482 (Procter & Gamble Company ) finally describes automatic dishwashing agents containing insoluble zinc salts, which are characterized by improved glass corrosion protection.
  • the insoluble zinc salts must have a particle size below 1.7 millimeters to achieve such an effect.
  • phosphate-containing automatic dishwashing detergents which contain a powdery to granular additive containing as essential constituents a crystalline layered silicate of the general formula NaMSi x O 2x + 1 y H 2 O, where M is sodium or hydrogen, x is a number from 1,9 to Is 22 and y is a number from 0 to 33, and (poly) polymeric polycarboxylic acid and in addition to glass or decor-preserving effects also have excellent cleaning performance.
  • an automatic dishwashing detergent additive should be provided which is suitable as a component of automatic dishwashing detergent of any kind, for example, as a component of powder, tablet, liquid formulations, cleaning foams or depot products, without restricting them by formulation.
  • the crystalline layer-form silicates of the formula (Ia) are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS, eg Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na -SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 . xH 2 O, Makatite).
  • Na-SKS eg Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite)
  • Na -SKS-2 Na 2 Si 14 O 29 .xH 2 O, magadiite
  • Na-SKS-3 Na 2 Si 8 O 17 .xH 2 O
  • Na-SKS-4 Na 2 Si 4 O 9 . xH 2 O, Makatite
  • x is 2.
  • Na-SKS-5 ⁇ -Na 2 Si 2 O 5
  • Na-SKS-7 ⁇ -Na 2 Si 2 O 5 , natrosilite
  • Na-SKS-9 NaHSi 2 O 5 ⁇ H 2 O
  • Na-SKS-10 NaHSi 2 O 5 ⁇ 3H 2 O, kanemite
  • Na-SKS-11 t-Na 2 Si 2 O 5
  • Na-SKS-13 Na-SKS-13
  • An overview of crystalline sheet silicates can be found, for example, in the article published on pages 805-808 in "Soaps Oils-Fette-Wachse, 116 Volume, No. 20/1990".
  • automatic dishwashing detergents or dishwashing auxiliaries which comprise a proportion by weight of the crystalline layered silicate of the general formula (Ia) of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular of 0.4 to 10 wt .-%, each based on the total weight of these agents on.
  • Agents to be used according to the invention contain, in addition to the crystalline layer-form silicates mentioned, zinc salts, preference being given to using both inorganic and organic salts.
  • a non-exhaustive list of some preferred zinc salts is shown in the following table: zinc salt solubility Zinc acetate dihydrate 430 g / l (20 ° C) zinc acetylacetonate 4 g / l (20 ° C) zinc bromide 820 g / l (25 ° C) zinc chloride 4320 g / l (25 ° C) zinc gluconate 100 g / l (20 ° C) zinc hydroxycarbonate Almost insoluble (20 ° C) zinc iodide 4500 g / l (20 ° C) Zinc nitrate hexahydrate 1843 g / l (20 ° C) Zinc nitrate tetrahydrate Slightly soluble (20 ° C) zinc oxide Insoluble zinc stearate 0.9 mg
  • the soluble inorganic interest salts that is, salts having a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and especially above 5 g / L , Preferred ingredient according to the invention to be used.
  • Preferred soluble inorganic salts include zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
  • the spectrum of the inventively preferred zinc salts of organic acids preferably organic carboxylic acids, ranging from salts which are not soluble in water, ie a solubility below 100 mg / L, preferably below 10 mg / L, in particular have no solubility, to such salts, the in water a solubility above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature).
  • the first group of zinc salts include, for example, zinc citrate, zinc laureate, zinc oleate, zinc oxalate, zinc tartrate, and zinc stearate.
  • the group of soluble organic zinc salts includes, for example, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, the zinc gluconate, the zinc valerate and the zinc salt of p-toluenesulfonic acid.
  • automatic dishwasher detergents or automatic dishwashing auxiliaries to be used according to the invention therefore comprise at least one zinc salt selected from the group of organic zinc salts, preferably from the group of soluble organic zinc salts, more preferably from the group of soluble zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluenesulfonate.
  • group of organic zinc salts preferably from the group of soluble organic zinc salts, more preferably from the group of soluble zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluenesul
  • compositions to be used according to the invention may also include mixtures of organic and inorganic zinc salts, in particular mixtures of soluble organic zinc salts with insoluble inorganic zinc salts or mixtures of soluble organic zinc salts with soluble inorganic zinc salts or mixtures of insoluble organic zinc salts with insoluble inorganic zinc salts or mixtures of insoluble organic zinc salts soluble inorganic zinc salts.
  • the weight fraction of the zinc salt is from 0.1 to 10% by weight, preferably from 0.2 to 7% by weight and in particular 0 , 4 to 4 wt .-% and regardless of which zinc salts are used, in particular therefore irrespective of whether organic or inorganic zinc salts, soluble or non-soluble zinc salts or mixtures thereof are used.
  • Means usable according to the invention are not subject to any restriction with respect to their packaging and forms of presentation. Automatic dishwashing or machine dishwashing aids in the context of the present invention can therefore be used both in solid and in liquid form.
  • active ingredients and / or active ingredient preparations in a timely manner.
  • This time-controlled release can take place through different mechanisms or, in other words, due to different "switches”.
  • these active substances are preferably added together but with a time offset to one or more further active ingredients and / or active substance preparations, such as builders (builders, cobuilders), surfactants, bleaches, bleach activators, enzymes , Dyes, fragrances, corrosion inhibitors or polymers are released.
  • the zinc salt and / or the phyllosilicate can be released into the aqueous liquor both before and after the release of these active substances.
  • the agent containing the zinc salt and the layered silicate is preferably contained in only one of these agents.
  • liquids, powders, granules, compactates, extrudates, casting bodies, gels, dispersions are considered as different types of preparation / physical states.
  • the assembly of such different means to a combination product can be done for example by means of a common, preferably water-soluble packaging having one, two, three, four or more receiving chambers. Methods for producing such packages are known in the art. These methods include, for example, thermoforming, injection molding or casting. In the following, with reference to single and two-chamber packaging, some preferred combinations of differently prepared compositions are described:
  • Receiving chamber 1 Inventive agent in a powder and liquid Composition according to the invention in a powder and further powder Inventive agent in a powder and granules Inventive agent in a powder and Kompaktat Inventive agent in a powder and extrudate Inventive agent in a powder and casting Inventive agent in a powder and dimensionally stable gel Inventive agent in a melt and liquid Composition according to the invention in a melt and further powder Inventive agent in a melt and granules Inventive agent in a melt and Kompaktat Composition according to the invention in a melt and extrudate Inventive agent in a melt and casting Inventive agent in a melt and dimensionally stable gel Inventive agent in a granule and liquid Composition according to the invention in granules and further powder Inventive agent in granules and granules Inventive agent in a granule and Kompaktat Composition according to the invention in a melt and extrudate Invent
  • Water-soluble or water-dispersible packaging with two receiving chambers Receiving chamber 1 Receiving chamber 2 Composition according to the invention in a dispersion liquid Composition according to the invention in a dispersion powder Composition according to the invention in a dispersion granules Composition according to the invention in a dispersion compacted Composition according to the invention in a dispersion extrudate Composition according to the invention in a dispersion casting body Composition according to the invention in a dispersion Dimensionally stable gel Composition according to the invention in a dispersion dispersion Inventive agent in a powder liquid Inventive agent in a powder powder Inventive agent in a powder granules Inventive agent in a powder compacted Inventive agent in a powder extrudate Inventive agent in a powder casting body Inventive agent in a powder Dimensionally stable gel Inventive agent in a powder dispersion Inventive agent in a powder dispersion Inventive agent in a granule liquid Inventive agent
  • the water-soluble and / or water-dispersible film for the preparation of the water-soluble and / or water-dispersible film, in principle all substances or mixtures of substances which can be formulated in the form of a film are suitable. However, particularly preferred is a process in which the water-soluble and / or water-dispersible film of (acetalized) Polyvinylakohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, starch and starch derivative (s), cellulose and cellulose derivative (s), in particular methylcellulose and / or mixtures of these substances exists, this list is to be regarded as exemplary.
  • the film (s) comprises / comprise one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof.
  • Particularly preferred embodiments of the water-soluble films also take account of the fact that the active substances and / or active-substance preparations contained in the receiving troughs are particularly advantageously-though not necessarily-soluble in water-solubility of the film material at a certain point in time of the washing, cleaning or rinsing process For example, upon reaching a certain temperature, or upon reaching a certain pH or a certain ionic strength of the wash liquor or due to other controllable events or conditions in the aqueous liquor can be fed.
  • the thickness of the water-soluble film is between 1 .mu.m and 1000 .mu.m, preferably between 5 .mu.m and 500 .mu.m and in particular between 10 .mu.m and 200 .mu.m.
  • Various film thicknesses with the aim of a delayed release of active substances and / or active substance preparations can also be realized, for example, advantageously by the multiple sealing of one or more receiving chambers by means of one or more identical or different water-soluble films. The thickness of the water-soluble film then results as the sum of the thicknesses of a receiving trough sealing, superimposed water-soluble individual sheets.
  • materials for the water-soluble films which-based on a certain thickness, which determines the thickness-dissolve at certain temperatures, pH values, ionic strengths, or after a certain residence time in the aqueous liquor.
  • a release process can capture the film as a whole or only a part thereof, so that parts of the film solve when setting a certain parameter combination, while other parts are not yet (but later) or not at all solved.
  • the latter can be achieved by different quality of the material as well as by different amounts of material (thickness) or different geometries of the water-insoluble container. For example, it is possible to impede the access of water by the outer shape of the water-insoluble container and thus delay the dissolution process.
  • the films may be made of materials of different water solubility, for example of polyvinyl alcohols (PVAL) with different residual acetate content.
  • PVAL polyvinyl alcohols
  • the water-soluble and / or water-dispersible film can also contain one or more washing and cleaning-active substances or consist of these substances (for example: polyvinyl alcohols as film material and builder) in addition to the ingredients mentioned.
  • washing active, cleaning active or active ingredients that are only present in small amounts in the preparations and their uniform incorporation is therefore not unproblematic, in the film or a part of the film, for example, one which is in the state of Washing, cleaning or rinsing dissolves, in which just the active ingredient is needed to be incorporated, whereby it is released when dissolving the film at the right time in the fleet.
  • An example of this may be fragrances which are desired in the final stage of the washing or cleaning or rinsing process, but also optical brighteners, UV protectants, dyes and other detergent-active, cleaning-active or rinse-active preparations.
  • a further embodiment of the present invention which is likewise preferred in the context of the present application is the time-controlled release of one or more of the active substances (s) and / or active substance preparation (s) contained in these agents by the incorporation of matrix or coating materials of different solubility or melting temperature.
  • matrix materials or coatings which have different melting temperatures.
  • meltable or softenable substances as matrix or coating material for the active substances or active substance preparations.
  • coating includes not only the coating of one or more sides or surfaces of an article, such as a solid particulate agent, but also the complete coating, ie the coating of this particulate article, as well as the sealing of a receptacle by a meltable substance by pouring on such a substance
  • active substances or “active substance preparations” includes both the zinc salts / phyllosilicates characteristic of the agents according to the invention and all others optionally present Ingredients.
  • Preferred fusible substances have a melting point above 30 ° C. If active substance preparations are to be released at different times, for example during the various rinses of a cleaning process, this can be done, for example, by using one or different fusible matrices or coatings.
  • the melting points are preferably adapted to the temperature profile of this cleaning process, the difference in the melting points being sufficient to ensure the separate dissolution of the individual matrices or coatings.
  • Such substances are preferred for the different matrices and / or coatings, which differ in their melting point by at least 5 ° C, preferably by 10 ° C, more preferably by 15 ° C and in particular by at least 20 ° C, wherein it further preferred in that the melting point of at least one of the fusible substances forming a matrix or a coating is below 30 ° C, while the melting point of at least one further substance forming a further matrix or coating is above 30 ° C.
  • this mass softenable under the influence of temperature can be mixed by mixing the desired further ingredients with this meltable or softenable substance and heating the mixture to temperatures in the softening range of this substance is processed shaping at these temperatures.
  • the softenable substances are used as coating agents, then such a coating can take place, for example, by dipping, spraying or circulating in a drum coater or coating pan.
  • waxes, paraffins, polyalkylene glycols, etc. as meltable or softenable substances for the matrices or the coatings.
  • meltable or softenable substances do not show a sharply defined melting point, as usually occurs in the case of pure, crystalline substances, but instead have a melting range which may be several degrees Celsius.
  • the meltable or softenable substances preferably have a melting range of between about 35 ° C and about 75 ° C. That is, in the present case, the melting range occurs within the specified temperature interval and does not denote the width of the melting range.
  • the width of the melting range is at least 1 ° C, preferably from about 2 to about 3 ° C.
  • Another preferred possibility for the delayed release of active substances or active substance preparations is the staggered spatial arrangement of these substances in the receiving chamber of a preferably water-soluble packaging or within a casting or compact (onion model) with the aim of a staggered release.
  • a spatially staggered arrangement is, for example, the layer or phase arrangement of the active ingredients or active substance preparations, for example, the layered tabletting or the layered pouring liquid active substances or mixtures of active ingredients and their subsequent solidification by solidification and / or crystallization are suitable. Since access of the solvent in compressed or cast moldings can take place only over their surface, this layered arrangement leads to the release of those active substances or active substance mixtures which are located on the surface of such a multiphase mixture. The phases are thus removed offset in time, the ingredients are released with a time delay.
  • a program for the automatic cleaning of dishes usually includes various cleaning cycles, the nature and number of these cleaning cycles can be determined by the consumer by means of a program selection. Examples of such cleaning cycles are the pre-wash cycle, intermediate and main washes or the rinse cycle. All these different cleaning operations require for an optimum result of the targeted dosage of appropriate active ingredients or active mixtures.
  • a controlled premature or delayed release of zinc salts and / or phyllosilicates and / or other active substances may be beneficial depending on the nature of the other active ingredients used.
  • Solid forms of automatic dishwashing or machine dishwashing auxiliaries are, for example, fine to coarse-grained powders, as obtained, for example, by spray-drying or granulation, compacted mixtures of roll compacting, but also solidified melts or shaped articles obtained by extrusion or tabletting.
  • Such moldings can in the context of the present invention have virtually all useful manageable embodiments, for example, in the form of a bar, in bar or bar form, a cube, a cuboid and the like Room element with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last embodiment covers the presentation form of the actual tablet to compact cylinder pieces with a height to diameter ratio above 1.
  • Preferred tabletted or extruded compositions have two or more phases, for example, by their composition, their share of the total volume of the molding and / or can distinguish their visual appearance.
  • the phases of such multiphase moldings can additionally be distinguished by a different dissolving behavior in the aqueous phase.
  • Such moldings are suitable for the time-controlled release of certain ingredients (controlled release), for example in certain rinses of the machine wash program.
  • one of the phases of the shaped body as the main constituent has meltable or softenable substances from the group of waxes, paraffins and / or polyalkylene glycols.
  • the melted or softenable substances contained molded body or molded body component is at least largely water insoluble.
  • the solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C and preferably be below 5 mg / l.
  • meltable or softenable substances should have the lowest possible water solubility, even in water at elevated temperature, in order to avoid as much as possible a temperature-independent release of the active substances.
  • the release of the active substance takes place in this way upon reaching the melting or softening point.
  • a further preferred procedure for obtaining a controlled release of ingredients, in particular the combination of zinc salt and sheet silicate according to the invention, from multiphase tablets is the compaction of the two or more individual phases with different pressures. Since the disintegration and dissolution properties of tablets or tablet phases are known to depend inter alia on the compaction pressure exerted on the tablet phase during tabletting, tablet phases having different disintegration and dissolution properties can be prepared solely by using different compaction pressures.
  • the combination of zinc salt and layered silicate are together in the phase which was exposed to the relatively higher tableting pressure and therefore decomposes later.
  • automatic dishwashing assistants are those which are added in addition to a commercial detergent, for example in the form of a special glass preservative. Such a dosage can take place both before the beginning of each rinsing program and in the form of a depot product which causes a continuous release of the agent according to the invention.
  • Preferred solid agents to be used according to the invention are in the form of a dosing unit which is sufficient for a cleaning cycle.
  • An example of such Kon Stammionsformen are dishwashing (auxiliary) stoffeltabletten.
  • the agents are in solid particulate form, but not in the form of separate metering units, the result for these agents is the problem of segregation of individual constituents, in which case the segregation of the zinc salts and silicates contained in the compositions according to the invention must be avoided.
  • Examples of such particulate forms of supply are powders or granules.
  • Preferred solid forms of automatic dishwashing agent contain, for example, fine to coarse-grained powders, as obtained, for example, by spray-drying or granulation.
  • Such powders can be marketed as a commercial product or used as a premix for compaction, for example for tableting, and generally have a particle size in the range from 0.1 to 10 mm.
  • it is preferred that these compounds have a particle size comparable to the powders.
  • a preferred subject matter of the present application is therefore a machine dishwashing detergent, characterized in that the particle size of the zinc salts and / or crystalline layered silicates compounded with one or more active and / or builder substances is 0.1 and 10 mm, preferably 0.2 and 8 mm and in particular 0.5 and 5 mm, wherein preferred particulate compounds to avoid segregation additionally a density of 0.1 to 2.0 g / cm 3 , preferably from 0.2 to 1.6 g / cm 3 and in particular from 0.4 to 1.2 g / cm 3 .
  • Preferred automatic dishwasher detergents are characterized in particular by the fact that the particles of the zinc salts and / or crystalline layered silicates compounded with one or more active and / or builder substances contain from 0.1 to 80% by weight of the zinc salts or crystalline layered silicates preferably from 0.2 to 70% by weight and particularly preferably from 0.5 to 60% by weight, in each case based on the total weight of the particles.
  • the abovementioned particulate compounds are preferably obtained by spray drying and / or granulation and / or extrusion and / or roller compaction and / or tabletting and / or solidification and / or crystallization, but in particular by spray drying and / or granulation.
  • an aqueous slurry (“slurry") is prepared in a first step of the process, which may contain other thermally stable active and / or builders in addition to the zinc salts, which neither volatilize nor decompose under the conditions of spray drying and this then conveyed by pumps in the spray tower and sprayed via located in the head of the tower nozzles. Ascending hot air dries the slurry and evaporates the adhering water so that the detergent ingredients at the outlet of the tower are obtained as fine powders. These may, if necessary, further Tempertur labile ingredients such. As bleaching agents or perfumes, are admixed.
  • the preparation of the means can be carried out except by the spray drying described above by a granulation process, wherein a fluidized bed process is particularly preferred in which on horizontal, perforated trays fine fine-grained bulk material, which may contain other active and / or builders in addition to the zinc salts of flows through the bottom of gases (eg hot air). Under certain flow conditions, this creates a state that is similar to that of a boiling liquid; the layer causes bubbles, and the particles of the bulk material are within the layer in a constant, swirling up and down movement and remain so to speak in the balance.
  • gases eg hot air
  • the large surface of the fluidized material then allows, for example, the reaction with other substances such as solvents, solutions of active and / or builders, liquid active substances or other ingredients that are present as solid at room temperature, by increasing the temperature and / or addition of very limited amounts of liquid But soften additives at least superficially and / or form an adhesive and adhesive strength under the influence of temperature.
  • Typical examples of the aforementioned substances are water and aqueous solutions, for example, aqueous solutions of zinc salts can be used at room temperature liquid or solid surfactant compounds, especially nonionic surfactants, or polymer compounds of synthetic and / or natural origin, for example (co) -polymere carboxylates.
  • Another preferred procedure for the granulation is the use of mixers / compressors, as they are provided for this purpose, among other providers, for example, by the company Lödige and which are particularly suitable for the production of ready-made particles, since they provide the user by variation various process parameters such as the number of revolutions of the mixer, the residence time of the individual components, the dosing of individual components during the mixing process, the geometry of the mixing elements used or the energy input offer the possibility of targeted control of the product properties of the resulting granules.
  • the grain size and / or density of granules can be influenced in this way, and the preparation of zinc salts with one or more further active and / or builder substance (s) in the aforementioned mixers / compressors is therefore particularly preferred.
  • the scaffolding and / or active substances which can be used in the preparation of preferred automatic dishwashing agents described above include, among other conventional ingredients of detergents, for example, builders, co-builders, surfactants, bleaches, bleach activators, enzymes, dyes, fragrances, corrosion inhibitors or polymers.
  • surfactants preferably the nonionic surfactants, and / or the polymeric carboxylates, in particular the polysulfocarboxylates.
  • silicates contained in the automatic dishwashing detergents or automatic dishwashing assistants are also present in these compositions prefabricated with other active substances or builders, in which case active substances or builders from the group of organic monocarboxylic or polycarboxylic acids, hydroxypolycarboxylic acids and phosphonic acids are used.
  • the particulate present, with one or more active and / or builders formulated zinc salts and / or crystalline layered silicates may be provided to protect environmental influences and thus to improve their storage stability or to influence the dissolution behavior with a coating (coating).
  • Coating materials and methods for coating particulate agents are widely described in the literature and will be explained below only with respect to particularly preferred embodiments.
  • fusible or softenable substances are particularly preferred.
  • coating means in the context of the present invention, in addition to the coating of single or multiple sides or surfaces of a particulate, ready-made agent also a complete coating, ie the envelope of this particulate article.
  • Preferred fusible substances have a melting point above 30 ° C on.
  • the ready-made zinc salts and / or crystalline layered silicates are to be released at different times, for example during the various rinses of a cleaning process, this can be done, for example, by the use of different fusible coatings which differ in their melting point, the melting points of these substances preferably being on the Adjusted temperature course of this cleaning process and the difference of the melting points is sufficient to ensure the separate dissolution of the individual matrices or coatings. If, for example, it is envisaged to release zinc salts and crystalline layer-form silicates at separate times, then such substances are preferred for the different coatings which, with respect to their melting point, are at least 5 ° C., preferably around 10 ° C., more preferably around 15 ° C.
  • the melting point of at least one of the fusible substances forming a coating is below 30 ° C, while the melting point of at least one further substance forming another matrix or coating, above 30 ° C is.
  • Such coatings can be applied, for example, by dipping, spraying or tumbling in a drum coater or coating pan. Particular preference is given to using waxes, paraffins, polyalkylene glycols, etc., as the meltable or softenable substances for the coatings.
  • meltable or softenable substances do not show a sharply defined melting point, as usually occurs in the case of pure, crystalline substances, but instead have a melting range which may be several degrees Celsius.
  • the meltable or softenable substances preferably have a melting range of between about 45 ° C and about 75 ° C. That is, in the present case, that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range.
  • the width of the melting range is at least 1 ° C, preferably from about 2 to about 3 ° C.
  • waxes are understood to mean a series of naturally or artificially produced substances which generally melt above 40 ° C. without decomposition and are already relatively low-viscosity and non-stringy just above the melting point. They have a strong temperature-dependent consistency and solubility.
  • the waxes are divided 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, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or crepe fat, mineral waxes such as ceresin or ozokerite (groundwax), or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.
  • vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, or montan wax
  • animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or crepe
  • the chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
  • Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. It is also possible to use as meltable or softenable substances for the compositions which cure by cooling, and compounds from other substance classes which meet the stated requirements with regard to the softening point.
  • suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, commercially available under the name Unimoll 66 ® (Bayer AG) is available, proven.
  • synthetic waxes made of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea) is available.
  • esters of lower alcohols can be used with fatty acids from natural sources.
  • This class of substances includes, for example, Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate.
  • Shellac for example shellac KPS three-ring SP (Kalkhoff GmbH) can also be used as meltable or softenable substances.
  • Wax alcohols are high, molecular, water-insoluble Fatty alcohols with usually about 22 to 40 carbon atoms.
  • the wax alcohols are, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes.
  • wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
  • the enclosure of the assembled zinc salts or crystalline layered silicates can optionally also contain wool wax alcohols which are understood to be understood triterpenoid and steroid alcohols, for example lanolin, available, for example, under the trade designation Argowax ® (Pamentier & Co).
  • wool wax alcohols which are understood to be understood triterpenoid and steroid alcohols, for example lanolin, available, for example, under the trade designation Argowax ® (Pamentier & Co).
  • fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.
  • meltable or softenable substances are those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) contains, with polyethylene glycols having molecular weights between 1500 and 36,000 are preferred, those with molecular weights from 2000 to 6000 particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred. Also, corresponding processes, which are characterized in that the plastically deformable mass (s) at least one substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) contains / are preferred.
  • Coating agents which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as sole meltable or softenable substances are preferred here.
  • PPG polypropylene glycols
  • PEG polyethylene glycols
  • Useful polypropylene glycols are polymers of propylene glycol having the following general formula satisfy, where n can take values between 10 and 2000.
  • Preferred PPG have molecular weights between 1000 and 10,000, corresponding to values of n between 17 and about 170.
  • polyethylene glycols are polymers of ethylene glycol, those of the general formula H- (O-CH 2 -CH 2 ) n -OH satisfy, where n can take values between 20 and about 1000.
  • the abovementioned preferred molecular weight ranges correspond to preferred ranges of the value n in formula IV of about 30 to about 820 (exactly: from 34 to 818), more preferably from about 40 to about 150 (exactly: from 45 to 136). and especially from about 70 to about 120 (exactly: from 68 to 113).
  • the coating materials contain paraffin wax.
  • Paraffin waxes have the advantage over the other natural waxes mentioned that there is no hydrolysis of the waxes in an alkaline detergent environment (as is to be expected, for example, with wax esters), since paraffin wax contains no hydrolyzable groups.
  • Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and cycloalkanes.
  • the paraffin to be used preferably has substantially no constituents with a melting point of more than 70 ° C., more preferably of more than 60 ° C. Shares of high-melting alkanes in the paraffin can fall below this melting temperature in the detergent leaving unwanted wax residue on the surfaces to be cleaned or the property to be cleaned. Such wax residues usually lead to an unsightly appearance of the cleaned surface and should therefore be avoided.
  • melt or softenable substances to be processed contain at least one paraffin wax with a melting range of 50 ° C to 60 ° C, preferred coating materials being characterized in that they contain a paraffin wax having a melting range of 50 ° C to 55 ° C.
  • the content of the paraffin wax used at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible.
  • the more solid wax constituents in a wax at room temperature the more useful it is.
  • the proportion of solid wax constituents increases, the end-of-processability of the process end products increases against impacts or friction on other surfaces, resulting in longer-lasting protection.
  • High levels of oils or liquid wax components can weaken the coating, opening pores and exposing the active ingredients to environmental conditions.
  • the meltable or softenable substances may contain, in addition to paraffin as the main constituent, one or more of the abovementioned waxes or waxy substances.
  • the mixture forming the meltable or softenable substances should be such that the composition and the coating formed therefrom are at least substantially insoluble in water.
  • the solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C and preferably be below 5 mg / l.
  • meltable or softenable substances should have the lowest possible water solubility, even in water at elevated temperature, in order to avoid as much as possible a temperature-independent release of the active substances.
  • Preferred coating materials to be processed are characterized in that they contain, as meltable or softenable substances, one or more substances having a melting range from 40 ° C. to 75 ° C. in amounts of from 6 to 30% by weight, preferably from 7.5 to 25% by weight .-% and in particular from 10 to 20 wt .-%, each based on the weight of the coating material.
  • the dissolution behavior of the zinc salt or silicate compounds can also be influenced by the abovementioned compaction methods.
  • aids such as binders
  • compacted silicates, in particular disilicates, and / or polycarboxylates and / or mixtures of various polycarboxylates are suitable as "depot substances" for the zinc salts or crystalline layered form due to their delayed solution / dispersion or due to gelling of these substances or substance mixtures in aqueous liquor silicates.
  • polymer matrices are particularly preferred form of the preparation of automatic dishwashing or machine dishwashing aids.
  • Such polymer matrices are universally applicable in various programs, are characterized by a simple and cost-effective method of preparation and may contain varying amounts of active agent.
  • the active ingredient-containing polymer matrices can be produced cheaply and in a high variety of forms.
  • the composition of the present invention can even be formulated as a package of automatic dishwashing detergents or as a basket into which the compositions are incorporated. It is also possible to combine both types of incorporation by, for example, a carrier basket of water-insoluble, active ingredient-containing polymer matrix containing a polymer body of water-soluble, active ingredient-containing polymer matrix.
  • Such products can release different levels of active agents from the various matrices at different times, resulting in an optimal concentration of active ingredient at each point in the cleansing program.
  • both the zinc salt and the silicates are packaged in a polymer matrix
  • this preparation can take place both in the same polymer matrix and in different matrices, that is to say that the zinc salt is present in polymer A, for example the silicate was formulated in a polymer B.
  • zinc salt and silicate can also be formulated by means of the same polymer, but in separate matrices.
  • Preferred automatic dishwashing or machine dishwashing aids are characterized in that the polymer matrix comprises one or more water-soluble polymer (s).
  • the polymer matrices can be formulated universally. For example, it is possible to provide pre-softeners, pre-rinsing agents, cleaning agents for the main rinse or rinse aid according to the invention. In addition, compositions may also be combination products which combine two or more of the aforementioned agents.
  • the active ingredient-containing polymer matrix can be particulate incorporated into the compositions of the invention, but it can also be a compact molded body, for example, either a core which fills a trough of a detergent tablet, or a shaped product, which as an addition product equal to a deodorant hanger in the dishwasher is introduced.
  • baskets which are suitable for receiving detergent tablets can be prepared from the active ingredient-containing polymer matrix.
  • the active ingredient-containing polymer matrix can also be used as a packaging for automatic dishwasher detergents. This is especially true for completely water-soluble active substance-containing polymer matrices attractive, since the consumer does not have to unpack the product, the direct contact with the product, which is perceived as undesirable, avoids and other packaging materials are saved.
  • the polymer matrix of the preferred agents comprises from 5 to 99.5% by weight of one or more polymers.
  • polymers in the context of the following application, based on the IUPAC definition, denotes substances which are composed of a collective of chemically uniformly structured, but generally differing in terms of degree of polymerization, molecular weight and chain length macromolecules.
  • a polymer is "a substance composed of a plurality of molecules in which one kind or more kinds of atoms or atomic groups" so-called constitutive units, basic units or repeating units repeats
  • the different sized macromolecules of a polymer are composed of so many identical or similar low molecular weight building blocks (monomers) that the physical properties of the substance, especially the viscoelasticity, do not appreciably change with a slight increase or decrease in the number of building blocks
  • the size of the macromolecules implies that the end groups have relatively little effect on the properties of the polymers, so that their explicit specification in the structural formulas given below is usually dispensed with.
  • the matrix forming polymers of the compositions may be of either natural or synthetic origin.
  • Preferred agents are characterized in that the polymer matrix from 7.5 to 95 wt .-%, preferably 10 to 90 wt .-%, particularly preferably 12.5 to 85 wt .-%, more preferably 15 to 82.5 wt .-% and in particular 20 to 80 wt .-% of one or more polymers, wherein the weights are based on the active ingredient-containing polymer matrix.
  • the average molar mass of the polymers contained in the preferred compositions is preferably at least 5000 g / mol, more preferably at least 10,000 g / mol and in particular at least 12,000 g / mol.
  • the preferred agents can contain both water-insoluble and water-soluble polymers and mixtures of these polymers.
  • Preferred compositions based on water-insoluble polymer matrices are characterized in that the polymer matrix comprises one or more water-insoluble polymers from the group polyethylene, polypropylene, polytetrafluoroethylene, polystyrene, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polyurethanes, polyamides and mixtures thereof.
  • the active substance-containing polymer matrix has, in addition to the polymer (s), a content of at least one zinc salt and / or at least one crystalline layered silicate of the general formula (Ia) which can be liberated from the matrix.
  • Preferred agents are characterized in that they contain at least one zinc salt and at least one crystalline layered silicate of the general formula (Ia), the sum of the proportions by weight of these constituents being from 1 to 90% by weight, preferably from 1.5 to 80% by weight. , more preferably 2 to 70 wt .-%, more preferably 2.5 to 60 wt .-% and in particular 3 to 50 wt .-%, each based on the total weight of the active ingredient-containing polymer matrix is.
  • the automatic dishwashing or machine dishwashing aids may contain the active ingredient-containing polymer matrix in different amounts.
  • the proportions of the active ingredient-containing polymer matrix can vary in the overall composition.
  • compositions which, based on the total mass of the composition, 1 to 40 wt .-%, preferably 1.5 to 35 wt .-%, particularly preferably 2 to 30 wt .-% and in particular 2.5 to 20 wt .-% of the active ingredient-containing polymer matrix included.
  • Particularly preferred polymer matrices contain at least one zinc salt in such amounts that the composition comprises zinc in oxidized form in proportions by weight of 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 wt .-%, each based on the total weight of the polymer matrix contains.
  • compositions in addition to conventional automatic dishwasher detergents, pre-soak or pre-rinse products, rinse aid, machine care or additional products can be provided as a composition.
  • a preferred embodiment of the composition provides that the polymer matrix is provided as a separate part to be introduced into the dishwasher, which releases the agents from the polymer matrix over several rinses.
  • This molding can either be a Dosierkörbchen for other products, such as the cleaner, but it can also embody the added benefit of glass preservation as a separate and independent molding. Possible shapes are based, for example, on the known dishwasher Dodorantien. Visually attractive is the design of the plastic part in translucent, opalescent or completely clear form, for example in the form of a stylized diamond. By such product designs, the gloss resulting from the glass preservation can be visualized close to the consumer.
  • the active ingredient-containing polymer matrices can be easily converted by conventional methods.
  • the shaping processing takes place according to the usual in the plastics processing industry process, in particular, the film production and processing, blow molding and injection molding are preferred. All methods have in common that a plastic granules are melted by means of an extruder and fed to forming tools.
  • the plastic granules may already contain the agents for glass corrosion inhibition, but these can also be added during the melting in the extruder, which allows a particularly cost-effective production of the preferred active ingredient-containing polymer matrices.
  • the automatic dishwashing or machine dishwashing aids are formulated in a manner which makes it possible to selectively apply and meter the active substances contained in these agents.
  • pen-shaped offer form similar to a glue stick, do not change their spatial-geometric shape during storage and transport, but these, the offer form is moved under the influence of pressure over a surface, in their contact area loses with the surface due to the shear forces occurring there.
  • the agent is smeared as a result of the shearing forces acting on the surface and remains there after the end of the action of the shear forces in its new spatial-geometric shape, so in turn is dimensionally stable.
  • the penetration rate is determined by pressing a specific measuring tool (TA-15 45 ° cone made of stainless steel) at a defined feed rate (0.5 mm / s) to a defined penetration depth (5.0 mm) into the test material and then with a defined speed (0.2 mm / s) is pulled out of this material.
  • the tested test materials had a temperature of 23 ° C, the measurements were carried out at 20 ° C room temperature. Based on the test setup described above, the measuring instrument determined a numerical value in units of grams [g]. This numerical value is called the penetration number.
  • the preferred dimensionally stable automatic dishwashing or machine dishwashing auxiliary penetration numbers of 200 to 1000 g, preferably from 250 to 900 g, more preferably from 300 to 800 g and in particular from 350 to 700 g.
  • dimensionally stable refers to automatic dishwashing or machine dishwashing aids which have an intrinsic dimensional stability which enables them to have a stable, non-disintegrating spatial form under normal conditions of manufacture, storage, transport and handling by the consumer which does not remain unchanged under the said conditions for a prolonged period, that is to say, for example, under the usual conditions of manufacture, storage, transport and handling by the consumer, in the spatial-geometric shape resulting from their manufacture does not melt.
  • the penetration number of 200 to 1000 g which is characteristic for preferred agents, can not be realized in their pure form by active substances such as zinc salts or layered silicates. It is therefore necessary to provide a carrier material or matrix material for these active substances which meets the said physical requirements for an agent.
  • a carrier material or matrix material for these active substances which meets the said physical requirements for an agent.
  • such a matrix should be compatible with active agents contained in it, ie in particular should not react with them, but stabilize them.
  • the carrier materials should not jeopardize the intended cleaning process, ie they should also be compatible with all other substances used during the cleaning and / or maintenance process.
  • the matrix material should preferably be water-soluble or water-dispersible in order to prevent the occurrence of residues to avoid after use of the remedy.
  • Preferred dimensionally stable, automatic dishwashing or dishwashing auxiliaries are therefore characterized in that they contain polyvinylpyrrolidone (s) and / or polyvinyl alcohol (s) and / or polyvinyl acetate (s) and / or polyacrylate (s) and / or polyalkylene glycol (s) and / or or fat (s) and / or fatty acid (s) and / or fatty acid ester and / or fatty acid amide (s) and / or fatty alcohols and / or wax (s) and / or parrafin (s) and / or wax alcohols and / or surfactant ( e), preferably nonionic surfactant (s), and / or dextrin (s) and / or starch ethers, wherein the weight fraction of this component / these components in the total weight of the dimensionally stable automatic dishwashing and / or dishwashing auxiliary preferably between 30 and 99 Wt.%, Particularly
  • Machine dishwashing detergents or dishwashing auxiliaries can, except in the described solid or dimensionally stable forms, also be formulated in the form of liquid or flowable agents.
  • the automatic dishwashing or machine dishwashing aids therefore have a viscosity of from 500 to 500,000 mPas, preferably from 900 to 200,000 mPas and in particular from 1300 to 100,000 mPas.
  • the viscosity of the compositions according to the invention is measured by conventional standard methods (for example Brookfield LVT-II viscosimeter at 20 rpm and 20 ° C., spindle 3).
  • the term "liquid or flowable agents" will be used hereafter for agents which have a viscosity of from 500 to 500,000 mPas, preferably from 900 to 200,000 mPas and especially from 1300 to 100,000 mPas.
  • such preferred liquid or flowable agents contain one or more non-aqueous solvents.
  • non-aqueous solvents are derived, for example, from the groups of monoalcohols, diols, triols or polyols, ethers, esters and / or amides.
  • nonaqueous solvents which are water-soluble, "water-soluble" solvents in the sense of the present application being solvents which are completely miscible with water at room temperature, ie without a miscibility gap.
  • Suitable nonaqueous solvents are preferably from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the given concentration range.
  • the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy
  • Nonionic surfactants which are liquid at room temperature are also preferred nonaqueous solvents in the context of the application.
  • a particularly preferred liquid or free-flowing machine dishwashing detergent or machine dishwashing auxiliary is characterized in that it contains nonaqueous solvents, the solvent (s) preferably being selected from the group of polyethylene glycols and polypropylene glycols, glycerol, glycerin carbonate, triacetin, ethylene glycol, Propylene glycol, propylene carbonate, hexylene glycol, ethanol and n-propanol and / or iso-propanol.
  • the solvent (s) preferably being selected from the group of polyethylene glycols and polypropylene glycols, glycerol, glycerin carbonate, triacetin, ethylene glycol, Propylene glycol, propylene carbonate, hexylene glycol, ethanol and n-propanol and / or iso-propanol.
  • PEG polyethylene glycols
  • PEG polymers of ethylene glycol which are of the general formula (II) H- (O-CH 2 -CH 2 ) n -OH (II) n, where n can assume values between 1 (ethylene glycol, see below) and about 16.
  • n can assume values between 1 (ethylene glycol, see below) and about 16.
  • PEG polyethylene glycols
  • Technically common is the indication of the average relative molecular weight following the indication "PEG”, so that "PEG 200” characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210. According to this nomenclature, the technically common polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used.
  • 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.
  • PPG polypropylene glycols
  • PPG polymers of propylene glycol which correspond to the general formula (III) n, where n can assume values between 1 (propylene glycol, see below) and about 12.
  • n can assume values between 1 (propylene glycol, see below) and about 12.
  • Glycerin is a colorless, clear, heavy-bodied, odorless sweet-tasting hygroscopic liquid of density 1.261 that solidifies at 18.2 ° C.
  • Glycerol was originally a by-product of fat saponification but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediates allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO 3 contact via the step of the glycide.
  • Glycerol carbonate is accessible by transesterification of ethylene carbonate or dimethyl carbonate with glycerol, as by-products of ethylene glycol or methanol incurred. Another synthetic route is based on glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO 2 to glycerol carbonate. Glycerine carbonate is a clear, easily agitated liquid with a density of 1.398 gcm -3 , which boils at 125-130 ° C (0.15 mbar).
  • Ethylene Glycol (1,2-Ethanediol, "Glycol”) is a colorless, viscous, sweet-tasting, highly hygroscopic liquid that is miscible with water, alcohols and acetone and has a density of 1.113.
  • the solidification point of ethylene glycol is -11.5 ° C, the liquid boils at 198 ° C.
  • ethylene glycol is recovered from ethylene oxide by heating with water under pressure. Promising manufacturing processes can also be built on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.
  • 1,3-Propanediol trimethylene glycol
  • 1,0597 a neutral, colorless and odorless, sweet-tasting liquid of density 1,0597, which solidifies at -32 ° C and boils at 214 ° C.
  • the preparation of 1,3-propanediol succeeds from acrolein and water with subsequent catalytic hydrogenation.
  • 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1.0381, which solidifies at 60 ° C and boils at 188 ° C.
  • 1,2-Propanediol is prepared from propylene oxide by water addition.
  • Propylene carbonate is a water-bright, easily mobile liquid, with a density of 1.21 gcm -3 , the melting point is -49 ° C, the boiling point at 242 ° C. Also propylene carbonate is industrially accessible by reaction of propylene oxide and CO 2 at 200 ° C and 80 bar.
  • the nonaqueous solvent (s) is / are in amounts of from 0.1% to 70%, preferably from 0.5% to 60%, most preferably 1% to 50 wt .-%, most preferably from 2 to 40 wt .-% and in particular from 2.5 to 30 wt .-%, each based on the total agent.
  • non-aqueous is to be understood as a state in which the free water content in the agents is significantly below 5% by weight, based on the agent. It is preferred that the level of the automatic dishwashing or machine dishwashing aids of the invention be free, i. not present in the form of water of hydration and / or water of constitution below 10% by weight, preferably below 8% by weight and in particular even below 6% by weight, in each case based on the agent. Accordingly, water can be introduced into the agent substantially only in chemically and / or physically bound form or as a constituent of the raw materials or compounds present as solid, but not as a liquid, solution or dispersion.
  • preferred liquid or flowable automatic dishwashing or machine dishwashing aids contain one or more nonionic surfactants, in short nonionic surfactants.
  • the amounts in which the nonionic surfactants are used are preferably between 5 and 30% by weight, with those agents which are particularly preferred being 1 to 25% by weight, preferably 2 to 22.5 wt .-%, particularly preferably 3 to 20 wt .-% and in particular 4 to 17.5 wt .-% nonionic (s) surfactant (s) included.
  • nonionic surfactants For a detailed description of these nonionic surfactants, reference is made to the following remarks on the preferred washing or cleaning active ingredients of preferred compositions to avoid repetition at these points.
  • the agents may contain other ingredients, with their use, for example, the settling or pourability or flowability can be controlled specifically.
  • the settling or pourability or flowability can be controlled specifically.
  • combinations of structurizers and thickeners have proven to be useful.
  • the structurant 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. Although conventional thickeners such as polyacrylates or polyurethanes fail in non-aqueous media, the viscosity control with the substances mentioned succeeds in the non-aqueous system.
  • Bentonites are contaminated clays caused by the weathering of volcanic tuffs. Due to their high content of montmorillonite, bentonites have valuable properties such as swellability, ion exchange capacity and thixotropy. It is possible to modify the properties of the bentonite according to the intended use. Bentonites are common as clay constituents in tropical soils and are used as sodium bentonite, e.g. mined in Wyoming / USA. Sodium bentonite has the most favorable application properties (swellability), so that its use is preferred. 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 by exchange of Ca for Na in the more swellable Na-bentonites.
  • montmorillonites The main constituents of the bentonites form so-called montmorillonites, which can also be used in their pure form.
  • Montmorillonites are too the clay silicates and here to the dioctahedral smectites belonging clay minerals, which crystallize monoclinic pseudohexagonal.
  • Montmorillonite form predominantly white, grayish-white to yellowish, completely amorphous appearing, easily friable, in the water swelling, but not plasticizing masses, by the general formulas Al 2 [(OH) 2 / Si 4 O 10 ] .nH 2 O or Al 2 O 3 ⁇ 4SiO 2 ⁇ H 2 O ⁇ nH 2 O or Al 2 [(OH) 2 / Si 4 O 10 ] (dried at 150 °) can be described.
  • Preferred automatic dishwashing detergents or dishwashing auxiliaries are characterized in that montmorillonites are used as structurants.
  • Montmorillonites have a three-layer structure consisting of two tetrahedral layers, which are electrostatically crosslinked via the cations of an octahedral intermediate 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, ⁇ -picolin, ammonium compounds, hydroxy-aluminosilicate ions, etc.
  • the above. Formulas are only approximate formulas since montmorillonites have a large ion exchange capacity.
  • Al can be exchanged for Mg, Fe 2+ , Fe 3+ , Zn, Cr, Cu and other ions.
  • a negative charge of the layers results, which is balanced by other cations, especially Na + and Ca 2+ .
  • At least partially etherified sorbitols can be used as structurants.
  • Sorbitol is a hexavalent 6-valent alcohol (sugar alcohol) that is relatively easy to split one or two moles of water intramolecularly and forms cyclic ethers (eg, sorbitan and sorbide). The removal of water is also possible intermolecularly, forming noncyclic ethers of sorbitol and the alcohols in question. Again, the formation of mono-ethers and bis-ethers is possible, with higher degrees of etherification such as 3 and 4 may occur.
  • Preferably at least partially etherified sorbitols are doubly etherified sorbitols, of which the dibenzylidenesorbitol is particularly preferred.
  • automatic dishwashing detergents which contain twice etherified sorbitols, in particular dibenzylidenesorbitol, as structurants are preferred.
  • the preferred liquid or free-flowing agents may contain the structurants in amounts of from 0.1 to 1.0% by weight, based on the total agent and on the active substance of the structurant.
  • Preferred agents contain the modifier in amounts of from 0.2 to 0.9% by weight, preferably in amounts of from 0.25 to 0.75% by weight and in particular in amounts of from 0.3 to 0.5% by weight. %, in each case based on the total mean.
  • the preferred liquid or flowable agents may contain inorganic salts from the group of carbonates, sulfates and amorphous or crystalline disilicates.
  • the said salts of all metals can be used, the alkali metal salts being preferred.
  • Alkali carbonate (s), alkali metal sulphate (s) and / or amorphous (s) and / or crystalline alkali metal disilicate (s), preferably sodium carbonate, sodium sulphate and / or amorphous or crystalline sodium disilicate, are particularly preferably used as thickener.
  • the preferred liquid or flowable agents contain the thickener in amounts of 5 to 30 wt .-%, based on the total agent.
  • Particularly preferred compositions contain the thickener (s) in amounts of 7.5 to 28 wt .-%, preferably in amounts of 10 to 26 wt .-% and in particular in amounts of 12.5 to 25 wt .-%, each based on the entire remedy.
  • the solids contained in the agents are used as finely divided as possible. This is particularly advantageous in the case of inorganic thickeners and bleaching agents.
  • automatic dishwashing detergents are preferred in which the average particle size of the bleaching agents and thickeners and of the optionally used builder is less than 75 ⁇ m, preferably less than 50 ⁇ m and in particular less than 25 ⁇ m.
  • the liquid automatic dishwashing detergents can also contain other viscosity regulators or thickeners for setting a possibly desired higher viscosity.
  • viscosity regulators or thickeners for setting a possibly desired higher viscosity.
  • all known thickening agents can be used, ie those based on natural or synthetic polymers.
  • Naturally derived polymers which are used as thickening agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein.
  • Modified natural products come mainly from the group of modified starches and celluloses, examples which may be mentioned here carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and core flour ethers.
  • Preferred liquid or flowable automatic dishwashing or machine dishwashing aids contain as thickening agents hydroxyethylcellulose and / or hydroxypropylcellulose, preferably in amounts of from 0.01 to 4.0% by weight, more preferably in amounts of from 0.01 to 3.0% by weight. and in particular in amounts of 0.01 to 2.0 wt .-%, each based on the total agent.
  • a large group of thickeners which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.
  • Thickeners from said substance classes are widely available commercially and are sold for example under the trade name Acusol ® -820 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ® -GT- 282-S (alkyl polyglycol ethers, Akzo), DEUTEROL ® polymer-11 (dicarboxylic acid copolymer, Schoner GmbH) deuteron ® -xg (anionic heteropolysaccharide based on ⁇ -D-glucose, D-mannose, D-glucuronic acid, Schoner GmbH ) deuteron ® -XN (nonionic polysaccharide Schoner GmbH), DICRYLAN ® -Verdicker-O (ethylene oxide adduct, 50% solution in water / isopropanol, Pfersse Chemie), EMA ® -81 and EMA ® -91 (ethylene-maleic
  • a preferred polymeric thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of from 2 to 15 million daltons.
  • Xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) with side chains.
  • the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.
  • thickeners are polyurethanes or modified polyacrylates, which, based on the total agent, for example, in amounts of 0.1 to 5 wt .-% can be used.
  • Polyurethanes are prepared by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula IV in which R 1 is a low molecular weight or polymeric diol radical, R 2 is an aliphatic or aromatic group and n is a natural number.
  • R 1 is preferably a linear or branched C 2-12 -alk (en) yl group, but may also be a residue of a higher-valent alcohol, whereby crosslinked polyurethanes are formed, which differ from the formula VIII given above in that the Rest R 1 further -O-CO-NH groups are bonded.
  • TDI 2,4- and 2,6-toluene diisocyanate
  • MDI C 6 H 4 -CH 2 -C 6 H 4
  • thickener based on polyurethane are, for example, under the names Acrysol ® PM 12 V (mixture of 3-5% modified starch and 14-16% polyurethane resin in water, Rohm & Haas), Borchigel ® L75-N (non-ionic polyurethane dispersion, 50% in water, Borchers), Coatex ® BR-100-P (PUR-dispersion, 50% in water / butyl glycol, Dimed), Nopco ® DSX-1514 (polyurethane dispersion, 40% in water / Butyltrigylcol, Henkel-Nopco), thickener QR 1001 (20% polyurethane emulsion in water / Digylcolether, Rohm & Haas) and Rilanit ® VPW-3116 (polyurethane dispersion, 43% in water, Henkel) available.
  • Acrysol ® PM 12 V mixture of 3-5% modified starch and 14-16% polyurethane resin in
  • aqueous dispersions When using aqueous dispersions, care must be taken to ensure that the water content of the agents remains within the abovementioned limits. If the use of the aqueous dispersions for these reasons is not possible, dispersions in other solvents, or even the solids can be used.
  • Modified polyacrylates which can be used are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula V.
  • R 3 is H or a branched or unbranched C 1-4 -alk (en) yl radical
  • X is NR 5 or O
  • R 4 is an optionally alkoxylated branched or unbranched, possibly substituted C 8-22- Alk (en ) ylrest
  • R 5 is H or R 4
  • n is a natural number.
  • modified polyacrylates are esters or amides of acrylic acid or of an ⁇ -substituted acrylic acid. Preferred among these polymers are those in which R 3 is H or a methyl group.
  • Preferred alkoxylation levels are between 2 and 30, with degrees of alkoxylation between 10 and 15 being particularly preferred.
  • the designation of the radicals bound to X represents a statistical mean value which, in individual cases, can vary with regard to chain length or degree of alkoxylation.
  • the formula V indicates only formulas for idealized homopolymers. However, it is also possible to use copolymers in which the proportion of monomer units satisfying formula V is at least 30% by weight. For example, it is also possible to use copolymers of modified polyacrylates and acrylic acid or salts thereof which still have acidic H atoms or basic -COO - groups.
  • Preferably used modified polyacrylates are polyacrylate-polymethacrylate copolymers which satisfy the formula Va in which R 4 is a preferably unbranched, saturated or unsaturated C 8-22 -alkenoyl radical, R 6 and R 7 independently of one another are H or CH 3 , the degree of polymerization n is a natural number and the degree of alkoxylation a is a natural number between 2 and 30, preferably between 10 and 20.
  • Products of formula Va are commercially available for example under the name Acusol ® 820 (Rohm & Haas) in the form of 30 wt .-% strength dispersion in water available.
  • R 4 is a stearyl
  • R 6 is a hydrogen atom
  • R 7 is H or CH 3
  • the degree of ethoxylation a is 20.
  • the above water content of the Mitttel said applies.
  • Preferred liquid or flowable automatic dishwashing or machine dishwashing aids are characterized in that they additionally contain 0.01 to 5 wt .-%, preferably 0.02 to 4 wt .-%, particularly preferably 0.05 to 3 wt .-% and in particular 0.1 to 1.5 wt .-%, of a polymeric thickener, preferably from the group of polyurethanes or modified polyacrylates, with particular preference to thickeners of formula VI in the R 3 is H or a branched or unbranched C 1-4 -alk (en) yl radical, X is NR 5 or O, R 4 is an optionally alkoxylated branched or unbranched, possibly substituted C 8-22- Alk (en ) yl radical, R 5 is H or R 4 and n is a natural number.
  • the solid or dimensionally stable and liquid or flowable automatic dishwashing or dishwashing aids can be offered to the consumer in conventional containers, for example bottles, screw jars, canisters, balloons, cups or spray jars, from which he dispenses these for use.
  • Higher viscosity products can also be offered in tubes or dispensers as known from toothpaste or sealants.
  • Such containers are today usually made of non-water-soluble polymers and may for example consist of all common water-insoluble packaging materials, which are well known to those skilled in the art. In particular, polymers based on hydrocarbons may be mentioned as preferred polymers.
  • Particularly preferred polymers include polyethylene, polypropylene (more preferably oriented polypropylene) and polymer blends such as blends of said polymers with polyethylene terephthalate. Also suitable are one or more polymers from the group consisting of polyvinyl chloride, polysulfones, polyacetals, water-insoluble cellulose derivatives, cellulose acetate, cellulose propionate, cellulose acetobutyrate and mixtures of said polymers or copolymers comprising said polymers.
  • a particularly preferred embodiment aims to provide the consumer with pre-portioned means according to the invention, so that he can use the dosing advantages known to him from the "tablet” offering and combine them with the rapid dissolution and release rates as well as the performance advantages of the agents according to the invention.
  • Such pre-portioned agents may also be present in water insoluble packages so that the consumer must properly open them prior to use.
  • Such packages include water-soluble or decomposable packages such as bags of water-soluble film (so-called pouches), bags or other packaging of water-soluble or decomposable nonwovens or flexible or rigid bodies of water-soluble polymers, preferably in the form of filled hollow body, which for example by deep drawing, injection molding , Blow molding, calendering, etc. can be made.
  • a preferred article is therefore dishwasher detergents according to the invention or automatic dishwashing auxiliaries which are packaged in portions in a water-soluble casing.
  • automatic dishwashing or dishwashing aids comprise a completely or partially water-soluble casing.
  • the shape of the wrapper is not limited to specific shapes. Basically, all Archimedean and Platonic bodies, ie three-dimensional shaped bodies, come into question as forms of envelopment. Examples of the shape of the wrapper are capsules, cubes, spheres, ovoid moldings, cuboids, cones, rods or bags. Also hollow body with one or more compartments are suitable as a sheath for the Geschirthesesmittel.
  • the wrappers are in the form of capsules, such as those used in pharmacy for drug delivery, spheres or bags. The latter are preferably welded or glued on at least one side, wherein the adhesive used in particularly preferred embodiments of the invention is an adhesive that is water-soluble.
  • the water-soluble polymer material partially or completely surrounding the automatic dishwashing or dishwashing auxiliary is a water-soluble packaging.
  • This is understood to mean a flat part which partially or completely surrounds the dishwashing detergent.
  • the exact form of such packaging is not critical and can be largely adapted to the conditions of use.
  • processed plastic foils or sheets, capsules and other conceivable forms come into consideration for various forms (such as hoses, cushions, cylinders, bottles, disks or the like).
  • films which, for example, can be glued and / or sealed to packagings such as hoses, cushions or the like, after they have been filled with partial portions of the cleaning agents or with the cleaning agents themselves.
  • plastic film packaging of water-soluble polymer materials are basically known from the prior art.
  • both hollow body of any shape which can be produced by injection molding, bottle blowing, deep drawing, etc., as well as hollow body of films, in particular bags (so-called pouches) as packages for portioned Medium preferred.
  • Preferred automatic dishwashing or machine dishwashing aids are thus characterized in that the water-soluble casing comprises a bag of water-soluble film and / or an injection-molded part and / or a blow-molded part and / or a deep-drawn part.
  • the one or more enclosures are completed. This has the advantage that the Geschirtherapiessch are optimally protected against the effects of the environment, especially against moisture.
  • the invention can be further developed such that the detergents to be used for protecting the content of the enclosure (s) from moisture contain at least one gas, see below.
  • Suitable materials for the completely or partially water-soluble coating are in principle all materials in question, which can completely or partially dissolve in the aqueous phase under the given conditions of a washing process, rinsing or cleaning process (temperature, pH, concentration of detergent components).
  • the polymer materials may particularly preferably the groups (optionally partially acetalized) polyvinyl alcohol, polyvinylpyrrolidone, poly-ethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, in particular modified starches, and mixtures (polymer blends, composites, coextrudates, etc.) of belong to the materials mentioned.
  • Particularly preferred are gelatin and polyvinyl alcohols and the two materials mentioned in each case in combination with starch or modified starch.
  • Preferred automatic dishwashing or machine dishwashing auxiliaries are characterized in that the casing comprises one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof.
  • the coating comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalised) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).
  • PVAL polyvinyl alcohol
  • PVAL polyvinylpyrrolidone
  • Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure in small proportions (about 2%) also structural units of the type contain.
  • polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups.
  • the polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
  • polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
  • Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable.
  • the water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
  • the coatings of polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • the coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 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 materials for the coating, it being preferred that the coating 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 , more preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 .
  • the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant). Particularly suitable polyvinyl alcohols are, for example Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88 and Mowiol ® 8-88.
  • polyvinyl alcohols are ELVANOL ® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK ).
  • the water solubility of PVAL can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • Polyvinyl alcohols which are acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly advantageous and particularly advantageous on account of their pronounced cold water solubility.
  • To use extremely advantageous are the reaction products of PVAL and starch.
  • the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.
  • Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVAL films under the name "SOLUBLON® ®” from Syntana bottlesgesellschaft E. Harke GmbH & Co. available PVAL films. Their solubility in water can be adjusted to the exact degree, and films of this product series are available which are soluble in aqueous phase in all temperature ranges relevant for the application.
  • PVP Polyvinylpyrrolidones
  • PVP are prepared by radical polymerization of 1-vinylpyrrolidone.
  • Commercially available PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.
  • Polyethylene oxides PEOX for short, are polyalkylene glycols of the general formula H- [O-CH 2 -CH 2 ] n -OH the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.
  • Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as the water-soluble shell material is especially in pharmacy in the form of hard or soft gelatin capsules extremely widespread. In the form of films, gelatin has little use because of its high price compared to the polymers mentioned above.
  • dishwashing detergents whose packaging consists of at least in part water-soluble film of at least one polymer from the group of starch and starch derivatives, cellulose and cellulose derivatives, in particular methylcellulose, and mixtures thereof.
  • Starch is a homoglycan, wherein the glucose units are linked ⁇ -glycosidically.
  • Starch is composed of two components of different molecular weight: from about 20 to 30% straight chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW about 300,000 to 2,000,000).
  • small amounts of lipids, phosphoric acid and cations are still included. While the amylose forms long, helical, entangled chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4-position, the chain branched in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like structure with about 1,500 to 12,000 molecules of glucose.
  • starch derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for producing water-soluble coatings of the detergent, detergent and cleaner portions.
  • Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5,000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • Preferred casings of at least partially water-soluble film comprise at least one polymer having a molecular weight between 5,000 and 500,000 g / mol, preferably between 7,500 and 250,000 g / mol and in particular between 10,000 and 100,000 g / mol.
  • the casing has different material thicknesses, preference being given to automatic dishwasher detergents or dishwashing auxiliaries in which the wall thickness of the casing is 10 to 5000 ⁇ m, preferably 20 to 3000 ⁇ m, particularly preferably 25 to 2000 ⁇ m and in particular 100 to 1500 ⁇ m.
  • the water-soluble film forming the coating preferably has a thickness of 1 to 300 ⁇ m, preferably 2 to 200 ⁇ m, more preferably 5 to 150 ⁇ m and in particular 10 to 100 ⁇ m, up.
  • these water-soluble films can be produced by various production methods. Blow molding, calendering and casting processes should be mentioned here in principle.
  • the films are blown starting from a melt with air through a mandrel to a hose.
  • the calendering process which is likewise one of the preferred production processes
  • the raw materials plasticized by suitable additives are atomized to form the films.
  • an aqueous polymer preparation is placed on a heatable drying roller, after the evaporation of the water is optionally cooled and the film is peeled off as a film.
  • this film is additionally powdered before or during the removal.
  • the casing is water-soluble as a whole, ie, when it is used as intended during mechanical cleaning, it completely dissolves when the conditions for release have been reached.
  • gelatin capsules advantageously of soft gelatin, or bags of (optionally partially acetalized) PVAL or balls of gelatin or (optionally partially acetalized) PVAL or of one or more organic and / or inorganic salts, preferably spheres of soft gelatin.
  • the essential advantage of this embodiment is that the sheath within a practically relevant short time - as a non-limiting example can be a few seconds to 5 min - at least partially dissolves under precisely defined conditions in the cleaning liquor and thus according to the requirements, the coated content, ie the cleaning-active material or several materials in the fleet brings.
  • the water-soluble coating comprises regions which are less soluble in water or only soluble in water at elevated temperature and regions which are readily soluble in water or soluble in water at low temperature.
  • the coating does not consist of a uniform material that has the same water solubility in all areas, but of materials of different water solubility.
  • areas of good water solubility are to be distinguished from areas with less good water solubility, with poor or even absent water solubility or areas in which the water solubility reaches the desired value only at a higher temperature or only at a different pH value or only when the electrolyte concentration has changed achieved, on the other hand.
  • an envelope provided with pores or holes is formed, into which water and / or liquor can penetrate, which can dissolve washing-active, rinse-active or cleaning-active ingredients and remove them from the casing.
  • wrapping systems in the form of multi-chamber bags or in the form of nested hollow bodies (eg balls: "onion system") can also be provided.
  • controlled release systems of the detergent-active, rinse-active or cleaning-active ingredients can be produced.
  • wraps can be provided in which a uniform polymeric material comprises small areas of incorporated compounds (for example, salts) which are more rapidly soluble in water than the polymeric material.
  • incorporated compounds for example, salts
  • several polymer materials with different water solubility can be mixed (polymer blend), so that the faster soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the slower soluble.
  • the less readily water-soluble or water-insoluble areas or areas of the enclosure that are water-soluble at higher temperatures are areas of a material that is chemically substantially the same as the water-soluble or water-soluble areas; however, has a higher layer thickness and / or has a modified degree of polymerization of the same polymer and / or has a higher degree of crosslinking the same polymer structure and / or a higher degree of acetalization (in 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
  • the water-soluble shell material is preferably transparent.
  • transparency is meant that the transmittance within the visible spectrum of the 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 the light has a transmittance greater than 20%, it is considered to be transparent.
  • Dishwashing agents packaged in transparent envelopes or containers may contain as an essential ingredient a stabilizer.
  • Stabilizing agents are materials which protect the detergent ingredients in their water-soluble, transparent wraps from decomposition or deactivation by light irradiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
  • antioxidants are the antioxidants.
  • the formulations may contain antioxidants.
  • antioxidants which may be used here are sterically hindered groups, substituted phenols, bisphenols and thiobisphenols. Further examples are propyl gallate, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long chain (C8-C22) esters of gallic acid, such as dodecyl gallate.
  • Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic palmitate, organosulfur compounds, such as the esters of 3,3'-thiodipropionic acid with C 1-18 alkanols, especially C 10-18 alkanols, metal ion deactivators capable of auto-oxidation catalyzing metal ions, such as Copper, such as nitrilotriacetic acid and its derivatives and their mixtures.
  • Antioxidants may be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.
  • UV absorbers can improve the light stability of the formulation ingredients. These are understood to be organic substances (light protection filters) which are able to absorb ultraviolet rays and to release the absorbed energy in the form of longer-wave radiation, for example heat. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position.
  • substituted benzotriazoles such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Ciba ® Fast H), phenyl-substituted in the 3-position 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 urocanic acid suitable.
  • the biphenyl and especially stilbene derivatives which are available commercially as Tinosorb ® FD or Tinosorb ® FR available ex Ciba.
  • 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, for example 3- (4-methylbenzylidene) camphor may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl sal
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
  • Sulfonic acid derivatives of 3-Benzylidencamphers such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.
  • UV-A filter in particular derivatives of benzoylmethane are suitable, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione and enamine compounds.
  • the UV-A and UV-B filters can also be used in mixtures be used.
  • insoluble photoprotective pigments namely finely dispersed, preferably nano-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.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape.
  • the pigments can also be surface-treated, ie hydrophilized or hydrophobized.
  • Typical examples are coated titanium dioxides, for example Titandioxid T 805 (Degussa) or Eusolex ® T2000 (Merck).
  • Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones.
  • micronized zinc oxide is used.
  • UV absorbers may be present in the dishwashing detergents 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.
  • fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and Benzimidazole systems and substituted by heterocycles pyrene derivatives.
  • fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and Benzimidazole systems and substituted by heterocycles pyrene derivatives.
  • Fluorescent substances can be present in the formulations 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% by weight.
  • the abovementioned stabilizers are used in any mixtures.
  • the stabilizers 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 to 5% by weight.
  • preferred automatic dishwashing or machine dishwashing aids comprise at least one washing or cleaning substance from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, electrolytes, pH adjusters, fragrances, perfume carriers, dyes, hydrotropes, Foam inhibitors, antimicrobial agents, germicides, fungicides, corrosion inhibitors, non-aqueous solvents.
  • bleaching agents bleach activators
  • polymers builders, surfactants, enzymes, electrolytes, pH adjusters, fragrances, perfume carriers, dyes, hydrotropes, Foam inhibitors, antimicrobial agents, germicides, fungicides, corrosion inhibitors, non-aqueous solvents.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 yH 2 O are preferred.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • both the monoalkali metal salts and the dialkali metal salts of carbonic acid as well as sesquicarbonates can be contained in the compositions.
  • Preferred alkali metal ions represent sodium and / or potassium ions.
  • Compounds of, for example, carbonate, silicate and optionally other auxiliaries such as, for example, anionic surfactants or other, in particular organic builders, may be present as a separate component in the finished compositions.
  • the alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits on machine parts or limescale deposits on the items to be washed and also contribute to the cleaning performance.
  • Suitable phosphates are the sodium dihydrogen phosphate, NaH 2 PO 4 , the disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , the trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 , the tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , by condensation of NaH 2 PO 4 and KH 2 PO 4 , respectively, form relatively high molecular weight sodium and potassium phosphates, in which cyclic representatives, which can distinguish sodium or potassium metaphosphates and chain types, the sodium and potassium polyphosphates, as well as the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate).
  • sodium phosphate In addition to the sodium phosphate, it is also possible to use the corresponding potassium salts or mixtures of these two; It is also possible to use 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.
  • Preferred automatic dishwashing or machine dishwashing aids do not contain sodium and / or potassium hydroxide.
  • water-soluble builders are, for example, tripotassium citrate and the potassium water glasses.
  • Preferred automatic dishwashing or dishwashing auxiliaries contain from 20 to 60% by weight of one or more water-soluble builders, preferably citrates and / or phosphates, preferably alkali metal phosphates with particular preference of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
  • water-soluble builders preferably citrates and / or phosphates, preferably alkali metal phosphates with particular preference of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
  • the level of water-soluble builders is within narrower limits.
  • the compositions may contain condensed phosphates as water-softening substances. These substances form a group of - because of their production also mentioned melting or annealing phosphates - phosphates, which can be derived from acidic salts of orthophosphoric acid (phosphoric acids) by condensation.
  • the condensed phosphates can be classified into the metaphosphates [Mnn (PO 3 ) n ] and polyphosphates (M 1 n + 2 P n O 3n + 1 or M 1 n H 2 P n O 3n + 1 ).
  • Metaphoaphates are obtained as accompanying substances of Graham's salt - mistakenly referred to as sodium hexametaphosphate - by melting NaH 2 PO 4 to temperatures above 620 ° C., so-called Maddrell's salt also being produced as an intermediate.
  • This and Kurrolsches salt are linear polyphosphates, which are usually not one of the metaphosphates today, but are also used with preference as water-softening substances.
  • the quenched, glassy melt is depending on Reaction conditions, the water-soluble Graham's salt, (NaPO 3 ) 40-50 , or a glassy condensed phosphate of the composition (NaPO 3 ) 15-20 , which is known as Calgon.
  • the misleading term hexametaphosphate is still in use.
  • Kurrol's salt (NaPO 3 ) n with n »5000, is also produced from the 600 ° C hot melt of Maddrell's salt, if this is left for a short time at about 500 ° C. It forms high polymer water-soluble fibers.
  • automatic dishwashing detergents or dishwashing auxiliaries which additionally contain one or more substances from the group of acidifying agents, chelating agents or coating-inhibiting polymers.
  • Acidifying agents are both inorganic acids and organic acids, provided that they are compatible with the other ingredients.
  • the solid mono-, oligo- and polycarboxylic acids are used. Again preferred from this group are citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and also polyacrylic acid.
  • the anhydrides of these acids can be used as Acidisersstoff, in particular maleic anhydride and succinic anhydride are commercially available.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • a commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (and adipic acid at most 33% by weight).
  • Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation over an ion to rings. The number of bound ligands depends on the coordination number of the central ion.
  • Preferred chelated complex images are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and Nitrilotriacetic acid (NTA).
  • Complex-forming polymers ie polymers which carry functional groups either in the main chain itself or in a pendent position, which can act as ligands and generally react with suitable metal atoms to form chelate complexes, can also be used.
  • the polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
  • Complexing groups (ligands) of conventional complexing polymers are iminodiacetic, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and Crown ether residues with z. T. very specific. Activities towards ions of different metals.
  • Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.
  • polycarboxylic acids a) are understood carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5.
  • Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA are preferred.
  • these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts.
  • alkali metal, ammonium or alkylammonium salts, in particular sodium salts are preferred.
  • Scale-inhibiting polymers may also be included in the compositions. These substances, which could be constructed chemically different, for example, from the groups of low molecular weight polyacrylates having molecular weights between 1000 and 20,000 daltons, with polymers having molecular weights below 15,000 daltons are preferred.
  • Scale-inhibiting polymers may also have co-builder properties.
  • organic cobuilders it is possible in particular to use polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates in the dishwasher detergents according to the invention. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning such carboxylic acids which carry more than one acidity function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates are suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • the organic cobuilders used may in particular be polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and also phosphonates. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures thereof.
  • 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 of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and more preferably from 1,200 to 4,000 g / mol, may again be preferred from this group.
  • Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions.
  • the sulfonic acid-containing copolymers will be described in detail below.
  • R 1 (R 2 ) C C (R 3 ) COOH (VII)
  • R 1 to R 3 independently of one another are -H-CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • R s (R 6 ) C C (R 7 ) -X-SO 3 H (VIII)
  • H 2 C CH-X-SO 3 H (VIIIa)
  • H 2 C C (CH 3 ) -X-SO 3 H (VIIIb)
  • HO 3 SX- (R 6 ) C C (R 7 ) -X-SO 3 H (VIIIc)
  • R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2
  • Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds.
  • the content of the polymers used according to the invention to monomers of group iii) is preferably less than 20% by weight, based on the polymer.
  • Particularly preferred polymers to be used consist only of monomers of groups i) and ii).
  • the copolymers used in the compositions may contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives of group i) with all representatives from group ii) and all representatives from group iii) can be combined.
  • Particularly preferred polymers have certain structural units, which are described below.
  • agents characterized by containing one or more copolymers containing structural units of formula IX - [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p- (IX), in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH 2 ) n - with n 0 to 4, for -O- (C 6 H 4 ) -, for -NH-C (CH 3 ) 2 - or -NH-CH (CH 2 CH 3 ) - stands, are preferred.
  • These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. Copolymerizing the sulfonic acid-containing acrylic acid derivative with methacrylic acid, one arrives at another polymer whose use in the agents according to the invention is also preferred and characterized in that the agents contain one or more copolymers, the structural units of the formula X.
  • maleic acid can also be used as a particularly preferred monomer from group i).
  • automatic dishwashing detergents or dishwashing auxiliaries which comprise one or more copolymers as ingredient b), the structural units of the formulas IX and / or X and / or XI and / or XII and / or XIII and / or XIV - [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (IX), - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (X), - [CH 2 -CHCOOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p (XI), - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] P (XII),
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • Corresponding agents which are characterized in that the sulfonic acid groups are partially or fully neutralized in the copolymer, are preferred according to the invention.
  • terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
  • the molecular weight of the polymers used in the agents can be varied to match the properties of the polymers to the desired end use.
  • Preferred automatic dishwashing detergents are characterized in that the copolymers Molar masses of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 have.
  • the content of one or more copolymers in the compositions may vary depending on the application and desired product performance, with preferred automatic dishwashing compositions according to the invention being characterized in that they contain the copolymer (s) in amounts of from 0.25 to 50% by weight. , preferably from 0.5 to 35 wt .-%, particularly preferably from 0.75 to 20 wt .-% and in particular from 1 to 15 wt .-%.
  • both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are used in the compositions.
  • the polyacrylates were described in detail above. Particularly preferred are combinations of the above-described sulfonic acid-containing copolymers with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons.
  • Such polyacrylates are commercially available under the trade name Sokalan ® PA15 and Sokalan ® PA25 (BASF).
  • 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 molecular weight relative to free acids is generally from 2000 to 100,000 g / mol, preferably from 20,000 to 90,000 g / mol and in particular from 30,000 to 80,000 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 compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • copolymers preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives are particularly preferred.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • 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.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the agents to be used may be builders, preferably from the group of silicates, carbonates, organic cobuilders and / or phosphates in amounts of from 0.1 to 99.5% by weight, preferably from 1 to 95% by weight, more preferably from 5 to 90 wt .-% and in particular from 10 to 80 wt .-%, each based on the composition.
  • Preferred cleaners contain one or more surfactants from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • surfactants of the sulfonate type preferably come C 9-13 alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and Disulfonates, as obtained for example from C 12-18 monoolefins having terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical having an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which can be obtained as commercial products of Shell Oil Company under the name DAN ® , are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow 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 surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable Alkypolyglycoside meet the general formula RO (G) z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides which consist of a glucose residue and an n-alkyl chain.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula (XV) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (XVI) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl
  • [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 then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants in detergents and cleaners for automatic dishwashing come as surfactants in general all surfactants in question.
  • the nonionic surfactants described above and, above all, the low-foaming nonionic surfactants are preferred for this purpose.
  • Particularly preferred are the alkoxylated alcohols, especially the ethoxylated and / or propoxylated alcohols.
  • the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols preferably in the context of the present invention, the longer-chain alcohols (C 10 to C 18 , preferably between C 12 and C 16 , such as, for example, C 11 -, C 12 -, C 13 -, C 14 -, C 15 -, C 16 -, C 17 - and C 18 -alcohols).
  • the longer-chain alcohols C 10 to C 18 , preferably between C 12 and C 16 , such as, for example, C 11 -, C 12 -, C 13 -, C 14 -, C 15 -, C 16 -, C 17 - and C 18 -alcohols.
  • a further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Also, if desired, by a final etherification with short-chain alkyl groups, such as preferably the butyl group, the substance class of the "closed" alcohol ethoxylates reach, which can also be used. Very particularly preferred are highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates.
  • Low-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, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • automatic dishwasher detergents which contain surfactants of the general formula XVII as nonionic surfactant (s) in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 and the indices w, x, y, z independently of one another are integers from 1 to 6.
  • surfactants of the general formula XVII as nonionic surfactant (s) in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 and the indices w,
  • the preferred nonionic surfactants of formula XVII 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 XVII may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as they are usually present in oxo alcohol radicals.
  • R 1 in formula XVII is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from - CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are suitable.
  • Preferred automatic dishwashing detergents are characterized in that R 2 and R 3 are each a residue -CH 3 , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.
  • nonionic surfactants which have a C 9-15 -alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
  • the automatic dishwasher detergents according to the invention contain a nonionic surfactant which has a melting point above room temperature.
  • preferred agents are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and most preferably between 26.6 and 43, 3 ° C, included.
  • Suitable nonionic surfactants in addition to the nonionic surfactants contained in the compositions, which have melting or softening points in the temperature range mentioned, are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant resulting from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 moles, more preferably at least 15 moles, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred room temperature solid nonionic surfactant is selected from a straight chain fatty alcohol of 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 -alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
  • C 16-20 alcohol a straight chain fatty alcohol of 16 to 20 carbon atoms
  • C 18 -alcohol preferably a C 18 -alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
  • the so-called “narrow range ethoxylates" are particularly preferred.
  • particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).
  • ethoxylated nonionic surfactant consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).
  • the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • Preferred automatic dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • 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 automatic dishwashing agent contains nonionic surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ], in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • dishwashing agents are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • R 1 and R 2 are linear or branched, saturated
  • Anionic, cationic and / or amphoteric surfactants may also be used in conjunction with the surfactants mentioned, these having only minor importance because of their foaming behavior in dishwasher detergents and usually only in amounts below 10% by weight, in most cases even below 5% by weight .-%, for example, from 0.01 to 2.5 wt .-%, each based on the agent used.
  • the agents may thus contain as surfactant component also anionic, cationic and / or amphoteric surfactants.
  • the automatic dishwashing or machine dishwashing aid s surfactant (s), preferably nonionic (s) surfactant (s), in amounts of 0.5 to 10 wt .-%, preferably from 0.75 to 7.5 wt. % and in particular from 1.0 to 5 wt .-%, each based on the total agent included.
  • surfactant preferably nonionic (s) surfactant (s)
  • s nonionic surfactant
  • Bleaching agents and bleach activators are important ingredients of detergents and cleaners, and a preferred automatic dishwashing or automatic dishwashing aid may contain one or more of the aforementioned groups.
  • sodium percarbonate has particular significance.
  • Further useful bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Sodium percarbonate is a term used in unspecified form for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts of sodium carbonate.
  • the commercial product has the average composition 2 Na 2 CO 3 ⁇ 3 H 2 O 2 and is therefore no peroxycarbonate.
  • Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm -3 , which readily decomposes into sodium carbonate and bleaching or oxidizing oxygen.
  • Dishwashing detergents may also contain bleaches from the group of organic bleaches.
  • Typical organic bleaches that can be used as ingredients in the diacyl peroxides, such as diacyl peroxides. Dibenzoyl.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decy
  • Chlorine or bromine releasing substances can also be used as bleaching agents for automatic dishwashing.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • Advantageous agents contain one or more bleaches, preferably from the group of oxygen or halogen bleaches, especially chlorine bleaches, with particular preference to sodium percarbonate and / or sodium perborate monohydrate, in amounts of from 0.5 to 40% by weight, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent.
  • one or more bleaches preferably from the group of oxygen or halogen bleaches, especially chlorine bleaches, with particular preference to sodium percarbonate and / or sodium perborate monohydrate, in amounts of from 0.5 to 40% by weight, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent.
  • detergents may contain bleach activators.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.
  • TAED tetraacet
  • bleach catalysts can also be incorporated into the detergents.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • compositions which contain one or more substances from the group of bleach activators in particular from the groups of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular n- Nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS) and n-methyl-morpholinium acetonitrile-methyl sulfate (MMA), in amounts of 0.1 to 20 wt .-%, preferably from 0.5 to 15 wt .-% and in particular from 1 to 10 wt .-%, each based on the total agent.
  • TAED tetraacetylethylenediamine
  • NOSI N-nonanoylsuccinimide
  • MMA n-methyl-morpholinium ace
  • the preferred bleach activators further include the "nitrile quats", cationic nitriles of the formula (XVIII), in which R 1 is -H, -CH 3 , a C 2-24 -alkyl or -alkenyl radical, a substituted C 2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -alkyl group and at least one further substituent on the aromatic ring, R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 - OH
  • the general formula (XVIII) includes a variety of cationic nitriles which can be used.
  • the detergent tablets contain cationic nitriles in which R 1 is methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl , n-hexadecyl or n-octadecyl.
  • R 2 and R 3 are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, wherein one or both radicals may advantageously also be a Cyanomethylenrest.
  • radicals R 1 to R 3 are identical, for example (CH 3 ) 3 N (+) CH 2 -CN X - , (CH 3 CH 2 ) 3 N (+) CH 2 -CN X -, (CH 3 CH 2 CH 2) 3 N (+) CH 2 -CN X -, (CH 3 CH (CH 3) 3 N (+) CH 2 -CN X -, or (HO- CH 2 -CH 2 ) 3 N (+) CH 2 -CN X - , wherein X - is preferably an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is.
  • Preferred automatic dishwashing or dishwashing aids are characterized by being the cationic nitrile of the formula (XVIII) in amounts of 0.1 to 20 wt .-%, preferably from 0.25 to 15 wt .-% and in particular from 0.5 to 10 wt .-%, each based on the total weight of the composition.
  • Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.
  • Bacillus subtilis Bacillus subtilis
  • Bacillus licheniformis Bacillus licheniformis
  • Streptomyceus griseus Streptomyceus griseus
  • Coprinus cinereus and Humicola insolens
  • enzymatically-derived variants derived from their genetically modified variants e.g., Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and - glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation.
  • Preferred agents contain enzymes, preferably in the form of liquid and / or solid enzyme preparations, in amounts of from 0.1 to 10% by weight, preferably from 0.5 to 8% by weight and in particular from 1 to 5% by weight, in each case based on the total mean.
  • Dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the dishes, so as not to stain it.
  • Preferred for use in automatic dishwashing or automatic dishwashing aids are all colorants which can be oxidatively destroyed in the cleaning process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.
  • One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020)., That is as a commercial product, for example as Basacid ® Green 970 from BASF, Ludwigshafen available, as well as mixtures thereof with suitable blue dyes.
  • Pigmosol come ® Blue 6900 (CI 74160), Pigmosol ® Green 8730 (CI 74260), Basonyl ® Red 545 FL (CI 45170), Sandolan® ® rhodamine EB400 (CI 45100), Basacid® ® Yellow 094 (CI 47005) Sicovit ® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), pigment Blue 15 (CI 74160), Supranol Blue ® GLW (CAS 12219-32-8, CI Acidblue 221 )), Nylosan Yellow ® N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan ® Blue (CI Acid Blue 182, CAS 12219-26-0) is used.
  • Perfumes are added to the compositions to enhance the aesthetics of the products and provide the consumer with a visually and sensory "typical and distinctive" product in addition to the performance of the product.
  • perfume oils or fragrances individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, Ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, ⁇ -isomethylionone and methyl cedrylketone , the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • fragrance oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • Detergents for machine dishwashing may contain corrosion inhibitors to protect the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate, as well as the manganese complexes [Me-TACN) Mn IV (m-0) 3 Mn IV (Me-TACN)] 2+ (PF 6 - ) 2 , [Me-MeTACN) Mn IV (m-0) 3 Mn IV (Me-MeTACN)] 2+ (PF 6 - ) 2 , [Me-TACN) Mn III (m-0) (m-0Ac) 2 Mn III (Me-TACN)] 2+ (PF 6 - ) 2 and [Me-MeTACN) Mn III (m-O) (m -O) (m
  • Automatic dishwasher detergents or dishwashing auxiliaries which additionally contain at least one silver protectant selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts of from 0.001 to 1% by weight are preferred. , preferably from 0.01 to 0.5 wt .-% and in particular from 0.05 to 0.25 wt .-%, each based on the total agent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Surface Treatment Of Glass (AREA)

Claims (8)

  1. Utilisation d'un composite contenant au moins un sel de zinc et au moins un silicate stratifié cristallin répondant à la formule générale (Ia)

            NaMSixO2x+1. y H2O,

    dans laquelle M représente le sodium ou l'hydrogène, x représente un nombre de 1,9 à 22, de préférence de 1,9 à 4, et y représente un nombre de 0 à 33, caractérisée en ce que le/les sel(s) de zinc et le/les silicate(s) stratifié(s) cristallin(s) répondant à la formule générale (la) sont contenus dans ces agents dans le rapport de 10:1 à 1:50, et le/les sel(s) de zinc contenu(s) et le/les silicate(s) stratifié(s) cristallin(s) contenu(s) sont présents à l'état confectionné avec une ou plusieurs autres substances actives et/ou de soutien, sous forme particulaire, en tant que composite, pour le lavage mécanique de la vaisselle.
  2. Utilisation selon la revendication 1, caractérisée en ce que, en ce qui concerne la/les autres substances actives et/ou de soutien, il s'agit d'un builder, d'un agent tensioactif, d'un agent de blanchiment, d'un activateur du blanchiment, d'une enzyme, d'un colorant, d'une substance odoriférante, d'un agent de protection contre la corrosion ou d'un polymère.
  3. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que, en ce qui concerne la/les autres substances actives et/ou de soutien, il s'agit d'un polycarboxylate polymère, de préférence d'un sel de métal alcalin de l'acide polyacrylique ou de l'acide polyméthacrylique.
  4. Utilisation selon la revendication 3, caractérisée en ce que le polycarboxylate polymère présente une masse moléculaire relative de 500 à 70.000 g/mole.
  5. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que, en ce qui concerne la/les autres substances actives et/ou de soutien, il s'agit d'un polyacrylate, de préférence d'un polyacrylate possédant une masse moléculaire de 1.000 à 20.000 g/mole.
  6. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que, en ce qui concerne la/les autres substances actives et/ou de soutien, il s'agit d'un copolymère d'acides carboxyliques insaturés, de monomères contenant des groupes d'acides sulfoniques et, si nécessaire, d'autres monomères ioniques ou non ionogènes.
  7. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que, en ce qui concerne la/les autres substances actives et/ou de soutien, il s'agit d'un polycarboxylate copolymère de l'acide acrylique avec l'acide méthacrylique, de l'acide acrylique avec l'acide maléique ou de l'acide méthacrylique avec l'acide maléique.
  8. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que, en ce qui concerne la/les autres substances actives et/ou de soutien, il s'agit d'un copolymère d'acide acrylique avec de l'acide méthacrylique, le copolymère contenant l'acide acrylique à concurrence de 50 à 90 % en poids et l'acide maléique à concurrence de 50 à 10 % en poids.
EP05027033A 2002-06-06 2003-05-28 Composé comprenant un sel de zinc et silicate cristallin à structure en couches Expired - Lifetime EP1657295B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10225116A DE10225116A1 (de) 2002-06-06 2002-06-06 Maschinelles Geschirrspülmittel mit verbessertem Glaskorrosionsschutz II
EP03735481.8A EP1509589B1 (fr) 2002-06-06 2003-05-28 Produits de lavage pour lave-vaisselle mecanique garantissant une protection amelioree contre la corrosion du verre

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EP03735481.8A Division EP1509589B1 (fr) 2002-06-06 2003-05-28 Produits de lavage pour lave-vaisselle mecanique garantissant une protection amelioree contre la corrosion du verre
EP03735481.8A Division-Into EP1509589B1 (fr) 2002-06-06 2003-05-28 Produits de lavage pour lave-vaisselle mecanique garantissant une protection amelioree contre la corrosion du verre

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EP1657295A1 EP1657295A1 (fr) 2006-05-17
EP1657295B1 true EP1657295B1 (fr) 2007-12-19

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EP03735481.8A Expired - Lifetime EP1509589B1 (fr) 2002-06-06 2003-05-28 Produits de lavage pour lave-vaisselle mecanique garantissant une protection amelioree contre la corrosion du verre
EP05027033A Expired - Lifetime EP1657295B1 (fr) 2002-06-06 2003-05-28 Composé comprenant un sel de zinc et silicate cristallin à structure en couches

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EP (2) EP1509589B1 (fr)
JP (1) JP2005534728A (fr)
AT (1) ATE381608T1 (fr)
AU (1) AU2003237704A1 (fr)
DE (2) DE10225116A1 (fr)
ES (2) ES2298919T3 (fr)
WO (1) WO2003104370A1 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10334047A1 (de) 2003-07-25 2005-02-24 Clariant Gmbh Adsorbat aus Schichtsilicat und seine Verwendung
US7241726B2 (en) 2003-10-16 2007-07-10 The Procter & Gamble Company Complete-cycle methods for protecting glassware from surface corrosion in automatic dishwashing appliances
US7271138B2 (en) 2003-10-16 2007-09-18 The Procter & Gamble Company Compositions for protecting glassware from surface corrosion in automatic dishwashing appliances
US7094740B2 (en) * 2003-10-16 2006-08-22 The Procter & Gamble Company Zinc corrosion protection agents for treating glassware surfaces
US20050119154A1 (en) * 2003-10-16 2005-06-02 The Procter & Gamble Company Methods for protecting glassware from surface corrosion in automatic dishwashing appliances
US7101833B2 (en) 2004-10-12 2006-09-05 The Procter & Gamble Company Methods for treating glassware surfaces using zinc corrosion protection agents
DE102005025332A1 (de) * 2005-05-31 2006-12-07 Henkel Kgaa Tensidcompound
DE102008017796A1 (de) * 2008-04-08 2009-10-15 Süd-Chemie AG Schichtsilicathaltige Geruchsadsorber auf der Basis von Zinkricinoleaten und verwandten Verbindungen
DE102008020275A1 (de) 2008-04-22 2009-10-29 Henkel Ag & Co. Kgaa Zinkhaltiger Wasch- oder Reinigungsmittelformkörper
DE102008020274A1 (de) 2008-04-22 2009-10-29 Henkel Ag & Co. Kgaa Verfahren zur Herstellung zinkhaltiger Wasch-oder Reinigungsmittelformkörper
EP2216393B1 (fr) * 2009-02-09 2024-04-24 The Procter & Gamble Company Composition de détergent
DE102011077865A1 (de) * 2011-06-21 2012-12-27 Henkel Ag & Co. Kgaa Geschirrspülmittel mit verbessertem Dekor-Schutz
MX2014002014A (es) 2011-10-19 2014-03-27 Basf Se Formulaciones, uso de las mismas como o para producir detergentes para lavado de vajillas y produccion de las mismas.
EP2981600B1 (fr) 2013-04-02 2018-03-21 Basf Se Formules, leur utilisation comme détergent pour lave-vaisselle et leur fabrication
JP5801941B1 (ja) * 2014-11-21 2015-10-28 株式会社ニイタカ 洗浄剤組成物、食器洗浄方法、液体洗浄剤組成物用キット及びカートリッジ洗浄剤

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3255117A (en) * 1963-10-08 1966-06-07 Fmc Corp Low-foaming dishwashing composition
DE2539531A1 (de) * 1975-09-05 1977-03-17 Henkel & Cie Gmbh Mittel zum maschinellen spuelen von geschirr
US4670617A (en) * 1985-12-30 1987-06-02 Amoco Corporation Propylation of toluene with a high surface area, zinc-modified, crystalline silica molecular sieve
US4933101A (en) * 1989-02-13 1990-06-12 The Procter & Gamble Company Liquid automatic dishwashing compositions compounds providing glassware protection
US4917812A (en) * 1989-02-13 1990-04-17 The Procter & Gamble Company Granular automatic dishwasher detergent composition providing glassware protection containing insoluble zinc compound
US6391839B1 (en) * 1992-08-01 2002-05-21 The Procter & Gamble Company Detergent bleach compositions containing layered silicate builder and percarbonate stabilized by EDDS
DE4437486A1 (de) * 1994-10-20 1996-04-25 Henkel Kgaa Kristalline Schichtsilikate in maschinellen Geschirrspülmitteln
DE69603226T2 (de) * 1995-05-25 2000-02-03 Mizusawa Industrial Chemicals, Ltd. Jodkomplex und dessen Verwendung
DE19819187A1 (de) * 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
DE19943470A1 (de) * 1999-09-11 2001-03-15 Clariant Gmbh Kristallines Alkalischichtsilikat
DE10039100A1 (de) * 2000-08-07 2002-02-28 Henkel Kgaa Desodorierendes Textilbehandlungsmittel
DE10140535B4 (de) * 2001-08-17 2006-05-04 Henkel Kgaa Maschinelles Geschirrspülmittel mit verbessertem Glaskorrosionsschutz
WO2003016444A2 (fr) * 2001-08-17 2003-02-27 Henkel Kommanditgesellschaft Auf Aktien Produits de lavage pour lave-vaisselle garantissant une protection amelioree contre la corrosion du verre

Also Published As

Publication number Publication date
EP1509589A1 (fr) 2005-03-02
WO2003104370A1 (fr) 2003-12-18
ES2298919T3 (es) 2008-05-16
EP1657295A1 (fr) 2006-05-17
ES2527542T3 (es) 2015-01-26
DE50308871D1 (de) 2008-01-31
ATE381608T1 (de) 2008-01-15
JP2005534728A (ja) 2005-11-17
EP1509589B1 (fr) 2014-10-22
DE10225116A1 (de) 2003-12-24
AU2003237704A1 (en) 2003-12-22

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