EP1309669A2 - Doses d'agent de lavage, de rin age ou de nettoyage a formulation liquide mecaniquement stables - Google Patents

Doses d'agent de lavage, de rin age ou de nettoyage a formulation liquide mecaniquement stables

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Publication number
EP1309669A2
EP1309669A2 EP01974141A EP01974141A EP1309669A2 EP 1309669 A2 EP1309669 A2 EP 1309669A2 EP 01974141 A EP01974141 A EP 01974141A EP 01974141 A EP01974141 A EP 01974141A EP 1309669 A2 EP1309669 A2 EP 1309669A2
Authority
EP
European Patent Office
Prior art keywords
detergent
water
active
cleaning
liquid
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.)
Granted
Application number
EP01974141A
Other languages
German (de)
English (en)
Other versions
EP1309669B1 (fr
Inventor
Hans-Jürgen Riebe
Rainer Geberzahn
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
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1309669A2 publication Critical patent/EP1309669A2/fr
Application granted granted Critical
Publication of EP1309669B1 publication Critical patent/EP1309669B1/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

  • the present invention relates to mechanically stable, liquid-formulated detergent, detergent or cleaning agent portions.
  • the present invention relates to detergent, dishwashing or cleaning agent portions in the form of formulations which are liquid during manufacture or filling and whose viscosity increases over time, which leads to the fact that coated formulations due to their thixotropic nature or pseudoplastic behavior are mechanically stable.
  • thickeners examples include agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar gum, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose and cellulose ether, hydroxyethyl cellulose, hydroxypropyl cellulose and the like, corn flour ether , Polyacrylic u. Polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas. The use of these thickeners to increase viscosity in a wide variety of liquids has long been like state of the art. The use of polymers in liquid detergents has also been known for a long time.
  • thickeners such as the thickeners mentioned leads to stable gels in liquid detergents only above certain surfactant contents.
  • Liquid detergents with surfactant contents below 35% by weight already show phase separation or agglomerate formation after a few days, which is noticeable in the formulation becoming opaque (“cloud formation”).
  • cloud formation the viscosity of such products drops drastically during storage
  • Gel formation usually only succeeds with a surfactant content of more than 35% by weight, so high surfactant contents are essential. Since high-viscosity liquid detergents are usually offered in transparent bottles to underline the aesthetic characteristics, it is also necessary that the thickeners used are stable to light, otherwise there will be a radical breakdown of the polymers, which will result in the destruction of the product color and - also - undesirable "cloud formation”.
  • Liquid detergents with viscosities between 500 and 20,000 mPas, preferably from 2,000 to 10,000 mPas, in which lamellar surfactant droplets are dispersed in an aqueous electrolyte phase are described in European patent application EP-A 691 399 (Colgate). These compositions contain 10 to 45% by weight of surfactant (s), at least one builder and 0.01 to 5% by weight of a mercapto-capped polymer with an average molecular weight between 1,500 and 50,000 gmol "1 .
  • boron compounds in aqueous liquid detergents are described in EP-A 381 262 (Unilever).
  • the liquid detergents described contain the boron compounds and a polyol as an enzyme stabilization system for a mixture of proteolytic and lipolytic enzymes, preferred stabilization systems consisting of a sorbitol / borax mixture. None is said in this document about the viscosity and stability of liquid detergents.
  • Liquid, aqueous detergent concentrates which maintain or increase their viscosity when diluted with water are described in EP-A 724 013 (Colgate). This effect is achieved by the use of two surfactants with different resistance to electrolytes and the addition of a dissolved electrolyte, the concentrate has a viscosity of less than 2,500 mPas and, when diluted with water, loses its micellar structure in favor of the formation of a lamellar phase.
  • WO96 / 01305 (Unilever) describes an aqueous detergent and liquid detergent which, when diluted with at least twice the amount of water, forms a microemulsion which has particle sizes of 10 to 100 nm.
  • the agent contains 20 to 70% by weight of water, 15 to 40% by weight of a surfactant system which contains at least one nonionic surfactant from the group of the alkoxylated alcohols and not more than 20% by weight of anions, cations, ampho - or zwitterionic surfactants contains 5 to 30 wt .-% solvent and 5 to 20 wt .-% water-insoluble oil.
  • Aqueous, highly viscous liquid detergents in bulk form with surfactants and other usual ingredients of detergents and cleaning agents and a thickening system made of polyurethanes or modified polyacrylates, a boron compound and one or more complexing agents, in particular low molecular weight hydroxycarboxylic acids, are described in WO 99/28430.
  • Portioned detergents, detergents or cleaning agents with thixotropic or pseudoplastic flow behavior of the wash-active, rinse-active or cleaning-active components contained therein cannot be found in this prior art.
  • Aqueous, highly viscous liquid detergents in bulk form with surfactants and other usual ingredients of detergents and cleaning agents and a thickening system consisting of a polymeric thickener or swelling agent, a boron compound and one or more complexing agents, in particular low molecular weight hydroxycarboxylic acids, are described in WO 99/27051 , Portioned detergents, detergents or cleaning agents with thixotropic or pseudoplastic flow behavior of the wash-active, rinse-active or cleaning-active components contained therein cannot be found in this prior art.
  • the preparations should have a viscosity of 300 to 5,000 cps (Brookfield; # 5 spindle at 50 rpm) without giving any information about non-Newtonian behavior of the preparations.
  • EP-A 0 738 778 discloses non-aqueous liquid detergent preparations in the form of stable suspensions of solid particles of bleaching agents, bleach activators, alkalis, builders and anionic surfactants in non-aqueous mixtures of anionic (alkali metal or alkanolamine) Alkyl polyalkoxylates) and nonionic (polyhydroxy fatty acid amides) surfactants and organic diluents (alcohol alkoxylates and less polar organic solvents).
  • the publication WO 97/00938 describes non-aqueous liquid detergent formulations in the form of stable dispersions of bleaching agents (e.g.
  • peroxy bleaching agents and optionally bleach activator and organic builders in non-aqueous mixtures of alkali metal salts of alkylbenzenesulfonates, Fatty alcohol ethoxylates and non-polar organic solvents.
  • the preparations should have a viscosity of 300 to 5,000 cps (Brookfield; # 5 spindle at 50 rpm) without giving any information about non-Newtonian behavior of the preparations.
  • non-aqueous surfactant preparations in the form of liquids, gels or pastes, the anionic and / or non-ionic surfactants , non-aqueous organic diluents (e.g. fatty alcohol alkoxylates or non-polar organic solvents) and clay-removing polymers (e.g. alkoxylated cat-ionic diamines or polyamines (WO 97/00936) or bleaching agents and salts of divalent metals as bleach activators (WO 97/00937)).
  • organic diluents e.g. fatty alcohol alkoxylates or non-polar organic solvents
  • clay-removing polymers e.g. alkoxylated cat-ionic diamines or polyamines (WO 97/00936) or bleaching agents and salts of divalent metals as bleach activators (WO 97/00937).
  • Preparations of the aforementioned type were usually given to the consumer in containers containing large quantities of liquid, such as plastic bottles.
  • the dosing was then carried out as required (degree of contamination of the items to be washed, washed or cleaned, amount of items to be washed, washed or cleaned) or, based on experience, in each individual case using suitable devices for measuring amounts of liquid.
  • such formulations can be incorporated into water-soluble gelatin capsules or foil bags and can thus be added to the items to be washed, washed or cleaned as a pre-metered portion of detergent, detergent or cleaning agent.
  • detergent, dishwashing detergent or cleaning agent portions based on liquid formulations of detergent-active, detergent-active or detergent-active components, the formulations having a high viscosity.
  • Particularly advantageous detergent, detergent or cleaning agent portions are obtained according to the invention in cases in which the liquid formulations during processing, for example when producing them from their wash-active, rinse-active or cleaning-active components, when stirring, when pumping over and when filling the the portions of detergent, detergent or cleaning agent provided (capsules, balls, bags) have a low viscosity, but after the mechanical action has subsided, they have a high viscosity.
  • a thixotropic or pseudoplastic - in any case non-Newtonian - behavior of the liquid formulations of wash-active, rinse-active or cleaning-active components unexpectedly leads to detergent, detergent or cleaning agent portions with significantly improved usage properties.
  • the invention therefore relates to a detergent, dishwashing or cleaning agent portion, comprising a fully or partially water-soluble capsule-shaped casing which completely surrounds a liquid-based formulation of at least one washing-active, rinsing-active or cleaning-active material, with a compression resistance> 1.0 N. at 23 ° C.
  • the invention relates to a detergent, dishwashing or cleaning agent portion, comprising a completely or partially water-soluble detergent.
  • Ball-shaped casing that completely surrounds a liquid-based formulation of at least one washing-active, rinsing-active or cleaning-active material, with a compression resistance> 1 N at 23 ° C.
  • the invention relates to a detergent, dishwashing or cleaning agent portion, comprising a completely or partially water-soluble envelope in the form of a bag, which completely surrounds a liquid-based formulation of at least one washing-active, rinsing-active or cleaning-active material, with one Compression resistance> 1 N at 23 ° C.
  • the invention further relates to a method for producing a detergent, dishwashing or cleaning agent portion, which comprises a completely or partially water-soluble casing in capsule form, in spherical form or in the form of a bag, which in turn completely completes a liquid-based formulation of at least one washing-active, rinsing-active or cleaning-active material surrounds, comprising the steps that one
  • step (d) if appropriate, immediately introduce the liquid mixture prepared according to step (c) into the casing and seal it around the liquid-based formulation.
  • the invention also relates to a washing process, a rinsing process and a cleaning process using the detergent, detergent or cleaning agent portions described below.
  • the term “detergent, detergent or cleaning agent portion” is understood to mean a sufficient amount of a detergent, detergent or cleaning agent for a washing, rinsing or cleaning process taking place in an aqueous phase.
  • This can be, for example, a machine Washing, rinsing or cleaning process, such as is carried out with commercially available washing machines or dishwashers or cleaning machines, but according to the invention this term also includes a handwashing cycle (for example carried out in a hand wash basin or in a bowl) or a dishwashing cycle carried out by hand or by means of a cleaning liquor in a vessel, such as a cleaning cycle carried out in a bucket or another process of washing, rinsing or cleaning.
  • the detergent, washing-up liquid or cleaning agent portions are preferred in the case of machines Washing, rinsing or cleaning processes are used.
  • detergent portion portion or “detergent portion portion” or “detergent portion portion” is understood to mean a portion of a detergent portion, detergent portion or detergent portion which is contained in another detergent portion, detergent portion or detergent portions of separate phase in spatial connection with other detergent, dishwashing or detergent portions of the same detergent, dishwashing or cleaning agent portion and is prepared by suitable measures so that it is separated from other detergents, dishwashing or cleaning agents - Portions of the same detergent, dishwashing or cleaning agent portion can be added to the liquor and, if necessary, dissolved or suspended in it.
  • a portion of washing, detergent or cleaning agent portion can contain the same ingredients as another detergent, dishwashing detergent.
  • two portions of detergent, dishwashing detergent or cleaning agent preferably contain the same portion of detergent, dishwashing detergent or cleaning agent, different ingredients, in particular different washing-active, dishwashing-active or cleaning-active preparations.
  • the detergent, dishwashing or cleaning agent portions contain measured amounts of at least one washing-active, washing-active or cleaning-active preparation, usually measured amounts of several washing-active, washing-active or cleaning-active preparations. It is possible that the portions only contain wash-active, rinse-active or cleaning-active preparations of a certain composition. According to the invention, however, it is preferred that several, usually at least two, wash-active, rinse-active or cleaning-active preparations of different compositions are contained in the detergent, detergent or cleaning agent portions.
  • the composition can differ in terms of the concentration of the individual components of the wash-active, rinse-active or cleaning-active preparation (quantitative) and / or in terms of the type of individual components of the wash-active, rinse-active or cleaning-active preparation (qualitative). It is particularly preferred that the components are adapted in terms of type and concentration to the tasks which the detergent, dishwashing or cleaning agent portions have to perform in the washing, washing or cleaning process.
  • wash-active preparation or “rinse-active preparation” or “cleaning-active preparation” (or “wash-active etc. material” or “wash-active etc. component”) in the context of the present invention relates to preparations, materials or components of all conceivable relevant substances with a washing, rinsing or cleaning process. These are primarily the actual detergents, rinsing agents or cleaning agents with their individual components, which are explained in more detail below.
  • active substances such as surfactants (anionic, non-ionic, cationic and amphoteric surfactants), builder substances (inorganic and organic builder substances), bleaching agents (such as peroxo bleaching agents and chlorine bleaching agents), bleach activators, bleach stabilizers, bleaching catalysts, enzymes, special polymers (for example those with cobuilder properties), graying inhibitors, dyes and fragrances (perfumes), without the term being restricted to these groups of substances.
  • active substances such as surfactants (anionic, non-ionic, cationic and amphoteric surfactants), builder substances (inorganic and organic builder substances), bleaching agents (such as peroxo bleaching agents and chlorine bleaching agents), bleach activators, bleach stabilizers, bleaching catalysts, enzymes, special polymers (for example those with cobuilder properties), graying inhibitors, dyes and fragrances (perfumes), without the term being restricted to these groups of substances.
  • active substances such as surfactants (anionic, non-ionic,
  • wash-active preparations materials, components
  • rinse-active preparations materials, components
  • cleaning-active preparations materials, components
  • cleaning aids examples of these are optical brighteners, UV protective substances Soil repellents, that is to say polymers which counteract re-soiling of fibers or hard surfaces, and silver protection agents, and laundry treatment agents such as fabric softener or dishwashing detergent additives such as rinse aid are also regarded according to the invention as wash-active or rinse-active preparations.
  • the detergent, dishwashing or cleaning agent portion according to the invention comprises a completely or partially water-soluble casing.
  • the shape of the envelope is not limited to certain shapes according to the invention. Basically, all Archimedean and Platonic bodies, i.e. three-dimensional shaped bodies, can be used as forms of wrapping. Examples of the shape of the covering are capsules, cubes, spheres, egg-shaped moldings, cuboids, cones, rods or bags. Hollow bodies with one or more compartments, as described in co-pending patent application No. DE 100 33 827.5 with the title “compartment hollow body”, are also suitable as a covering for the washing-active, rinsing-active or cleaning-active materials.
  • the envelopes are in the form of capsules, such as those used in pharmacy for the administration of pharmaceuticals, of spheres or sachets, the latter preferably being welded or glued on at least one side, an adhesive being the adhesive in particularly preferred embodiments of the invention is used, which is water-soluble.
  • all materials which can dissolve completely or partially in the aqueous phase under the given conditions of a washing process, rinsing process or cleaning process are suitable as materials for the completely or partially water-soluble coating.
  • the polymer materials can particularly preferably be the groups (optionally partially acetalized) of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives, starch and their derivatives, in particular modified starches, and mixtures (polymer blends, composites, coextrudates etc.) belong to the materials mentioned.
  • Gelatin and polyvinyl alcohols and the two materials mentioned are particularly preferred in each case in combination with starch or modified starch.
  • Inorganic salts and mixtures thereof can also be used as materials for the at least partially water-soluble coating.
  • Polyvinyl alcohols are polymers of the general structure
  • [-CH 2 -CH (OH) -CH (OH) -CH 2 -j contain. Since the corresponding monomer (vinyl alcohol) is not stable in free form, polyvinyl alcohols are obtained via polymer-analogous reactions by hydrolysis, technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols, preferably with methanol. These technical processes also make PVAL accessible which contain a predetermined residual proportion of acetate groups.
  • PVAL e.g. Mowiol ® types from Hoechst
  • PVAL are commercially available as white-yellow powders or granules with degrees of polymerization in the range from approximately 500 to 2500 (corresponding to molecular weights from approximately 20,000 to 100,000 g / mol) and have different degrees of hydrolysis, for example 98 to 99 or 87 to 89 mol%. They are therefore partially saponified polyvinyl acetates with a residual acetyl group content of, for example, approximately 1 to 2 or 11 to 13 mol%.
  • PVAL water solubility of PVAL can be reduced by aftertreatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to the desired values.
  • PVAL films are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVAL films examples include the PVAL films available from Syntana bottlesgesellschaft E. Harke GmbH & Co. under the name “SOLUBLON ® ". Their solubility in water can be adjusted to the degree, and films of this product series are available, which are soluble in the aqueous phase in all temperature ranges relevant to the application.
  • PVP Polyvinylpyrrolidones
  • PVP are made by radical polymerization of 1-vinyl pyrrolidone.
  • Commercial PVPs have molar masses in the range from approx. 2,500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.
  • Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula
  • Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is primarily obtained by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as a water-soluble coating material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.
  • detergent, detergent and cleaning agent portions are also preferred, the packaging of which consists of at least partially water-soluble film made from at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.
  • Starch is a homoglycan, with the glucose units linked ⁇ -glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% straight-chain amylose (MW. Approx. 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW. Approx. 300,000 to 2,000,000). In addition there are still few Contain quantities of lipids, phosphoric acid and cations.
  • amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules due to the binding in the 1,4 position
  • the chain in the amylopectin branches after an average of 25 glucose units through 1,6 binding to form a knot-like structure with about 1,500 to 12,000 molecules of glucose.
  • starch derivatives which can be obtained by polymer-analogous reactions from starch are also suitable for producing water-soluble coatings for the detergent, dishwashing detergent and cleaning agent portions.
  • chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Starches in which the hydroxy groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ß-1,4 polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5,000 glucose units and consequently have average molar masses of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • Preferred coverings made of at least partially water-soluble film consist of a polymer with a molecular weight between 5,000 and 500,000 g / mol, preferably between 7,500 and 250,000 g / mol and in particular between 10,000 and 100,000 g / mol.
  • the water-soluble film which forms the covering preferably has a thickness of 1 to 300 ⁇ m, preferably 2 to 200 ⁇ m, particularly preferably 5 to 150 ⁇ m and in particular 10 to 100 ⁇ m.
  • These water-soluble films can be produced by various manufacturing processes. In principle, blowing, calendering and casting processes should be mentioned here. In a preferred method, the films are blown from a melt with air through a blow mandrel to form a tube.
  • the raw materials plasticized by suitable additives are atomized to form the films.
  • an aqueous polymer preparation is placed on a heatable drying roller; after the water has evaporated, cooling is optional and the film is removed as a film. If necessary, this film is additionally powdered before or during the removal.
  • Organic and / or inorganic salts are also suitable as materials for the coating of the detergent, detergent or cleaning agent portion according to the invention.
  • these are salts which can be formed into a coating, for example by crystallization, pressing, compacting or other suitable processes, and which dissolve in sufficient time in water or aqueous liquor under the conditions of the washing, rinsing or cleaning process.
  • salts are used which can also perform other functions in a washing, rinsing or cleaning process.
  • the covering is water-soluble as a whole, that is to say it dissolves completely when used as intended in washing, rinsing or cleaning, for example in machine washing, rinsing or cleaning, when the conditions for dissolving have been reached.
  • Particularly preferred as completely water-soluble coatings are, for. B. capsules made of gelatin, advantageously made of soft gelatin, or bags made of (optionally partially acetalized) PVAL or balls of gelatin or (optionally partially acetalized) PVAL or of one or more organic and / or inorganic salts, preferably balls made of soft gelatin.
  • a significant advantage of this embodiment is that the covering at least partially dissolves in a practically relevant short time - as a non-limiting example, a few seconds to 5 minutes - under precisely defined conditions in the washing liquor, rinsing liquor or cleaning liquor, and thus according to the requirements, the wrapped content, ie the washing-active, rinsing-active or cleaning-active material or several materials, is brought into the fleet.
  • the water-soluble covering comprises areas which are less or not water-soluble or only water-soluble at a higher temperature and areas which are water-soluble or water-soluble at a low temperature.
  • the covering does not consist of a uniform material which has the same water solubility in all areas, but of materials of different water solubility. Areas of good water solubility are to be distinguished on the one hand from areas with less good water solubility, with poor or no water solubility or from areas in which water solubility is only at a higher temperature or at a different pH value or only when the electrolyte concentration has changed achieved, on the other hand.
  • the invention is not subject to any restrictions for the formation of such systems. Enclosures can be provided in which a uniform polymer material comprises small areas of incorporated compounds (for example salts) which are more water-soluble than the polymer material. On the other hand, several polymer materials with different water solubility can also be mixed (polymer blend), so that the more rapidly soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the more slowly soluble one.
  • water-soluble areas of the casing are areas made of a material which chemically essentially corresponds to that of the readily water-soluble areas or corresponds to water-soluble regions at a lower temperature, but has a higher layer thickness and / or has a changed degree of polymerization of the same polymer and / or has a higher degree of crosslinking of the same polymer structure and / or has a higher degree of acetalization (in the case of PVAL) and / or a content of water-insoluble salt components has and / or contains a water-insoluble polymer.
  • the casing does not completely detach, detergent, detergent or cleaning agent portions according to the invention can thus be provided which have advantageous properties when releasing the detergent-active, detergent-active or detergent-active components into the respective liquor.
  • a further embodiment of the invention which is likewise preferred on account of the advantageous properties, provides detergent, dishwashing or cleaning agent portions in which the completely or partially water-soluble coating contains one or more washing-active, washing-active or cleaning-active components, in particular those components which are incorporated in Detergents, detergents or cleaning agents are only present in small quantities.
  • Such components are, for example, bleach or at least partial amounts thereof, bleach activators, enzymes, dyes, fragrances, optical brighteners and / or soil repellants, but also other components of the detergent, detergent or cleaning agent portions.
  • liquid-based is understood to mean that the formulation of a wash-active, rinse-active or cleaning-active material or a plurality of wash-active, rinse-active or cleaning-active materials is, at least during production, a formulation based on liquid components, as is the case are explained in detail below, even if this formulation contains solid components (suspended or dispersed) in large quantities and / or after the production in the absence of shear forces, an increase in viscosity, for example by at least 10%, preferably by at least 50%, more preferably by at least 100%, so that it can no longer be called "liquid” in the narrower sense.
  • Liquid-based formulations of the detergent, dishwashing or cleaning agent portions according to the invention which are completely surrounded by the envelopes can be either low-water formulations or essentially water-free formulations.
  • Low-water formulations comprise water as an essential component in an amount of, for example, ⁇ 15% by weight, based on the weight of all components of the formulation.
  • non-aqueous or essentially water-free formulations comprise water only in small amounts, preferably in amounts ⁇ 5% by weight, more preferably in amounts of 1 to 3% by weight, in each case based on the weight of all components of the formulation, non-aqueous or essentially water-free formulations are particularly preferred.
  • the formulations contain surfactant (s), anionic, nonionic, cationic and / or amphoteric surfactants being used. Mixtures of anionic and nonionic surfactants are preferred from an application point of view, the proportion of nonionic surfactants being greater than the proportion of anionic surfactants.
  • the total surfactant content of the detergent, detergent or cleaning agent portions is preferably above 30% by weight, based on the total liquid detergent.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol and an average of 2 to 8 moles of EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ⁇ 2- i8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 alcohol with 3 EO and C 12- i8 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used the. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO 90/13533.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula I, R1
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R ⁇ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z 1 ] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula II
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 alkyl or phenyl radicals being preferred
  • [Z 2 ] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this residue.
  • [Z 2 ] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the content of preferred formulations of nonionic surfactants is 5 to 95% by weight, preferably 10 to 60% by weight and in particular 15 to 50% by weight, in each case based on the total composition.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Suitable surfactants of the sulfonate type are preferably C 8-13 - alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from 2- C ⁇ ⁇ 8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from C 2-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerin esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 0 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulphates and Cj are 2 - C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates of preferably.
  • 2,3-alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and as commercial products from Shell Oil Company under the name DAN ® are suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched C 8-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12- 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see above).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as, for example, mono-, di- or triethanolamine, monoisopropanolamine or triisopropanolamine.
  • the anionic surfactants are preferably in the form of their ammonium salts, in particular their ammonium salts with at least one long-chain alkyl radical or alkanolamine radical on ammonium nitrogen.
  • the content of preferred detergent, detergent or cleaning agent portions of anionic surfactants is 5 to 95% by weight, preferably 10 to 60% by weight and in particular 15 to 50% by weight, in each case based on the total portion.
  • the detergent, dishwashing or cleaning agent portions according to the invention irrespective of whether they contain water or low in water or essentially water-free - can contain further ingredients which further improve the technical and / or aesthetic properties of the agent improve.
  • preferred detergent, detergent or cleaning agent portions contain, in addition to the surfactant (s), one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH adjusting agents, fragrances, perfume carriers, fluorescers, colorants, hydrotropes, Schauminhibito-ren, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, shrink preventatives, anticrease agents, dye transfer inhibitors, antimicrobial active ingredients, germicides, fungicides, anti-oxidants, corrosion inhibitors, antistats, ironing aids, water-repellents and impregnating agents, swelling and sliding resistant agents and UV absorbers.
  • surfactant s
  • silicates As builders, which can be contained in the detergent, detergent or cleaning agent portions according to the invention, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances are to be mentioned in particular.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 ⁇ 2 O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A 0 164 514.
  • Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 -yH 2 O are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the process described in international patent application WO-A 91/08171.
  • Amorphous sodium silicates with a Na 2 O: SiO 2 modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used solvent- are delayed and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene - Oxide groups, C 2 -C 5 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated Isotridecanoles.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates As builders, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
  • bleaching agents which serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -supplying acid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleach activators can be incorporated into the detergent portions.
  • 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.
  • bleach catalysts can also be incorporated into the wash-active preparations for the portions according to the invention.
  • These fabrics are bleached strengthening transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Enzymes for use in detergent, detergent or cleaning agent portions are, in particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned.
  • the hydrolases help remove stains such as protein, fat or starchy stains and graying in laundry, for example.
  • Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils.
  • Oxireductases can also be used to bleach or inhibit the transfer of color.
  • Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest for the detergent, detergent or cleaning agent portions according to the invention.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different types of cellulase differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition, or can also be embedded in the water-soluble coatings according to the invention.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, approximately 0.1 to 5% by weight, preferably 0.12 to approximately 2% by weight.
  • a wide number of different salts can be used as electrolytes from the group of inorganic salts.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl 2 in the agents according to the invention is preferred.
  • the proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.
  • Non-aqueous solvents that can be used in the detergent, detergent or cleaning agent portions according to the invention come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanoI, 3-methyl-3- methoxybutanol, propylene glycol t-butyl ether, N-butoxyprop
  • pH adjusting agents In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 2% by weight of the total formulation. In order to improve the aesthetic impression of the detergent, detergent or cleaning agent portions according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the formulation and to light, and no pronounced substance to textile fibers in order not to dye them.
  • Foam inhibitors that can be used in the detergent, detergent or cleaning agent portions according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.
  • Suitable antiredeposition agents which are also referred to as “soil repellents”, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and also the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof preferred among the compounds mentioned are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
  • Optical brighteners can be added to the detergent portions according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances absorb onto the fiber and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible, longer-wave light convert, the ultraviolet light absorbed from the sunlight being emitted as a slightly bluish fluorescence and resulting in pure white with the yellow tone of the grayed or yellowed laundry.
  • Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2'- stilbene disulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, cu marine, dihydroquinolinones, 1, 3-diarylpyrazolines, naphthalic acid imides, benzoxazole, benzisoxazole and benzimidazole systems as well as those substituted by hetero-cyclen renderivate.
  • the optical brighteners are usually used in amounts between 0.05 and 0.3% by weight, based on the formulation.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • water-soluble colloids of mostly organic nature are suitable, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures in amounts of 0.1 to 5% by weight, based on the composition, used.
  • graying inhibitors based on optionally modified polyacrylates and their copolymers are also suitable.
  • detergents according to the invention may contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
  • the detergent, dishwashing or cleaning agent portions according to the invention can contain antimicrobial active ingredients.
  • antimicrobial active ingredients Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halogenophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely in the portions according to the invention.
  • the formulations can contain antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve.
  • External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • External antistatic agents are described, for example, in patent applications FR 1, 156.513, GB 873 214 and GB 839 407.
  • the lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents, an additional finishing effect being achieved.
  • silicone derivatives can be used in the detergent portions according to the invention. These additionally improve the rinsing behavior of the portions according to the invention due to their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are wholly or partly fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 mPas, and the silicones can be used in amounts between 0.2 and 5% by weight, based on the total agent.
  • the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers.
  • encryption Bonds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active through radiationless deactivation and have substituents in the 2- and / or 4-position.
  • Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.
  • Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) or of their derivatives or derivatives, and also alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • anionic polyelectrolytes such as polymaleates and polysulfonates.
  • a preferred class of complexing agents are the phosphonates, which in preferred detergent, dishwashing or cleaning agent portions in amounts of 0.01 to 1.5% by weight, preferably 0.02 to 1% by weight and in particular 0 , 03 to 0.5 wt .-% are included.
  • These preferred compounds include, in particular, organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane -1, 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
  • organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DE
  • the low-water formulation comprises a thickening system.
  • This can consist of one or more components.
  • a component is regularly a polymeric thickener.
  • These organic high-molecular substances which are also called swelling agents, absorb liquids, swell and finally convert into viscous real or colloidal solutions, come from the groups of natural polymers, modified natural polymers and fully synthetic polymers.
  • Polymers derived from nature that are used as thickeners are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, carob bean flour, starch, dextrins, gelatin and casein.
  • Modified natural products mainly come from the group of modified starches and celluloses, examples include carboxymethylceilulose and cellulose ethers, hydroxyethyl and propyl cellulose and core meal ether.
  • thickeners that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.
  • Thickeners from said substance classes are widely available commercially and are sold for example under the trade name Acusol ® -820 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ® -GT -282-S (alkyl polyglycol ether, Akzo), Deuterol ® polymer 11 (dicarboxylic acid copolymer, Schoener GmbH), Deuteron ® -XG (anionic heteropolysaccharide based on ß-D-glucose, D-manose, D-glucuronic acid, Schoener GmbH), Deuteron ® -XN (non-ionic polysaccharide, Schönes GmbH), Dicrylan ® -Dickener-O (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA ® -81 and EMA ® -91 (
  • Preferred low-water formulations contain, as a component of the thickening system, 0.01 to 4% by weight, preferably 0.1 to 3% by weight and in particular 0.4 to 1.5% by weight, of a polysaccharide.
  • a preferred polymeric polysaccharide thickener is xanthan, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions, and a molecular weight from 2 to 15 million g / mol.
  • Xanthan is formed from a chain with ß-1, 4-bound glucose (cellulose) with side chains.
  • the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan.
  • Xanthans and modified xanthans can be used with particular advantage on account of their extensive acid stability and oxidation stability.
  • Xanthan can be described by the following formula:
  • Preferred aqueous formulations of the detergent, detergent or cleaning agent portions contain, as component a) of the thickening system, in each case based on the total composition, 0.01 to 4% by weight, preferably 0.1 to 3% by weight and in particular 0.4 to 1.5% by weight, xanthan.
  • component a) of the thickening system in each case based on the total composition, 0.01 to 4% by weight, preferably 0.1 to 3% by weight and in particular 0.4 to 1.5% by weight, xanthan.
  • Further components of the thickening system are described in the prior art, for example in publication WO 99/27051: there the second component of the thickening system is a boron compound which is used in amounts of 0.5 to 7% by weight.
  • boron compounds which can be used in the context of the present invention are boric acid, boron oxide, alkali metal borates such as ammonium, sodium and potassium ortho, meta and pyroborates, borax in its various hydration stages and polyborates such as alkali metal pentaborates , Organic boron compounds such as esters of boric acid can also be used.
  • Preferred portions of liquid detergent contain 0.0001 to 5% by weight, preferably 0.001 to 4% by weight and in particular 0.01 to 3% by weight of a boron compound.
  • the detergent, detergent or cleaning agent portions according to the invention can contain 0 to 20% by weight of a complexing agent.
  • complexing agent means low molecular weight hydroxycarboxylic acids such as citric acid, tartaric acid, malic acid, or gluconic acid or salts thereof.
  • liquid detergent contains citric acid or sodium citrate as component c) of the thickening system, portions of liquid detergent being preferred which are 1.0 to 15.0% by weight, preferably 2.0 to 10.0% by weight and in particular 2.0 to 7.0% by weight, contain sodium citrate.
  • the first component of the thickening system is a polyurethane or a modified polyacrylate, which, based on the total portion, is used in amounts of 0.2 to 5% by weight.
  • Polyurethanes are produced from polyhydric alcohols and isocyanates by polyaddition and are described by the general formula III:
  • R 3 is a low molecular weight or polymeric diol residue
  • R 4 is an aliphatic or aromatic group
  • n is a natural number.
  • R 3 is preferably a linear or branched C 2-12 -alk (en) yl group, but can also be a residue of a higher alcohol, whereby cross-linked polyurethanes are formed which differ from the above formula III in that the R 3 further -O-CO-NH groups are bound.
  • TDI 2,4- or 2,6-toluenediisocyanate
  • MDI C 6 H 4 -CH 2 -C 6 H 4
  • HMDI, R 4 (CH 2 ) 6 ].
  • PUR-based thickeners are, for example, under the names Acrysol ® PM 12 V (mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas), Borchigel ® L75-N (non-ionic PUR Dispersion, 50% in water, Borchers), Coatex ® BR-100-P (PUR dispersion, 50% in water / butylglycol, Dimed), Nopco ® DSX-1514 (PUR dispersion, 40% in water / Butyltriglycol, Henkel-Nopco), thickener QR 1001 (20% PUR emulsion in water / digylcol ether, Rohm & Haas) and Rilanit ® VPW-3116 (PUR dispersion, 43% in water, Henkel) available.
  • Preferred detergent, detergent or cleaning agent portions contain 0.01 to 4% by weight, preferably 0.1 to 3% by weight and in particular 0.5 to 1.5% by weight of a
  • Modified polyacrylates that can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula IV:
  • R 5 is H or a branched or unbranched C to C 4 alk (en) yl radical
  • X is NR 7 or O
  • R 6 is an optionally alkoxylated branched or unbranched, optionally substituted C 8 to C 22 alk ( en) yl radical
  • R 7 is H or R 6 and n is a natural number.
  • modified polyacrylates are generally esters or amides of acrylic acid or an ⁇ -substituted acrylic acid. Preferred among these polymers are those in which R 3 represents H or a methyl group.
  • the two hydrocarbon radicals attached to the N atom are, independently of one another, can be selected from optionally alkoxylated branched or unbranched C 8 to C 22 alk (en) yl radicals.
  • the designation of the radicals bound to X represents a statistical mean, which can vary in individual cases with regard to chain length or degree of alkoxylation.
  • Formula IV only provides formulas for idealized homopolymers. Can be used in the frame of the present invention, but also copolymers in which the proportion of monomer units which satisfy the formula IV is at least 30% by weight. For example, it is also possible to use copolymers of modified polyacrylates and acrylic acid or salts thereof which still have acidic H atoms or basic -COO " groups.
  • Modified polyacrylates to be preferably used in the context of the present invention are polyacrylate-polymethacrylate copolymers which satisfy the formula IVa
  • R 6 represents a preferably unbranched, saturated or unsaturated C 8 to C 22 alk (en) yl radical
  • R 8 and R 9 independently of one another are H or CH 3
  • the degree of polymerization n is a natural number
  • the degree of alkoxylation a is one is a natural number between 2 and 30, preferably between 10 and 20.
  • Products of formula IVa are commercially strength, for example, under the name Acusol ® 820 (Rohm & Haas) in the form of 30 wt .-% dispersions in water available.
  • Acusol ® 820 Rohm & Haas
  • R 6 is a stearyl radical
  • R 8 is a hydrogen atom
  • R 9 is H or CH 3
  • the degree of ethoxylation a is 20.
  • Preferred detergent, detergent or cleaning agent portions contain, based on the total detergent, 0.01 to 4% by weight, preferably 0.1 to 3% by weight and in particular 0.5 to 2.0% by weight. % of a modified polyacrylate of the formula IV.
  • this water-poor or water-free formulation preferably comprises one or more anionic surfactant (s) and / or one or more Nioten- to adjust its rheological parameters.
  • the anionic surfactant (s) is / are selected from the group of the sulfonates and sulfates and their mixtures and / or the / the nonionic surfactant (s) is / are selected from the group of alkoxylated alcohols, alkoxylated fatty acid alkyl esters, alkyl glycosides and their mixtures.
  • the connection groups mentioned were explained in detail above.
  • polymers with a thickening effect which can also be used as associative thickeners.
  • These can be, for example (but not necessarily), acrylate-based polymers which, for. T. can have relatively high molecular weights in the range of> 1,000,000 g / mol. They are used in the washing-active, rinsing-active or cleaning-active formulations in amounts of 0.01 to 10% by weight, for example in amounts of 0.5 to 4% by weight.
  • Suitable products are, for example, the products marketed by Rohm & Haas under the name Acusol R , which are predominantly polyacrylates with different alkylation or crosslinking or hydrophobically modified nonionic polyols, or the products marketed by BF Goodrich under the name Carbopol R Polyacrylates or copolymers of acrylic acid and alkylated (preferably C 5 - to C 10 -alkylated) acrylic acids, or the products marketed by BF Goodrich under the name Pemulen R , which are high-molecular acrylic copolymers of the type acrylic / C 10 - up to C 30 alkyl acrylate Are cross polymer.
  • polyacrylate or polyurethane thickeners can also be used in water-free or essentially water-free systems which offer the possibility of adjusting the viscosity via a different mode of action (ie not associatively) in the presence of small amounts of water.
  • the liquid-based formulations show non-Newtonian flow behavior, preferably thixotropic or pseudoplastic flow behavior.
  • the liquid-based formulations have a low viscosity during manufacture, for example a viscosity in the range from 10 to 50 mPa.s, and the liquid-based formulations have a higher viscosity during storage, for example in the range from 10 to 100,000 mPas, preferably from 100 to 20,000 mPas, more preferably a viscosity in the range from 200 to 10,000 mPas.
  • the viscosity can be lower than in systems in which solid components (which are visually noticeable in a turbidity) are present; the latter thickens regularly during storage ("setting") and can even become pasty.
  • Detergent, detergent or cleaning agent portions according to the present invention which are present, for example, in capsule form, in spherical form or in the form of bags, have a (depending on the shape) high mechanical stability, which leads to the portions burst or burst much less often.
  • the mechanical stability can be measured as compression resistance by methods known per se (and described in more detail in the examples). This is generally defined as the resistance that the molded body opposes to a stamp pressure applied to it (under standardized conditions) and, as stated above, depends on the shape of the portion, but also on the strength of its ingredients, the temperature and if necessary, of further parameters.
  • Detergent, dishwashing or cleaning agent portions in capsule form according to the invention have a crush resistance of> 1 N at 23 ° C, preferably from 1 to 10 6 N at 23 ° C, more preferably from 10 to 10 5 N at 23 ° C and more preferably from 10 2 to 10 4 N at 23 ° C.
  • Spherical, detergent or cleaning agent portions according to the invention have a crush resistance of> 1 N at 23 ° C, preferably from 1 to 10 6 N at 23 ° C, more preferably from 10 to 10 5 N at 23 ° C and even further ahead moves from 10 2 to 10 4 N at 23 ° C.
  • Portions of detergent, dishwashing detergent or cleaning agent in the form of pouches according to the invention have a crush resistance of> 1 N at 23 ° C, preferably from 1 to 10 6 N at 23 ° C, more preferably from 10 to 10 5 N at 23 ° C and more preferably from 10 2 to 10 4 N at 23 ° C.
  • the liquid-based formulations of at least one washing-active, washing-active or cleaning-active material contained in the coatings of the detergent, dishwashing or cleaning agent portion can be clear solutions of one or more washing-active, washing-active or cleaning-active component (s) or microemulsions.
  • the liquid-based formulations contain one or more solids suspended or dispersed, in particular when low-water or essentially water-free formulations are used. This is an advantage over the prior art, since water-sensitive components of wash-active, rinse-active or cleaning-active materials can be kept stable and uniformly distributed in the liquid phase and problems with a reduction in activity do not occur.
  • the method for producing the detergent, detergent or cleaning agent portions is in principle not subject to any restrictions. It is usually carried out by simply mixing the constituents in stirred tanks, water, non-aqueous solvents and liquid surfactant (s) which may be present are expediently introduced and the further constituents are added in portions. A separate heating during production is not necessary, if it is desired, the temperature of the mixture should not exceed 80 ° C.
  • the process for the preparation of a detergent, dishwashing or cleaning agent portion which comprises a completely or partially water-soluble envelope in capsule form, in spherical form or in the form of a bag, which in turn comprises a liquid-based formulation of at least one wash-active, rinse-active or cleaning-active material completely surrounds the steps that one
  • step (d) if appropriate, immediately introduce the liquid mixture prepared according to step (c) into the casing and seal it around the liquid-based formulation.
  • the liquid mixture prepared according to step (c) can only be introduced into the casing with a time delay and the casing sealed with the liquid-based formulation.
  • the particular shear force that is applied to the liquid-based formulation of at least one wash-active, rinse-active or cleaning-active material in order to incorporate the remaining (in particular solid) components into this formulation can be particularly advantageous at> 0 , 01 min "1 , preferably in the range from 0.1 to 50,000 min " 1 , more preferably in the range from 5 to 20,000 min "1 , even more preferably in the range from 30 to 10,000 min " 1 .
  • the invention also relates to a washing method, in particular a method for machine washing in a commercially available washing machine, comprising the steps that
  • the invention also relates to a washing method, in particular a method for machine washing in a commercially available dishwasher, comprising the steps that
  • the invention also relates to a cleaning process comprising the steps that one
  • the portions according to the present invention can also be used in other areas.
  • they are also conceivable as a cleaner for toilet cisterns for the continuous delivery of a cleaning agent and disinfectant to the toilet flushing water, if necessary, or as a cleaner for pipes, etc.
  • such cleaners can also contain gas-releasing systems (eg an acid such as citric acid with a carbonate such as sodium carbonate).
  • the strength of detergent, detergent or cleaning agent portions according to the invention was determined using the following standardized method: The determination was carried out using a Zwick type 1425 universal testing machine.
  • At least 10 samples of each variety were tested. As a rule, the samples were checked immediately after air conditioning. At the request of the client, however, prior storage in various climatic conditions can also take place.
  • the samples were conditioned for at least 24 hours before each test.
  • the test was carried out in a normal climate at 23 ° C / 50% rel. Humidity.
  • test samples were basically tested in a plastic bag as a splash guard.
  • the material of this bag should be at least 100 ⁇ m thick.
  • the foil bag was placed in the center of the splash protection bag on the lower base plate. This was placed vertically under the upper base plate.
  • the printing press was set to an upsetting speed of 10 mm / min. set. The test process was then started. The force [N] exerted on the bag at the bursting moment was printed out on the connected printer.
  • the bag burst strength is given in N.
  • the tensile stress is given in N / cm 2 .
  • the filled area of the bag is also required. This is calculated from the height and width of the entire bag, minus the respective welding or sealing edges. The two internal dimensions were measured to within 0.1 cm and the area calculated. Examples 1 to 7
  • ABS powder alkyl benzene sulfonate 90%
  • Unger Sulfopon 1218 G C 12 - to C 18 -fatty alcohol sulfate granules
  • Cognis Lutensol AO7 C 13 - to cis-oxo alcohol ethoxylate with 7 mol
  • Lutensol AO5 C 1 3 to C 15 -Oxoalcohol ethoxylate with 5 mol
  • company Cognis Dehydol LS5 C ⁇ 2 - to C 1 - Fatty alcohol ethoxylate with 5 moles of EO
  • Cognis Dehypon LS54 C 12 - to -C 4 fatty alcohol ethoxylate /
  • Genapol UD-79 C ⁇ oxo alcohol ethoxylate with 7 mol EO
  • Clariant Tixogel MP 250 organically modified layered silicate
  • Südchemie Thixatrol Plus diamide wax mixture
  • Rheox TAED tetraacetyl diamine
  • Warwick Triacetin glycerin triacetate
  • Cognis Na-SKS-6 Clariant Sokalan CP 5 polycarboxylate
  • BASF Turpinal 2NZ hydroxyethane diphosphonic acid di-sodium salt
  • Cognis Velvetol 251 C terephthalic acid-ethyleglycol-PEG polyester
  • Rhodia Tinopal CBS-X opt.
  • Marlinat 242 / 90M Ci 2 - C 14 - fatty alcohol polyethylene glycol (2EO) ether sulfate -
  • a conventional free-flowing detergent formulation was filled into a gelatin ball from Swisscaps, which is equivalent to Examples 1 to 7 given above.
  • the recipe is given in Table 2 below.
  • the viscosity was also determined using the Brookfield method.
  • the crush resistance of the filled gelatin balls according to Examples 1 to 7 and according to the comparative example was measured by the method described above. The results show that the stability of spheres filled with non-Newtonian or higher-viscosity liquids was greater than that of spheres filled with a free-flowing product.

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

Abstract

L'invention concerne une dose d'agent de lavage, de rinçage ou de nettoyage comportant une enveloppe entièrement ou partiellement soluble dans l'eau se présentant sous forme de capsule, de sphère, ou de poche. Ladite enveloppe renferme entièrement une formulation à base liquide d'au moins une substance active de lavage, de rinçage, ou de nettoyage avec une résistance à l'écrasement > 1 N à 23 DEG C. L'invention concerne également un procédé de fabrication d'une telle dose d'agent de lavage, de rinçage ou de nettoyage, ainsi qu'un procédé de lavage, de rinçage, ou de nettoyage faisant intervenir ladite dose d'agent de lavage, de rinçage ou de nettoyage.
EP01974141A 2000-08-17 2001-08-08 Doses d'agent de lavage, de rin age ou de nettoyage a formulation liquide mecaniquement stables Revoked EP1309669B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10040724 2000-08-17
DE10040724A DE10040724A1 (de) 2000-08-17 2000-08-17 Mechanisch stabile, flüssig formulierte Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen
PCT/EP2001/009173 WO2002014460A2 (fr) 2000-08-17 2001-08-08 Doses d'agent de lavage, de rinçage ou de nettoyage a formulation liquide mecaniquement stables

Publications (2)

Publication Number Publication Date
EP1309669A2 true EP1309669A2 (fr) 2003-05-14
EP1309669B1 EP1309669B1 (fr) 2006-10-04

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EP01974141A Revoked EP1309669B1 (fr) 2000-08-17 2001-08-08 Doses d'agent de lavage, de rin age ou de nettoyage a formulation liquide mecaniquement stables

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Country Link
US (1) US20040063598A1 (fr)
EP (1) EP1309669B1 (fr)
AT (1) ATE341611T1 (fr)
AU (1) AU2001293743A1 (fr)
DE (2) DE10040724A1 (fr)
ES (1) ES2272543T3 (fr)
WO (1) WO2002014460A2 (fr)

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Also Published As

Publication number Publication date
EP1309669B1 (fr) 2006-10-04
DE10040724A1 (de) 2002-03-07
US20040063598A1 (en) 2004-04-01
WO2002014460A2 (fr) 2002-02-21
ATE341611T1 (de) 2006-10-15
DE50111157D1 (de) 2006-11-16
WO2002014460A3 (fr) 2002-05-10
AU2001293743A1 (en) 2002-02-25
ES2272543T3 (es) 2007-05-01

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