EP1194523B1 - Portion de detergent ou nettoyant - Google Patents

Portion de detergent ou nettoyant Download PDF

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Publication number
EP1194523B1
EP1194523B1 EP00947888A EP00947888A EP1194523B1 EP 1194523 B1 EP1194523 B1 EP 1194523B1 EP 00947888 A EP00947888 A EP 00947888A EP 00947888 A EP00947888 A EP 00947888A EP 1194523 B1 EP1194523 B1 EP 1194523B1
Authority
EP
European Patent Office
Prior art keywords
water
temperature
washing
laundry
soluble material
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.)
Revoked
Application number
EP00947888A
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German (de)
English (en)
Other versions
EP1194523A1 (fr
Inventor
Thomas Holderbaum
Bernd Richter
Christian Nitsch
Jürgen Härer
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 EP1194523A1 publication Critical patent/EP1194523A1/fr
Application granted granted Critical
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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
    • C11D17/0047—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
    • C11D17/04—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
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines

Definitions

  • the present invention relates to a detergent or cleaner portion with an enclosure made of a water-soluble material.
  • the present invention a detergent or detergent portion for loading a washing or dishwashing machine for one in an aqueous phase running program run of the machine.
  • the prior art knows a multiplicity of washing or cleaning agent formulations, the consumer in the form of spray-dried or granulated Powder products or alternatively provided as liquid products become. These are supplied by the consumer by means of supplied standard containers in the corresponding filling container of washing machines or dishwashers or - in particular when washing laundry - in supplied water permeable and so that vessels flushable by the liquor, which are added to the laundry, dosed. The dosing process was often perceived as a nuisance.
  • Formulations were developed in the form of ready-to-use portions of a washing or cleaning agent which are exactly or cleaning course. Such portions can be both solid and be liquid detergent or cleaner formulations.
  • Such solid Detergent formulations can be in the form of powders or of shaped articles obtained by compression, for example tablets, Blocks, briquettes or rings o. ⁇ . Are present.
  • Advanced packaging and wrapping, in particular plastic films, which fulfill the above purposes have already been water-soluble in the prior art.
  • the consumer was thus able to immediately place the portion pack in the washing or cleaning cycle or in a bucket or in a sink or sink throw, without tearing the packaging and its contents to appropriate Deposit or deposit.
  • the packaging or serving then dissolved in the course of the washing or cleaning cycle or before or during the hand washing, cleaning or rinsing (s) and brought by the contents in contact with the aqueous medium.
  • DE-AS 11 30 547 (Procter & Gamble) discloses packages of water-soluble Sheets of polyvinyl alcohol containing non-liquid, synthetic Detergents are filled.
  • a single dose of a detergent or bleach in a pouch containing a suture or more seams of water-sensitive material is in the Document EP-A 0 143 476 (Akzo N.V.).
  • a water-sensitive Suture is a mixture of anionic and / or nonionic water-binding polymer and a cationic adhesive material.
  • the object of the invention is pursued Fact that individual components of a washing or Detergent preparation with other components of the same preparation can not be compatible or that a component of a detergent or cleaning composition needed in a wash or cleaning cycle is or is desirable, but not in another, or that one particular Component of a detergent or cleaner preparation not included
  • All temperatures of a washing or cleaning process works equally well and to ensure an optimal effect of the liquor at the temperature added should be, which corresponds to the optimum effect. This applies, for example for enzymes that regularly have an optimum effect at a certain temperature have, or for bleach activators, in a detergent or cleaning preparation be incorporated to wash or clean at temperatures of 60 ° C or below to achieve an improved bleaching effect.
  • inventive washing or Detergent portion is at least the second measured amount of a wash-active preparation of one at a temperature above the first Temperature water-soluble material includes.
  • the invention further relates to a washing method, in particular method for machine washing, wherein a detergent portion according to the above Information and the following detailed description in a Washer or a suitable for washing vessel placed and through Adding water and adjusting the temperature to the temperature value at which the water-soluble material comprising the respective washing agent partial portion dissolves, the detergent portion in the wash liquor releases, while the other Detergent partial portions protected from contact with the wash liquor are and will be released at other temperatures.
  • the invention further relates to a purification process, in particular process for machine cleaning of dishes, wherein a detergent portion according to the above information and the following detailed description in a dishwasher or suitable for rinsing Placed on the vessel and by adding water and adjusting the temperature on the Temperature value at which the respective detergent partial portion comprehensive water-soluble material dissolves, the detergent portion in the cleaning solution releases while the other detergent portion portions before protected from contact with the cleaning liquor and at other temperatures be released.
  • detergent or cleaner portion is used in the context of present invention for a take place in an aqueous phase Washing or cleaning process sufficient amount of a detergent or Cleaner understood.
  • this can be a machine washing or cleaning process, as it is with commercial washing machines or Dishwashers is performed.
  • the washing or cleaning agent portions are preferred used in mechanical washing or cleaning operations.
  • washing or cleaning agent portion is under the present invention, a subset of a washing or cleaning agent portion understood that in one of other washing or cleaning agent portions separated phase in spatial communication with other washing or detergent partial portions of the same detergent or cleaner portion present and prepared by appropriate measures so that they are separated from other washing or cleaning agent portions of the same Detergent or cleaning agent portion added to the liquor and optionally can be solved or suspended in it.
  • a washing or cleaning agent partial portion the same ingredients as another wash or Detergent portion of the same detergent or cleaner portion contain; However, preferably two detergent or cleaner partial portions contain same detergent or detergent portion different Ingredients, in particular different active washing preparations.
  • the detergent or detergent portions contain measured Quantities of washing preparations. It is possible that the Servings only washing active preparations of a certain composition contain. However, according to the invention it is preferred that several, usually at least two, washing-active preparations of different composition contained in the washing or cleaning agent portions.
  • the Composition can be in terms of the concentration of each Components of the detergent-active preparation (quantitatively) and / or in terms of the nature of the individual components of the detergent-active preparation (qualitative) be different. It is particularly preferred that the components in terms of Type and concentration are adapted to the tasks that the washing or cleaning agent portions have to meet in the washing or cleaning process.
  • the partial portions are in the context of the present invention prefers the first encompassed by various water-soluble materials, second and possibly third or even higher (fourth, fifth etc.) measured quantities of one or more washing preparation (s) containing combined into a washing or cleaning agent portion according to the invention are.
  • detergent-active preparation is understood to mean all conceivable substances of relevance in connection with a washing or cleaning process. These are primarily the actual detergents or cleaners with their individual components further explained in the further course of the description. These include active ingredients such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builders (inorganic and organic builders), bleaches (such as peroxy bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, specialty polymers, Dyes and fragrances (perfumes), without the term being restricted to these substance groups.
  • detergent compositions is also understood to mean detergents and cleaning auxiliaries. Laundry-treating agents such as fabric softeners or dishwashing detergent additives such as rinse aid are also considered according to the invention as detergent-active preparations.
  • Preferred according to the invention is an embodiment of the washing or cleaning agent portion, in the at least the second measured amount of a wash-active preparation of one at a temperature above the first Temperature water-soluble material is included.
  • the first washing-active Preparation in measured quantity in the detergent or cleaner portion is included, one for the pre-wash or Vorthesesgang, especially for the pre-rinse, suitable composition, while the second detergent preparation, which in measured amount in the Detergent or detergent portion is included, one for the main wash or Hauptmossgang, especially for the main rinse, suitable Composition is.
  • the first wash-active preparation goes to one Temperature below or equal to a first temperature in the aqueous phase over, while the second detergent preparation at a temperature in the aqueous phase which is below or equal to a second temperature, which is above the first temperature
  • the main wash or Skin rinse adapted wash active preparation of a suitable water-soluble Surrounded by material It is at least the second, so in this case for the main wash or Skin rinse adapted wash active preparation of a suitable water-soluble Surrounded by material.
  • the second detergent preparation during the pre-wash or pre-rinse cycle includes, d. H. against the ingress of water or washing or rinsing liquor and thus an impairment of effectiveness and / or reduction protects the effective amount.
  • the water-soluble material comprising the second detergent preparation first is soluble in water at a temperature above that of the prewash cycle or the prewash.
  • prewash or prewash During the regularly at lower Temperature, usually with cold water, carried out prewash or prewash therefore remains the enclosure of the second detergent preparation obtained by the (second) water-soluble material. This will be before the Access is protected by water or aqueous liquor and thus remains in full and obtained in full effectiveness for the main wash or main wash.
  • an embodiment is preferred according to which the first measured Amount of a washing active preparation for the pre-wash or Rinse under the detergent or cleaning agent portion according to Invention is conveniently and consumed ready to use and also against contact by unauthorized persons or the consumer and also against the ingress of moisture protected by being comprised of a water-soluble material, which allows the first measured amount of a detergent preparation at a temperature below or equal to a first temperature in the aqueous phase or liquor passes.
  • washing-active preparation comprehensive material brings thereby the substantial
  • the advantage is that the washing or cleaning agent portion for a washing or cleaning process, in particular in a washing machine or dishwasher, dosed and not only all for the washing or cleaning process required components in a unit to be placed in the machine but the washing-active components are also in an optimized ratio to each other and in a way they in the washing or cleaning cycle at a time in the fleet releases, to which they the optimal Effectiveness can also develop.
  • this has the first measured Amount of a water-soluble preparation comprising water Material a water solubility, which is the transition of the detergent preparation allowed in the aqueous phase or liquor at the temperatures at which the first course of the washing or cleaning process is carried out in the this detergent preparation should be effective; in the present For example, this is the pre-wash or pre-wash.
  • this gear at cold water temperatures such as maximum at ambient temperature, for example at 3 to 25 ° C, preferably at 5 to 20 ° C, even more preferably at 7 to 18, even more preferably at 15 to 18 ° C performed
  • the solubility of this material must be adjusted so that a Solve reliably at the maximum temperature of the cold water phase of a Washing or cleaning program occurs.
  • the first active washing preparation in measured amount in the Detergent or detergent portion is included, one for the pre-wash or Vorthesesgang, especially for the prewash, suitable composition and is the second active washing preparation that is in measured Amount contained in the detergent or cleaner portion, one for the Main wash or main wash, especially for the main wash, suitable composition, while a further existing third washing-active preparation, which is likewise metered in the washing or detergent portion is present, one for the post-wash or Rinse cycle is suitable composition.
  • the first washing active preparation goes in at a temperature below or equal to a first temperature in the aqueous phase over, and the second detergent-active preparation is at a Temperature in the aqueous phase over, which is below or equal to a second Temperature is which is above the first temperature, while the third washing-active preparation passes into the aqueous phase at a temperature, which is above the second temperature.
  • the second in this case is at least the second, so in this case for the main wash or skin rinse adapted washing active preparation of one surrounded by suitable water-soluble material. Its nature is similar in the case described above, in which the washing or detergent portion of only two active washing preparations for the Prewash or pre-wash and for the main wash or main wash consists. Also in this case it is particularly preferred if the first measured Amount of a washing active preparation of one in the low temperature range water-soluble material is included, since this is a convenient and ready-to-use dosage of the detergent compositions in the inventive Detergent and detergent portion ensures and before entering the washing or cleaning agent portion according to the invention in the washing or Rinse the first measured amount of a detergent preparation before direct contact with the consumer or even an unauthorized person, eg. B. from contact with or ingestion by children, and also causes that the individual components of the first measured amount of a washing active Preparation against being affected by environmental conditions (eg Moisture) and / or a reduction in the effective amount.
  • environmental conditions e
  • washing or cleaning agent portion which also includes a third measured amount of a detergent preparation also contains the third measured amount of a detergent preparation to protect against a transfer to the washing or cleaning fleet a temperature at which the main wash or main wash is still running, surrounded by a suitable water-soluble material.
  • This is preferably so that it is the third detergent-active preparation during pre-wash or pre-wash and during the main wash cycle or main rinse, d. H. from access of water or from Washing or rinsing eye and thus a deterioration of the effectiveness and / or reducing the effective amount.
  • this includes the third detergent-active preparation water-soluble material is only soluble in water at a temperature above the temperature of the main wash or the main wash cycle is. While regularly at low temperature, usually with cold water, carried out pre-wash or pre-wash and during the regular at medium temperature, preferably at> 20 to 55 ° C, more preferably> 25 to below about 45 ° C, for example at> 30 to 45 ° C, carried out main wash
  • the main wash cycle therefore, remains the enclosure of the third detergent Preparation obtained by the (third) water-soluble material. This is protected from the entry of water or aqueous liquor and remains so in full quantity and in full effectiveness for the post-wash cycle (eg soft wash cycle) or rinse cycle received.
  • the first wash-active preparation measured in a measured amount in the washing or detergent portion is included, one for the main wash or Main cleaning course, in particular for the main rinse, suitable composition, while an existing second wash-active preparation used in also measured amount in the washing or cleaning agent portion is present, a suitable composition for the post-wash cycle or rinse cycle is.
  • the first wash-active preparation is at a temperature below or equal to a first temperature in the aqueous phase, in the present example, the temperature of the main wash or the Wort Hughesgangs is, for example, at a temperature of 45 ° C or less, preferably at a temperature of 30 ° C or less, and the second detergent-active Preparation is at a temperature in the aqueous phase, above the first temperature is, ie at the temperature of the post-wash cycle Rinse cycle, for example at a temperature of over 45 ° C, preferably at 50 to 55 ° C.
  • the second detergent preparation for the post-wash cycle or wash cycle or rinse cycle adapted washing active Preparation surrounded by a suitable water-soluble material.
  • This must be such that it is the second detergent preparation during of the main wash or main wash cycle, d. H. before an entrance of Water or washing or soapy water and thus an impairment of Effectiveness and / or reduction of the effective amount protects.
  • the second detergent preparation comprehensive water-soluble material only at a temperature soluble in water that is above the temperature of the main wash or main wash cycle lies.
  • the enclosure of the second detergent preparation remains through obtained the (second) water-soluble material. This will be done before the entry of Protected in water or aqueous liquor and thus remains in full and in full effectiveness for the post-wash cycle or rinse cycle received.
  • the first measured Amount of a washing active preparation of one in the lower temperature range ie in the range of the temperature of the main wash cycle or main wash cycle
  • water-soluble material is included, since this is a convenient and ready-to-use dosage of the detergent compositions in the inventive Detergent and detergent portion ensures and before entering the washing or cleaning agent portion according to the invention in the washing or Rinse the first measured mangle of a detergent preparation before direct contact with the consumer or even an unauthorized person, eg. B.
  • the individual components of the first measured amount of a washing active (here the one intended for the main wash or main rinse) Preparation against being affected by environmental conditions (eg moisture) and / or a reduction in the effective amount.
  • a first, second and possibly also higher (eg third) measured Amount of one each washing active preparation, in a washing or cleaning agent portion are included according to the invention, for the main wash or Hauptmassgang suitable and intended compositions are, while an even higher (eg third or possibly fourth) measured Amount of a detergent in the detergent or cleaner portion a suitable and intended for the Nachwasch- or rinse cycle Composition is.
  • the first, second and possibly third, for the Main wash or main wash provided composition go at a temperature in different places of the temperature profile of the main wash cycle or main cleaning cycle is, one after the other, short successively or even partially simultaneously and partially successively into the aqueous phase over, while the even higher (third or possibly fourth) measured amount of a detergent preparation only at a temperature goes into the aqueous phase, which is above the aforementioned temperatures, for example, at the temperature of Vietnamese Stamms lies.
  • the at the lowest temperature water-soluble material dissolves at a relatively low, in the temperature profile at the beginning temperature of the main wash or Hauptmossgangs and sets covered by this material Wash-active preparation in the fleet free.
  • the water solubility of the second (and optionally third) water-soluble Material solves / dissolve these (s) at the corresponding higher temperatures of the main wash or main cleaning and sets / set successively the respective washing active preparation (s) into the liquor free.
  • a first measured Provide a portion of a detergent preparation as a partial portion, which in a Temperature below or equal to a first temperature in the aqueous phase passes; a second measured amount of a second detergent preparation to provide as a partial portion at a temperature below or equal a second temperature, which is above the first temperature, in the aqueous Phase passes, and provide a water-soluble material, both washing-active preparations together.
  • the water solubility of the water-soluble material is adjusted so that the Conditions, for example at the temperature, triggers at which the first needed washing-active preparation should be released into the liquor.
  • This case analogously, of course, is more active on three or even more than three partial portions Preparations applicable.
  • the first measured amount of a detergent preparation is one for the Main wash or main wash adapted and intended preparation, in the form of a powder or in the form of particles or in the form of a shaped body present and together with a second measured amount of a wash-active preparation of an enclosure in the form of a water-soluble Surrounded material whose water solubility is set to the lowest Main wash or main wash cycle temperature.
  • the second washing active Preparation may be one for the main wash or main wash be in a second stage or may be one for the post-wash cycle or rinse cycle.
  • Particularly preferred is the second Active washing preparation in a form in which this second detergent preparation from immediate contact with water and subsequent release in the fleet is protected at the time the first metered Amount of a detergent preparation already included in Water dissolves.
  • the form in which the second measured amount of a washing-active Preparation may be, for example, a form in the latter of its own water-soluble material is included, the water solubility first at another, for example, a higher, temperature occurs.
  • the second detergent-containing preparation a in be a matrix incorporated detergent formulation in which the matrix material protects the detergent-active preparation from contact with water and only then allows contact with water (for example by dissolving, melting or the like), if other conditions exist, such as a higher temperature is reached.
  • a at low temperature water-soluble material an immediately for the washing or Cleaning process at low temperature soluble, such as powdery detergent-active preparation together with a particulate material or a Shaped body of a second detergent-active preparation (and optionally natural also a third detergent-active preparation), which is solution-delayed prepared by the person skilled in the art Measures such as pressing, coating, surrounding with a water-soluble at higher temperature material or similar measures can be achieved.
  • Another embodiment of the invention may be consist in that two measured amounts of washing active preparations are covered by the same water-soluble material, for example, in the lowest temperature is soluble at which the detergent or detergent portion should be used, but the two preparations for a different Solubility were conditioned in an aqueous medium, for example by different degrees of pressing and / or by coating or coating with different water-soluble coatings (and or by Coaten only in the case of a detergent preparation) and / or by incorporation into matrix materials with different properties (and / or introduction into a Matrix only in the case of a detergent preparation), etc. All the above cases are of course also for from three or more detergent preparations existing Combinations applicable, especially for those cases where several Washing-active preparations for delayed release in one Wash or rinse are provided.
  • Another detergent or cleaner portion according to the invention is characterized preferred that certain ingredients separate from others in the liquor and thus contribute to an improved effect.
  • a cleaning agent in particular a dishwashing detergent, can be active in washing preparations against other components washing preparations are sensitive, only then full effectiveness unfold if this sensitivity is taken into account.
  • Enzymes are typical examples of such substances. Even if they are regarding the temperature of their use are optimized, they act in the presence of Bleaching agents significantly worse. Therefore, enzymes according to the invention already be released into the liquor before the bleaching agents by Bleach by a water-soluble enclosure prevents too early in the Fleet to arrive; only after the enzymes - possibly already at lower Temperature, d. H. in the Vorthesesgang - have been working for a while bleaches are released into the liquor by they dissolve surrounding enclosure in water. It is just as possible to use enzymes first use in the main cleaning cycle and other detergent-active preparations, which are intended for the main course, delayed by the enzymes in the To give liquor, for example by pressing, Coaten, embracing with one water-soluble enclosure, etc. This allows the enzyme reaction time (preferred even in the time of VorrBanks) extend and the cleaning or Significantly improve the rinsing result.
  • agents with antimicrobial effect before o-der / and after the washing or cleaning agent components of the main wash cycle to be used.
  • the use of active ingredients with antimicrobial Effect in Vorthesesgang has the advantage that the spread and Prevention of microbial growth in the main wash cycle is prevented or at least reduced becomes. The active ingredient is then, however, washed away with the wash liquor.
  • an antimicrobial agent can be used in Nachthesesgang to precipitate on laundry and machine and so a long-lasting develop antimicrobial activity. The corresponding mode of action can be achieved when the antimicrobial agent passes through a water-soluble enclosure is protected, either already at the temperatures of the pre-wash cycle or dissolves in the water only at the temperatures of the rinse cycle.
  • components such as e.g. Perfume, bleach and bleach activators throughout the wash or cleaning cycle be constantly dosed. This can e.g. be achieved by this Components in all separate, dissolving at different temperatures, water-soluble enclosures are present.
  • detergent or cleaner portions are usable containing two detergent portions (e.g. for pre-washing or pre-cleaning with cold water-soluble enclosure and for main wash or main cleaning with hot water soluble enclosure or for main washing or main cleaning with warm water-soluble Surrounding and for washing or post-cleaning with hot water soluble Enclosing), or detergent or detergent portions are also usable, contain the three or even more washing or cleaning agent portions, d. H. one each for the pre-, main- and follow-up of the washing or cleaning process or even those in which individual courses of the overall procedure several partial portions are provided.
  • wash-active preparations at the exact time and in the quality and quantity in the washing or cleaning process are available for which they have the optimum effect, without being disturbed by any detergent components that have the optimum effect affect.
  • Preferred according to the invention is an embodiment of the washing or cleaning agent portion, in the at least the second measured amount of a is surrounded by a water-soluble material, the is soluble at a temperature above the first temperature, that is a temperature, which is above the temperature at which the first wash or cleaning cycle takes place. This is advantageously achieved that the second Protective washing preparation is protected from contact with the liquor until the first wash or cleaning cycle is completed.
  • Another release system for the targeted release of active ingredients is based that it cools down to a certain temperature heated air volume per ° Kelvin to a volume decrease of about 1/272 comes.
  • a suitable dosage form for example a capsule with Perforation, may be due to the resulting air volume contraction
  • Underpressure material from the environment can be sucked into the dosage form and secondary processes such as corrosion, solution, heating or gas formation trigger, which allow a release of the desired ingredients.
  • Such (physico-) chemical switches are used, which in a Change in the pH of the application fleet a change in the physicochemical Experience properties.
  • such substances are used as (physico-) chemical switches due to a change in the pH occurring in the application liquor have increased solubility in water.
  • such Switch substances are preferred, which in the corresponding change in pH the application fleet a change, in particular a decrease in Have diffusion density.
  • the thermodynamic solubility also the dissolution kinetics of a filmed substance or the decrease their mechanical stability is important.
  • pH-sensitive switches can be used for all applications, in particular use in the washing, rinsing or cleaning agent area in which a Active ingredient in a lowering of the pH from the alkaline to the Neutrals should be released.
  • a Active ingredient in a lowering of the pH from the alkaline to the Neutrals should be released.
  • This can be both in the area of washing in the washing machine as well as machine dishwashing the case.
  • parts of a detergent formulation for automatic dishwashing e.g., surfactants, perfume, soil repellant, acid, complexing agents, builders etc., or preparations containing these active ingredients
  • so formulated be that they are not released in the main rinse at high pH, but released in the subsequent rinse cycle with lower pH become.
  • Another release system is enzyme-controlled drug release.
  • enzymatically degradable (enzyme-sensitive) materials either as a carrier or as a coating material, in particular of shaped articles, for example Tablets, or capsules of active ingredients of washing, rinsing or Detergents used.
  • rinsing or cleaning agents contained enzymes cause after a certain exposure time a degradation of the enzyme-sensitive support material and, consequently, a Release of the or in the carrier material or in the coated moldings, Granules or capsules contain active ingredients of the washing, rinsing or detergent.
  • Another release system for targeted release of drugs is a (physico-) chemical switch, in which a redox system is used.
  • the redox materials as either carrier or as a coating material, in particular of shaped articles, for example tablets, or capsules of active ingredients of washing, rinsing or cleaning agents be used.
  • rinsing or cleaning agents contained redox-active components there is a chemical change of the redox-sensitive carrier or Coating material and concomitant release of the or in the carrier material or in the coated moldings, granules or capsules included active ingredients of detergents, dishwashing or cleaning agents.
  • a chemical switch can be used, which is an electrolyte-controlled Drug release causes.
  • automatic dishwashing detergent can the difference in the electrolyte content between the cleaning cycle and the rinse cycle in automatic dishwashing be exploited.
  • this is at least comprising the second measured amount of a detergent preparation water-soluble material a water-soluble packaging.
  • a water-soluble packaging Including one flat trained part understood that the second completed lot completely surrounds a detergent preparation.
  • the exact form of such Packaging is not critical and can largely circumvent the usage requirements be adjusted.
  • there are different forms such as hoses, cushions, cylinders, bottles, disks, etc.
  • films which, for example, are too Packaging such as hoses, cushions o. ⁇ . Glued and / or sealed can, after having partial portions of the washing or Detergent portions were filled.
  • plastic film packaging from water-soluble films.
  • Such films are in principle known from the prior art. You can especially prefer the Groups (acetalated) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, Gelatin, cellulose and derivatives thereof and mixtures of said materials To belong.
  • Polyvinyl alcohols are polymers of the general structure [-CH 2 -CH (OH) -] n in small quantities also structural units of the type [-CH 2 -CH (OH) -CH (OH) -CH 2 -] contain. Since the corresponding monomer (vinyl alcohol) is not stable in free form, polyvinyl alcohols are obtained via polymer-analogous reactions by hydrolysis, in particular by alkali-catalyzed transesterification of polyvinyl acetates with alcohols, preferably with methanol. By these technical methods, PVAL are also available which contain a predetermined residual amount of acetate groups.
  • PVAL e.g., Mowiol® grades from Hoechst
  • PVAL e.g., Mowiol® grades from Hoechst
  • PVAL water solubility
  • aldehydes Acetalization
  • dichromates boric acid
  • Borax Borax reduce and so targeted to desired Set values.
  • PVAL films are largely impermeable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide but pass water vapor.
  • suitable water-soluble PVAL films are those under designation "SOLUBLON®” by Syntana bottlesgesellschaft E. Harke GmbH & Co. available PVAL films. Their solubility in water can be accurate to the degree and there are transparencies available in this range, which are available in all for the Application relevant temperature ranges are soluble in the aqueous phase.
  • PVP Polyvinylpyrrolidones
  • PVP are prepared by radical polymerization of 1-vinylpyrrolidone.
  • Commercially available PVP have molecular weights in the range of about 2500 to 750,000 g / mol and are as white, hygroscopic powder or as aqueous Solutions offered.
  • Polyethylene oxides PEOX for short, are polyalkylene glycols of the general formula H- [O-CH 2 -CH 2 ] n -OH the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.
  • Gelatine is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), the predominantly by hydrolysis of the collagen contained in the skin and bones of animals is obtained under acidic or alkaline conditions.
  • the amino acid composition the gelatin largely corresponds to that of collagen, from which it was won and varies depending on it Provenance.
  • the use of gelatin as the water-soluble shell material is especially in pharmacy in the form of hard or soft gelatin capsules extremely widespread. In the form of slides, gelatin is because of their compared to the above-mentioned polymers of high price only minor use.
  • washing and cleaning agent portions are also preferred, their packaging of water-soluble film of at least a polymer from the group starch and starch derivatives, cellulose and Cellulose derivatives, in particular methylcellulose and mixtures thereof.
  • Starch is a homoglycan, with the glucose units linked ⁇ -glycosidically are.
  • Starch is composed of two components of different molecular weight: from about 20 to 30% straight-chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (M.W., about 300,000 to 2,000,000).
  • small amounts of lipids, phosphoric acid and cations are still included. While the amylose due to binding in 1,4-position long, helical, forms entangled chains of about 300 to 1200 glucose molecules, the chain branches in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like structure with about 1,500 to 12,000 molecules of glucose.
  • starch derivatives by polymer-analogous reactions are available from starch.
  • Such chemically modified starches include in this case, for example, products from esterifications or etherifications, in which Hydroxy hydrogen atoms were substituted. But also strengths in which the Hydroxy groups against functional groups that do not have an oxygen atom are substituted, can be used as starch derivatives.
  • Group of starch derivatives include, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino acids.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • Preferred enclosures of water-soluble film consist of a polymer with a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons and in particular between 10,000 and 100,000 Dalton.
  • the water-soluble film forming the enclosure preferably has a thickness of 1 to 150 microns, preferably from 2 to 100 microns, more preferably from 5 to 75 microns and especially from 10 to 50 microns, on.
  • these water-soluble films can be produced by various production methods become. Blow molding, extrusion and casting processes are in principle here too call.
  • the films are going starting blown from a melt with air through a blow pin to a hose.
  • the extrusion process which is also the preferred method of preparation belongs, are the plasticized by suitable additives raw materials atomises to form the films.
  • the casting process which is also one of the preferred preparation, is an aqueous Polymer preparation placed on a heatable drying roller, after the Evaporation of the water is optionally cooled and the film peeled off as a film.
  • this film is additionally powdered before or during the removal.
  • polyvinyl alcohol films as enclosing for the second measured amount of a detergent preparation used in a temperature are soluble in a range corresponding to the temperature range of Washling or cleaning cycle corresponds, in which the second measured Amount of a detergent preparation is used.
  • the Temperature of the main rinse for example in the range of> about 20 to about 55 ° C, preferably> 25 ° C to below 45 ° C, more preferably a temperature above 30 ° C to, for example, 40 ° C.
  • the temperature of the rinse is for example > 45 ° C, z. In the range of 50 to 55 ° C or even higher.
  • other temperature ranges for example up to about 25 ° C for prewash, up to about 90 ° C for main wash and up about 30 ° C for after washing.
  • the temperatures, in which the water-soluble film dissolves be adjusted in wide ranges or film materials are commercially available (see the above Films of the MOWIOL® type or the above-mentioned films of the SOLUBLON® type), which limits the water solubility to a certain range are set; the expert can then such films accordingly select the requirements.
  • the water-soluble material that is the second measured amount of a detergent Preparation is a water-soluble capsule.
  • Such capsules are also known from the prior art. You can, for example, without that is to be understood as a limitation, capsules of PVAL, gelatin or be similar materials. Such capsules are commercially available and will be in the context of pharmaceutical preparations or food additives widely used. Capsules have proven particularly useful made of hard gelatin or soft gelatin, and they are therefore according to the invention particularly preferred.
  • a water-soluble coating In a further, likewise preferred embodiment of the invention that is comprising at least the second measured amount of a detergent preparation water-soluble material a water-soluble coating.
  • a detergent preparation water-soluble material a water-soluble coating.
  • Such coatings or encapsulating substances are already used for coating washing-active substances State of the art used and can be - comparable to the film materials - in terms of their physical and chemical properties such as in terms of water solubility, the melting point or Melting set exactly to specific technical requirements.
  • the purposes of the present invention are for wrapping washing-active preparations Coatings that are water-soluble in the narrower sense, just as well suited as Coatings arising in aqueous environment while adjusting certain physical or chemical conditions such as a particular one Temperature or a certain pH dissolve, for example because they melt and the coating substances are then dispersed in water and the release previously encapsulated ingredients.
  • water-soluble in the context of the present Invention generally not only the property of the enclosures of the washing active Preparations, from an aqueous medium (in the narrower sense) dissolved too but also the property (in the broad sense), in setting certain physical or chemical conditions in the aqueous environment to change so that the physical integrity is lost and the enclosure releases the ingredients into the aqueous phase.
  • the melting and subsequent Dispersing the material of the enclosure in the aqueous phase a typical (but not limiting) example.
  • the coatings or encapsulants should have a melting range in have such a temperature range in which the to be wrapped detergent substances are not exposed to high thermal stress.
  • the melting range must be sufficiently high to at least slightly elevated temperature still provides adequate protection for the trapped to provide wash-active substances.
  • the substances of the coatings or the enamels on melting ranges between about 45 ° C and about 75 ° C.
  • the term "melting range” means in this Case that the melting range occurs within said temperature interval and does not denote the width of the melting range.
  • waxes As particularly effective In this context, coatings of waxes have been found, though applied directly to the detergent preparation or its individual components and such coatings are therefore because of the ease of application and the ability to precisely adjust the water solubility and thus on optimally match the circumstances, particularly preferred.
  • waxing is understood to mean a number of natural or artificial substances, which usually melt above 40 ° C without decomposition and already slightly above the melting point is relatively low viscosity and non-stringy are. They have a strong temperature-dependent consistency and solubility.
  • the waxes are divided into three groups, natural ones Waxes, chemically modified waxes and synthetic waxes.
  • Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, japan wax, esparto wax, cork wax, Guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (Wool wax), or raffia fat, mineral waxes such as ceresin or ozokerite (earth wax) or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.
  • vegetable waxes such as candelilla wax, Carnauba wax, japan wax, esparto wax, cork wax, Guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax or montan wax
  • animal waxes such as beeswax, shellac wax, spermaceti, lanolin (Wool wax), or
  • the chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
  • Synthetic waxes are generally polyalkylene waxes or polyalkylene glycol waxes Understood.
  • shell materials or coatings can be used also compounds from others Substance classes that meet the above-mentioned requirements with respect to the softening point fulfill.
  • suitable synthetic compounds have become for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, commercially available under the name Unimoll® 66 (Bayer AG), proved.
  • synthetically produced waxes from lower Carboxylic acids and fatty alcohols for example dimyristyl tartrate, which under the name Cosmacol® ETLP (Condea) is available.
  • Cosmacol® ETLP Condea
  • too Synthetic or semi-synthetic esters of lower alcohols with fatty acids can be used from native sources.
  • the product falls into this class of substance Tegin® 90 (Goldschmidt), a glycerol mono-stearate palmitate.
  • Shellac KPS-Dreiring-SP Korean Chemical Company
  • Shell material or coating can be used.
  • Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 Carbon atoms.
  • the wax alcohols come, for example in the form of Waxiest higher molecular weight fatty acids ("wax acids”) as the main component many natural waxes.
  • Waxiest higher molecular weight fatty acids Waxiest higher molecular weight fatty acids
  • Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
  • the wax-active preparations may also contain wool wax alcohols including triterpenoid and steroidalcohols, for example Lanolin, understands, for example, under the trade name Argowax® (Company Pamentier & Co.) is available. Also at least proportionately as wrapping material
  • wool wax alcohols including triterpenoid and steroidalcohols, for example Lanolin, understands, for example, under the trade name Argowax® (Company Pamentier & Co.) is available.
  • wrapping material it is possible to use fatty acid glycerol esters or fatty acid alkanolamides, but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.
  • the coating substance preferably contains in the coatings used according to the invention mostly paraffin wax. More preferably, at least 50% by weight is of the total contained encapsulating substances, more preferably still more, Paraffin waxes. Particularly suitable are paraffin wax contents (based on the total shell substance) of about 60% by weight, about 70% by weight, or about 80% Wt .-%, with even higher proportions, for example, more than 90 wt .-% particularly are preferred. In a very particular embodiment of the invention If the total amount of shell substance used is paraffin wax.
  • Paraffin waxes are superior to the other natural ones mentioned Grow in the context of the present invention has the advantage that in one alkaline washing or cleaning environment no hydrolysis of the Waxes take place, as is to be expected, for example, in wax esters Paraffin wax contains no hydrolyzable groups.
  • Paraffin waxes consist mainly of alkanes and low levels Iso- and cycloalkanes.
  • the preferred to use paraffin waxes have essentially no ingredients with a melting point greater than 70 ° C to, more preferably more than 60 ° C. Proportions of high - melting alkanes in the Paraffin wax may fall below the melting temperature in the washing or detergent liquor unwanted wax residues on the to be washed Leave laundry or the goods to be cleaned. Such wax residues lead to an unsightly appearance of laundry or cleaning goods and should therefore be avoided.
  • the envelope substances used in the context of present invention contain a paraffin wax with a Melting range from 50 ° C to 60 ° C.
  • the content of the paraffin wax used is at ambient temperature (about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible.
  • the encapsulant may be in addition to paraffin waxes as a main ingredient or one contain more of the above-mentioned waxes or waxy substances.
  • the mixture forming the shell substance or the coating should be such that the particles coated with it at least largely are water insoluble.
  • the solubility in water should be at a temperature of 30 ° C does not exceed about 10 mg / l and should preferably be 5 mg / l.
  • the coating should have the lowest possible water solubility also in water at elevated temperatures to one from the temperature independent release of the washing-active substances as far as possible to avoid.
  • the above principle serves for the delayed release of detergents Preparations at a certain point in the washing or cleaning cycle and can be particularly advantageous if, for example when washing dishes in the main course at a relatively lower temperature (for example 45 ° C) is rinsed, so that the detergent-active substance from a rinse aid comprehensive coated particles only in the rinse cycle at higher Temperatures (eg> 55 ° C) is released.
  • enveloping substances or coatings comprise one or more substances with a melting range of 40 ° C to 75 ° C in amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20% by weight, in each case based on the particle weight.
  • this material is a non-cold water soluble material. This can be prevented that the second detergent-active preparation in the Fleet arrives before the temperature of the washing or cleaning cycle for the main wash or main wash required temperature (in the case that the second detergent preparation for the main wash or main wash is thought) or required for the post-wash cycle or rinse Temperature (in the case that the second detergent preparation for the Nachwaschgang or Vietnamesegang is thought) reached.
  • the first and optionally the third and even further (fourth, fifth, etc.) washing-active preparations which contained in the washing or cleaning agent portions according to the invention are singular (i.e., the first or the third, or ....) or each (i.e., the first and the third and ....) or even partially (i.e. the first and the third or the first and fourth or .7) of a water-soluble material or water-soluble Materials are included.
  • These materials can be the same physical Group (film, capsule, coating, etc.) or chemical group (PVAL films; PVP films, PEOX films, etc.) or belong to different groups.
  • PVAL films physical Group
  • PVP films polyvinyl-ethylene glycol
  • PEOX films polyethylene
  • the expert can, in analogy to the above for the Surrounding the second measured amount of a detergent preparation given disclosure also an enclosure for the first measured Amount of a detergent preparation and / or an enclosure for the optionally existing third measured amount of a detergent preparation and / or an enclosure for optionally existing further measured
  • choose quantities of washing preparations taking in the first place has to pay attention to which components the respective washing active preparations as partial portions of the washing or cleaning agent portion according to the invention contain when (and at what temperatures) they are released into the fleet and how fast this should happen.
  • the criteria given above apply to the other water-soluble materials analogous.
  • a further preferred embodiment of the invention corresponds to a Detergent or detergent portion, wherein additionally the first measured Amount of a detergent-active preparation of a first water-soluble material is included and this first water-soluble material at a temperature is below or equal to the first temperature water-soluble material.
  • the Temperature is in the case that the first detergent-active preparation is a preparation for the pre-wash or pre-rinse, is the maximum temperature of a pre-wash or prewash and is usually the temperature of the cold Water.
  • the first detergent-active preparation is a preparation for the main wash or main wash is the maximum temperature of a Main wash or Haupt Whygangs and is usually one during rinsing Temperature below 45 ° C, more preferably a temperature in the range from 30 to 45 ° C.
  • the third measured Amount of a detergent-active preparation of a third water-soluble material is included and this third water-soluble material at a temperature above the second temperature is water-soluble material.
  • this consist of pre, main and Nachwasch- or - Hugheskomponente existing Detergent or detergent portions according to the invention.
  • the first and the second and optionally the third measured amounts of washing active preparations in the form of interconnected, separate from the first, second and optionally third water-soluble material included partial portion packs.
  • the washing or cleaning agent portions are not total two or optionally three washing-active preparations and these individually limited to waterborne materials but can be the same well also include four or five or more partial-portion packs that too a washing or cleaning agent portion are connected.
  • the single ones Detergent formulations may each be derived from the water-soluble material be encompassed, the water solubility exactly on the conditions (for example the temperature conditions) is set at which an optimal and rapid solubility of the preparation comprising water-soluble Set up materials in the fleet and thus the contents of the respective portion portion into the fleet.
  • the two, three or more sub-units are to one Detergent or detergent portion according to the invention connected.
  • the subunits of the washing or cleaning agent portion according to the invention For example, from bags of two, possibly also three or more, different types of foil or capsules with two, if necessary also three or more, chambers of materials of different composition consist.
  • the different types of foil bags or different Materials of the chambers of the capsules are based on a solubility in water in different conditions, for example at different temperatures or at different residence times in the aqueous liquor. They then set their respective content, i. H. the first, second and possibly free third and further detergent preparations in the liquor when the Conditions occur on the water solubility of the respective materials are set. These are preferably the temperatures of the respective washes or rinses, but may as well others, in the wash or rinse cycle be reproducibly adjustable conditions.
  • the first, second and optionally third measured amounts washing-active preparations in each case independently of one another mold-body-like, powdery, gel or liquid detergent or cleaner preparations.
  • mold-like washing or cleaning agent preparations are present as granules, tablets, blocks, briquettes, rings or other shaped bodies; especially tablets, blocks or briquettes can be uniform be shaped body or body, the depressions, recesses, grooves o. ⁇ ., To accommodate particular components of the preparations serve or also for application purposes up or attached were.
  • Liquid detergents or cleaners preparations can Solutions, suspensions or other, known for washing and cleaning purposes be liquid systems.
  • the washing and cleaning agent portions according to the invention contain one or more Substances from the group of surfactants, surfactant compounds, builders, bleaches, bleach activators, Enzymes, foam inhibitors, dyes and fragrances and - in the case that the washing or Detergent portions at least partially present as a shaped body - binding and disintegration aids.
  • surfactants surfactant compounds
  • builders bleaches, bleach activators, Enzymes, foam inhibitors, dyes and fragrances and - in the case that the washing or Detergent portions at least partially present as a shaped body - binding and disintegration aids.
  • the washing and Detergent portions surfactants from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants for economic reasons and due to their Power spectrum are clearly preferred.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • Suitable surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as, for example, from C 12-18 -monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of 2-sulfofatty acids for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
  • fatty acid glycerine esters are the mono-, di- and triesters and their mixtures too Understand how they are produced by esterification of a monoglycerol with 1 to 3 moles of fatty acid or with the transesterification of triglycerides with 0.3 to 2 moles of glycerol are obtained.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example, caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates prepared, for example, according to U.S. Patents 3,234,258 or 5,075,041, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or sulfosuccinic acid esters, and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, Palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants including soaps may be in the form of their sodium, Potassium or ammonium salts and as soluble salts of organic bases, such as Mono-, di- or triethanolamine present.
  • the anionic Surfactants in the form of their sodium or potassium salts in particular in the form of the sodium salts in front.
  • surfactants used in the form of their magnesium salts are surfactants used in the form of their magnesium salts.
  • washing and cleaning agent portions preferably, the 5 to 50 wt .-%, preferably 7.5 to 40 wt .-% and in particular 15 to 25% by weight of one or more anionic ten-sid (e), contained, in each case based on the washing and cleaning agent portion.
  • anionic surfactants used in the washing and cleaning agent portions according to the invention are used, the liberty of expression can not be met Restrictions in the way.
  • Preferred washing and cleaning agent portions according to the However, the invention has a soap content of 0.2% by weight, based on the total weight the washing and cleaning agent portion, exceeds.
  • Preferably used anionic Surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, with preferred Detergent and detergent portions 2 to 20 wt .-%, preferably 2.5 to 15 wt .-% and in particular from 5 to 10% by weight of fatty alcohol sulfate (e), in each case based on the weight of the washing and detergent portion, included
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, and mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants used either alone nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described, for example, in Japanese Patent Application JP 58/217598 are described or preferably according to the in the international patent application WO-A-90/13533 be prepared described methods.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable Alkypolyglycoside meet the general formula RO (G) z , in which R is a linear or branched, especially methyl-branched in the 2-position, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • linear alkyl polyglucosides ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
  • the washing and cleaning agent portions according to the invention may be preferred Alkylpolyglycoside containing levels of washing and cleaning agent portions to APG over 0.2 wt .-%, based on the total Shaped bodies are preferred.
  • Particularly preferred washing and cleaning agent portions contain APG in amounts of 0.2 to 10 wt .-%, preferably in amounts of 0.2 to 5 wt .-% and in particular in amounts of 0.5 to 3% by weight.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides may be suitable.
  • the amount of this nonionic Surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.
  • polyhydroxy fatty acid amides of the formula (I) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred, and is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to the teaching of international application WO-A-95/07331, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • an alkoxide as catalyst is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • anionic and nonionic surfactants also to use cationic surfactants.
  • Their use is preferably as Washing power booster, with only small amounts of cationic surfactants required are.
  • cationic surfactants are used, they are in the agents preferably in amounts of 0.01 to 10 wt .-%, in particular from 0.1 to 3.0 Wt .-% included.
  • detergents usually contain one or more surfactant (s) in total amounts of 5 to 50 wt .-%, preferably in Amounts of 10 to 35 wt .-%, wherein in partial portions of the inventive Detergent portions of surfactants may be contained in greater or lesser amount can.
  • the amount of surfactant is not in all partial portions equal; Rather, partial portions with relatively larger and partial portions with relatively smaller surfactant content can be provided.
  • detergent especially dishwashing detergent
  • these usually contain one or more surfactants in total amounts from 0.1 to 10 wt .-%, preferably in amounts of 0.5 to 5 wt .-%, wherein in partial portions of the detergent portions of the invention surfactants may be contained in greater or smaller amount.
  • the Quantity of surfactant is not at all with cleaning or dishwashing detergents Equal portions; Rather, partial portions with relatively larger and Partial portions are provided with relatively smaller surfactant content.
  • builders are the most important ingredients of laundry detergents. and detergents.
  • detergents and cleaning agent portions according to the invention can Usually be used in detergents and cleaning agents builders, in particular So zeolites, silicates, carbonates, organic cobuilders and - where no ecological Prejudices against their use exist - even the phosphates.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 .H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
  • Such crystalline layered silicates are described, for example, in European Patent Application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred, and ⁇ -sodium disilicate can be obtained, for example, by the method described in International Patent Application WO-A-91/08171.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024.
  • Especially preferred are densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • a fine crystalline, synthetic and bound water-containing zeolite optionally used is preferably zeolite A and / or P.
  • Zeolite MAP eg, commercial product: Doucil A24 from Crosfield
  • zeolite X is particularly preferred as the P-type zeolite.
  • zeolite X is particularly preferred as the P-type zeolite.
  • zeolite X is particularly preferred as the P-type zeolite.
  • mixtures of A, X and / or P are also suitable, however, are zeolite X and mixtures of A, X and / or P.
  • zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2 - 2.5) SiO 2 • (3.5-5.5) H 2 O can be described.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • detergents also an insert of the well-known Phosphates as builders possible, if such a use not should be avoided for environmental reasons.
  • sodium salts of orthophosphates, pyrophosphates and in particular the tripolyphosphates are suitable.
  • Useful organic builders are, for example, in the form of their Sodium salts usable polycarboxylic acids, among polycarboxylic acids
  • Such carboxylic acids are understood to carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, Malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that its use is ecological Reasons are not objectionable, as well as mixtures of these.
  • preferred Salts are the salts of polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures this. The acids themselves can also be used.
  • polymeric polycarboxylates are suitable. These are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrene acids are generally significantly higher than the molecular weights specified in the context of the present invention.
  • Suitable polymers are in particular polyacrylates, which are preferably a molecular weight from 2,000 to 20,000 g / mol. Because of their superior solubility In turn, the short-chain polyacrylates may be preferred from this group be, the molecular weights of 2,000 to 10,000 g / mol, more preferably from 3,000 to 5,000 g / mol.
  • copolymeric polycarboxylates in particular those of Acrylic acid with methacrylic acid or acrylic acid or methacrylic acid with maleic acid.
  • copolymers of acrylic acid with maleic acid containing 50 to 90% by weight of acrylic acid and 50 to 10% by weight Contain maleic acid.
  • Their relative molecular weight, based on free acids is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be either as a powder or as an aqueous Solution can be used.
  • the content of the washing or Detergent portions of (co) polymeric polycarboxylates are preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.
  • the polymers may also be allyl sulfonic acids, for example, in EP-B 0 727 448, allyloxybenzenesulfonic acid and Methallylsulfonic acid as a monomer.
  • biodegradable polymers from more than two different monomer units for example, those according to the DE-A 43 00 772 as monomers salts of acrylic acid and maleic acid and Vinyl alcohol or vinyl alcohol derivatives or according to DE-C 42 21 381 as monomers Salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.
  • copolymers are those described in the German patent applications DE-A 43 03 320 and DE-A 44 17 734 are described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and Contain vinyl acetate.
  • builder substances are polymeric aminodicarboxylic acids, to mention their salts or their precursors.
  • polyaspartic acids or their salts and derivatives of which in the German patent application DE-A 195 40 086 discloses that they next Co-builder properties also have a bleach-stabilizing effect.
  • polyacetals which are obtained by reaction of Dialdehydes can be obtained with polycarboxylic acids containing 5 to 7 carbon atoms and at least 3 hydroxy groups, for example as described in European Patent Application EP-A 0 280 223.
  • Preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and of polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable organic builders are dextrins, for example Oligomers or polymers of carbohydrates obtained by partial hydrolysis of Strengths can be obtained.
  • the hydrolysis can be carried out according to customary, for example acid or enzyme catalyzed process can be performed.
  • Preferably are hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol.
  • This is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, preferred where DE is a common measure of the reducing effect of a polysaccharide is compared to dextrose, which has a DE of 100.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are described in particular in European Patent Applications EP-A 0 232 202, EP-A 0 427 349, EP-A 0 472 042 and EP-A 0 542 496 and in International Patent Applications WO 92/18542 WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608.
  • an oxidized oligosaccharide according to the German patent application DE-A 196 00 018.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • EDDS ethylenediamine-N, N'-disuccinate
  • glycerol disuccinates and glycerol trisuccinates as described for example in the US Pat. Nos. 4,524,009 and 4,639,325, European Patent Application EP-A 0 150 930 and Japanese Patent Application JP-A 93 / 339,896.
  • Suitable amounts are zeolithumblen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic co-builders include acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which at least 4 carbon atoms and at least contain a hydroxy group and a maximum of two acid groups.
  • Such co-builders For example, in International Patent Application WO 95/20029.
  • phosphonates are in particular hydroxyalkane or aminoalkanephosphonates.
  • hydroalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • aminoalkanephosphonates preferably ethylenediamine tetramethylenephosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question.
  • ETMP ethylenediamine tetramethylenephosphonate
  • DTPMP Diethylentriaminpentamethylenphosphonat
  • the washing or cleaning agent portions according to the invention also contain bleach, preferably, aminoalkanephosphonates, in particular DTPMP, or mixtures of the said phosphonates to use.
  • inventive Detergents or cleaning agents more in detergents or cleaners typical ingredients from the group of bleaches, bleach activators, enzymes, Perfumes, perfume carriers, fluorescers, dyes, foam inhibitors, Silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, Color transfer inhibitors contain corrosion inhibitors and rinse aid surfactants.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxy-caproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonylamidoperoperuccinate; and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diper
  • chlorine or bromine-releasing substances are, for example heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, Tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • suitable chlorine or bromine releasing materials are, for example heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, Tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • bleach activators may be incorporated into the wash and detergent portions are incorporated.
  • bleach activators can Compounds which under perhydrolysis conditions are aliphatic peroxycarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, can be used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups.
  • TAED tetraacety
  • bleach catalysts in the washing and cleaning agent portions be incorporated.
  • These substances are bleach-enhancing Transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are used as bleach catalysts usable.
  • Enzymes are those from the class of proteases, lipases, amylases, Cellulases or mixtures thereof in question. Particularly suitable are from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably Subtilisin-type proteases and in particular proteases derived from Bacillus lentus be used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or Protease, lipase and cellulase, but especially cellulase-containing mixtures of special interest. Also have peroxidases or oxidases proved to be suitable in some cases.
  • the enzymes can bind to carriers adsorbed and / or embedded in encasing substances to counter them protect against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the compositions of the invention may, for example about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-% amount.
  • Enzymes are in the prior art primarily a detergent formulation added, in particular added to a dishwashing detergent, which is intended for the main rinse. Disadvantage was that the optimum effect enzymes used limited temperature choice and also problems occurred in the stability of the enzymes in a strongly alkaline medium. With the Washing or cleaning agent portions according to the invention it is possible enzymes also to use in the pre-wash and thus the pre-wash additionally for the main rinse for an enzyme action on soiling of the dishes to use.
  • the one intended for the preliminary rinse cycle detergent-active preparation or partial portion of a detergent portion Add enzymes and then such a preparation - further preferred - With a water-soluble at low temperature material too
  • the enzymes are more preferred for use under the conditions of the pre-wash, so for example in cold water, optimized.
  • the detergent portions according to the invention can then be when the enzyme preparations are liquid, as they are sometimes commercially available because then a fast effect can already be expected that already in the (relatively short and carried out in cold water) pre-wash occurs.
  • the enzymes are used in solid form and these are provided with an enclosure of a water-soluble material, which is already soluble in cold water, the enzymes can already before Main wash or main cleaning cycle unfold their effect.
  • Advantage of Use of an enclosure of water-soluble material, in particular of cold-water-soluble material is that the enzyme / enzymes in cold water after dissolving the enclosure comes quickly to effect / come. So that can whose duration of action will be extended, giving the washing or rinsing result benefits.
  • washing or cleaning agent portions according to the invention comprise according to
  • further additives such as they are known in the art as additives for detergent preparations are known.
  • These can be either one or more, in the If necessary, all partial portions (washing active preparations) of the invention
  • Detergent or detergent portions are added or - as in the co-pending patent application no. 199 29 098.9 entitled "Active ingredient portion pack" described - in the water-soluble, the washing-active Preparations comprehensive materials, so for example in the water-soluble Films, but also in the capsules or coatings according to the invention be incorporated.
  • optical Brighteners Can be used here in the usual optical detergents Brighteners. These are used as an aqueous solution or as a solution in an organic Solvent added to the polymer solution, which is converted into the film becomes, or become a part-portion (washing active preparation) one Was added detergent or cleaning agent in solid or liquid form.
  • optical brighteners are derivatives of diaminostilbene disulfonic acid or their Alkali metal salts. Suitable z. B.
  • Salts of 4, 4'-bis (2-anilino-4-morpholino1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which, instead of the morpholino group, are a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group wear.
  • brighteners of the type substituted diphenylstyrene in the partial portions (washing active preparations) contain the washing or cleaning agent portions of the invention be, z.
  • UV protection substances are substances that are involved in the washing process or released in the subsequent wash cycle in the wash liquor and accumulate on the fiber accumulatively, then a UV protection effect to achieve. Suitable are those under the name Tinosorb im Trading products of Ciba Specialty Chemicals.
  • preferred additives are Surfactants which in particular influence the solubility of the water-soluble film but also their wettability and foaming on dissolution can control, as well as foam inhibitors, but also bitter substances that are an accidental Ingestion of such packaging or parts of such packaging prevent from children.
  • dyes in particular water-soluble or water-dispersible dyes.
  • the dyes are according to the invention in the washing or detergent portions in amounts below 0.01% by weight.
  • polymers Another class of additives according to the invention the washing or cleaning agent portions can be added are polymers.
  • polymers On the one hand polymers come into question when washing or cleaning or rinsing Cobuilder properties show, so for example polyacrylic acids, also modified polyacrylic acids or corresponding copolymers.
  • a another group of polymers are polyvinylpyrrolidone and other grayness inhibitors, such as copolymers of polyvinyl pyrrolidone, cellulose ethers and the like.
  • Soil Repellents these are polymers based on fibers or pick up hard surfaces and counteract any unwanted contamination there. Relevant compounds of this type are the detergent specialist known. These are polyesters of terephthalic acid and ethylene glycol, which are partially modified with sulfonic acid groups.
  • bleach catalysts in particular Bleach catalysts for automatic dishwashing or laundry detergents.
  • bleach catalysts used here are complexes of manganese and cobalt, in particular with nitrogen-containing ligands.
  • silver protectants are a variety of mostly cyclic organic Compounds which are also familiar to the person skilled in the art are and contribute to the tarnishing of silver-containing objects to prevent during the cleaning process.
  • the washing or cleaning agent portions also contain components that the oil and Fettauswaschles from textiles positively influence, so-called Soil Repellents. This effect becomes particularly clear when a textile is contaminated, which is already before several times with a detergent according to the invention, this oil and fat dissolving Component contains, was washed.
  • nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups from 15 to 30% by weight and of hydroxypropoxy groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether
  • nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups from 15 to 30% by weight and of hydroxypropoxy groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether
  • the known from the prior art polymers of phthalic acid and / or the Terephthalic acid or derivatives thereof in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these.
  • sulfonated derivatives of phthalic and terephthalic acid polymers are especially preferred of these.
  • Rinse aid surfactants are in liquid form and are widely described in the art. Your Task is mainly to limescale and deposits on the cleaned Prevent dishes. Rinse aid surfactants are usually low-foaming Nonionic surfactants.
  • All of these additives become the washing or cleaning agent portions according to the invention in amounts up to at most 30% by weight, preferably 2 to 20 Wt .-%, added.
  • the addition can also become a material a water-soluble enclosure that encloses the or one of the washing-active (s) Preparation (s).
  • the plastic material for the enclosure either increase in its weight, so as to the depot effect of according to the invention is achieved, or exploit the additives mentioned at least in addition Partially to keep in the remaining detergent preparation. This is however less preferred.
  • Fragrances are the washing and cleaning agent portions of the invention added to the overall aesthetic impression of the products too improve and the consumer in addition to the technical performance (softening result) a sensory typical and distinctive product available to deliver.
  • perfume oils or perfumes individual fragrance compounds used, for example, the synthetic products of Type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, Phenoxyethyl isobutyrate, p-t-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, Allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • To the ethers include, for example, benzyl ethyl ether.
  • the aldehydes include, for. B. linear alkanals of 8 to 18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lileal and Bourgeonal.
  • the ketones include the ionones, ⁇ -isomethylionone, and methyl cedryl ketone.
  • the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol.
  • the hydrocarbons mainly count Terpenes like limes and pinas.
  • mixtures are different Used fragrances that are coordinated so that they work together create an appealing scent.
  • perfume oils can also be natural Contain fragrance mixtures, as they are accessible from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • the content of fragrances is in the range up to 2 wt .-% of the total Detergent or detergent portion.
  • the fragrances can be incorporated directly into the detergent preparations become; but it can also be advantageous to apply the fragrances to carriers, which strengthen the adhesion of the perfume on the linen and by a slower fragrance release provide for long-lasting fragrance of the textiles.
  • support materials have proven, for example, cyclodextrins.
  • the cyclodextrin-perfume complexes can be further enriched with other excipients be coated.
  • the perfumes and fragrances can basically be in any of the partial portions (washing-active preparations) of the washing or cleaning agent portions according to the invention be included. However, it is particularly preferred that they are in a detergent in an intended for post-washing or fabric conditioning cycle Part-detergent-portion or in a detergent, especially in a dishwashing detergent, provided in a rinse or rinse cycle Part-detergent portion, especially partial-detergent portion, included are.
  • washing and cleaning agent portions according to the invention can be used in one present a whole series of different configurations. Such embodiments may depend on the particular components used, However, in particular of the detergent compositions, but can also in certain limits freely selectable.
  • washing-active preparations are in the form of powders or powder mixtures before, so it offers washing and cleaning agent portions according to the invention as combinations of powdered components to provide, for example, as combinations of powdered components in Foil bags with several chambers or layers or as combinations powdered components in capsules.
  • the solid, for example, powdery, Components are processed into granules or pearls and in the form of Granules or pearls - similar to powders - in bags of foil with several Layers or chambers or packed in capsules, in what form they are then immediately used for washing or cleaning.
  • the washing or cleaning agent portions also in the form of to bodies compressed solids, which may have any shape; such Shaped bodies (such as tablets, blocks, briquettes, rings or the like) are out of order known in the art and may also be within the scope of the present invention Find use.
  • such shaped bodies can also depressions, Hollows, cuts or similar have the special purposes of housing serve individual washing active preparations.
  • too Moldings in combination with powders, in combination with liquids (the latter For example, then in an enclosure of a water-soluble material according to of the invention) or in combination with a fusible matrix embedded washing-active preparation in the context of the present invention.
  • the invention also includes a washing process, in particular A process for machine washing, wherein a detergent portion according to the above detailed description placed in a washing machine and by adding water and adjusting the temperature to the temperature value, in which the water-soluble part comprising the respective detergent portion Dissolves material that releases detergent portion into the wash liquor while the other detergent portion portions before contact with the Wash liquor are protected and released at other temperatures, and a cleaning method, in particular method for machine cleaning of dishes, wherein one has a detergent portion according to one of the above detailed description placed in a dishwasher and by adding water and adjusting the temperature to the temperature value at to which the respective detergent partial portion comprehensive water-soluble Dissolves material that releases detergent portion into the cleaning solution, while the other detergent partial portions before contact with the Cleaning Fleet are protected and released at other temperatures.
  • the Detergent portion as described in detail above, in the Dosing chamber of a dishwasher or in wasserum Whyten interior a dishwasher placed.
  • the cleaner preparation was divided into component groups or individual components K0 to K4 according to the quantitative distribution given in Table 2.
  • component Wt .-% Quantity [g] K0 K1 K2 K3 K4 sodium tripolyphosphate 55.0 13.8 - - - - Calc. soda 22.6 5.7 - - - - silicate 5.0 1.3 - - - - perborate 10.0 - 2.5 - - - TAED 2.0 - - - 0.5 - amylase 2.0 - - 0.5 - - protease 1.4 - - 0.4 - - C 12/14 fatty alcohol carboxylate (EO 5 / PO 4 ) 2.0 - - - - 0.5
  • the weight percentage is based on the total weight of the cleaner components.
  • "K0”, “K1", “K2" etc. designate the number of the cleaner component or group of cleaner components in Table 3.
  • the PVAL films were SOLUBLON films from Syntana bottlesgesellschaft E. Harke GmbH & Co. of types KA30 (kwl), BP (40) and LA (60).

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Claims (35)

  1. Portion de détergent ou de produit nettoyant, en particulier pour charger une machine à laver ou un lave-vaisselle, pour un déroulement de programme ayant lieu dans une phase aqueuse, contenant
    une première quantité dosée d'une préparation à action lavante, qui passe dans la phase aqueuse à une température inférieure ou égale à une première température;
    une deuxième quantité dosée d'une préparation à action lavante, qui passe dans la phase aqueuse à une température inférieure ou égale à une deuxième température, qui est supérieure à la première température;
    les première et deuxième et éventuellement troisième quantités dosées de préparations à action lavante existent sous la forme de paquets de portions partielles, liés entre eux, contenus séparément par la première, deuxième et éventuellement par la troisième matière hydrosoluble, et au moins une matière contenant au moins l'une des quantités dosées étant hydrosoluble à une température définie.
  2. Portion de détergent ou de produit nettoyant selon la revendication 1, dans laquelle au moins la deuxième quantité dosée d'une préparation à action lavante est contenue par une matière hydrosoluble à une température supérieure à la première température.
  3. Portion de détergent ou de produit nettoyant selon la revendication 1 ou la revendication 2, contenant en outre une troisième quantité dosée d'une préparation à action lavante, qui passe dans la phase aqueuse à une température supérieure à la deuxième température.
  4. Portion de détergent ou de produit nettoyant selon l'une quelconque des revendications 1 à 3, dans laquelle la matière hydrosoluble contenant la deuxième quantité dosée d'une préparation à action lavante, est un emballage hydrosoluble, de préférence une feuille polymère hydrosoluble, de manière particulièrement préférée une feuille de poly(alcool vinylique), de manière tout particulièrement préférée une feuille de poly(alcool vinylique), hydrosoluble à une température supérieure à 30°C;
  5. Portion de détergent ou de produit nettoyant selon l'une quelconque des revendications 1 à 3, dans laquelle la matière hydrosoluble contenant la deuxième quantité dosée d'une préparation à action lavante, est une capsule hydrosoluble, de préférence une capsule de gélatine, de manière particulièrement préférée une capsule de gélatine molle.
  6. Portion de détergent ou de produit nettoyant selon l'une quelconque des revendications 1 à 3, dans laquelle la matière hydrosoluble contenant la deuxième quantité dosée d'une préparation à action lavante est un enrobage, de préférence un enrobage constitué d'une ou plusieurs cires, de manière particulièrement préférée un enrobage constitué d'une ou plusieurs cires fondant à une température supérieure à 30°C, non hydrosolubles à une température inférieure à celle-ci.
  7. Portion de détergent ou de produit nettoyant selon l'une quelconque des revendications 4 à 6, dans laquelle la matière hydrosoluble est une matière non hydrosoluble à froid, de préférence une matière non hydrosoluble à une température inférieure ou égale à la première température.
  8. Portion de détergent ou de produit nettoyant selon l'une quelconque des revendications 1 à 7, dans laquelle en outre la première quantité dosée d'une préparation à action lavante est contenue par une première matière hydrosoluble et cette première matière hydrosoluble est une matière hydrosoluble à une température inférieure ou égale à la première température.
  9. Portion de détergent ou de produit nettoyant selon l'une quelconque des revendications 2 à 8, dans laquelle la troisième quantité dosée d'une préparation à action lavante est contenue par une troisième matière hydrosoluble, et cette troisième matière hydrosoluble est une matière hydrosoluble à une température supérieure à la deuxième température.
  10. Portion de détergent ou de produit nettoyant selon l'une quelconque des revendications 8 et 9, dans laquelle la première quantité dosée d'une préparation à action lavante est contenue par une première matière hydrosoluble et cette première matière hydrosoluble est une matière hydrosoluble à une température inférieure ou égale à la première température, et dans laquelle en outre la troisième quantité dosée d'une préparation à action lavante est contenue par une troisième matière hydrosoluble et cette troisième matière hydrosoluble est une matière hydrosoluble à une température supérieure à la deuxième température.
  11. Portion de détergent ou de produit nettoyant selon l'une quelconque des revendications 1 à 10, dans laquelle les première, deuxième et éventuellement troisième quantités dosées de préparations à action lavante, sont entourées par une matière hydrosoluble à une température inférieure ou égale à la première température.
  12. Portion de détergent ou de produit nettoyant selon la revendication 11, dans laquelle la deuxième et éventuellement troisième quantité dosée de préparations à action lavante en plus de la première quantité d'une préparation à action lavante existent sous une forme qui retarde leur passage dans la phase aqueuse, de préférence sous une forme à libération retardée, ou sous une forme contenue par une matière insoluble dans l'eau à une température supérieure ou égale à la première température.
  13. Portion de détergent ou de produit nettoyant selon l'une quelconque des revendications 11 ou 12, dans laquelle les première, deuxième et/ou éventuellement troisième et/ou d'autres quantités dosées de préparations à action lavante sont des préparations à action lavante qui passent en totalité ou du moins en partie, dans la phase aqueuse aux mêmes températures, ou à des températures successives du même cycle de lavage ou de nettoyage.
  14. Portion de détergent ou de produit nettoyant selon l'une quelconque des revendications 1 à 13, dans laquelle la deuxième matière hydrosoluble et éventuellement la première et troisième matière hydrosoluble, qui contiennent la deuxième quantité dosée et éventuellement la première et troisième quantité dosée de préparations à action lavante, qui sont des matières de composition chimique similaire, qui présentent une hydrosolubilité différente.
  15. Portion de détergent ou de produit nettoyant selon la revendication 14, dans laquelle la deuxième matière hydrosoluble et éventuellement la première et troisième matière hydrosoluble contiennent des feuilles polymères hydrosolubles, de manière particulièrement préférée des feuilles de poly(alcool vinylique), de manière tout particulièrement préférée des feuilles de poly(alcool vinylique) hydrosolubles à des températures de l'étape respective du processus de lavage ou de nettoyage.
  16. Portion de détergent ou de produit nettoyant selon l'une quelconque des revendications 1 à 15, dans laquelle les première, deuxième et éventuellement troisième quantités dosées de préparations à action lavante constituent à chaque fois de façon indépendante des préparations de détergent ou de produit nettoyant du type corps moulé, sous forme de poudre, sous forme de gel, ou liquides.
  17. Portion de détergent ou de produit nettoyant selon l'une quelconque des revendications 1 à 16, contenant
    une première quantité dosée d'une préparation à action lavante pour un cycle de pré-nettoyage ou prélavage; et
    une deuxième quantité dosée d'une préparation à action lavante pour un cycle de nettoyage principal ou de lavage principal.
  18. Portion de détergent ou de produit nettoyant selon l'une quelconque des revendications 1 à 16, contenant
    une première quantité dosée d'une préparation à action lavante pour un cycle de pré-nettoyage ou un cycle de prélavage;
    une deuxième quantité dosée d'une préparation à action lavante pour un cycle de nettoyage ou un cycle de lavage principal; et
    une troisième quantité dosée d'une préparation à action lavante pour un cycle de rinçage ou un cycle de post-lavage.
  19. Portion de détergent ou de produit nettoyant selon l'une quelconque des revendications 1 à 16, contenant
    une première quantité dosée d'une préparation à action lavante pour un cycle de nettoyage ou un cycle de lavage principal; et
    une deuxième quantité dosée d'une préparation à action lavante pour un cycle de rinçage ou un cycle de post-lavage.
  20. Portion de détergent ou de produit nettoyant selon l'une quelconque des revendications 1 à 16, contenant
    (a) une première et deuxième quantité dosée et éventuellement d'autres quantités de préparations à action lavante pour l'un des cycles : cycle de prélavage/pré-nettoyage, cycle de lavage principal/nettoyage principal, ou cycle de post-lavage/post-nettoyage; et éventuellement
    (b) une ou plusieurs quantités dosées supplémentaires d'une ou plusieurs préparations à action lavante pour un ou plusieurs cycles de lavage ou de nettoyage, dans lesquelles les quantités dosées de préparation(s) à action lavante, citées sous (a), ne passent pas dans la phase aqueuse.
  21. Portion de détergent selon l'une quelconque des revendications 1 à 20, contenant
    (a) éventuellement une quantité dosée d'un produit de prélavage, qui est contenu éventuellement par une première matière hydrosoluble;
    (b) une quantité dosée d'un détergent, qui est contenu par une deuxième matière hydrosoluble; et éventuellement
    (c) une quantité dosée d'un produit de post-lavage, qui est contenu éventuellement par une troisième matière hydrosoluble.
  22. Portion de détergent selon la revendication 21, dans laquelle
    (a) la première matière hydrosoluble éventuellement présente est hydrosoluble au-dessous de la température maximale du cycle de lavage à froid d'une machine à laver;
    (b) la deuxième matière hydrosoluble est hydrosoluble au-dessus de la température maximale du cycle de lavage à froid et au-dessous de la température maximale du cycle principal d'une machine à laver; et
    (c) la troisième matière hydrosoluble éventuellement présente est hydrosoluble à la température du cycle de post-lavage d'une machine à laver.
  23. Portion de détergent selon l'une quelconque des revendications 21 et 22, dans laquelle la température maximale du cycle de lavage à froid est de 20°C, la température du cycle de lavage principal est > 20 à 90°C, et la température du cycle de post-lavage est d'environ 30 °C.
  24. Portion de produit nettoyant selon l'une quelconque des revendications 1 à 20, contenant
    (a) éventuellement une quantité dosée d'un produit de pré-nettoyage, qui est contenu éventuellement par une première matière hydrosoluble;
    (b) une quantité dosée d'un produit nettoyant, qui est contenu par une deuxième matière hydrosoluble; et éventuellement
    (c) une quantité dosée d'un produit de post-nettoyage, qui est contenu éventuellement par une troisième matière hydrosoluble.
  25. Portion de produit nettoyant selon la revendication 24, dans laquelle
    (a) la première matière hydrosoluble éventuellement présente est hydrosoluble au-dessous de la température maximale du cycle de nettoyage à froid d'un lave-vaisselle;
    (b) la deuxième matière hydrosoluble est hydrosoluble au-dessus de la température maximale du cycle de nettoyage à froid et au-dessous de la température maximale du cycle de nettoyage d'une lave-vaisselle; et
    (c) la troisième matière hydrosoluble éventuellement présente est hydrosoluble à la température du cycle de rinçage d'un lave-vaisselle.
  26. Portion de produit nettoyant selon l'une quelconque des revendications 24 ou 25, dans laquelle la quantité dosée du produit nettoyant, qui est entouré par la deuxième matière hydrosoluble, contient au moins un composant, dans lequel un additif de post-traitement est contenu, qui passe dans la lessive de nettoyage seulement à des températures supérieures à 50°C, de préférence à une température supérieure à 55°C, et qui agit comme produit de post-traitement.
  27. Portion de produit nettoyant selon la revendication 26, dans laquelle l'additif de post-traitement avec un enrobage sensible à la température, est pourvu d'une substance fondant à une température déterminée, ou d'un revêtement hydrosoluble à une température déterminée, permettant le passage dans la lessive de nettoyage à la température réglée.
  28. Portion de produit nettoyant selon la revendication 24 ou la revendication 25, dans laquelle le produit de post-traitement est un corps moulé qui, du fait de ses dimensions, ne peut traverser le filtre de la pompe à lessive d'un lave-vaisselle.
  29. Portion de produit nettoyant selon l'une quelconque des revendications 24 à 28, dans laquelle la première quantité dosée d'une préparation à action lavante, qui est entourée par une matière hydrosoluble à froid, est un produit de prétraitement pour le lavage de vaisselle en machine, de préférence un agent d'alcalinisation, une enzyme hydrosoluble à froid, un agent d'acidification, un véhicule chloré alcalin, un agent de blanchiment, une préparation tensio-active, une composition de blanchiment acide et/ou un agent anti-bactérien, de manière particulièrement préférée une enzyme hydrosoluble à froid.
  30. Portion de produit nettoyant selon l'une quelconque des revendications 24 à 29, dans laquelle la deuxième ou troisième quantité dosée d'une préparation à action lavante, qui est contenue par une matière hydrosoluble à une température plus élevée, est un produit de post-traitement pour le lavage de vaisselle en machine, de préférence une préparation contenant un ou plusieurs tensio-actifs de rinçage et/ou une préparation contenant un ou plusieurs parfums.
  31. Portion de produit nettoyant selon l'une quelconque des revendications 24 à 30, dans laquelle la première température est la température maximale de la phase aqueuse froide d'un programme de nettoyage et/ou dans laquelle la deuxième température se trouve autour de 45°C, de préférence autour de 30 °C.
  32. Portion de produit nettoyant selon l'une quelconque des revendications 24 à 30, dans laquelle la première température se trouve autour de 45 °C, de préférence autour de 30°C et/ou la deuxième température se trouve au-dessus de la première température, de préférence au-dessus de 45°C.
  33. Procédé de lavage, en particulier procédé pour le lavage en machine, dans lequel on place une portion de détergent selon l'une quelconque des revendications 1 à 23 dans une machine à laver et en ajoutant de l'eau et en réglant la température à la valeur de température à laquelle se dissout la matière hydrosoluble contenant la portion partielle respective de détergent, qui libère la portion partielle de détergent dans la lessive de lavage, tandis que les autres portions partielles de détergent sont protégées d'un contact avec la lessive de lavage et sont libérées à d'autres températures.
  34. Procédé de nettoyage, en particulier un procédé pour le nettoyage de vaisselle en machine, dans lequel on place une portion de produit nettoyant selon l'une quelconque des revendications 1 à 20 et 24 à 32 dans un lave-vaisselle, et en ajoutant de l'eau et en réglant la température à la valeur de température à laquelle se dissout la matière hydrosoluble comprenant une portion partielle respective de produit nettoyant, qui libère la portion partielle de produit nettoyant dans la lessive de nettoyage, tandis que les autres portions partielles de produit nettoyant sont protégées d'un contact avec la lessive de nettoyage et sont libérées à d'autres températures.
  35. Procédé de nettoyage selon la revendication 34, dans lequel on place la portion de produit nettoyant selon l'une quelconque des revendications 1 à 21 et 24 à 32 dans le compartiment de dosage d'un lave-vaisselle ou dans l'espace intérieur rincé par l'eau d'un lave-vaisselle.
EP00947888A 1999-07-09 2000-06-28 Portion de detergent ou nettoyant Revoked EP1194523B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19932205 1999-07-09
DE19932205 1999-07-09
PCT/EP2000/005999 WO2001004258A1 (fr) 1999-07-09 2000-06-28 Portion de detergent ou nettoyant

Publications (2)

Publication Number Publication Date
EP1194523A1 EP1194523A1 (fr) 2002-04-10
EP1194523B1 true EP1194523B1 (fr) 2005-11-30

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US (1) US6448212B1 (fr)
EP (1) EP1194523B1 (fr)
JP (1) JP2003504491A (fr)
AT (1) ATE311434T1 (fr)
AU (1) AU6152900A (fr)
CA (1) CA2313506A1 (fr)
DE (1) DE50011759D1 (fr)
ES (1) ES2252027T3 (fr)
WO (1) WO2001004258A1 (fr)

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CA2313506A1 (fr) 2001-01-09
EP1194523A1 (fr) 2002-04-10
JP2003504491A (ja) 2003-02-04
US6448212B1 (en) 2002-09-10
DE50011759D1 (de) 2006-01-05
ATE311434T1 (de) 2005-12-15
AU6152900A (en) 2001-01-30
WO2001004258A1 (fr) 2001-01-18
ES2252027T3 (es) 2006-05-16

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