EP1044256A1 - Verfahren zur herstellung eines geschirrspülmittelformkörpers - Google Patents

Verfahren zur herstellung eines geschirrspülmittelformkörpers

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Publication number
EP1044256A1
EP1044256A1 EP98965858A EP98965858A EP1044256A1 EP 1044256 A1 EP1044256 A1 EP 1044256A1 EP 98965858 A EP98965858 A EP 98965858A EP 98965858 A EP98965858 A EP 98965858A EP 1044256 A1 EP1044256 A1 EP 1044256A1
Authority
EP
European Patent Office
Prior art keywords
particularly preferably
complexes
cobalt
weight
ingredient
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.)
Ceased
Application number
EP98965858A
Other languages
German (de)
English (en)
French (fr)
Inventor
Rudolf Piel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1044256A1 publication Critical patent/EP1044256A1/de
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • C11D17/0091Dishwashing tablets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • C11D17/0078Multilayered tablets

Definitions

  • the invention relates to washing or cleaning-active tablets, primarily tablets such as dishwasher tablets, detergent tablets, bleach tablets, stain remover tablets or water softening tablets for household use, in particular for mechanical use, and a process for producing these tablets and their use.
  • Shaped or active cleaning moldings in particular tablets, have a number of advantages over powdered agents, such as advantageous handling, simple dosing and low packaging volume requirements.
  • the application relates to a process in which a shaped body is produced which contains a defined ingredient (I) in a defined area, the shaped body consisting of at least two primary shaped bodies which are pre-pressed on a conventional tablet press, mechanically fed to one another and then to be compressed into a common tablet.
  • the shaped articles are pretreated by suitable cutouts in such a way that a homogeneous surface without edges is produced after the final pressing of the entire shaped article under conventional pressure.
  • the one primary molding is like a negative impression of the other (or further) primary molding (s).
  • the ingredient (I) can be a bleaching agent from the group of chlorine and / or oxygen bleaching agents, a bleach activator, a silver protection agent and / or a soil release compound, an enzyme, a surfactant or a component or a compound for dissolving be security check.
  • the ingredient (I) can also be a mixture of these ingredients.
  • the ingredient (I) is a mixture of a component or a compound for solubility control and at least one further ingredient from the group consisting of bleach and / or bleach activator and / or silver protective agent and / or soil release compound and / or enzyme and / or a surfactant.
  • the volume of the area with the ingredient (I), the solubility, the surface and the type of compression can also have a decisive influence on the properties of the tablet.
  • the range does not exceed 40% by volume, preferably between 1 and 30% by volume, particularly preferably between 2 and 25% by volume, very particularly preferably between 3 and 20% by volume of the shaped body contains more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, very particularly preferably the total amount of an ingredient (I) present .
  • the shaped body according to the invention also has a positive effect if the region with more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, very particularly preferably the total amount of an ingredient present ( I) is surrounded by other ingredients of the molded body in exactly three spatial directions.
  • a desirable influence on the overall result can also be achieved if the range with more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, very particularly preferably the total amount of an ingredient present (I) dissolves faster than the and / or the remaining areas of the shaped body by more than 5%, preferably more than 10%, very particularly preferably more than 25%, very particularly preferably more than 50% and extremely preferably more than 100% .
  • the area with the ingredient (I) does not cover more than 40% of the surface, preferably between 5 and 30%, particularly preferably between 10 and 25%, very particularly preferably between 15 and 20% by volume. of the molded body and contains more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, very particularly preferably the total amount of an ingredient (I) present.
  • the solubility can be influenced by components and / or compounds to accelerate solubility (disintegrant) or to delay solubility.
  • disintegrants known in the prior art can be used as disintegrants. Particular reference is made to the textbooks Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology” (6th edition, 1987). Substances such as starch, cellulose and cellulose derivatives, alginates, dextrans, cross-linked polyvinylpyrrolidones and others are particularly suitable; systems made from weak acids and carbonate-containing agents, especially citric acid and Tartaric acid in combination with bicarbonate or carbonate as well as polyethylene glycol sorbitan fatty acid ester.
  • German patent application DE 938 566 it is proposed to convert acetylsalicylic acid into granular form before pressing, to dry it gently but completely and then to coat it with highly disperse silica.
  • the acetylsalicylic acid granules powdered with finely divided silica can then be mixed with further tablet ingredients, which may be in powder or granular form, and compressed into tablets.
  • the separating layer of highly disperse silica not only acts as an insulating layer and protection against unwanted reactions, but also contributes to the rapid disintegration of the tablets even after a long storage period.
  • German patent application DE 12 28 029 describes the production of tablets, powder mixtures without prior granulation being first mixed with cellulose powder and optionally highly disperse silica, ground according to a preferred embodiment and then pressed.
  • German patent application DE 41 21 127 in turn shows that a particularly good auxiliary in the manufacture of pharmaceutical tablets has cellulose particles on the surface of which a laminating agent is fixed.
  • the excipient is used in the finest possible form; mean particle sizes below 200 ⁇ m are shown to be particularly advantageous.
  • the classic tablet disintegrants of the first mentioned substance class are mixed in very fine-particle form either before pressing with the other tablet ingredients, which can be in fine or granular form, or the other tablet ingredients are coated or powdered with the tablet disintegrant.
  • disintegrants which are known from the manufacture of pharmaceuticals can also be used.
  • Swelling layer silicates such as bentonites, natural substances and natural substance derivatives on starch and cellulose are mentioned as disintegrants.
  • These disintegrants can be mixed with the granules to be compressed, but can also be incorporated into the granules to be compressed.
  • EP-A-0 466485, EP-A-0 522 766, EP-A-0 711 827, EP-A-0 711 828 and EP-A-0 716 144 describe the production of cleaning-active tablets, using compact, particulate material with a particle size between 180 and 2000 ⁇ m.
  • the resulting tablets can have both a homogeneous and a heterogeneous structure.
  • EP-A-0 522 766 at least the particles which contain surfactants and builders are coated with a solution or dispersion of a binder / disintegrant, in particular polyethylene glycol.
  • binders / disintegrants are, in turn, the disintegrants which have already been described several times and are known, for example starches and starch derivatives, commercially available cellulose derivatives such as crosslinked and modified cellulose, microcrystalline cellulose fibers, crosslinked polyvinylpyrrolidones, layered silicates, etc.
  • weak acids such as citric acid or tartaric acid, which, in connection with carbonate-containing sources, lead to bubbling effects when they come into contact with water and which, according to Römpp's definition, belong to the second class of disintegrants, can be used as a coating material.
  • disintegrants whose particle size distribution (sieve analysis) is designed in such a way that there is a maximum of 1% by weight, preferably less, of dust components and a total of (including any dust components present) less than 10 %
  • By weight of the disintegrant granules are smaller than 0.2 mm.
  • At least 90% by weight of the disintegrant granules advantageously have a particle size of at least 0.2 mm and a maximum of 3 mm.
  • These disintegrants are particularly suitable for the present invention.
  • Agents from the group of organic acids such as. B. citric acid, or a mixture of citric acid / bicarbonate and / or the celluloses and cellulose derivatives.
  • the dissolution time of the entire molded body is preferably shorter than the duration of the main wash cycle of a conventional dishwasher, i.e. shorter than 40 min, particularly preferably shorter than 30 min, very particularly preferably shorter than 20 min and extremely preferably shorter than 10 min.
  • Paraffins and / or microwaxes and / or the high molecular weight polyethylene glycols which are described in detail in the prior art, are generally used as the material for delaying dissolution.
  • the use of mixtures as mentioned in the unpublished publication DE 197 27 073 and the disclosure of which is hereby expressly incorporated into this document is particularly suitable for the present application.
  • the dissolution time of the entire molded body in 20 ° C. cold water is longer than the pre-rinse cycle of a commercially available dishwasher, that is to say longer than 5 min, preferably longer than 10 min.
  • homogeneous or heterogeneous moldings of known design are provided.
  • These include in particular cylindrical tablets, these tablets preferably having a diameter of 15 to 60 mm, in particular 30 +/- 10 mm.
  • the height of these tablets is preferably 5 to 30 mm and in particular 15 to 28 mm.
  • the edge lengths are preferably between 15 to 60 mm, in particular 30 +/- 10 mm.
  • the weight of the individual tablets, in particular the tablets, is preferably 15 to 60 g and in particular 20 to 40 g per tablet or tablet; the consistency of the shaped bodies or tablets, on the other hand, usually has values above 1 kg / dm 3 , preferably from 1.1 to 1.4 kg / dm 3 .
  • the water hardness range or the level of contamination 1 or more, for example 2 to 4, moldings, in particular tablets, can be used.
  • Further shaped bodies according to the invention can also have smaller diameters or dimensions, for example around 10 mm.
  • a homogeneous shaped body is understood to mean those in which the ingredients of the shaped body are homogeneously distributed except for the area with ingredient (I) in such a way that no different ingredients and / or active ingredients are perceptible to the naked eye.
  • the grain structure of the solids used can of course still be recognized.
  • a further area (phase) is present,
  • heterogeneous shaped bodies are understood to mean those which do not have a homogeneous distribution of the ingredients present in addition to the ingredient (I).
  • heterogeneous moldings can be produced, for example, by the different ingredients having different colors and / or carrying a different fragrance component.
  • Another case, which according to the invention is to be counted as the non-uniform (heterogeneous) shaped bodies comprises an embodiment in which a shaped body is pressed which, in addition to the area with the ingredient (I), has several layers (phases), that is to say at least two layers. It is e.g. B. possible that these different layers have different disintegration and dissolution rates and / or carry different ingredients. This can result in advantageous performance properties of the molded articles. If, for example, ingredients are contained in the moldings that have a mutually negative effect, it is possible to se separate.
  • a defined sequence of cleaning conditions is to be created in a machine, it is possible to integrate one (or more) component (s) in a (or) the more rapidly disintegrating and / or more quickly soluble layer and the other (n) component Incorporate into one or more slowly disintegrating layers so that one component can act with a lead time or has already reacted if another component goes into solution.
  • a preferred embodiment of the invention consists in that in addition to the area with the ingredient (I) there are two further phases. It is particularly advantageous if the volume ratios of the two further phases are between 10: 1 and 1:10, preferably between 5: 1 and 1: 5, particularly preferably between 2: 1 and 1: 2.
  • Another particularly preferred embodiment is characterized in that three or more further phases are present.
  • the layer structure of the shaped bodies can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the shaped body when the outer layers have not yet been completely detached or disintegrated; however, a complete and / or partial covering of the inner layer (s) can also be achieved by the layers lying further outwards, which leads to a prevention and / or delay in the early dissolution of components of the inner layer (s).
  • a tablet consists of at least three layers, that is to say two outer and at least one inner layer, at least one peroxy bleaching agent being contained in at least one of the inner layers, while in the case of the tablet in the form of a tablet, the two outer layers and in the case of the envelope However, the outermost layers of the tablet are free of peroxy bleach. It is also possible to spatially separate peroxy bleaching agents and any bleach activators or bleach catalysts and / or enzymes present in a tablet / molded article. Such configurations have the advantage that no undesirable interactions would be feared in the molded articles according to the invention.
  • Another cheap and preferred embodiment of the invention is that one of the bleaching component or components, especially the chlorine component, is not assembled together with the perfume component in one phase.
  • Another cheap and preferred embodiment of the invention is that the silver protection compo- is not made up with any of the bleaching components.
  • Another cheap and preferred embodiment of the invention is that one of the component or components for solubility control is packaged together with the bleach activator.
  • Another cheap and preferred embodiment of the invention is that one of the component or components for solubility control is packaged together with the enzymes.
  • Another cheap and preferred embodiment of the invention is that one of the component or components for solubility control is packaged together with the bleach.
  • Another cheap and preferred embodiment of the invention is that one of the component or components for solubility control is assembled together with the silver protection component.
  • Another cheap and preferred embodiment of the invention is that one of the component or components for solubility control together with at least 50 wt .-%, preferably more than 70 wt .-%, particularly more than 90 wt .-% of a surfactant or the total surfactant mixture is assembled.
  • agents according to the invention can also be produced by other methods.
  • the ingredient (s) in the form of a liquid generally through solution and / or melt
  • a viscosity of more than 1500 mPas preferably more than 2000 mPas, particularly preferably between 2000 and 15000 mPas, very particularly preferably between 2500 and 7000 mPas and extremely preferably between 3000 and 4000 mPas has proven particularly useful.
  • meltable carrier substances have proven particularly effective. In principle, this includes all substances with a solidification point at or especially above room temperature.
  • Non-ionic surfactants (Dehypon® LT 104, Dehypon® LS 54, Dehydol® LS 30, Lutensol® AT 80), polyethylene glycols with different molecular weights (PEG 400, 12000), soaps (Lo- rol® C 16), stearate (Cutina® GMS), but also thickened sodium hydroxide and meltable Salts such as sodium carbonate decahydrate.
  • the advantages and disadvantages of the individual ingredients can be understood by the expert on the basis of tests.
  • parts of the shaped body and / or components of the shaped body are treated by irradiation with microwaves in order to positively influence strength, moisture content and solubility.
  • Special ingredients (I) which are used in the context of the invention are oxygen bleaching agents, preferably the alkali metal perborates and their hydrates and the alkali metal percarbonates, sodium perborate, as mono- or tetrahydrate, or sodium percarbonate and their hydrates preferably being used in the context of the invention.
  • the persulphates can also be used.
  • Typical oxygen bleaches are also organic peracids.
  • the organic peracids used with preference include above all the excellently active phthalimidoperoxycaproic acid, but in principle all other known peracids can also be used.
  • bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1, 5-diacetyl-2,2-dioxo-hexahydro-1, 3,5-triazine DADHT and isatoic anhydride ISA.
  • N- or O-acyl groups such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD
  • aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used as bleach activators.
  • Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • 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 acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran, n-methyl-morpholin
  • hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16770 and international patent application WO 95/14075 are also preferably used.
  • the combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
  • the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleaching catalysts.
  • the transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267, which consist of the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium described in German patent application DE 196 05 688 -, vanadium and Copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 196 20411, the manganese, copper and cobalt complexes described in German patent application DE 4416 438, the cobalt complexes described in European patent application EP 0 272 030, the manganese complexes known from European patent application EP
  • bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775.
  • Bleach activators from the group of multi-acylated alkylenediamines in particular tetraacetylethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (NOBS) or isobenzene sulfonate (N-) iso , MMA, preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, based on the total Means used.
  • TAED tetraacetylethylene diamine
  • NOSI N-nonanoylsuccinimide
  • Bleach-boosting transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular 0.0025% by weight. % to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, in each case based on the total composition. But in special cases, more bleach activator can be used.
  • Dishwashing detergents according to the invention can contain corrosion inhibitors as ingredient (I) to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the field of automatic dishwashing.
  • silver protection agents in particular can be selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
  • detergent formulations often contain agents containing active chlorine, which can significantly reduce the corrosion of the silver surface.
  • agents containing active chlorine which can significantly reduce the corrosion of the silver surface.
  • oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds.
  • Salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used.
  • transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • Zinc compounds can also be used to prevent corrosion on the wash ware.
  • Special ingredients (I) which are used in the context of the invention are substances which prevent the re-soiling of surfaces and / or facilitate the detachment of dirt after a single application (so-called “soil release compounds”).
  • the soil release compounds used according to the invention include all compounds known in the prior art.
  • Cationic polymers such as those used for. B. are known from the following publications:
  • EP-A-0 167 382 EP-A-0 342 997 and DE-OS-26 16 404 cleaning agents are added cationic polymers in order to achieve a streak-free cleaning of the surfaces.
  • EP-A-0 167 382 describes liquid detergent compositions which can contain cationic polymers as thickeners. Hydroxypropyltrimethylammonium guar; Copolymers of aminoethyl methacrylate and acrylamide and copolymers of dimethyldiallylammonium chloride and acrylamide are described.
  • EP-A-0 342 997 describes general-purpose cleaners which can contain cationic polymers, in particular polymers with imino groups being used.
  • DE-OS-26 16 404 describes cleaning agents for glass which contain cationic cellulose derivatives. The addition of the cationic cellulose derivatives in the agents a better drainage of the water in order to obtain streak-free cleaned glass.
  • EP-A-0 467 472 e.g. B. cleaning agents for hard surfaces which contain cationic homo- and / or copolymers as soil-release polymers. These polymers have quaternized ammonium alkyl methacrylate groups as monomer units. These connections are used to equip the surfaces in such a way that the dirt can be removed more easily during the next cleaning process.
  • the cationic polymers are particularly preferably selected from cationic polymers of copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or acrylamide; Dialkyldiallyldiammonium salts; polymer-analogous reaction products of ethers or esters of polysaccharides with ammonium side groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternary ethylene imine polymers and polyesters and polyamides with quaternary side groups as soil release compounds.
  • monomers such as trialkylammonium alkyl (meth) acrylate or acrylamide; Dialkyldiallyldiammonium salts; polymer-analogous reaction products of ethers or esters of polysaccharides with ammonium side groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternary
  • Natural polyuronic acids and related substances as well as polyampholytes and hydrophobicized polyampholytes, or mixtures of these substances, are also exceptionally preferred in the context of this application.
  • enzymes between 0 and 5% by weight of enzymes, based on the entire preparation, can be added to the cleaning agent in order to increase the performance of the cleaning agents or to guarantee the same quality of cleaning performance under milder conditions.
  • the most commonly used enzymes include lipases, amylases, cellulases and proteases.
  • Preferred proteases are e.g. B. BLAP®140 from Biozym, Optimase®-M-440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo.
  • cellulases and lipases are Celluzym® 0.7 T and Lipolase® 30 T from Novo Nordisk.
  • Duramyl® and Termamyl® 60 T and Termamyl® 90 T from Novo Duramyl® and Termamyl® 60 T and Termamyl® 90 T from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades find particular use as amylases.
  • Other enzymes can also be used.
  • ingredients (I) described above can also take on the function of other ingredients if the condition of the inventive area is met by other ingredients.
  • water-soluble and water-insoluble builders can be used especially for binding calcium and magnesium.
  • Water-soluble builders are preferred because they generally have less tendency to form insoluble residues on dishes and hard surfaces.
  • Customary builders which can be present in the scope of the invention between 10 and 90% by weight, based on the entire preparation, are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and silicates.
  • Water-insoluble builders include the zeolites, which can also be used, as well as mixtures of the abovementioned builder substances.
  • Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicate and / or metasilicate are preferably used.
  • Alkali carriers can be present as further constituents.
  • Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the abovementioned substances are considered to be alkali carriers, alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate being preferred for the purposes of this invention.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.
  • all surfactants can be used as surfactants.
  • the alkoxylated alcohols, particularly the ethoxylated and / or propoxylated ones, the alkyl polyglycosides and the alkyl polyglucamides are particularly preferred.
  • alkoxylated alcohols to mean 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 , e.g. B. Cn-, C 12 -, C 13 -, C 14 -, C 15 -, C 16 -, C 17 - and C 18 -alcohols).
  • n moles of ethylene oxide and one mole of alcohol form a complex mixture of addition products of different degrees of ethoxylation, depending on the reaction conditions.
  • a further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • final etherification with short-chain alkyl groups such as preferably the butyl group, can also give the substance class of the “closed” alcohol ethoxylates, which can also be used for the purposes of the invention.
  • Highly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.
  • Alkyl polyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols using the relevant methods of preparative organic chemistry, with a mixture of monoalkylated, oligomeric or polymeric sugars depending on the type of preparation.
  • Preferred alkyl polyglycosides can be alkyl polyglucosides, the alcohol being particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols and the degree of oligomerization of the sugars being between 1 and 10.
  • Fatty acid polyhydroxylamides are acylated reaction products of the reductive amination of a sugar (glucose) with ammonia, whereby long-chain fatty acids, long-chain fatty acid esters or long-chain fatty acid chlorides are generally used as acylating agents.
  • Secondary amides are formed when reducing with methylamine or ethylamine instead of with ammonia, such as. B. in S ⁇ FW-Journal, 119, (1993), 794-808.
  • Carbon chain lengths of C 6 to C 12 in the fatty acid residue are preferably used.
  • the areas of the molded body can be colored. It is particularly preferred if one or more or all areas of the shaped body are colored differently in the shaped body. In one special embodiment of the molded body, the color is red. In another special embodiment of the molded body, the color is green. In another special embodiment of the shaped body, the color is yellow. In another special embodiment of the shaped body, the color is a mixture of different colors.
  • the storage stability of the shaped body is particularly important. It is particularly preferred according to the invention if the weight increase in the area contributes to the ingredient (I) Storage under normal household conditions, ie between 15 and 30 ° C. and between 5 and 55% atmospheric humidity, preferably 15 and 35% atmospheric humidity for a period of 30 days, preferably 60 days, particularly preferably 90 days, not more than 50% by weight, preferably not more than 40% by weight, very particularly preferably not more than 30% by weight, extremely preferably not more than 20% by weight and extremely preferably not more than 10% by weight, at best not more than 5% by weight. -%.
  • the loss of active substance of the ingredient (I) during storage under normal household conditions i. H. between 15 and 30 ° C. and between 5 and 55% atmospheric humidity, preferably 15 and 35% atmospheric humidity for a period of 30 days, preferably 60 days, particularly preferably 90 days, not more than 50% by weight, preferably not more than 40% %, very particularly preferably not more than 30% by weight, extremely preferably not more than 20% by weight and extremely preferably not more than 10% by weight, at best not more than 5% by weight.
  • the absorption maximum of a 1% solution of a colored area or a colored component during storage under normal household conditions ie between 15 and 30 ° C. and between 5 and 55% atmospheric humidity, preferably 15 and 35% atmospheric humidity for the duration of 30 days, preferably 60 days, particularly preferably 90 days not more than 100 wave numbers, preferably not more than 50 wave numbers, very particularly preferably not more than 30 wave numbers, extremely preferably not more than 20 wave numbers and extremely preferably not more than 10
  • wave numbers are not more than 5 wave numbers.
  • the builder system of the framework recipe above can also be composed as follows (all other ingredients are the same as in a).
  • test formulation (V) was used:
  • test formulation (V) was used:
  • each formulation can also be the constituents of a single phase, i.e. the proportions then do not relate to the overall formulation as usual, but to the composition of the individual phase.
  • each of the recipes can also contain other ingredients that are common in MGSM (e.g. fillers, preservatives, etc.) in extremely small quantities, with the other ingredients being proportionately varied accordingly.
  • MGSM e.g. fillers, preservatives, etc.
  • a preferred embodiment of the shaped body of the first claim contains a depression in a tablet, this depression containing the ingredient (I).
  • the production takes place in such a way that an indentation is embossed into a shaped body and this indentation is filled.
  • the embossing can be done on a rotary press from Korsch. In the present case, a tablet press from Fette was used.
  • a round tablet shape (26 X 36 mm) was selected and embossed on one side with a stamp 5 mm deep, the base area being chosen such that a volume of 1 ml could be filled in and the tablet subsequently had a smooth surface.
  • the ingredient (I) according to the invention was previously reduced in the amount in the corresponding recipe, which surrounds the filled area, and in the existing examples and studies in the surrounding areas are omitted.
  • the special properties of the agents according to the invention were compared with known agents using the example of storage stability.
  • the special properties of the agents according to the invention were compared with known agents using the example of tea cleaning.
  • the special properties of the agents according to the invention were tested in comparison to known agents using the example of cleaning enzyme-relevant soiling.
  • the special properties of the agents according to the invention were checked by technically untrained persons under practice-relevant conditions in comparison to homogeneous tablets. Apart from instructions for the dosage and general safety instructions, no influence was taken on the handling of the agents by the group of people in standard dishwashers. This comparison test turned out to be particularly good. The cleaning results were rated as particularly favorable here.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP98965858A 1997-12-30 1998-12-21 Verfahren zur herstellung eines geschirrspülmittelformkörpers Ceased EP1044256A1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19758177 1997-12-30
DE19758177A DE19758177A1 (de) 1997-12-30 1997-12-30 Verfahren zur Herstellung eines Geschirrspülmittelformkörpers
PCT/EP1998/008365 WO1999035233A1 (de) 1997-12-30 1998-12-21 Verfahren zur herstellung eines geschirrspülmittelformkörpers
CA002298842A CA2298842A1 (en) 1997-12-30 2000-03-02 A process for the production of a dishwasher detergent shaped body

Publications (1)

Publication Number Publication Date
EP1044256A1 true EP1044256A1 (de) 2000-10-18

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Application Number Title Priority Date Filing Date
EP98965858A Ceased EP1044256A1 (de) 1997-12-30 1998-12-21 Verfahren zur herstellung eines geschirrspülmittelformkörpers

Country Status (10)

Country Link
EP (1) EP1044256A1 (zh)
JP (1) JP2002500269A (zh)
CN (1) CN1283221A (zh)
CA (1) CA2298842A1 (zh)
CZ (1) CZ20002494A3 (zh)
DE (1) DE19758177A1 (zh)
HU (1) HUP0101376A2 (zh)
PL (1) PL341436A1 (zh)
SK (1) SK10022000A3 (zh)
WO (1) WO1999035233A1 (zh)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE29911486U1 (de) * 1998-07-17 1999-11-18 The Procter & Gamble Co., Cincinnati, Ohio Reinigungsmitteltablette
DE29911484U1 (de) * 1998-07-17 2000-02-24 The Procter & Gamble Co., Cincinnati, Ohio Reinigungsmitteltablette
DE19838127A1 (de) * 1998-08-21 2000-02-24 Henkel Kgaa Reinigungsmittelformkörper
GB9911949D0 (en) 1999-05-21 1999-07-21 Unilever Plc Detergent compositions
DE29911485U1 (de) * 1999-07-01 1999-11-25 The Procter & Gamble Co., Cincinnati, Ohio Reinigungsmitteltablette
DE29911487U1 (de) * 1999-07-01 1999-11-25 The Procter & Gamble Co., Cincinnati, Ohio Reinigungsmitteltablette
DE19937428A1 (de) * 1999-08-07 2001-02-08 Henkel Kgaa Reinigungs- und Waschmittelformkörper
DE60001795T2 (de) * 1999-12-17 2003-10-23 Unilever N.V., Rotterdam Verwendung von Geschirrspülmitteln
AU2002239349A1 (en) 2000-11-27 2002-06-03 The Procter & Gamble Company Detergent products, methods and manufacture
EP1491622B1 (en) * 2003-06-24 2005-12-21 Unilever N.V. Detergent compositions
GB0718944D0 (en) * 2007-09-28 2007-11-07 Reckitt Benckiser Nv Detergent composition
CN105996935B (zh) * 2016-05-24 2019-06-18 佛山市顺德区美的洗涤电器制造有限公司 洗碗机的洗碗方法和用于洗碗机的洗涤剂
CN109897744A (zh) * 2019-03-22 2019-06-18 东莞市宏裕生物科技有限公司 一种生物酶清洁颗粒及其制作工艺
CN110184129B (zh) * 2019-06-24 2021-01-15 广东水卫仕生物科技有限公司 洗涤剂组合物及其制备方法和应用
CN111117794A (zh) * 2019-12-30 2020-05-08 杨粞淋 一种洗碗机复合洗涤剂的制备工艺

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* Cited by examiner, † Cited by third party
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DE3541146A1 (de) * 1985-11-21 1987-05-27 Henkel Kgaa Mehrschichtige reinigungsmitteltabletten fuer das maschinelle geschirrspuelen
US5133892A (en) * 1990-10-17 1992-07-28 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing detergent tablets
ATE198349T1 (de) * 1995-07-13 2001-01-15 Benckiser Nv Geschirrwaschmaschinenspülmittel in form einer tablette

Non-Patent Citations (1)

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Title
See references of WO9935233A1 *

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HUP0101376A2 (hu) 2001-08-28
JP2002500269A (ja) 2002-01-08
DE19758177A1 (de) 1999-07-01
PL341436A1 (en) 2001-04-09
CZ20002494A3 (cs) 2001-12-12
CA2298842A1 (en) 2000-05-13
WO1999035233A1 (de) 1999-07-15
SK10022000A3 (sk) 2000-12-11
CN1283221A (zh) 2001-02-07

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