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WO1999035225A2 - Corps moules detergents pour lave-vaisselle, renfermant des agents tensio-actifs - Google Patents

Corps moules detergents pour lave-vaisselle, renfermant des agents tensio-actifs Download PDF

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Publication number
WO1999035225A2
WO1999035225A2 PCT/EP1998/008373 EP9808373W WO9935225A2 WO 1999035225 A2 WO1999035225 A2 WO 1999035225A2 EP 9808373 W EP9808373 W EP 9808373W WO 9935225 A2 WO9935225 A2 WO 9935225A2
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WO
WIPO (PCT)
Prior art keywords
component
molded body
body according
group
weight
Prior art date
Application number
PCT/EP1998/008373
Other languages
German (de)
English (en)
Other versions
WO1999035225A3 (fr
Inventor
Jürgen Härer
Thomas Otto Gassenmeier
Christian Nitsch
Hans-Josef Beaujean
Bernd Richter
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to SK999-2000A priority Critical patent/SK9992000A3/sk
Priority to PL98342079A priority patent/PL342079A1/xx
Priority to EP98966386A priority patent/EP1045893A2/fr
Priority to HU0100620A priority patent/HUP0100620A2/hu
Priority to JP2000527612A priority patent/JP2002500264A/ja
Publication of WO1999035225A2 publication Critical patent/WO1999035225A2/fr
Publication of WO1999035225A3 publication Critical patent/WO1999035225A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • 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
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • 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
    • C11D3/395—Bleaching agents
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3915—Sulfur-containing compounds
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • the invention relates to washing or cleaning active moldings, primarily tablets such as dishwasher tablets, detergent tablets, bleach tablets, stain remover tablets or water softening tablets for use in the home, in particular for mechanical use, and a process for producing these moldings and their use.
  • tablets such as dishwasher tablets, detergent tablets, bleach tablets, stain remover tablets or water softening tablets for use in the home, in particular for mechanical use, and a process for producing these moldings and their use.
  • Shaped or active cleaning moldings in particular tablets, have a number of advantages over powder-form agents, such as advantageous handling, simple dosing and low packaging volume requirements.
  • the application therefore relates to a molded article containing builder substances, alkali carriers, bleaches and enzymes, characterized in that in an area not greater than 40% by volume, more than 80% by weight, of an active substance (I) with a constituent from the Group of surfactants is included.
  • the ingredient (I) can also contain at least one bleach from the group of chlorine and / or oxygen lead agents, a bleach activator, a silver protection agent and / or a soil release compound, an enzyme or a component or a compound for solubility control contain.
  • the ingredient (I) can also be a mixture of several of these ingredients.
  • the ingredient (I) is a mixture of a component or a compound for solubility control, a surfactant and at least one other ingredient from the group consisting of bleaching agent and / or bleach activator and / or silver protective agent and / or soil release - Compound and / or enzyme and / or a surfactant.
  • the solubility of the area with the ingredient (I), the surface and the type of compression and the storage stability can also have a decisive influence on the properties of the tablet.
  • the range 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 in exactly three spatial directions is surrounded by other ingredients of the molded body.
  • a desirable influence on the overall result can also be achieved if the weight increase of the area containing more than 80% by weight of the content (I) when stored 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.
  • a desirable influence on the overall result can also be achieved if the loss of .active substance (I) in the region containing more than 80% by weight of an ingredient when stored 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.
  • a desirable influence on the overall result can also be achieved if the absorption maximum of a 1% solution of a colored area or a colored component when stored under normal household conditions, ie between 15 and 30 ° C. and between 5 and 55% atmospheric humidity, preferably 15 and 35% humidity for a period 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 melir than 20 wavenumbers and most preferably not more than 10 wavenumbers, at best not more than 5 wavenumbers.
  • the molded 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.
  • 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 Rompp (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; systems of weak acids and carbonate-containing agents, in particular citric acid and tartaric acid in combination with bicarbonate or carbonate as well as polyethylene glycol sorbitan fatty acid esters.
  • 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. Subsequently, the acetylsalicylic acid granules powdered with finely divided silica can be mixed with other tablet ingredients, which may be in powder or granular form, and pressed 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 initially containing cellulose powder and mixed if necessary, highly disperse silica, mixed according to a preferred embodiment and then pressed.
  • German patent application DE 41 21 127 again 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 class of substances mentioned are mixed in very fine-particle form either before being compressed with the other tablet ingredients, which may 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. Swelling layer silicates such as bentonites, natural substances and natural substance derivatives based on starch and cellulose, alginates and the like, potato starch, methyl cellulose and / or hydroxypropyl cellulose are mentioned as disintegrants. These disintegrants can be mixed with the granules to be milled, but can also be incorporated into the granules to be milled.
  • 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 active cleaning tablets, using compact, particulate material with a particle size between 180 and 2000 ⁇ m.
  • the resulting tablets can both have a homogeneous as well as 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 again the disintegrants already described and 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 or tartaric acid or tartaric acid which, in connection with carbonate-containing sources, lead to sprinkling effects when in 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 a maximum of 1% by weight, preferably less, of dust components is present and overall (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.
  • the dissolution time of the entire molded article 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. If a component for delaying dissolution is included, the dissolution time of the entire molded body in 20 ° C. cold water is longer in a preferred embodiment than the pre-rinse cycle of a commercially available dishwasher, that is to say longer than 5 minutes, preferably longer than 10 minutes.
  • homogeneous or heterogeneous molded bodies 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.
  • Shaped bodies with a diameter of 32, 33, 34, 35, 36, 37, 38 and 39 mm have proven to be particularly favorable. In special designs, the height is 24, 25, 26, 27 or 28 mm.
  • the edge lengths are preferably between 15 to 60 mm, in particular 30 +/- 10 mm.
  • the weight of the individual shaped bodies, in particular the tablets, is preferably 15 to 60 g and in particular 20 to 40 g per shaped body or tablet; the consistency of the molded body or tablets, however, usually has values above 1 kg / dm, preferably from 1.1 to 1.4 kg / dm.
  • the water hardness range or the level of contamination 1 or more, for example 2 to 4, molded articles, in particular tablets, can be used.
  • the 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 fora 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.
  • Heterogeneous shaped bodies are accordingly understood to mean those which do not have a homogeneous distribution of the ingredients present in addition to the ingredient (I).
  • heterogeneous shaped bodies 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) molded bodies comprises an embodiment in which a molded 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 having. 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 application properties of the molded body. If, for example, ingredients are contained in the moldings that mutually influence each other, it is possible to separate them.
  • 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 faster dissolving 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 when another 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 molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded 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 of the inner layers containing a peroxy bleach, while in the case of the tablet in the form of a tablet, the two outer layers and in the case of the shell-like one
  • 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 there would be no fear of undesired interactions in the inventive moldings.
  • 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 component is not made up with one or more 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 trolleys 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 all of them - is mixed.
  • the agents according to the invention are produced by the customary methods of molding production.
  • the ingredient (s) (I) 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 (Lorol® C 16 ), Stearates (Cutina® GMS), but also thickened sodium hydroxide solution and meltable salts, such as sodium carbonate - decahydrate.
  • Waxes are particularly preferred as meltable components in the context of the present invention. "Waxing” is understood to mean a number of natural or artificially obtained substances which generally melt above 40 ° C.
  • waxes without decomposition and which are relatively low-viscosity and not stringy even a little above the melting point. They have a strongly temperature-dependent consistency and solubility.
  • the waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.
  • Natural waxes include, for example, vegetable waxes such as candeliu wax, carnauba wax, japan wax, esparto grass wax, korl wax, guaruma wax, rice germ oil wax, sugar toluene wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), mineral wax, or shearling fat Ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.
  • vegetable waxes such as candeliu wax, carnauba wax, japan wax, esparto grass wax, korl wax, guaruma wax, rice germ oil wax, sugar toluene wax, ouricury wax, or montan wax
  • animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), mineral wax, or shearling fat Cer
  • the chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
  • Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes.
  • Wax alcohols are high molecular weight, water-insoluble fatty alcohols with more than 28 to 40 carbon atoms.
  • the wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes.
  • wax alcohols are lignoceryl alcohol (1-tetracosanol) or melissyl alcohol.
  • the fusible component can optionally also contain wool wax alcohols, which means trite phene and steroid alcohols, for example lanolin.
  • fatty acid glycerol esters or fatty acid alkanolamides but also, if appropriate, water-insoluble or only slightly water-soluble polyalkylene glycol compounds can likewise be used at least in part as part of the meltable component.
  • the fusible component preferably contains paraffin wax. That is, at least 50% by weight of the fusible component, preferably more Paraffin wax exist. Paraffin wax contents in the coating of approximately 60% by weight, approximately 70% by weight or approximately 80% by weight are particularly suitable, with even higher proportions of, for example, more than 90% by weight being particularly preferred. In a special embodiment of the invention, the fusible component consists exclusively of paraffin wax.
  • Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that there is no hydrolysis of the waxes in an alkaline detergent environment (as is to be expected, for example, from the wax esters), since paraffin wax contains no hydrolyzable groups.
  • Paraffin waxes consist mainly of alkanes, as well as low proportions of iso- and cycloalkanes.
  • the paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Portions of high-melting alkanes in the paraffin can leave undesired wax residues on the surfaces to be cleaned or the goods to be cleaned if the melting temperature in the detergent solution drops below this. Such wax racks usually lead to an unsightly appearance of the cleaned surface and should therefore be avoided.
  • the coating according to the invention preferably contains at least one paraffin wax with a melting point of about 57 ° C. to about 60 ° C.
  • paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature is preferably as high as possible.
  • the more solid wax components present in a wax at room temperature the more useful it is within the scope of the present invention.
  • With increasing proportion of solid wax components the resilience of the coating to impacts or friction on other surfaces increases, which leads to a longer-lasting protection of the coated particles.
  • High .Share of oils or liquid wax components can weaken the coating, which opens pores and the with the Meltable component assembled particles are exposed to the environmental influences mentioned above.
  • the solidified, meltable component can break under impact or friction.
  • additives can optionally be added to the fusible component. Suitable additives must be able to be mixed completely with the molten wax, must not significantly change the melting range of the coating, must improve the elasticity of the solidified fusible component at low temperatures, must not and must not generally increase the permeability of the solidified fusible component to water or moisture do not increase the viscosity of the melt of the coating material to such an extent that processing becomes difficult or even impossible.
  • Suitable additives which reduce the brittleness of a sheath consisting essentially of paraffin at low temperatures are, for example, EVA copolymers, hydrogenated resin acid methyl ester, polyethylene or copolymers of ethyl acrylate and 2-ethylhexyl acrylate.
  • the fusible component can also contain one or more of the above-mentioned waxes or wax-like substances as the main constituent.
  • the mixture forming the cover should be such that the cover is at least largely water-insoluble.
  • the solubility in water should not exceed about 10 mg 1 at a temperature of about 30 ° C. and should preferably be below 5 mg / 1.
  • parts of the molded body and / or components of the molded body are treated by irradiation with microwaves in order to positively influence strength, moisture content and solubility. But a simple pressing of the components is also possible.
  • microtabs and molded articles of smaller dimensions than the final molded article can also be used.
  • Special ingredients (I) which are used in the context of the invention are the surfactants.
  • 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 sense of the present invention the longer-chain alcohols (C 1 -C 1, preferably between C 12 and C 16 , such as Cn-, C ⁇ 2 -, C ⁇ -, C ⁇ 4 -, C ⁇ 5 -, C ⁇ 6 -, C ⁇ 7 - and C ⁇ 8 alcohols).
  • C 1 -C 1 preferably between C 12 and C 16 , such as Cn-, C ⁇ 2 -, C ⁇ -, C ⁇ 4 -, C ⁇ 5 -, C ⁇ 6 -, C ⁇ 7 - and C ⁇ 8 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.
  • Another embodiment is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • a final etherification with short-chain alkyl groups can also lead to the "closed" alcohol ethoxylate class, which can also be used in the context 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.
  • the alkoxylated alcohols containing hydroxyl groups are particularly preferred, as described in EP 300 305, the disclosure of which is expressly incorporated here.
  • these hydroxy mixed ethers have an excellent rinse aid effect. This applies particularly preferably in mixtures with other nonionic surfactants, such as Dehypon LS 54, and also in mixtures with Dehydol LS 4, but also in mixtures with hydroxy mixed ether and .APG.
  • these surfactant mixtures even in a homogeneous mixture, decisively reduced the stress corrosion crack on plastic.
  • Alkyl polyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols according to the relevant procedures in 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 rank 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.
  • 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 T.AHD, but also pen- taacetylglucose PAG, l, 5-diacetyl-2,2-dioxo-hexahydro-l, 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 tetraacetylhexyl
  • 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 are substances which carry O- and / or N-acyl groups of the stated number of carbon atoms and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines in particular tetraacetylethylenediamine (T.AED), acylated triazine derivatives, in particular l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine (D.ADHT), acylated glycolurils, in particular tetraacetylglycoluril, are preferred (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, especially acylated trihydric alcohols, acylated polyhydric alcohols, koldiacetate, 2,5-diacetoxy-2,5-dihydrofuran,
  • hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 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.
  • bleaching catalysts In addition to the conventional bleach activators listed above or in their place, those from European patent specifications EP 0 446 982 and Known EP 0 453 003 sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes may be included as so-called bleaching catalysts.
  • the transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE 195 29 905 and their N-analogue compounds known from German patent application DE 196 20 267 Manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes known from German patent application DE 195 36 082, the manganese, iron, cobalt, ruthenium, molybdenum, Titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 196 20 411, the M.
  • German patent application DE 44 16 438 angan copper and cobalt complexes, the cobalt complexes described in European patent application EP 0 272 030, the manganese com. known from European patent application EP 0 693 550 plexes, the manganese, iron, cobalt and copper complexes known from European patent EP 0 392 592 and / or those described in European patent EP 0443 651 or European patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP 0 544 490 and EP 0 544 519 described manganese complexes.
  • 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 0J% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, based on the total composition, 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 up to 5% by weight, in particular from 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 entire funds. 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.
  • 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.
  • the known subsets of the prior art such as. B. described in DE 43 25 922, DE 41 28 672 or DE 43 38 724.
  • silver protection agents selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used.
  • Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
  • Agents containing active chlorine which can significantly reduce the corroding of the silver surface, are also frequently found in Remiger formulation oranges.
  • chlorine-free cleaners especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, 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 consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • Zinc compounds can also be used to prevent corrosion on the wash ware.
  • 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: In 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 all-purpose cleaners which can contain cationic polymers, in particular polymers with imino grapples 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 soiling 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 grapples; 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
  • 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.
  • BL.AP®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.
  • Particularly suitable cellulases and lipases are Celluzym® 0.7 T and Lipolase® 30 T from Novo Nordisk.
  • Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades find particular use as amylases.
  • Other enzymes can also be used.
  • all of the 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.
  • 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.
  • the areas of the molded body can be colored. It is particularly preferred if one or more or all areas of the molded body are colored differently in the molded 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 molded body, the color is yellow. In another special embodiment of the molded body, the color is a mixture of different colors.
  • the storage stability of the molded body is particularly important. It is particularly preferred according to the invention if the weight increase in the area of the ingredient (I) when stored under normal household conditions, ie. 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.
  • normal household conditions ie. 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
  • the loss of active substance of the ingredient (I) when stored 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 most 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.
  • hydroxy mixed ethers in particular show outstanding rinse aid effects and reduce stress corrosion cracking on plastics. Furthermore, they have the advantageous property that their wetting behavior is constant over the entire usual temperature range.
  • the use of the substances mentioned as a rinse aid component in automatic dishwashing detergents has hitherto not been described in the prior art. So far, only pure “cleaning agents” or pure “rinse aid” for automatic dishwashing have been disclosed.
  • Another object of the present invention is therefore on the one hand the use of hydroxy mixed ethers and / or mixtures of hydroxy mixed ethers and nonionic surfactants as a rinse aid component in automatic dishwashing detergents and on the other hand the use of hydroxy mixed ethers and / or mixtures of hydroxy mixed ethers and nonionic surfactants as a component for preventing stress corrosion cracking in machine dishwashers Dishwashing detergents.
  • hydroxy mixed ethers not alone, but in a mixture with other surfactants, preferably nonionic surfactants and in particular with nonionic surfactants from the group of ethoxylated fatty alcohols.
  • Uses which are characterized in that the hydroxy mixed ethers in a mixture with fatty alcohols Thoxylates are therefore preferred.
  • propoxylated or ethoxylated and propoxylated fatty alcohols can also be used in addition to the ethoxylated fatty alcohols.
  • Such preferred uses are characterized in that the hydroxy mixed ethers are present in a mixture with fatty alcohol ethoxy propoxylates.
  • the following recipes were mixed and pressed into shaped bodies.
  • the ingredients in parentheses are examples of the substance class but can be replaced by other substances listed in the application.
  • the frame formulations represent preferred areas of the invention.
  • the builder system of the framework recipe above can also be composed as follows (all other ingredients are the same as in a).
  • each formulation can also be the constituents of an individual phase, ie 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 commonly used in MGSM (e.g. fillers, preservatives, etc.) in extremely small quantities, with the other ingredients being proportionately varied accordingly.
  • a preferred embodiment of the molded body of the first speech contains a depression in a tablet, this depression containing the ingredient (I).
  • the production takes place in such a way that a depression is embossed into a molded body and this depression is filled.
  • the embossing can be done on a Korsch rotary press.
  • 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.
  • a liquid mixture of paraffin and an active ingredient (I) in the present case surfactant (Dehypon LS54, hydroxy mixed ether, mixtures of the two classes of substances) was then poured in and allowed to cool. This cooling can be supported by conventional apparatus methods.
  • the ingredient (I) according to the invention was previously reduced in quantity in the corresponding recipe which surrounds the filled area and was omitted in the surrounding areas in the examples and investigations at hand.
  • the special properties of the agents according to the invention were checked by technically untrained persons under practical 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. In an experiment, samples analogous to Ra or Val were used which contained surfactants as active ingredient (I) once in a homogeneous distribution in the tablet and once according to approach 1, so that the surfactant component was largely separated from other components. The cleaning results were very good.
  • the rinse aid results were also checked. With the effect of using a mixture of surfactant (hydroxy mixed ether) and paraffin in a standard program at 55 ° C, the results were better than with molded articles without area (I), homogeneously distributed component (I) and commercially available cleaners. The results show a positive influence of the paraffin. Changing the melting range of the paraffin also has an effect on the washing result.
  • melt emulsions of different surfactants were produced in coating substances, which prove the positive effects.
  • trough-shaped bodies weight: 24 g
  • Table 1 shows the composition (in% by weight, based on the premix) and thus the mold body:
  • melt dispersions SDE 1 to 5 were produced, the composition (% by weight, based on the melt) of which is given in the table below:
  • the melt emulsions were poured into the moldings in the manner mentioned above and allowed to cool.
  • the moldings had a weight of 24 g before being infested and were each filled with 1.3 g of the melt emulsion.
  • the cleaning performance (rinsing effect) of the molded bodies El to E5 filled with the melt emulsions SDE 1 to SDE 5 was tested on different substrates (plates, glasses, knives, plastic plates). For this purpose, the soiled objects were cleaned in a normal household dishwasher, whose rinse aid tank was empty:
  • the rinse aid effect of the detergents was carried out visually by experts and was graded, the score "0" meaning water stains and no difference to rinsing without rinse aid on a scale of 0-8 and "8" meaning absolutely clean.
  • the rinse aid effects were measured for washing conditions 55 ° C / 16 ° d water hardness in the main rinse cycle (ie "hard conditions").
  • a Miele G 590 with a universal program was used as the dishwasher.
  • the table below shows the rinse aid results achieved with agents El to E5 compared to an unfilled molded article V

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Abstract

L'invention concerne des corps moulés renfermant des adjuvants, des supports alcalins, des agents de blanchiment, des enzymes et des agents tensio-actifs. L'invention permet d'obtenir des corps moulés particulièrement performants, de stabilité élevée au stockage, d'un excellent profil parfumé et d'un profil de solubilité défini, et est caractérisée, en conséquence, en ce qu'un domaine ne constituant pas plus de 40 % en volume du corps moulé, renferme plus de 80 % en poids de la teneur totale d'une substance active (I) contenue dans le corps moulé, avec un composant appartenant au groupe des tensio-actifs.
PCT/EP1998/008373 1997-12-30 1998-12-21 Corps moules detergents pour lave-vaisselle, renfermant des agents tensio-actifs WO1999035225A2 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
SK999-2000A SK9992000A3 (en) 1997-12-30 1998-12-21 Moulded body containing activating agents, alkali carriers, bleaching agents and enzymes, and use thereof
PL98342079A PL342079A1 (en) 1997-12-30 1998-12-21 Surfactans containing dish washing agent compected body
EP98966386A EP1045893A2 (fr) 1997-12-30 1998-12-21 Corps moules detergents pour lave-vaisselle, renfermant des agents tensio-actifs
HU0100620A HUP0100620A2 (hu) 1997-12-30 1998-12-21 Tenzideket tartalmazó mosogatószer formatest
JP2000527612A JP2002500264A (ja) 1997-12-30 1998-12-21 界面活性剤を含有する食器洗浄機用洗剤成形体

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19758176A DE19758176A1 (de) 1997-12-30 1997-12-30 Geschirrspülmittelformkörper mit Tensiden
DE19758176.5 1997-12-30
CA002300643A CA2300643A1 (fr) 1997-12-30 2000-03-07 Objets sous forme de detergent pour lave-vaisselle contenant des surfactants

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WO1999035225A2 true WO1999035225A2 (fr) 1999-07-15
WO1999035225A3 WO1999035225A3 (fr) 1999-09-23

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JP (1) JP2002500264A (fr)
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DE (1) DE19758176A1 (fr)
HU (1) HUP0100620A2 (fr)
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WO2001048132A1 (fr) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh & Co. Kg Pastilles de detergent
US6387861B1 (en) 1999-05-21 2002-05-14 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions
US6797687B2 (en) 2001-08-07 2004-09-28 Cognis Deutschland Gmbh & Co. Kg Gemini surfactant compositions
US11518961B2 (en) 2019-09-27 2022-12-06 Ecolab Usa Inc. Concentrated 2 in 1 dishmachine detergent and rinse aid

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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
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JP2012111810A (ja) * 2010-11-22 2012-06-14 Kao Corp 自動洗浄機用粉末洗浄剤組成物
JP6067168B1 (ja) * 2016-05-30 2017-01-25 株式会社ニイタカ 自動洗浄機用洗浄剤組成物
CN111225970A (zh) 2017-11-14 2020-06-02 埃科莱布美国股份有限公司 固体控释苛性碱洗涤剂组合物
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Publication number Priority date Publication date Assignee Title
US6387861B1 (en) 1999-05-21 2002-05-14 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions
WO2001048132A1 (fr) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh & Co. Kg Pastilles de detergent
US7087570B2 (en) 1999-12-24 2006-08-08 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
US6797687B2 (en) 2001-08-07 2004-09-28 Cognis Deutschland Gmbh & Co. Kg Gemini surfactant compositions
US11518961B2 (en) 2019-09-27 2022-12-06 Ecolab Usa Inc. Concentrated 2 in 1 dishmachine detergent and rinse aid
US11905493B2 (en) 2019-09-27 2024-02-20 Ecolab Usa Inc. Concentrated 2 in 1 dishmachine detergent and rinse aid

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SK9992000A3 (en) 2000-12-11
DE19758176A1 (de) 1999-07-01
JP2002500264A (ja) 2002-01-08
PL342079A1 (en) 2001-05-21
HUP0100620A2 (hu) 2001-06-28
CZ20002487A3 (cs) 2001-11-14
WO1999035225A3 (fr) 1999-09-23
EP1045893A2 (fr) 2000-10-25
CA2300643A1 (fr) 2000-05-29

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