EP1044255A1 - Geschirrspülmittelformkörper mit bleichaktivatoren - Google Patents

Geschirrspülmittelformkörper mit bleichaktivatoren

Info

Publication number
EP1044255A1
EP1044255A1 EP98965662A EP98965662A EP1044255A1 EP 1044255 A1 EP1044255 A1 EP 1044255A1 EP 98965662 A EP98965662 A EP 98965662A EP 98965662 A EP98965662 A EP 98965662A EP 1044255 A1 EP1044255 A1 EP 1044255A1
Authority
EP
European Patent Office
Prior art keywords
molded body
component
weight
body according
cobalt
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
EP98965662A
Other languages
German (de)
English (en)
French (fr)
Inventor
Hans-Josef Beaujean
Jürgen Härer
Christian Nitsch
Thomas Holderbaum
Bernd Richter
Thomas Otto Gassenmeier
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 EP1044255A1 publication Critical patent/EP1044255A1/de
Ceased legal-status Critical Current

Links

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
    • C11D17/0078—Multilayered 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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 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 object of the present invention was therefore powerful, easy-to-handle washing or cleaning-active molded articles, especially dishwasher tablets, detergent tablets, stain remover tablets or water softening tablets for household use, in particular for machine use with high storage stability, low packaging expenditure, good fragrance profile and defined To provide a solubility profile, which above all results in high customer satisfaction.
  • the application is therefore a molded article containing builders, alkali carriers, bleaching agents, enzymes and surfactants, characterized in that in an area not greater than 40 vol .-%, more than 80 wt .-%, an active substance (I) with one ingredient from the group of bleach activators is included.
  • the ingredient (I) can additionally be an oxygen or chlorine-based bleach, a silver preservative and / or a soil release compound, an enzyme, a surfactant or a component or a compound for solubility control.
  • 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, in addition to the agent from the group of bleach activators and at least one other ingredient from the group consisting of bleach and / or silver protection 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 corrosion 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 is surrounded by other ingredients of the molded body in exactly three spatial directions.
  • a desirable effect on the overall result can also be obtained by increasing the weight of the area with no more than 40% of the surface containing more than 80% by weight of an ingredient (I) when stored under normal household conditions, i.e. 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.
  • an ingredient (I) when stored under normal household conditions, i.e. 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%
  • a desirable effect on the overall result can also be obtained if the loss of active substance (I) in the area 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, especially 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 most preferably not more than 10 wave numbers, at best not more than 5 wave numbers.
  • 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, Dextran, 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.
  • EP-A-0 466 485, 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 described, using compact, particulate material with a particle size between 180 and 2000 microns.
  • 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 already described and known several times, for example starches and starch derivatives, commercially available cellulose derivatives such as crosslinked and modified cellulose, microcrystalline cellulose fibers, crosslinked polyvinylpyrrolidones, layered silicates etc. Also weak acids such as citric acid or tartaric acid, which in In connection with carbonate-containing sources when they come into contact with water lead to bubbling effects and according to the definition according to Römpp belong to the second class of disintegrants can be used as 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.
  • Detergent tablets containing disintegrants in granular or, if appropriate, cogranulated form are also described in German patent applications DE 197 09 991 (Stefan Herzog) and international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • disintegration aids described in the cited documents are within the scope of the present invention preferably used as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier.
  • the dissolution time of the entire molded article is preferably shorter than the duration of the main wash cycle of a conventional dishwasher, that is to say shorter than 40 minutes, particularly preferably shorter than 30 minutes, very particularly preferably shorter than 20 minutes and extremely preferably shorter than 10 min.
  • the region which is more rapidly soluble according to the invention contains at least one acidifying agent.
  • acidifying agents are boric acid and
  • Alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used.
  • organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent.
  • the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. Tartaric acid and succinic acid are preferred from this group. Malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
  • Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).
  • detergent tablets in which a substance from the group of the organic di-, tri- and oligocarboxylic acids or mixtures thereof are used as the acidifying agent in the more rapidly dissolving region, the use of citric acid being particularly preferred .
  • the acidifying agents mentioned are preferably either sole component I or at least part of the same. It is therefore preferred within the scope of the present invention if at least 80 % By weight, preferably more than 90% by weight, particularly preferably more than 95% by weight and very particularly preferably the total amount of the acidifying agent contained in the molded body are in the more rapidly soluble region.
  • the more rapidly dissolving region in preferred embodiments of the present invention can contain further ingredients, for which the criterion applicable to ingredient I is also advantageously to be used, that is to say that at least 80% by weight, preferably more than 90, of these ingredients also applies % By weight, particularly preferably more than 95% by weight and very particularly preferably the total amount of the total ingredient contained in the molded body are in the more rapidly soluble region.
  • further ingredients are, for example, carbonates and / or hydrogen carbonates, the use of which, in combination with acidifying agents, leads to a gas release upon contact with water, which further reduces the dissolution times.
  • Such an effervescent system can be formulated with an excess of acidifying agent, which enables an acidic pre-rinse cycle, but other ingredients can also be inco ⁇ orated in the more quickly soluble area, so that the effervescent system releases the other ingredients more quickly.
  • the dissolving time of the more rapidly dissolving area is preferably still below the values mentioned above, i.e. less than 10 min, preferably less than 5 min and in particular less than 2 min.
  • Such quick-dissolving areas can bring significant benefits to cleaning performance.
  • 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 in a preferred embodiment than the pre-rinse cycle of a commercially available dishwasher, i.e. longer than 5 min, preferably longer than 10 min.
  • a smaller area of the molded body can be delayed in release, so that the majority of the molded body makes up the more rapidly soluble area.
  • Such measures to delay dissolution can only release certain ingredients, for example, only in the rinse cycle, whereby further advantages in cleaning performance can be achieved.
  • a component for accelerating release can also be used.
  • Such components preferably originate from the group of polyethylene glycols with molecular weights between 1500 and 4000, preferably between 1500 and 3000.
  • 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, shaped bodies, 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 molded body is understood to mean those in which the ingredients of the molded 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 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. 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 use one (or integrate several component (s) in one (or the) more rapidly disintegrating and / or more quickly soluble layer and incorporate the other component (s) in one (or) the more slowly disintegrating layer (s) so that one component can work with lead time or has already reacted if 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, complete and or partial encapsulation of the inner layer (s) can also be achieved by the layers lying further outside, 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 undesired interactions would be feared in the molded bodies 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 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 assembled 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 made up together with the enzymes.
  • Another cheap and preferred embodiment of the invention is that one of the component or components for solubility control is made up 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 consists in 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.
  • the preparation of the agents according to the invention is carried out according to the usual methods of molding production.
  • 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) are particularly suitable for the purposes of the present invention.
  • Polyethylene glycols with different molecular weights PEG 400, 12000
  • soaps Lirol® C 16
  • stearates Cutina® GMS
  • thickened sodium hydroxide solution and meltable salts such as sodium carbonate - decahydrate.
  • 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.
  • 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, 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 tetraacetylhexylenediamine
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. 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.
  • 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.
  • 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 known from German patent application DE 196 20 411 Amine complexes, the manganese, copper and cobalt complexes described in German patent application DE 44 16 438, 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 tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n-) or iso-NOBMA are preferred , 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 composition, used.
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group consisting of manganese and or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes , the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are added in customary amounts, preferably in an amount of 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, based in each case on the total composition. But in special cases, more bleach activator can be used.
  • soil release compounds are substances that connect the re-soiling of surfaces and / or facilitate the removal of dirt after a single application.
  • 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; Dialkyldiallyldiamrononium 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.
  • natural polyuronic acids and related substances as well as polyampholytes and hydrophobized polyampholytes, or mixtures of these substances, are also exceptionally preferred.
  • 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.
  • Particular 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.
  • 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.
  • 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 can be selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, 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.
  • oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. As 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.
  • 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 builders.
  • 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 disilicates and / or metasilicates are preferably used.
  • Alkali carriers can be present as further constituents.
  • Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates are considered to be alkali carriers.
  • Alkali metal sesquicarbonates alkali silicates, alkali metasilicates, and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, preferably being used for the purposes of this invention.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.
  • all surfactants can be used as surfactants. Preference is given to the nonionic surfactants and in particular the low-foaming nonionic surfactants, but other low-foaming surfactants are also suitable.
  • the alkoxylated alcohols, particularly the ethoxylated and or propoxylated ones, the alkyl polyglycosides and the alkyl polyglucamides are particularly preferred.
  • alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the sense of the present invention the longer-chain alcohols (Cio to C ⁇ 8 , preferably between Cj 2 and C ⁇ 6 , such as Cn-, C 12 -, C 13 -, Cj 4 -, C ⁇ -, C ⁇ 6 -, C ⁇ - and C ⁇ - 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 class of "closed" alcohol ethoxylates, which can also be used in the context of the invention.
  • highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates are.
  • 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 from C 6 to C 2 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 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 increase in the weight of the ingredient (I) 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 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. It is also particularly preferred according to the invention if the loss of active substance of the ingredient (I) during storage under normal household conditions, ie between 15 and 30 ° C.
  • 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% humidity, preferably 15 and 35% 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.
  • Frame formulations represent preferred areas of the invention.
  • the selected ingredient (I) was transferred to the area according to the invention.
  • the other area the other areas
  • 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 recipe can also be the components 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 molded body of the first claim contains a depression in a tablet, this depression containing the ingredient (I) (bleach activator).
  • the production takes place in such a way that an indentation is embossed into a molded body and this indentation is filled.
  • the embossing can be done on a Rotary presses 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.
  • a liquid mixture of paraffin and an active ingredient (I) was then introduced and allowed to cool. This cooling can be supported by common equipment 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.
  • melt dispersions of n-methyl-Mo ⁇ holinium-acetonitrile-methyl sulfate (MMA) were produced in easily soluble coating substances, which demonstrate the positive effects with accelerated release.
  • trough-shaped bodies (weight: 24 g) were produced by pressing with a press ram which had a pin.
  • Table 1 shows the composition (in% by weight, based on the premix) and thus the mold body:
  • melt dispersions SDE 1 to 5 were prepared, the composition (% by weight, based on the melt) of which is given in the table below:
  • MMA n-methyl-Mo ⁇ holinium-acetonitrile-methyl sulfate
  • the melt dispersions were introduced into the moldings in the manner mentioned above and allowed to cool.
  • the molded articles had a weight of 24 g before filling and were each filled with 1.3 g of the melt dispersion.
  • the cleaning performance of the molded bodies El to E5 filled with the melt dispersions SDE 1 to SDE 5 was tested on tea soiling. For this purpose, a tea stain was produced according to (1) and the soiled cups were cleaned in a household dishwasher:
  • 16 l of cold city water (16 ° d) are briefly heated to boiling in a water treatment boiler.
  • 96 g of black tea are drawn in the nylon net with the lid closed for 5 minutes and the tea is transferred to a diving apparatus with heating and agitator.
  • teacups are dipped into the prepared tea brew 25 times at one-minute intervals at 70 ° C. The cups are then removed and placed on a tray with the opening facing down to dry.
  • a Miele G 590 with a universal program was used as the dishwasher.

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP98965662A 1997-12-30 1998-11-09 Geschirrspülmittelformkörper mit bleichaktivatoren Ceased EP1044255A1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19758180A DE19758180A1 (de) 1997-12-30 1997-12-30 Geschirrspülmittelformkörper mit Bleichaktivatoren
DE19758180 1997-12-30
PCT/EP1998/007151 WO1999035229A1 (de) 1997-12-30 1998-11-09 Geschirrspülmittelformkörper mit bleichaktivatoren
CA002298847A CA2298847A1 (en) 1997-12-30 2000-02-28 Dishwasher detergent shaped bodies containing bleach activators

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JP (1) JP2002500265A (cs)
CA (1) CA2298847A1 (cs)
CZ (1) CZ20002489A3 (cs)
DE (1) DE19758180A1 (cs)
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ATE226979T1 (de) * 1998-07-15 2002-11-15 Henkel Kgaa Verfahren zur herstellung mehrphasiger wasch- und reinigungsmittelformkörper
GB9911949D0 (en) 1999-05-21 1999-07-21 Unilever Plc Detergent compositions
DE19932569A1 (de) * 1999-07-13 2001-01-18 Henkel Kgaa Wasch- und Reinigungsmittelformkörper, insbesondere für das maschinelle Geschirrspülen
DE19937428A1 (de) * 1999-08-07 2001-02-08 Henkel Kgaa Reinigungs- und Waschmittelformkörper
AU2003297077A1 (en) 2002-12-18 2004-07-29 The Procter And Gamble Company Organic activator
DE202008011292U1 (de) * 2008-02-12 2008-11-06 Thurn, Adolf Reinigungsmittel
JP2012111810A (ja) * 2010-11-22 2012-06-14 Kao Corp 自動洗浄機用粉末洗浄剤組成物
JP2022104274A (ja) * 2020-12-28 2022-07-08 花王株式会社 洗浄剤組成物

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GB911204A (en) * 1960-07-28 1962-11-21 Unilever Ltd Bleaching compositions
DE4315048A1 (de) * 1993-04-01 1994-10-06 Henkel Kgaa Verfahren zur Herstellung stabiler, bifunktioneller, phosphat-, metasilikat- und polymerfreier niederalkalischer Reinigungsmitteltabletten für das maschinelle Geschirrspülen
EP0741776B2 (en) * 1994-01-25 2001-10-24 Unilever N.V. Process for the preparation of detergent tablets
EP0842257B1 (de) * 1995-07-13 2000-12-27 Benckiser N.V. Geschirrwaschmaschinenspülmittel in form einer tablette

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Title
See references of WO9935229A1 *

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HUP0004888A2 (hu) 2001-05-28
PL341382A1 (en) 2001-04-09
CA2298847A1 (en) 2000-05-13
CZ20002489A3 (cs) 2001-11-14
SK9972000A3 (en) 2000-12-11
DE19758180A1 (de) 1999-07-01
WO1999035229A1 (de) 1999-07-15

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