EP1305396B1 - Corps creux compartimentes contenant une dose d'un produit de lavage, de nettoyage ou de rincage - Google Patents

Corps creux compartimentes contenant une dose d'un produit de lavage, de nettoyage ou de rincage Download PDF

Info

Publication number
EP1305396B1
EP1305396B1 EP01967120A EP01967120A EP1305396B1 EP 1305396 B1 EP1305396 B1 EP 1305396B1 EP 01967120 A EP01967120 A EP 01967120A EP 01967120 A EP01967120 A EP 01967120A EP 1305396 B1 EP1305396 B1 EP 1305396B1
Authority
EP
European Patent Office
Prior art keywords
active
dishwashing
cleaning
washing
detergent
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
EP01967120A
Other languages
German (de)
English (en)
Other versions
EP1305396A2 (fr
Inventor
Henriette Weber
Sandra Hoffmann
Frank Meier
Rolf Bayersdörfer
Christian Block
Wilfried Rähse
Markus Semrau
Dieter Jung
Karl-Martin Faeser
Paul Birnbrich
Dieter Nickel
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27437838&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1305396(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from DE2000133827 external-priority patent/DE10033827A1/de
Priority claimed from DE2000148448 external-priority patent/DE10048448A1/de
Priority claimed from DE2000158647 external-priority patent/DE10058647A1/de
Priority claimed from DE2001107878 external-priority patent/DE10107878A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP05014861A priority Critical patent/EP1586631B1/fr
Publication of EP1305396A2 publication Critical patent/EP1305396A2/fr
Application granted granted Critical
Publication of EP1305396B1 publication Critical patent/EP1305396B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045—Multi-compartment

Definitions

  • the present invention relates to washing, cleaning or rinsing agent portions which are dimensionally stable Hollow bodies are contained with at least one compartment.
  • the invention relates also methods for producing such washing, cleaning or detergent portions containing Compartment hollow body.
  • the invention relates to washing, cleaning and rinsing methods, in which the detergent, cleaning agent and detergent formulations in dimensionally stable Hollow bodies are dosed with one or more separate compartment (s).
  • the earlier patent application DE 198 31 703 discloses a portioned washing or detergent preparation in a bag of water-soluble film, in particular in a pouch of (optionally acetalized) polyvinyl alcohol (PVAL) wherein at least 70% by weight of the particles of the detergent or cleaner preparation particle sizes> 800 have ⁇ m.
  • PVAL polyvinyl alcohol
  • Such bags or “pouches” are indeed very consumer friendly and easier dosing, however, are not in all cases the appropriate form for dosing Detergent, cleaning and rinsing agent preparations, especially if solid and liquid washing, cleaning or rinse-active preparations are to be dosed side by side. Further such bags allow the incorporation of unstable or volatile phases Detergent, cleaning agent or detergent preparations in the detergent, cleaning agent or detergent portion not to.
  • the document DE-A 20 65 153 describes surfactant shaped bodies comprising several components, the outer shell of sodium silicate and detergent components included therein consist.
  • the silicate shell is produced by pressure forming in two hemispheres, which after filling the amount sufficient for a wash amount of the detergent components composed and connected to the shaped body. The procedure is extremely impractical and does not lead to it useful detergent portions.
  • the document DE-A 20 07 413 describes detergent moldings from a core of one or several detergent component (s) and a shell of press-molded, predominantly made Sodium metal silicate existing shell material.
  • the compression of the wrapping material to half shells and the filling and welding of the half shells to the finished molding require a complex Technology, and many of the moldings break before they get into the washing process.
  • the documents DE-A 198 34 181, DE-A 198 34 180 and DE-A 198 34 172 describe detergent, dishwashing or cleaning / decalcifying agent preparations of a tablet made by compression molding, consisting of two equal halves from one or more detergents, dishwashing detergent or cleaning agent components and a core optionally provided with an additional coating from a further detergent, dishwashing detergent or cleaning agent component.
  • the preparation can be made in this case only in a kompti extenten, multi-stage process, only a solid core can be incorporated into the tablet wrapper, if not premature release of the tablet should be initiated from the inside.
  • WO 01/85895 discloses dimensionally stable dosing units for detergents or cleaners. These dosing units have no walls, which spatially separate the same or different washing-active, cleaning-active or rinsing-active components or preparations.
  • the invention was based on the object, detergent, cleaning agent or detergent preparations in which volatile as well as less volatile washing-active, cleaning active or flushing active components can be assembled or mechanically unstable components can be incorporated; without them - for example, at Pressing into moldings - impaired in terms of their integrity.
  • the invention was continue the task, detergent, detergent or detergent components spatially to separate them and still in the same detergent, detergent or Make up a washing-up liquid with the aim of making a substance Exchange or mutual interference, which may involve loss of activity may be connected as little as possible.
  • one detergent, detergent or detergent portions can fill in dimensionally stable hollow body with several separate compartment (s) and thus can provide dosages of the respective agents which are more compact Moldings or packaged preparations in pouches significant performance advantages exhibit.
  • the invention further relates to a process for the preparation of one in one or more dimensionally stable Hollow body (s), with at least one compartment contained detergent, makesmittel- or A detergent portion according to any one of claims 1 to 20, comprising the steps of being applied per se known way one or more dimensionally stable (s), that is already before filling with one or independent of several washing-active, rinsing-active or cleaning-active component (s), self-supporting, produces hollow body, wherein under pressing proceeding process for the preparation of the hollow body (s) are excluded, this (s) hollow body with one or more Wall / walls, which are the same or different washing active, cleaning active or rinse active Components or spatially separate / separate, and provides the compartments with at least one detergent-active, cleaning-active or rinse-active preparation from the nonionic group
  • detergent, detergent or detergent portion is used in the context of present invention for a washing, cleaning or rinse sufficient amount of a detergent, detergent or Rinsing agent understood. This can, for example, a machine washing, cleaning or Rinsing process, as with commercial washing machines or dishwashers is carried out. According to the invention, however, a term (for example in a hand basin or in a bowl) hand wash or by hand carried out dishwashing or other process of washing or cleaning Understood. According to the invention, the detergents, cleaning agents or detergents are preferred Detergent portions used in automatic washing, cleaning or rinsing operations.
  • detergent or detergent or detergent partial portion is in within the scope of the present invention, a subset of a detergent or cleaning agent or detergent portion understood in one of other detergents or cleaning agents or Detergent partial portions separate phase in spatial association with others Detergent or detergent or detergent partial portions of the same detergent or Detergent or detergent portion is present, for example in a separate compartment in a dimensionally stable hollow body according to the invention, and by suitable measures prepared so as to be separate from other detergents or cleaners. or detergent portion portions of the same detergent or detergent or detergent portion can be added to the liquor and optionally dissolved or suspended in it.
  • a detergent or detergent or detergent partial portion the same Ingredients such as another detergent or cleaning agent portion same detergent or cleaning agent or detergent portion contain; prefers however, contain two detergent or detergent or detergent partial portions thereof Detergent or cleaning agent or detergent portion different ingredients, in particular different detergent-active, cleaning-active or rinse-active preparations.
  • the detergents or cleaning agent or detergent portions contain measured amounts of at least one washing active, cleaning active or rinse active Preparation, usually measured amounts of several washing active, cleaning active or rinse-active preparations. It is possible that the portions only wash active, cleaning active or rinse-active preparations of a particular composition. However, according to the invention it is preferred that several, usually at least two, Washing-active, cleaning-active or rinse-active preparations of different composition contained in the detergent or detergent or detergent portions.
  • the Composition can be in terms of the concentration of the individual components of the washing-active, cleaning-active or rinse-active preparation (quantitatively) and / or with regard to the nature of the individual components of the detergent-active, cleaning-active or rinse-active preparation (qualitatively) be different. It is particularly preferred that the components in terms of Nature and concentration are adapted to the tasks performed by the detergents or cleaners or detergent partial portions in the washing, cleaning or rinsing process to meet to have.
  • washing-active or cleaning-active or rinse-active preparation are used in the In the context of the present invention preparations of all conceivable, in connection with understood a washing or cleaning or rinsing relevant substances. This are primarily the actual detergents or cleaners or dishwashing detergents with theirs in the further course of the description explained in more detail individual components.
  • Active substances such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builders (inorganic and organic builders), bleaches (such as Peroxo bleach and chlorine bleach), bleach activators, bleach stabilizers, Bleach catalysts, enzymes, special polymers (for example those with cobuilder properties), Grayness inhibitors, dyes and fragrances (perfumes), without the Term is restricted to these substance groups.
  • surfactants anionic, nonionic, cationic and amphoteric surfactants
  • builders inorganic and organic builders
  • bleaches such as Peroxo bleach and chlorine bleach
  • bleach activators bleach stabilizers
  • Bleach catalysts enzymes
  • special polymers for example those with cobuilder properties
  • Grayness inhibitors dyes and fragrances (perfumes)
  • dyes and fragrances perfumes
  • washing-active or cleaning-active or rinse-active preparations It is referred to as "washing-active or cleaning-active or rinse-active preparations"
  • detergents and cleaning aids or rinse aid understood. Examples of these are optical brighteners, UV protection substances, so-called. Soil repellents, ie Polymers that cause re-soiling of fibers or hard surfaces (including Tableware), as well as silver protectants, colorants and decolorizing agents.
  • laundry treatment such as fabric softener or dishwashing additives such as rinse aid according to the invention as washing-active or as cleaning-active or as dishwashing active preparations considered.
  • the detergent, cleaning agent or detergent portions are in one or more dimensionally stable hollow body (s) having at least one compartment.
  • the exact shape of the hollow body is just as critical in this context as its Size; The only requirement in this regard is that the shape and size comply with the later use, so use in a washing, cleaning or Rinsing process, especially in conventional washing machines or dishwashers.
  • Hollow body in spherical, ellipsoidal, cubic, cuboid, trapezoidal, conical or pyramidal or Trochoidform; Cuboid or trochoid-shaped hollow body have the invention best proven and can therefore be used with advantage.
  • the size of the hollow body is in preferred embodiments of the invention such that the Hollow body in the dispenser of a commercial washing machine or dishwasher, can be entered in running in the laundry nets or bags o. ⁇ .
  • Especially preferred embodiments of the detergent, cleaning agent or detergent portions do not exceed a length (longest axis) of 10 cm while the sizes of the width and height are much lower, for example at 1 to 5 cm.
  • dimensionally stable hollow body is understood according to the invention that the Detergent, detergent or detergent portions containing moldings an inherent dimensional stability which enables them, under normal conditions of manufacture, the Storage, transport and handling by the consumer against breakage and / or pressure to have stable, non-coincident structure, which is also among the Influence, whether this structural stability out of due to various mentioned below Parameter-yielding properties of the dimensionally stable hollow body alone or (even) from the Presence of compartmentalization devices results.
  • the dimensionally stable hollow bodies themselves have a sufficient intrinsic dimensional stability On, as this is beneficial to the movement in machines in the production of Hollow body and the filling during the preparation of the detergent according to the invention, Detergent or detergent portions.
  • the pressure resistance of the dimensionally stable hollow body according to the invention is in the (se usual) way measured so that unfilled and optionally with compartmentalizing facilities provided hollow body with films or lids are closed and to this Hollow body at room temperature an internally applied, steadily increasing vacuum is applied until the hollow body begins to collapse.
  • the inherent dimensional stability of the hollow body should be particularly preferably be such that in such vacuum collapse tests unfilled and optionally with Kompartiment michss adopteden provided hollow body collapse not before reaching a Vacuum of 900 mbar, preferably from 750 mbar and in particular from 500 mbar begins.
  • the hollow bodies used according to the invention fundamentally differ from films or so-called “pouches", as they are used to provide detergents, cleaners or Detergents are also used. These collapse already at a pressure that only slightly below atmospheric pressure.
  • the differences dimensionally stable hollow body according to the invention also of (subsequently on shaped bodies applied) coatings:
  • the hollow body according to the invention provide an independent, self-supporting Envelope already before filling with one or more washing active, rinse active or cleaning active component (s) exists and then filled becomes.
  • coatings are applied to already existing moldings (eg pressed bodies, Granules, extrudates, etc.) applied and then dried or cured; they form only afterwards an enclosure surrounding the molding.
  • the walls of the hollow bodies used according to the invention continue to form a good diffusion barrier in the same way as the devices for compartmentalization which are to be explained in detail below, in particular for substances which are detrimentally active in washing, detergent or dishwashing active preparations, in particular gaseous substances and especially water vapor.
  • a diffusion of water vapor should preferably be possible in a maximum amount of 350 g / (m 2 • 24 h), more preferably only in an amount of not more than 100 g / (m 2 • 24 h), more preferably in one Amount of maximum 50 g / (m 2 • 24 h). more preferably only in an amount in the range of at most 100 g / (m 2 • 24 h), more preferably in a maximum amount of 50 g / (m 2 • 24 h).
  • Particularly preferred embodiments of the detergent, cleaning agent or detergent portions in the dimensionally stable hollow bodies also take into account that with particular advantage - although not mandatory - the portions contained in the hollow bodies by a - preferably controllable - water solubility of the hollow body material a certain time of washing, cleaning or rinsing or on reaching a certain pH or ionic strength of the wash liquor or due to other controllable events or conditions are fed into the aqueous liquor can.
  • the quality of the material as well as its quantity / strength take on this Solubility properties direct influence.
  • materials for the hollow bodies which - based on a certain wall thickness that determines the stability - at certain temperatures, pH values, ionic strengths, or after a certain residence time in the aqueous liquor.
  • a release process the hollow body as a whole capture or only a part thereof, so that parts of the hollow body when setting a certain parameter combination, while other parts are not yet (but only later) or not at all.
  • the latter can be due to different quality of the material as well as by different amounts of material (thickness of the wall) or even different Geometries of the hollow body can be achieved. For example, it is possible by the hollow body geometry To complicate the access of water and thus delay the dissolution process.
  • the walls of the hollow body different To make thick (nevertheless from the same material) and thus to the thinner ones Make an earlier release possible.
  • the walls of the hollow body made of materials of different water solubility For example, from Polyvinalalkoholen (PVAL) with different. Residual acetate content. This leads to the formation of perforated walls, which prevent water from entering Hollow body and / or leakage of dissolved or undissolved ingredients from the Allow hollow body.
  • PVAL Polyvinalalkoholen
  • a active, active cleaning or active washing active ingredient for which PVAL as a builder an example is, or contain such.
  • cleansing or active ingredients that are active only in small amounts in the preparations are present and their uniform incorporation therefore not unproblematic is, in the material of the wall of the hollow body or in a part of the material of the wall of the hollow body, for example one which is in the state of washing, cleaning or rinsing triggers, in which just the active ingredient is needed, incorporated and at Release the material of the wall at the right time to be released into the liquor.
  • fragrances that in the last phase of the washing or cleaning or Rinsing are desired, but also optical brighteners, UV-protective substances, dyes and other detergent-active, cleansing or rinse-active preparations.
  • optical brighteners UV-protective substances
  • dyes dyes and other detergent-active, cleansing or rinse-active preparations.
  • the basic principle the incorporation of such (usually incorporated in small quantities) Components in the materials that surround the detergent, detergent or Make detergent portions, the patent application WO-A-0100781 is published from 4.1.05 of Applicant entitled "Wirkstoff-Portionspackung".
  • the walls of the dimensionally stable hollow bodies containing the detergent, cleaning agent or detergent portions consist of different materials, so have a heterogeneous structure.
  • a wall of the hollow body forming polymer material islands be dispersed in a non-soluble in the polymer foreign material, for example from a other polymer (with different water solubility) or even from a completely different Substance (for example, an inorganic or organic substance).
  • water-soluble salts such as sodium sulfate, sodium chloride, sodium carbonate, calcium carbonate; organic acids such as citric acid, tartaric acid, adipic acid, phthalic acid; Sugars such as maltoses, dextrose, sorbitol, etc .; zeolites; silicates; crosslinked, for example weakly crosslinked polymers such as, for example, polyacrylates, cellulose esters, Cellulose ethers such as carboxymethylcellulose.
  • Such a structure can be particularly preferred embodiments of the invention be associated with the advantage that the other substance dissolves more quickly in water than the polymer, causing water ingress allows the hollow body and thus for accelerated release washing active, rinse active or cleaning-active components of the portion contributes.
  • the whole is dimensionally stable hollow body dissolves faster in such an assembly than a molded body from a pure polymer material.
  • the walls of the Hollow body of layers of two or more polymers form which in particularly preferred Embodiments can be chosen so that they are in terms of their properties (Stability, heat resistance, water solubility, gas barrier properties, etc.) optimally complete.
  • the dimensionally stable hollow body according to the invention contains in its interior several compartments or Chambers, each one or more washing active, cleaning active or rinse active Preparation (s) included. Examples of these are cuboidal or trochoidal dimensionally stable Hollow bodies having two, three or four or even more compartments, each one or contain several washing active, cleaning active or rinse active preparation (s).
  • a big advantage this embodiment of the invention is that the various washing active, detergent-active or rinse-active preparations can be distributed to the compartments, as it is best for the specific requirements.
  • components that are mutually exclusive adversely affect their effectiveness for example, enzymes, alkali, bleach, etc.
  • themselves otherwise - for example due to the state of aggregation - would mix with each other (For example, solid and liquid components)
  • washing, cleaning or rinsing should be released into the respective fleet, spatially separate from each other and give each at the optimum time in the fleet.
  • the size and shape of the individual compartments within a dimensionally stable hollow body is not critical and can be focused largely on the needs of the case.
  • certain detergent-active, cleaning-active or rinse-active preparations or Mixtures thereof which are present in larger quantities, provided larger compartments are used as preparations that are present only in small quantities.
  • mixtures of certain preparations, which are provided at the beginning of the washing, cleaning or rinsing and in certain Quantities are present, spatially from other or in other quantities required components be separated and arranged in compartments of other sizes.
  • one in a dimensionally stable hollow body with several compartment (s) contained detergents, cleaning agents or detergent portion are two or more, one or more washing-active, compartments containing detergent or rinse-active preparation (s) of the Hollow body includes, which are arranged enclosing each other.
  • the compartments with the washing-active, cleaning-active or rinse-active preparation (s) are therefore in the Hollow bodies not arranged side by side or above / below each other, but enclosing each other, for example, more or less concentric (“onion model”) or more or less coaxial (“multilayer rod model”) or such that the innermost compartment is complete is surrounded by the next outer, this possibly completely from in the following, etc.
  • the washing active, cleaning active or detergent substances should be distributed to the compartments in such a way that or rinsing as the first required components in the outermost one Compartment are the first to be exposed to water or liquor is, while (later) required component (s) in (one) further inside Compartment (s) is / are arranged and before the entry of water through the farther outside Protected compartments is / are protected.
  • the internal compartments completely enclosed by the outer are; a partial enclosure is also within the scope of the present invention.
  • Another embodiment relates to a detergent, Detergent or detergent portion containing two or more dimensionally stable hollow body at least one washing-active, cleaning-active or rinsing-active preparation wholly or partially surrounding enclosure of one or more under washing, cleaning or Rinsing conditions of disintegratable, non-pressed material (s) with at least one each Compartment, wherein the compartment (s) one or more detergent active, cleaning or rinse-active preparation (s).
  • the size, shape and arrangements of the / the compartment (s) and the at least a washing-active, cleaning-active or rinse-active preparation should be designed as well as in the context of the embodiments described above, d. H. it can be in a dimensionally stable Hollow body one or more compartments of any shape and size, each with one or more be arranged washing active, cleaning active or rinse active preparation (s). in the However, in the present case several such dimensionally stable hollow body are present together.
  • the hollow body (s) include, but are not limited to, one or more water-soluble (s).
  • Polymer (s) preferably one or more materials from the group (optionally acetalated) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, Cellulose, and their derivatives and mixtures thereof, more preferably (optionally acetalized) Polyvinyl alcohol (PVAL).
  • the dimensionally stable hollow body (s) contain one or more materials from the group acrylic acid-containing Polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, Polyesters and polyethers and mixtures thereof include / include.
  • the at least one washing-active, rinse-active or cleaning-active Preparation of surrounding enclosure from a shape giving stability to the hollow body, not pressed material.
  • non-pressed material is a material understood, not - as in the prior art - by pressing (for example) washing-active, rinse-active or cleaning-active components or preparations Obtaining a compact is made, in which then other detergent, rinse or be embedded cleaning-active components or preparations, but by any other molding techniques, as explained in detail below. Exemplary Deep drawing, casting, injection molding, sintering, etc. For inorganic materials, the can also be used, the casting can also be a preferred method of preparation be.
  • the two or more dimensionally stable hollow body made of two or more different materials may be selected from the materials listed above, but others Materials may include.
  • the walls of these hollow bodies of two or more similar materials For example, materials from the same monomer building blocks, but materials with different properties, exist. Examples of this may include similar materials different molecular weight (and thus different solubility), PVAL materials with different degrees of acetalization (and thus different solubility or different Solution temperature in water), materials with different amounts of grafted Co-monomers o. ⁇ . Be.
  • these dimensionally stable hollow body different geometric Have shape. This can advantageously lead to different release behavior or different kinetics of the release of the in the compartment (s) of the hollow body contained detergent, detergent or detergent portion.
  • the detergent, cleaning agent or detergent portions in which the two or more dimensionally stable hollow body a - particularly preferred, but not necessarily releasable - composite form.
  • a composite of two or more dimensionally stable hollow bodies can be used with particular advantage if either detergent, detergent or detergent portions differ Composition are to be dosed (for example, heavy duty detergent and colored laundry detergent, in the latter
  • Composition for example, heavy duty detergent and colored laundry detergent, in the latter
  • bleaching components are not or not in the same concentration desired as in the former; the bleach-containing hollow body could then be used by the user be removed if you want to wash colorful laundry
  • Detergent or detergent portion should be used.
  • Such a composite could be made by gluing, fusing, welding or brazing the dimensionally stable hollow body are produced; a mechanical stapling also allowed the easy release of the composite.
  • such composite hollow body in aqueous environment again detachable, for example by using a water-soluble adhesive this could be ensured be that used in automatic washing, cleaning or rinsing composite completely dissolved and with the washing, cleaning or rinsing solution from the machine is deducted.
  • the above information on the materials of dimensionally stable hollow body accordingly.
  • the compartmentalization facilities within the dimensionally stable Hollow body made of the same materials as the hollow body itself. This allows the one-piece Production in one process step and makes the production process particularly economical.
  • the compartmentalization device (s) is / are one (or more) an activity reduction of at least one component a washing-active, cleaning-active or rinse-active preparation inhibiting device (s).
  • a washing-active, cleaning-active or rinse-active preparation inhibiting device examples include all the cases where components are washing-active, cleaning-active or spolutiv preparations taking into account a mutual interference their activity spatially separated.
  • the compartmentalization facilities should then have properties that meet these requirements, for example, be substantially impermeable to water vapor to bleach free from To keep moisture, or should be acid or alkali free, to prevent enzymes from premature disintegration to protect.
  • Such inhibition of activity reduction not only contributes directly a better activity of the respective protected component, but also allows the To reduce amounts of such components, since an excess in anticipation of otherwise usual loss of activity is no longer necessary.
  • the compartmentalization device (s) is / are (one) the quality and / or quantity of the release of components a washing-active, cleaning-active or rinse-active preparation determining Device (s). It can be used in cases where the compartmentalization facilities have such function, advantageously either components of the washing active, detergent-active or rinse-active preparations at different times of Washing, cleaning or rinsing process are discharged into the fleet (qualitative control), or different amounts of certain (qualitatively identical) preparations into the fleet (quantitative control).
  • a dimensionally stable hollow body for example, several compartments on whose walls a different solubility (or temperature of dissolution) in water or in the fleet.
  • the compartments contain (washing, cleaning, rinsing) active components for the first, second and possibly further (washing, cleaning, rinsing) Gears that have different compositions and set them to different Times or at different temperatures of the washing, cleaning or rinsing process free.
  • the dimensionally stable hollow body for example only - Have walls and compartmentalization facilities, incorporated into the materials which are at different temperatures or under different other boundary conditions to solve.
  • small holes first form in the compartment walls, the one only weak mass transfer between individual compartments and the Outdoor environment allow and therefore only small amounts of a washing active, cleaning active or flushing preparation into the liquor; under other, later adjustable conditions the holes or pores are enlarged because soluble in other conditions Loosen wall components; through the larger holes, larger amounts of substance can be between the interior of the compartment (s) and the outside environment (ie the fleet) and thus the desired higher concentrations of the washing active, cleaning active or rinse-active preparation in the liquor.
  • the compartmentalization device (s) is / are (a) the activity of at least one component of a detergent active detergent or dishwashing preparation controlling device (s).
  • a detergent active detergent or dishwashing preparation controlling device s.
  • This embodiment is particularly relevant in cases where it is necessary that the release one or more active ingredients a washing active, cleaning active or rinse active Preparation takes place with a predetermined kinetics in the washing, cleaning or rinsing liquor.
  • a particular example is a so-called "controlled release" release, which differs according to the above parameters about the properties of the wall of the dimensionally stable hollow body and / or the compartmentation devices. On this way one can destructive influence of the liquor or alone of the water on the active substance decreases and the substance is actively released into the liquor over a longer period of time.
  • one or more Compartmentalizing device a part or the total amount of at least one Component of at least one detergent-active, cleaning-active or rinse-active preparation contains / contain.
  • Another preferred embodiment is one in one or more dimensionally stable hollow body (s) containing at least one compartment detergent, Detergent or detergent portion in which the dimensionally stable hollow body of a n limiting Has surfaces having non-spherical hollow body, one of which Surface assumes the function of a "lid", which concludes a method of manufacturing the detergent, cleaning or rinsing agent portions according to the invention, d. H. after filling the compartment (s) inside the hollow body with one or more washing active, active cleaning or rinse active preparation (s), closing the hollow body is applied.
  • the “lid” is particularly preferably made of a material with controllable water solubility and can be glued to the rest of the hollow body, for example with a water-soluble glue, fusing, welding or one on associated with other known methods for joining materials.
  • a water-soluble glue for example, a water-soluble glue, fusing, welding or one on associated with other known methods for joining materials.
  • These Embodiment is for the preparation of detergent, cleaning agent according to the invention or detergent portions particularly advantageous because a gradual filling of the / the compartments with one or more washing-active, cleaning-active or rinse-active preparation is possible and the handling leads to optimal results in later use, in particular to a reliable control of the access of water or aqueous liquor to the interior of the dimensionally stable hollow body or the outlet of washing active, cleaning active or rinse-active preparation from the interior of the hollow body.
  • the detergent, cleaning or rinsing agent portions according to the invention contain one or more substances from the group of nonionic surfactants, zeolites, silicates, carbonates, Bleaching agents, bleach activators, foam inhibitors, dyes and fragrances and - in the case that the detergent or cleaner portions at least partially as a shaped body present - binding and disintegration aids.
  • nonionic surfactants zeolites, silicates, carbonates
  • Bleaching agents, bleach activators, foam inhibitors, dyes and fragrances and - in the case that the detergent or cleaner portions at least partially as a shaped body present - binding and disintegration aids.
  • the washing and cleaning agent portions according to the invention surfactants from the nonionic group, Containing surfactants.
  • 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 used 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 esters, 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.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable alkylpolyglycosides satisfy the general formula RO (G) z , in which R is a linear or branched, in particular in the 2-position methyl-branched, 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.
  • the detergent, cleaning agent or detergent portions according to the invention can preferably contain alkylpolyglycosides, wherein contents of the washing and cleaning agent portions to APG over 0.2 wt .-%, based on the total preparation are preferred.
  • Particularly preferred detergent, detergent or detergent 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 wt .-%.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide may be suitable.
  • the amount of these 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 and 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 [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • 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
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy or N-aryloxy-substituted compounds can then be converted by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides be transferred.
  • the detergent, cleaning agent or detergent portions to detergent 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 detergent portions of the invention surfactants in larger or smaller quantity.
  • the amount of surfactant must not be the same in all portions; Rather, partial portions with relatively larger and Partial portions are provided with relatively smaller surfactant content.
  • the detergent, cleaning agent or washing-up liquid detergent, especially dishwashing detergent usually contain one or more surfactants in total amounts of from 0.1 to 10 Wt .-%, preferably in amounts of 0.5 to 5 wt .-%, wherein in partial portions of the inventive Detergent or detergent portions Surfactants in larger or smaller quantities may be included.
  • the amount of surfactant must also in cleaning or Dishwashing detergents should not be the same in all partial portions; rather, partial portions with relatively larger and partial portions are provided with relatively smaller surfactant content.
  • cleaning agent or detergent portions can usually be used in detergents, detergents or dishwashing detergents used builders, so zeolites, silicates, carbonates, organic cobuilders.
  • 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, 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.
  • the silicate particles may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments.
  • densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are especially preferred.
  • 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.
  • polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts the polyacrylic acid or polymethacrylic acid, for example those with 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 preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, this group may again, the short-chain polyacrylates may be preferred, 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 Methacrylic acid or acrylic acid or methacrylic acid with maleic acid.
  • copolymers of acrylic acid with maleic acid the 50 to 90 wt .-% Acrylic acid and 50 to 10 wt .-% maleic acid.
  • Their relative molar mass, 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 used either as a powder or as an aqueous solution become.
  • the content of the washing or cleaning agent portions according to the invention of (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers may also allylsulfonic, such as Allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • allylsulfonic such as Allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • Biodegradable polymers of more than two different are also preferred Monomer units, for example those containing as monomers salts of acrylic acid and the Maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those which as monomers preferably acrolein and Acrylic acid / Acryiklaresalze or acrolein and vinyl acetate.
  • builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, which in addition to co-builder properties also a bleach-stabilizing Have effect.
  • polyacetals obtained by reaction of dialdehydes can be obtained with Polyolcarbonklaren, the 5 to 7 carbon atoms and at least Have 3 hydroxy groups.
  • Preferred polyacetals are selected from dialdehydes such as glyoxal, Glutaraldehyde, terephthalaldehyde and mixtures thereof and from Polyolcarbon Textren such Gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes be performed.
  • they are hydrolysis products with middle Molar masses in the range of 400 to 500,000 g / mol.
  • This is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, especially from 2 to 30, preferably, wherein A common measure of the reducing effect of a polysaccharide compared to Dextrose is which has a DE of 100.
  • DE dextrose equivalent
  • 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. Also suitable is an oxidized oligosaccharide. 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 are also preferred. Suitable quantities are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic co-builders include acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.
  • phosphonates these are in particular hydroxyalkane or aminoalkanephosphonates.
  • hydroalkane phosphonates For example, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • aminoalkanephosphonates preferably, ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of the neutral reacting sodium salts, e.g.
  • the washing or cleaning agent portions according to the invention also contain bleach, be preferred to use Aminoalkanphosphonate, in particular DTPMP, or mixtures to use from the said phosphonates.
  • the inventive Detergents, cleaning agents or dishwashing detergents in washing, cleaning or rinsing agents conventional ingredients from the group of bleaches, bleach activators, alkalizers, Acidifiers, enzymes, fragrances, perfume carriers, fluorescers, dyes, Foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, Color transfer inhibitors, decolorizing and Flekcenstoff, antibacterial substances and corrosion inhibitors.
  • 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-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidoperuccinate; and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazel
  • chlorine may also be used or bromine-releasing substances are used.
  • suitable chlorine or bromine releasing materials include, for example, heterocyclic N-bromo- and N-chloroamides, for example, trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or Dichloroisocyanuric acid (DICA) and / or salts thereof with cations such as potassium and sodium in Consideration.
  • DICA Dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • an improved Bleach activators can be added to the detergent, cleaning or detergent portions are incorporated.
  • bleach activators compounds, which under perhydrolysis aliphatic peroxycarboxylic acids preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted Perbenzoic acid, are used. Suitable substances are the O and / or N-acyl groups of said carbon atom number and / or optionally substituted benzoyl groups wear.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, Ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • TAED tetraace
  • Bleach catalysts in the detergent, detergent or detergent 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 as Bleach catalysts usable.
  • the detergent, cleaner or detergent portions according to the invention contain According to a particularly preferred embodiment, further additives, as known from the State of the art as additives for detergent or dishwashing detergent preparations are known. These can either one or more, if necessary, too all partial portions (washing active, cleaning active or rinsing active preparations) of the invention Detergent, detergent or detergent portions are added or - as in WO-A-0 100 781 entitled "Active ingredient portion pack" described in the water-soluble, the washing active, cleaning active or rinse-active preparations comprising materials of dimensionally stable hollow body, ie For example, in the / the water-soluble wall material (s) are incorporated.
  • optical brighteners used here can be used in detergents usual optical brightener. These are called aqueous solution or as a solution in an organic solvent added to the polymer solution, which is converted into the wall of the dimensionally stable hollow body, or be a portion (washing active preparation) of a washing 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 similar compounds instead of the morpholino group, a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group.
  • Brightener of the type of substituted Diphenylstyryle in the partial portions (washing-active Preparations) of the washing or cleaning agent portions according to the invention be, z.
  • UV protection substances are substances that are released during the washing process or in the subsequent fabric softening process in the wash liquor and that accumulate accumulatively on the fiber, in order then to achieve a UV protection effect. Suitable are the products marketed under the name Tinosorb R Ciba Specialty Chemicals.
  • additives which are preferred in specific embodiments are surfactants which in particular the solubility of the water-soluble wall of the dimensionally stable hollow body or influence the compartmenting device, but also their wettability and control the foaming on dissolution, as well as foam inhibitors, but also bitter substances, the accidental ingestion of such hollow body or parts of such hollow body can prevent by children.
  • dyes in particular water-soluble or water-dispersible dyes.
  • Preferred here are dyes, as they to improve the visual appearance of products in detergents and cleaning agents and Rinsing agents are usually used.
  • the selection of such dyes prepares the Expert no difficulties, especially since such conventional dyes high storage stability and insensitivity to the other ingredients of the detergent, cleaning active or rinse-active preparations and against light and no pronounced Have substantivity to textile fibers so as not to stain them.
  • the dyes are According to the invention in the detergent or detergent or detergent portions in Levels of less than 0.01 wt .-% present.
  • Another class of additives which according to the invention is the detergent, cleaning agent or detergent portions may be added are polymers.
  • these polymers come on the one hand polymers in question, which during washing or cleaning or rinsing co-builder properties show, so for example polyacrylic acids, and modified polyacrylic acids or corresponding copolymers.
  • Another group of polymers are polyvinylpyrrolidone and other grayness inhibitors such as copolymers of polyvinylpyrrolidone, cellulose ethers and the same.
  • According to a further embodiment of the invention come as polymers Also so-called soil repellents in question, as the detergent and cleaning specialist are known and described in detail below.
  • bleach catalysts especially bleach catalysts for automatic dishwashing or laundry detergents.
  • complexes of the Manganese and cobalt, especially with nitrogen-containing ligands are used.
  • silver protectants are a variety of mostly cyclic organic compounds, the Also addressed to this person skilled in the art and help to startup prevent silver-containing objects in the cleaning process. Special examples can triazoles, benzotriazoles and their complexes with metals such as Mn, Co, Zn, Fe, Mo, W or Cu.
  • the detergent, detergent or detergent portions Soil repellents, ie polymers based on fibers or hard Apply surfaces (for example on porcelain and glass), the oil and Fettauswaschles from textiles and the Fettabwaschles of porcelain and glass positively influence and thus specifically counteract re-soiling.
  • This effect becomes particularly clear if a textile or a hard object (porcelain, glass) is contaminated, that already previously several times with a washing or cleaning agent according to the invention which contains this oil and fat dissolving component was washed.
  • nonionic cellulose ethers such as methyl cellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and at hydroxypropoxy groups from 1 to 15 wt .-%, each based on the nonionic Cellulose ethers
  • nonionic cellulose ethers such as methyl cellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and at hydroxypropoxy groups from 1 to 15 wt .-%, each based on the nonionic Cellulose ethers
  • the known from the prior art polymers of phthalic acid and / or terephthalic acid or its derivatives in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these.
  • Particularly preferred of these are the sulfonated derivatives phthalic and terephthalic acid polymers.
  • additives are the inventive detergent, cleaning or Detergent portions in amounts up to at most 30 wt .-%, preferably 2 to 20 wt .-%, added.
  • the additive may also be a material of a water-soluble Surrounding the dimensionally stable hollow body or to a material of the water-soluble compartmentalization device (s) that the one or more of the active washing (s), cleaning active (s) or rinse-active preparation (s) or holds in the Kormpartiment (s).
  • the polymer material for the wall of the hollow body or for the compartmentation device (s) either to increase in its weight, so as to achieve the depot effect achieved according to the invention is to exploit, or else the additives mentioned additionally at least partially in the to keep remaining wash-active preparation.
  • this is less preferred.
  • Fragrances are the detergent, cleaner or detergent portions of the invention added to improve the overall aesthetic appearance of the products and the consumer in addition to the technical performance (softening result) a sensory typical and to provide distinctive product.
  • perfume oils or perfumes For example, it is possible to use individual fragrance compounds, for example the synthetic ones Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-t-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • Ethers include, for example, benzyl ethyl ether.
  • To the aldehydes include z.
  • the ketones include the ionone, ⁇ -isomethylionone, and methyl cedryl ketone.
  • To the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol.
  • the hydrocarbons mainly include terpenes such as limonene and pinene.
  • perfume oils can also contain natural fragrance mixtures, as accessible from plant sources are. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are nutmeg oil, sage oil, camomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden flower oil, Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, nererool, orange peel oil and sandalwood oil.
  • the content of fragrances is in the range up to 2 wt .-% of the total Detergent, detergent or detergent portion.
  • the fragrances can be incorporated directly into the detergent-active, cleaning-active or rinse-active preparation (s) to be incorporated; but it may also be advantageous, the fragrances on carriers to increase the adhesion of the perfume on the laundry and by a slower Fragrance replacement for long-lasting fragrance of textiles.
  • carrier materials For example, cyclodextrins have been proven. This can be the cyclodextrin-perfume complexes additionally be coated with other excipients.
  • the fragrances and fragrances can basically be used in any of the partial portions (washing-active or detergent-active or rinse-active preparations) of the detergent, cleaning agent or detergent portions may be included. However, it is particularly preferred that they are provided in a detergent in a post-washing or fabric conditioning cycle Part detergent portion or in a detergent, especially in a dishwashing detergent, in a part-detergent portion intended for rinsing or rinsing, special partial-detergent portion, are included.
  • the detergent, detergent or detergent portions contain in a dimensionally stable hollow body having at least one compartment one or more washing-active, cleaning-active or rinse-active preparations in such amounts that they are suitable for a Washing, cleaning or rinsing sufficient.
  • a dosage of two Units (hollow body) under special conditions helicopter soiled, eg heavily greasy Laundry; heavily harnessed dishes
  • one in or a plurality of dimensionally stable hollow body with at least one compartment contained detergent, Detergent or detergent portion which at least one, preferably the plurality, wash-active, cleaning-active or rinse-active preparation (s) in one or more Molds from the group of powders, granules, extrudates, pellets, pearls, tablets, tabs, rings, Blocks, briquettes, solutions, melts, gels, suspensions, dispersions, emulsions, Foams and gases.
  • the shape of one or more compartments of the dimensionally stable Hollow body contained washing active, cleaning active or rinse active preparation is so no limit set as long as the hollow body can be used in the intended manner.
  • the detergent, cleaning agent or detergent portions disclosed herein consist of an outer mold containing one or more fillings.
  • the mold divided by partitions into several compartments, creating several fillings may be present separately within the same hollow body.
  • the invention also provides filled hollow body, which only partially from a sub Washing, cleaning or rinsing conditions disintegratable, the / the hollow body (s) dimensional stability lending, non-pressed material, while the remaining parts of the enclosure not necessarily dimensionally stable in the above defined sense must be.
  • a preferred Embodiment provides the provision of open, dimensionally stable molds ("shells") which are filled and closed later, closing with a Slide special importance.
  • Another object of the invention is therefore a washing, cleaning or detergent portion in the form according to claim 6.
  • the term "enclosure” characterizes the wall a body that completely surrounds a washing, cleaning or purging preparation.
  • This body, inside which the washing, cleaning or rinsing active preparation is present, may be completely or partially from one under washing, cleaning or rinsing conditions disintegratable, the / the hollow body (s) dimensional stability imparting, not pressed Material exist.
  • the term “hollow body” in the context of the present invention the body, the from enclosure and contents (according to washing, cleaning or rinsing preparation) is formed.
  • the term “hollow body” includes both the individual parts (a) or (b) in the sense the invention as well as the entire agent according to the invention, by joining the Parts (a) and (b) is formed.
  • that of the enclosure (A) is enclosed washing, cleaning or rinse-active preparation as a macroscopic object as well (filled) "hollow body” in the sense of the present invention as the washing, Cleaning or rinsing agent portion.
  • the latter is characterized in that they at least has two spatially separate areas, the different fillings can contain. These spatially separated areas are "compartments" in the Meaning of the present invention.
  • compartments can not only by subdivision of the part-hollow body, by the Enclosures (A) and (B) are enclosed, be configured. It is according to the invention additionally possible, further partial hollow bodies, which of enclosures (C), (D), (E), (F) etc. enclosed with the enclosing of the enclosures (A) and (B) part-hollow bodies to unite to the total portion.
  • a preferred embodiment provides the provision of open, dimensionally stable Hollow forms ("bowls”), which are filled and sealed later, the Closing with a film is of particular importance.
  • inventive Washing, cleaning or detergent portions preferred in which the enclosures (A) and (B) and optionally further enclosures to 20 to 90%, preferably to 30 to 80% and in particular from 40 to 70% of their surface of dimensionally stable, optionally one or several devices (s) for compartmentalizing comprehensive shells, while the Rest is formed by a water-soluble film.
  • the partial hollow body is accordingly produced by producing an open shell any shape, filling this shell and then sealed with a foil.
  • Creure is to be understood in the context of the present invention that the film, the Closes the opening of the shell (s), adheres firmly to the edges of the shell.
  • the film which closes the opening of the shell, is applied to the opening and adherent connected with their edges, which for example by gluing, partial melting or by chemical reaction.
  • the closing foil may also be a laminate of several different ones composite films, on different compositions of individual Foil layers can open the shell at certain times in the wash and cleaning cycle be released.
  • Preferred film materials are the polymers known from the prior art. Especially preferred are films of a polymer having 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 daltons. With regard to the media, in the detergents and cleaners are usually introduced, in particular portions according to the invention are preferred, in which the film consists of a water-soluble polymer.
  • Such preferred polymers may be of synthetic or natural origin. Become Polymers on a native or partnative basis are used as the film material, so are preferred Film materials selected from one or more substances of the group carrageenan, Guar, pectin, xanthan, cellulose and its derivatives, starch and its derivatives, and gelatin.
  • Carrageenan is a named after the Irish coastal town of Carragheen, educated and similar to Agar built extract of North Atlantic, belonging to the Floridean red algae.
  • the carrageenan precipitated from the algae's hot water extract is a colorless to sand-colored powder with molecular weights of 100,000-800,000 and a sulphate content of about 25%, which is very slightly soluble in warm water.
  • Carrageenan has three main components:
  • the yellow-forming f- fraction consists of D-galactose-4-sulfate and 3,6-anhydro- ⁇ -D-galactose, which are alternately glycosidically linked in the 1,3- and 1,4-positions (Agar, in contrast, contains 3,6-anhydro- ⁇ -L-galactose).
  • the non-gelling I fraction is composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues and is readily soluble in cold water.
  • the i-carrageenan composed of D-galactose-4-sulfate in 1,3-bond and 3,6-anhydro-aD-galactose-2-sulfate in 1,4-bond is both water-soluble and gel-forming.
  • Other types of carrageenan are also denoted by Greek letters: ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ .
  • the type of cations present K, NH 4, Na, Mg, Ca
  • Semisynthetic products which contain only one type of ion and can also be used as film materials in the context of the present invention are also called Carrag (h) eenates.
  • Guar also known as guar flour, which can be used as a film material in the context of the present invention, is an off-white powder obtained by grinding the endosperm of guar bean (Cyamopsis tetragonobolus).
  • the main constituent of guar is up to about 85% by weight of the dry substance guar gum (guar gum, cyamopsis gum); Secondary components are proteins, lipids and cellulose.
  • Guaran itself is a polygalactomannan, ie a polysaccharide whose linear chain of unsubstituted (see formula I) and in the C6 position with a galactose radical substituted (see formula (II) mannose units in ⁇ -D- (1 ⁇ 4 ) Link is established.
  • the ratio of I: II is about 2: 1; the II units are not strictly alternating, contrary to initial assumptions, but arranged in pairs or triplets in the polygalactomannan molecule.
  • Data on the molecular weight of the guaran vary with values of about 2.2 ⁇ 10 5 -2.2 ⁇ 10 6 g / mol, depending on the degree of purity of the polysaccharide - the high value was determined on a highly purified product - significant and correspond to about 1350 -13,500 sugar units / macromolecule. Guaran is insoluble in most organic solvents.
  • the pectins which can likewise be used as film material, are high molecular weight glycosidic plant substances which are very widespread in fruits, roots and leaves.
  • the pectins consist essentially of chains of 1,4- ⁇ -glycoside. connected galacturonic acid units whose acid groups are esterified to 20-80% with methanol, with a distinction between highly esterified (> 50%) and low-esterified pectins ( ⁇ 50%).
  • the pectins have a leaflet structure and are thus in the middle of starch and cellulose molecules. Their macromolecules still contain some glucose, galactose, xylose and arabinose and have weakly acidic properties.
  • Fruit pectin contains 95%, beet pectin to 85% galacturonic acid.
  • the molecular weights of the various Pectins vary between 10,000 and 500,000. Also, the structural properties are strongly dependent on the degree of polymerization; thus, e.g. the fruit pectins in a dried state Asbestos-like fibers, the flax pectins, however, fine, granular powders.
  • pectins become by extraction with diluted acids predominantly from the internal portions made of citrus fruit peel, Obstresten or sugar beet cuttings.
  • xanthan is inventively used as a film material.
  • Xanthan gum is a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular mass of 2 to 15 million daltons.
  • Xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.
  • Xanthan can be described by the following formula:
  • the celluloses and their derivatives are also suitable as film materials.
  • 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.
  • Cellulosic sheet materials 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.
  • starch and starch derivatives can also be used as film materials.
  • Suitable nonionic organic film materials are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can.
  • the hydrolysis can be carried out by conventional, for example acid or enzyme catalyzed Procedures are performed.
  • they are hydrolysis products with middle Molar masses in the range of 400 to 500,000 g / mol.
  • It is a polysaccharide with a Dextrose equivalent (DE) in the range of 0.5 to 40, especially from 2 to 30 is preferred, wherein A common measure of the reducing effect of a polysaccharide in comparison to dextrose, which has a DE of 100.
  • DE Dextrose equivalent
  • Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2000 to 30000 g / mol.
  • oxidized derivatives of such dextrins are their reaction products with oxidizing agents capable of at least one alcohol function of the saccharide ring to oxidize the carboxylic acid function.
  • Starch can also be used as a film material for the portions according to the invention.
  • Starch is a homoglycan, wherein the glucose units are linked ⁇ -glycosidically.
  • Starch is composed of two components of different molecular weight: about 20-30% straight-chain amylose (MW 50,000-150,000) and 70-80% branched-chain amylopectin (MW 300,000-2,000,000); Amounts of lipids, phosphoric acid and cations.
  • amylose forms long, helical, entangled chains with about 300-1200 glucose molecules as a result of the binding in the 1,4-position
  • the chain branched in amylopectin after an average of 25 glucose building blocks by 1,6-bond to a branch-like structure with about 1500-12000 molecules of glucose.
  • suitable foil materials in the context of the present invention are starch derivatives which are obtainable from starch by polymer-analogous reactions.
  • Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.
  • CMS carboxymethyl starch
  • gelatin has a prominent importance as a film material.
  • Gelatin is a polypeptide (molecular weight: about 15,000-> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as water-soluble coating material is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules.
  • Water-soluble polymers in the context of the invention are those polymers which are at room temperature in water to more than 2.5 wt .-% are soluble.
  • the films may be made of any of the aforementioned polymers, it However, it is also possible to use mixtures or multilayered layer structures of the polymers become.
  • the polymers are described in more detail below.
  • Polyvinyl alcohols are polymers of the general structure [-CH 2 -CH (OH) -] n in small proportions also structural units of the type [-CH 2 -CH (OH) -CH (OH) -CH 2 ] contain. Since the corresponding monomer, the vinyl alcohol, is not stable in free form, polyvinyl alcohols are prepared via polymer-analogous reactions by hydrolysis, but especially by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol) in solution. By these technical methods also PVAL are accessible, which contain a predeterminable residual portion of acetate groups.
  • polyvinyl alcohol in the context of the present invention Hompolymere fall of vinyl alcohol, copolymers of vinyl alcohol with copolymerizable monomers or hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with copolymerizable Monomers.
  • polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molecular weights of about 4000 to 100,000 g / mol) offered have degrees of hydrolysis of 98-99 or 87-89 mol%, so they still contain a residual content of acetyl groups.
  • the polyvinyl alcohols are characterized by pages the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
  • polyvinyl alcohols are soluble in water and a few strongly polar ones organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); of (chlorinated) Hydrocarbons, esters, fats and oils are not attacked.
  • polyvinyl alcohols are classified as toxicologically harmless and are biologically at least partially degradable.
  • the water solubility can be achieved by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, Boric acid or Borax decrease.
  • the coatings of polyvinyl alcohol are broad impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide but pass water vapor.
  • the film consists of a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mole%
  • Polyvinyl alcohols of a certain molecular weight range are preferably used in the film, with portions according to the invention being preferred in which the film consists of a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol -1 , preferably from 11,000 to 90,000 gmol -1 , more preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 .
  • the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and more preferably between about 260 to about 1500th
  • polyvinyl alcohols described above are widely available commercially, for example under the trademark Mowiol® (Clariant).
  • Mowiol® Commercially, for example under the trademark Mowiol® (Clariant).
  • especially suitable polyvinyl alcohols are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88 as well as Mowiol® 8-88.
  • polymers which are suitable according to the invention are water-soluble amphopolymers.
  • Amphoteric polymers ie polymers which contain both free amino groups and free -COOH or SO 3 H groups in the molecule and are capable of forming internal salts, are zwitterionic polymers which contain quaternary ammonium groups in the molecule. COO - - or -SO 3 - groups, and summarized those polymers containing -COOH or SO 3 H groups and quaternary ammonium groups.
  • amphopolymer which can be used according to the invention is the acrylic resin obtainable under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters.
  • Amphomer® is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters.
  • amphopolymers are composed of unsaturated carboxylic acids (for example acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (for example acrylamidopropyltrimethylammonium chloride) and optionally further ionic or nonionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be seen.
  • unsaturated carboxylic acids for example acrylic and methacrylic acid
  • cationically derivatized unsaturated carboxylic acids for example acrylamidopropyltrimethylammonium chloride
  • optionally further ionic or nonionic monomers as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be seen.
  • Terpolymers of acrylic acid, methyl acrylate and Methacrylamidopropyltrimoniumchlorid as they are commercially available under the name Merquat®2001 N, according to
  • amphoteric polymers are, for example, the octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers available under the names Amphomer® and Amphomer® LV-71 (DELFT NATIONAL).
  • Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copoly-merisate and their alkali and ammonium salts are preferred zwitterionic polymers.
  • suitable Zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are disclosed in US Pat the name Amersette® (AMERCHOL) are commercially available.
  • Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, Vinyl benzoate and as esters of acrylic acid or methacrylic acid those with aliphatic Low molecular weight alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are proven.
  • Suitable polyalkylene glycols are, in particular, polyethylene glycols and polypropylene glycols.
  • n can assume values between 1 (ethylene glycol) and several thousand.
  • Technically common is the indication of the average relative molecular weight following the indication "PEG”, so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210.
  • polyethylene glycols for example, under the trade name Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HUBS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone -Poulenc), Lutrol® E300 (BASF) and the corresponding trade name with higher numbers.
  • the polyethylene glycol used has a molecular weight between 200 and more Million, preferably between 300 and 30,000.
  • the nonionic monomers may be of very different types and among these the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, Diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.
  • the nonionic monomers can equally be of very different types, among these, particularly preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, Maleic acid, acrylic acid and methacrylic acid are contained in the graft polyamides.
  • crosslinking agents used are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho, meta- and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose having 2 to 5 allyl groups per molecule saccharin.
  • polycarboxylates are suitable as film materials in the case of the anionic polymers / Polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins which are described below.
  • Useful organic film materials are, for example, those in the form of their sodium salts but also usable in free form polycarboxylic acids.
  • Polymeric polycarboxylates 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 polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular mass of 2000 to 20,000 g / mol. Because of their superior solubility, this can be Group again the short-chain polyacrylates, the molecular weights of 2000 to 10,000 g / mol, and particularly preferably from 3000 to 5000 g / mol, have to be preferred.
  • copolymeric polycarboxylates in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • copolymeric polycarboxylates in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • acrylic acid with maleic acid the 50 to 90% by weight Acrylic acid and 50 to 10 wt .-% maleic acid.
  • Their relative molecular mass, related to free acids, is generally 2000 to 70000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid
  • Particularly preferred as film materials are also biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar Derivatives included.
  • copolymeric film materials are those which are preferably used as monomers Acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • film materials are polymeric aminodicarboxylic acids, their To name salts or their precursors. Particularly preferred are polyaspartic acids or their salts and derivatives.
  • polyacetals which by reaction of dialdehydes with polyol carboxylic acids having 5 to 7 C atoms and at least 3 hydroxyl groups, can be obtained.
  • Preferred polyacetals are selected from dialdehydes such as glyoxal, Glutaraldehyde, terephthalaldehyde and mixtures thereof and from Polyolcarbon Textren such Gluconic acid and / or glucoheptonic acid.
  • polymers are cationic polymers.
  • the cationic polymers are the permanent cationic polymers are preferred.
  • "permanently cationic" according to the invention refers to such polymers which are independent the pH of the agent (ie both the film and the remaining portion) a cationic Group have. These are usually polymers containing a quaternary nitrogen atom, for example, in the form of an ammonium group.
  • Cationic polymers preferred according to the invention are quaternized cellulose derivatives as well polymeric dimethyldiallylammonium salts and their copolymers.
  • Cationic cellulose derivatives, in particular the commercial product Polymer® JR 400, are very particularly preferred cationic polymers.
  • a washing, cleaning or washing detergent portion comprises two areas that contain different ingredients or different Release mechanisms and dissolution kinetics can be realized.
  • the in a compartment contained active substance can be any state of aggregation or any kind of presentation accept.
  • Preferred washing, cleaning or detergent portions contain the further active substance in at least one compartment in liquid, gelatinous, pasty or solid form, see below.
  • the enclosure closed by the film can be completely filled with washing, cleaning or rinse-active preparation to be filled. But it is also possible, the respective mold only partially fill before closing, thus allowing a movement of the filled To allow particles or liquids within the mold. Especially at the Filling with regularly shaped larger particles can be attractive visual effects realize. Washing, cleaning or rinsing agent portions are preferred in which the volume ratio of that enclosed by the film and the further enclosure Room for the washing, cleaning or rinsing active preparation contained in this room 1: 1 to 100: 1, preferably 1.1: 1 to 50: 1, more preferably 1.2: 1 to 25: 1 and in particular 1.3: 1 to 10: 1. In this terminology, a volume ratio of 1: 1 means that the mold is completely filled.
  • the hollow body (s) giving shape stability, not pressed material and the sheet material may be the time when the laundering or rinse-active Preparation is released, be predetermined.
  • the film can almost suddenly be soluble, so that the washing, cleaning or rinse-active preparation right at the beginning the washing or cleaning cycle is dosed into the washing or cleaning liquor (or as soon as the film gets in contact with the washing, cleaning or rinsing liquor, i. in cases, in where the portion according to the invention has no film on its outer surface, according to the Falling apart of the portion in the partial hollow body (A) or (B)).
  • the shape of the "shell” can be chosen freely, with certain geometric Shapes such as hemispheres have been found to be preferred for aesthetic reasons. But also box shapes or sargdeckelä Ober shaped trays are according to the invention realizable.
  • the "shell” may have an edge that only has the material thickness, they but can also have a web edge, as a larger adhesive and sealing surface for the film serves.
  • the "shell” is after produced by injection molding of water-soluble thermoplastics. In this process If necessary, any partitions for the later formation of several compartments can be sprayed on become. Also, the production of the "shell” from a Schmelzgußhabilit suitable substances (see below) is preferred.
  • the closing of the filled trays with foil is carried out by adherent connection with their Edges, such as by gluing, partial melting or by chemical Reaction can take place.
  • the cover film can not only at the subdivided shells Rims of the outer shell circumference be tightly sealed, but also with the upper Edge of the inner partitions, so that a close conclusion of the compartments also against each other is guaranteed.
  • the covering film can also be designed so that differently prepared film areas over the different compartments come to rest, so the disintegration kinetics in aqueous solution and thus the release of the individual preparations from the compartments.
  • the enclosures (A) and (B) and possibly further enclosures and / or further Ingredients of the portions according to the invention form in their entirety the inventive Washing, cleaning or detergent portion. It is preferred that the enclosures (A) and (B) and possibly other enclosures are joined together so that not surface of the washing, cleaning or detergent portion to at least 80%, preferably at least 90% and in particular exclusively from the / the hollow body (s) dimensional stability imparting, not pressed Material exists.
  • the separately manufactured part-hollow body are joined together so that only a small part (in a particularly preferred case no part at all) of the surface of the Washing, cleaning or detergent portion according to the invention is formed by film. Rather, there is the "outer skin" of the washing, cleaning or detergent portion of the invention for the most part (in particularly preferred cases: complete) from the non-pressed material which imparts dimensional stability to the hollow body.
  • washing, cleaning or rinsing agent portions contain washing, cleaning or rinse-active preparations. These can be used in any form of packaging in be contained in the part-hollow bodies or compartments. Particularly preferred washing, Cleaning or rinsing agent portions are characterized in that at least one washing, cleaning or rinsing active preparation in the enclosures (A) or (B) in liquid Form is present.
  • This liquid must be chosen so that they do not cover the materials of the envelope attacks.
  • the coating is transparent, or at least is translucent to the aesthetic appeal of liquid filling also visible from the outside allow.
  • inventive washing, cleaning or detergent portions particularly preferred in which at least one enclosure is transparent or translucent is, wherein the wall thickness of the wholly or partly from a washing under, cleaning or Rinsing conditions disintegratable, the / the hollow body (s) dimensional stability imparting, not pressed material 100 to 5000 microns, preferably 200 to 3000 microns, more preferably 300 to 2000 microns and in particular 500 to 1500 microns.
  • the washing, cleaning or rinsing agent portions according to the invention have at least two areas in which washing, cleaning or rinsing active preparation is located.
  • these preparations are preferably liquid.
  • the second Preparation may also be a liquid (optionally different composition) But it is also possible to use here solids of any packaging. Especially preferred it is this, the second cavity with a powdered to granular preparation to fill.
  • the washing, cleaning or rinsing agent portions according to the invention can preferably be used for the separation of incompatible active ingredients by their division into a plurality of separate regions.
  • the table below gives a non-limiting overview of possible drugs and their division into different compartments. It was additionally specified in which packaging the corresponding preparation is contained in the partial hollow body.
  • partial hollow body which washing, cleaning or rinse-active preparation in the enclosures (A) or (B) are combined with each other to the detergent, detergent according to the invention or detergent portion combined this is not according to the invention bound to connect only two partial hollow body. Rather, it is also possible to have more Part-hollow body, which washing, cleaning or rinse active preparation in other enclosures (C) or (D), etc., to add.
  • partial hollow bodies preferably have flat connecting surfaces. Of course one is not bound to only filled part-hollow body together for the invention Detergent, detergent or detergent portion to connect.
  • partial hollow body which washing, cleaning or active ingredient in enclosures (A) or (B), with further washing, cleaning or to combine rinse-active preparations in a solid, dimensionally stable form.
  • enclosures (A) or (B) with further washing, cleaning or to combine rinse-active preparations in a solid, dimensionally stable form.
  • the portions according to the invention are in particular suitable, various washing, cleaning or rinse-active preparations from the enclosures (A) or (B) release at different times.
  • the release from the enclosures (A) or (B) can either by be achieved at different times that the parts of the respective enclosure, which consist of the hollow body dimensional stability-conferring material, different Have dissolution or Ddsintegrations horren. This is for example through Choice of matepal strength possible.
  • the other part of the enclosure in preferred Embodiments: The film closing the shell) in the enclosures (A) or (B) to choose differently and in this way a different release of the preparation to reach from the enclosures (A) and (B).
  • inventive washing, Cleaning or rinsing agent portions preferred in which the enclosures (A) and (B) from a film-sealed injection-molded half-shell are formed, wherein the wall thickness the half shells of the enclosures (A) and (B) 100 to 1000 microns; preferably 150 to 700 microns and in particular 250 to 500 microns and the thickness of the film of the enclosure (A) 10 to 200 .mu.m, preferably 20 to 100 .mu.m and in particular 40 to 80 microns and the Thickness of the film of the enclosure (B) 20 to 250 microns, preferably 40 to 200 microns and in particular 60 to 150 microns
  • the injection molding process can be facilitated by adding to the polymers external plasticizers (e.g., glycerin) or "internally" plasticized Polymers used.
  • either the film of the enclosure (B) can be made thicker and / or chemically modifying the film to make it easier to dissolve.
  • inventive Washing, cleaning or detergent portions are preferred in which the film the enclosures (A) and (B) consists of thermoplastic polymers, wherein the film of the Encapsulation (B) in the application liquor is slower or more delayed than that of the film Enclosure (A).
  • Corresponding films of water-soluble thermoplastics are commercially available.
  • a polyvinyl alcohol film which at 20 ° C. already dissolves sufficiently quickly
  • the enclosure (B) in a seichen Fall a Film is selected with slower dissolution kinetics at 20 ° C, for example, one with a better solubility above 40 ° C or 50 or 60 ° C.
  • washing, cleaning or rinsing agent portions are characterized that the compound of the closed enclosures (A) and (B) with a water-soluble Hot-melt adhesive, so that the portion in the application liquor within 60 s, preferably within 30 seconds, so disintegrated that the film of the closed enclosures (A) or (B) gets in contact with the application fleet.
  • the filling of the partial hollow body (A) or (B) can be chosen completely arbitrary, with numerous Examples are already described above. Particularly preferred are in the context of present invention washing, cleaning or detergent portions in which the closed Enclosure (A) a nonionic surfactant-based detergent composition, preferably a Liquid detergent contains, while the closed enclosure (B) preferably a Composition having further utility, in particular a bleaching composition and / or an enzyme composition and / or a fragrance preparation and / or a discoloration, Graying or hardness inhibiting composition and / or a softening composition, contains.
  • a nonionic surfactant-based detergent composition preferably a Liquid detergent contains
  • the closed enclosure (B) preferably a Composition having further utility, in particular a bleaching composition and / or an enzyme composition and / or a fragrance preparation and / or a discoloration, Graying or hardness inhibiting composition and / or a softening composition, contains.
  • the ingredients for the above preparations are detailed above described.
  • the above principle can also be used for cleaning agents adapt, for example, for automatic dishwashing detergents in which the closed enclosure (A) contains a builder-rich detergent composition while the closed Enclosure (B) preferably a composition of further use, in particular a Rinse aid composition and / or a Fragrance preparation and / or a complexing agent composition and / or a Polymer composition containing.
  • step (i) is a Injection molding process, preferably at a pressure between 100 and 5000 bar, preferably between 500 and 2500 bar, more preferably between 750 and 1500 bar and in particular between 1000 and 1250 bar and preferably at temperatures between 100 and 250 ° C, preferably between 120 and 200 ° C and in particular between 140 and 180 ° C, is carried out.
  • the individual hollow body are preferably not completely filled.
  • the Hollow bodies or compartments in step (ii) to 20 to 100%, preferably to 30 to 95%, more preferably from 40 to 90% and in particular from 50 to 85% of their volume with washing, cleaning or rinsing active preparations are filled.
  • the Film has a thickness of 1 to 150 microns, preferably from 2 to 100 microns, more preferably from 5 to 75 ⁇ m and in particular from 10 to 50 ⁇ m.
  • inventive methods are preferred in the combination of enclosures (A) and (B) and, where appropriate, other enclosures and / or other washing, cleaning or rinse-active preparations in solid, dimensionally stable form for Washing, cleaning or rinsing agent portion in step (iv) by cold sealing, gluing with water-soluble hot melt adhesives, gluing with adhesive solutions or mechanical connection he follows.
  • the partial hollow bodies In the context of the present invention, it is preferred to stick the partial hollow bodies together with adhesion promoters. It is possible to use substances as adhesion promoters which impart sufficient adhesiveness ("stickiness") to the surfaces to which they are applied, so that the partial hollow bodies adhere permanently to one another.
  • adhesion promoters which impart sufficient adhesiveness ("stickiness") to the surfaces to which they are applied, so that the partial hollow bodies adhere permanently to one another.
  • the substances mentioned in the relevant textbook literature and in particular in the monographs are suitable here, in the context of the present invention the application of melts which are used in the context of the present invention in which the sealing of the hollow bodies takes place by sealing with a water-soluble film, the film having a thickness of 1 to 150 ⁇ m, preferably 2 to 100 ⁇ m, particularly preferably 5 to 75 ⁇ m and in particular 10 to 50 ⁇ m.
  • the partial hollow bodies with adhesion agents.
  • adhesion agents can be used substances that the surfaces, to which they are applied, impart sufficient adhesion ("stickiness") to it the partial hollow body permanently adhere to each other.
  • adhesion agents can be used substances that the surfaces, to which they are applied, impart sufficient adhesion ("stickiness") to it the partial hollow body permanently adhere to each other.
  • step iv) as a primer melting one or several substances are used with a melting range of 40 ° C to 75 ° C, are therefore preferred.
  • the Schmelz supportivetica Solidification behavior on the other hand, however, the material properties in the solidified area at ambient temperature. Since the adhered part-hollow body When transporting or storage should hold together permanently, the bond must a high stability against, for example, occurring during packaging or transport shock loads exhibit.
  • the bonding agents should therefore either at least partially elastic or have at least plastic properties in order to impact on a occurring elastic or plastic deformation to respond and not to break.
  • the adhesion agents should have a melting range (solidification range) in such a temperature range, in which the partial hollow body or the preparations contained in them not too high thermal Be exposed to stress. On the other hand, however, the melting range must be sufficient be high to still provide effective adhesion at least slightly elevated temperature.
  • the coating substances preferably have a melting point above 30 ° C.
  • Width of the melting range of the primer also has an immediate effect on the Procedure:
  • the provided with primer part-hollow body must in the following Process step are brought into contact with the / the other part-hollow body (s) - In the meantime, the adhesion must not be lost. After the sticking together should the Adhesion should be reduced as quickly as possible to avoid unnecessary loss of time or Caking and stagnation in subsequent process steps or handling and Avoid packaging. In the case of the use of melts, the reduction of the Adherence by cooling (for example, blowing cold air) are supported.
  • adhesion promoters do not have a sharply defined melting point show how it usually occurs in pure, crystalline substances, but one under Circumstances have several degrees Celsius melting range.
  • the adhesion promoters preferably have a melting range of between about 45 ° C and This means in the present case that the melting range within the specified temperature interval occurs and does not denote the width of the melting range.
  • the width of the melting region is at least 1 ° C, preferably about 2 to about 3 ° C.
  • waxes are usually met by so-called waxes.
  • “Waxing” is understood to mean a number of natural or estrogenic substances found in the Melt above 40 ° C without decomposition and just above the melting point are relatively low-viscosity and non-stringy. They have a strong temperature-dependent Consistency and solubility.
  • the waxes are divided into three groups, the natural waxes, chemical modified waxes and the 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 (woolwax), or raffia fat, mineral waxes such as ceresin or Ozokerite (ground wax), or petrochemical waxes such as petrolatum, paraffin waxes or Microcrystalline waxes.
  • 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 (woolwa
  • the chemically modified waxes include, for example, hard waxes such as Montanester waxes, Sassol waxes or hydrogenated jojoba waxes.
  • synthetic waxes are usually polyalkylene waxes or Polyalkylene glycol waxes understood. It is also possible to use compounds as adhesion promoters other substance classes meeting the stated softening requirement. Suitable synthetic compounds are, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG) available, proved. Also suitable are synthetically produced waxes from lower Carboxylic acids and fatty alcohols, for example dimyristyl tartrate, under the name Cosmacol® ETLP (Condea) is available. Conversely, synthetic or semisynthetic .. Esters of lower alcohols can be used with fatty acids from natural sources.
  • Tegin® 90 Goldschmidt
  • Shellac for example shellac KPS three-ring SP (Kalkhoff GmbH) is inventively as Adhesive can be used.
  • the Wax alcohols are higher molecular weight, water-insoluble Fatty alcohols with usually about 22 to 40 carbon atoms.
  • the waxy alcohols come for example in the form of wax esters of higher molecular weight fatty acids (wax acids) as Main ingredient of many natural waxes.
  • wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
  • the adhesion promoter in step iv) may optionally also contain wool wax alcohols, including triterpenoid and Steroidal alcohols, such as lanolin, understands, for example, under the Trade name Argowax® (Pamentier & Co) is available. Also at least proportionately as Component of the adhesion promoter can be used in the context of the present invention Fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.
  • wool wax alcohols including triterpenoid and Steroidal alcohols, such as lanolin, understands, for example, under the Trade name Argowax® (Pamentier & Co) is available.
  • Component of the adhesion promoter can be used in the context of the present invention Fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.
  • the adhesion promoters should have the lowest possible water solubility, even in water with increased Temperature, exhibit a temperature-independent release of the enveloped To avoid active substances as much as possible.
  • the adhesion promoters to be applied in process step iv) can be pure substances or substance mixtures be. In the latter case, the melt may contain varying amounts of adhesion promoter and excipients.
  • the principle described above is for the delayed release of the in step iv) adhered part-hollow body from each other at a given time, for example in the cleaning cycle of a dishwasher and can be used particularly advantageously when rinsing in the main rinse at a lower temperature (for example, 55 ° C), so that the Active substance from the adhesive layer only in the rinse cycle at higher temperatures (about 70 ° C) is released.
  • a lower temperature for example, 55 ° C
  • the said principle can also be reversed to the effect that the partial hollow body is not Delayed, but accelerated to be resolved from each other.
  • This can be in the invention Achieve process in a simple manner in that as a primer in step iv) not Lcaptivateverzögerer, but release accelerators are used, so that the partial hollow body not slower, but faster.
  • Adhesion agent readily soluble in water.
  • the water solubility of the primer can be determined by certain Additives can be significantly increased, for example, by incorporating easily soluble Salts or effervescent systems.
  • the release acceleration can also be achieved by certain geometric factors or get supported. Detailed comments can be found below.
  • adhesion promoters for the accelerated release are those mentioned above synthetic waxes from the group of polyethylene glycols and polypropylene glycols.
  • PEG and PPG are of course also Other substances can be used provided they have a sufficiently high water solubility and a Melting point above 30 ° C.
  • step iv) of the process according to the invention be applied as a primer.
  • other substances can also be used in step iv) of the process according to the invention be applied as a primer.
  • a primer for example, are concentrated Salt solutions after application of the active ingredients by crystallization or evaporation / evaporation be transferred into an adhesion-promoting salt crust. It can of course also supersaturated solutions are used or solutions of salts in solvent mixtures.
  • a primer in step iv) are also solutions or suspensions of water-soluble or dispersible polymers, preferably polycarboxylates.
  • the mentioned Fabrics have already been described because of their co-builder properties.
  • adhesion promoters are solutions of water-soluble substances the group (acetalated) polyvinyl alcohol, polyvinylpyrrolidone, gelatin and mixtures thereof. These substances have already been described above as Folienmatertialien.
  • adhesion promoter to preferably the edge region of the closed part-hollow body can be done in different ways. It is possible, for example, the sealed part-hollow body in the dipping process on one side with adhesive to wet and then to place in the cavity. This technique is technologically easy to implement, But there is a risk that the adhesive wets the entire film and thus possibly a provided controlled by the film controlled release difficult.
  • the amount of Adhesive can in this variant by varying the rheological properties of the adhesion promoter to be controlled.
  • adhesion promoter apply consists of the surfaces to be wetted (usually the edges of the partial hollow body) to pass adhesive metering systems. This is achieved by adhesion promoter dosing Nozzles, adhesives impregnated brushes or nonwovens or by rolling. The latter Process design is particularly easy to implement.
  • the bonding agent when joining two partial hollow bodies with their flat surfaces do not apply to the bonding surface, but only Apply "primer points" at the edge or at the corners. These are the Water access when used immediately exposed, so that the two partial hollow body separate faster. Become in this way two part-hollow body with square Contact surface connected to each other, the bonding agent must not be applied to all four edges become. It can rather contribute to even faster separation of the compound, only Apply to the four corners bonding agent points. For even faster separation can on Methods for thermoforming polymers by deep drawing are known in the art known as such.
  • a plate or foil of a polymer is made by means of a punch and Swaging existing deep-drawing press at elevated temperature to the desired blank formed a dimensionally stable polymer.
  • Disadvantage of this procedure for the present case of Production of a hollow body is the fact that when removing the blank a vacuum in the Inside of the hollow body is formed, which must be canceled by blowing a gas. As a result, the otherwise technically simple deep-drawing press becomes expensive.
  • let yourself with the procedure of deep drawing only very irregular wall thickness s of dimensionally stable Realize hollow body.
  • dimensionally stable Hollow bodies with compartmentalizing devices can not be produced in one step.
  • blanks for dimensionally stable hollow body by Pouring of the polymer can be prepared in appropriately prepared forms.
  • the Process variant of the casting not only allows the use of fusible polymers as Wall materials, but also other fusible substances.
  • thermoplastic polymers can after This method is excellent for dimensionally stable hollow bodies, in particular optionally too dimensionally stable hollow bodies which contain in their interior means for compartmentalizing, are processed.
  • the injection molding of suitable materials is carried out according to known per se Procedures at high pressures and temperatures, for example at temperatures between 100 and 220 ° C, in particular devishalöb the softening point of the thermoplastic, for example at 140 ° C and higher, in particular at about 180 ° C, and a pressure between 500 and 2,000 bar, preferably of> 1,000 bar, in particular at about 1,400 bar, with the steps of closing the mold connected to the extruder for injection, injection of the polymer at high Temperature and high pressure, cooling of the injection molded molding, opening the mold and Remove the molded blank. Further optional steps, such as the application of release agents, removal from the mold, etc., are known to the person skilled in the art and can be carried out according to technology known per se be performed.
  • the detergent, cleaning agent or detergent portions disclosed herein consist of an outer mold containing one or more fillings.
  • the mold through Partitions should be divided into several compartments, creating multiple fillings within the same hollow body can be present separately.
  • the fillings are besides to the compatibility with the material of the mold no requirements, so that portion both solid and liquid phases (systems).
  • a hollow body is injection-molded, which has a plurality of spaces for receiving having washing, rinsing or cleaning active preparations.
  • the injection molding of suitable materials takes place according to known procedures at high pressures and temperatures with the Steps of closing the mold connected to the extruder for injection, injection the polymer at high temperature and high pressure, cooling the injection-molded molding, Opening the mold and removing the molded blank.
  • Other optional steps like that Application of release agents, demolding, etc. are known in the art and can after known technology.
  • step (i) is performed at a pressure between 100 and 5000 bar, preferably between 500 and 2500 bar, more preferably between 750 and 1500 bar and in particular between 1000 and 1250 bar performed.
  • step (i) is carried out at temperatures between 100 and 250 ° C, preferably between 120 and 200 ° C and in particular between 140 and 180 ° C, performed.
  • the tools that receive the materials are preferably pre-tempered and have Temperatures above room temperature, with temperatures between 25 and 60 ° C and in particular from 35 to 50 ° C are preferred.
  • the thickness of the wall can be varied.
  • the should Wall on the one hand be selected so thin that a speedy resolution or disintegration achieved and the ingredients are released quickly into the application fleet, but is also one certain minimum thickness required to give the mold the desired stability, in particular Dimensional stability, to confer.
  • dimensionally stable hollow body By the term “dimensionally stable hollow body” is meant that the Detergent, detergent or detergent portions containing moldings an inherent dimensional stability which enables them, under normal conditions of manufacture, storage, transport and handling by the consumer is stable against breakage and / or pressure, to have non-coincident structure, which also differs under the mentioned conditions not changed for a long time. It is according to the invention without influence, whether this structural stability from the properties of the product resulting from the following parameters: dimensionally stable hollow body alone or (even) from the presence of compartmentalizing devices results.
  • the dimensionally stable hollow body itself a sufficient inherent dimensional stability, since this is advantageous on the mobility in machines in the production of the hollow body and the filling during the Preparation of the Detergent, Detergent or Detergent Portions of the Invention effect.
  • the pressure resistance of the dimensionally stable hollow body according to the invention is in the (se usual) way measured so that unfilled and optionally with compartmentalizing facilities provided hollow body with films or lids are closed and to this Hollow body at room temperature an internally applied, steadily increasing vacuum is applied until the hollow body begins to collapse.
  • the inherent dimensional stability of the hollow body should be particularly preferably be such that in such vacuum collapse tests unfilled and optionally with Kompartiment michss adopteden provided hollow body collapse not before reaching a Vacuum of 900 mbar, preferably from 750 mbar and in particular from 500 mbar begins.
  • the hollow bodies used according to the invention fundamentally differ from films or so-called “pouches", as they are used to provide detergents, cleaners or Detergents are also used. These collapse already at a pressure that only slightly below atmospheric pressure.
  • the differences dimensionally stable hollow body according to the invention also of (subsequently on shaped bodies applied) coatings:
  • the hollow body according to the invention provide an independent, self-supporting Envelope already before filling with one or more washing active, rinse active or cleaning active component (s) exists and then filled becomes.
  • coatings are applied to already existing moldings (eg pressed bodies, Granules, extrudates, etc.) applied and then dried or cured; they form only afterwards an enclosure surrounding the molding.
  • hollow bodies are produced in step (i) which does not collapse before reaching a vacuum of 250 mbar, preferably 100 mbar and in particular from 20 mbar begins.
  • Preferred methods are therefore characterized in that the wall thickness of the In step (i) produced enclosure (b) 100 to 5000 .mu.m, preferably 200 to 3000 .mu.m, especially preferably 300 to 2000 microns and in particular 500 to 1500 microns.
  • MFI flow index
  • a one-step procedure is especially preferred when in addition to solid preparations and liquid components Comprehensive preparations (dispersions or emulsions, suspensions) or even gaseous Components comprehensive preparations (foams) in the detergent, detergent or Detergent portions are to be incorporated in the hollow bodies.
  • Polymers are particularly suitable as materials for the hollow body to be produced in step (i) in which process according to the invention are preferred, in which those prepared in step (i) Enclosure (b) one or more materials from the group of acrylic acid-containing polymers, Polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters and polyethers and their mixtures.
  • water-soluble polymers as material for the hollow body.
  • the in step (i) produced Enclosing (b) one or more water-soluble polymer (s), preferably a material from the Group (optionally acetalated) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, Polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof, more preferred (optionally acetalated) polyvinyl alcohol (PVAL).
  • PVAL polyvinyl alcohol
  • PVAL polyvinylpyrrolidone
  • Polyethylene oxide polyethylene oxide
  • gelatin gelatin
  • cellulose and their derivatives and mixtures thereof
  • PVAL more preferred (optionally acetalated) polyvinyl alcohol
  • polyvinyl alcohols are particularly preferred as coating materials.
  • Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure in small proportions (about 2%) also structural units of the type contain.
  • polyvinyl alcohols which are known as white-yellowish powder or granules with Degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol) are offered, have degrees of hydrolysis of 98-99 or 87-89 mol%, so contain one more Residual content of acetyl groups.
  • the polyvinyl alcohols are characterized by the manufacturers by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the Saponification number or solution viscosity.
  • polyvinyl alcohols are soluble in water and a few strongly polar ones organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); of (chlorinated) Hydrocarbons, esters, fats and oils are not attacked.
  • Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable.
  • the Water solubility can be achieved by post-treatment with aldehydes (acetalization), by Complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax reduce.
  • the coatings of polyvinyl alcohol are largely impermeable to gases such as Oxygen, nitrogen, helium, hydrogen, carbon dioxide, however, allow water vapor to pass through.
  • the Hollow body consist of a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 Mol%.
  • Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the hollow bodies, preference being given to processes according to the invention in which the hollow bodies produced in step (i) consist of a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol -1 , preferably from 11,000 to 90,000 gmol -1 , more preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 .
  • the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and more preferably between about 260 to about 1500.
  • polyvinyl alcohols described above are widely available commercially, for example under the trademark Mowiol® (Clariant).
  • Mowiol® Commercially, for example under the trademark Mowiol® (Clariant).
  • especially suitable polyvinyl alcohols are, for example Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88 and Mowiol® 8-88.
  • polyvinyl alcohols suitable as material for the hollow mold are ELVANOL® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademark of Nippon Gohsei K.K.).
  • the hollow body Plasticizing aids included. This can be particularly advantageous if as a material for the hollow bodies polyvinyl alcohol or partially hydrolyzed polyvinyl acetate were selected. Of the Proportion of plasticizer (based on the polymer) is usually up to 15 wt .-%, with values between 5 and 10 wt .-% are preferred. As plasticizing aids have in particular glycerol, triethanolamine, ethylene glycol, propylene glycol, diethylene or Dipropylene glycol, diethanolamine and methyldiethylamine proven.
  • mold release additives are important auxiliary substances that can be used in the injection molding compositions.
  • stearic acid and / or stearates and fumed silicas (Aerosil.RTM.) And talcum have proved to be particularly useful in the context of the present invention from the groups of fatty substances and finely divided substances.
  • the proportion of demolding additives (based on the polymer) is usually up to 5 wt .-%, with values between 0.5 and 2.5 wt .-% are preferred. Further substances which can be used as mold release additives come in particular from the group of fatty substances.
  • fatty substances are understood to mean liquid to solid substances from the group of the fatty alcohols, the fatty acids and the fatty acid derivatives, in particular the fatty acid esters, at normal temperature (20 ° C.). Reaction products of fatty alcohols with alkylene oxides count in the present application to the surfactants (see above) and are not fatty substances in the context of the invention.
  • Fatty substances which can be used according to the invention are preferably fatty alcohols and fatty alcohol mixtures, fatty acids and fatty acid mixtures, fatty acid esters with alkanols or diols or polyols, fatty acid amides, fatty amines, etc.
  • fatty alcohols which are obtainable from native fats and oils are 1-hexanol (caproic alcohol), 1-heptanol (oenanthalcohol), 1-octanol (caprylic alcohol), 1-nonanol (pelargon alcohol), 1-decanol (capric alcohol), 1-undecanol , 10-undecene-1-ol, 1-dode-canol (lauryl alcohol), 1-tridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexa-decanol (cetyl alcohol), 1-heptadecanol, 1-octadecanol ( Stearyl alcohol), 9-cis-octadecen-1-ol (oleyl alcohol), 9-trans-octadecen-1-ol (erucyl alcohol), 9-cis-octadecene-1,12-diol (ricinoleic alcohol), all
  • Guerbet alcohols and oxo alcohols for example C 13-15 oxo alcohols or mixtures of C 12-18 alcohols with C 12-14 alcohols, can also be used without problems as fatty substances.
  • alcohol mixtures for example those such as C 16-18 -alcohols produced by ethylene polymerization according to Ziegler.
  • Specific examples of alcohols which can be used as component b) are the abovementioned alcohols as well as lauryl alcohol, palmityl and stearyl alcohol and mixtures thereof.
  • Preferred removal additives are C 10-30 fatty alcohols, preferably C 12-24 fatty alcohols with particular preference to 1-hexadecanol, 1-octadecanol, 9-cis-octadecen-1-ol, all-cis-9,12-octadecadiene 1-ol, all-cis-9,12,15-octadecatrien-1-ol, 1-docosanol and mixtures thereof.
  • fatty acids can be used as a mold release additive. These are largely derived from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage. For example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc.
  • Fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanic acid (palmitic acid), octadecanoic acid (stearic acid), eicosansäwe (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and the unsaturated Sezies 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-o
  • tridecanoic acid pentadecanoic acid, margaric acid, nonadecanoic acid, erucic acid, elaeostearic acid and arachidonic acid can be used.
  • Such mixtures are for example coconut oil (about 6 wt .-% C 8 , 6 wt .-% C 10 , 48 wt .-% C 12 , 18 wt .-% C 14 , 10 wt .-% C 16 , 2 wt % C 18 , 8% by weight C 18 ' , 1% by weight C 18 " ), palm kernel oil fatty acid (about 4% by weight C 8 , 5% by weight C 10 , 50% by weight C 12 , 15 wt .-% C 14 , 7 wt .-% C 16 , 2 wt .-% C 18 , 15 wt .-% C 18 ' , 1 wt .-% C 18 " ), tallow fatty acid (ca.
  • % C 16 ' 1% by weight C 17 , 2% by weight C 18 , 70% by weight C 18' , 10% by weight C 18 " , 0.5% by weight C 18 ''' ), technical palmitic / stearic acid (about 1 wt .-% C 12 , 2 wt .-% C 14 , 45 wt .-% C 16 , 2 wt .-% C 17 , 47 wt .-% C 18 , 1 wt .-% C 18 ' ) and soybean oil fatty acid (about 2 wt .-% C 14 , 15 G % by wt. C 16 , 5 wt.% C 18 , 25 wt.% C 18 ' , 45 wt.% C 18 " , 7 wt.% C 18'” ).
  • fatty acid esters it is possible to use the esters of fatty acids with alkanols, diols or polyols, fatty acid polyol esters being preferred.
  • Fettklarepotyolester come mono- or diesters of Fatty acids with certain polyols into consideration.
  • the fatty acids that esterify with the polyols are preferably saturated or unsaturated fatty acids having 12 to 18 carbon atoms, For example, lauric, myristic, palmitic or stearic, preferably the technically produced mixtures of the fatty acids are used, for example, those of coconut, Palm kernel or tallow derived sesame mixtures.
  • acids or mixtures of acids with 16 to 18 carbon atoms such as tallow fatty acid are esterified with the polyvalent ones Suitable alcohols.
  • polyols which are esterified with the fatty acids mentioned above in the context of the present invention sorbitol, trimethylolpropane, neopentylglycol, Ethylene glycol, polyethylene glycols, glycerol and polyglycerols.
  • Preferred embodiments provide that as a polyol with Fatty acid (s) is esterified, glycerol is used. Consequently, as demolding additives Fatty substances from the group of fatty alcohols and fatty acid glycerides are preferred. Especially preferred Entformungszu accounts are fatty substances from the group of fatty alcohols and Fatty acid monoglycerides. Examples of such preferred fatty substances used are glycerol monostearic acid esters or glycerol monopalmitinklareester.
  • antioxidants may contain.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, Catechols and aromatic amines and organic sulfides, polysulfides, dithiocarbamates, Phosphites and phosphonates.
  • the material for the mold, the wall thickness and the size of the mold chosen so that the hollow body in unmoved water of 20 ° C in less than 300 seconds, preferably dissolves in less than 60 seconds or the ingredients of the Filling releases. It is not necessary that the entire body spontaneously dissolves. Rather, it is sufficient if all components within the period of application among the Resolve application conditions. For usual washing or rinsing processes this means Temperatures of 20 ° C and above, mechanical action and times of less than 200 Minutes, preferably less than 60 minutes, in particular less than 20 minutes. The release of the However, ingredients of at least one compartment should preferably be less than 300 Seconds, especially in less than 60 seconds. This can be done by using Disintegration aids, by sealing a compartment with a thin, water-soluble film, by dissolution of an opening occluding "stopper" or on other common way.
  • the production of injection-molded hollow bodies, wherein the injection molding compound water-soluble polymers has not been described in the prior art.
  • Another subject of the present The invention is therefore an injection molding process for hollow bodies which comprise such polymers, ie a method for the production of hollow bodies by injection molding, which is characterized in that the injection molding compound contains one or more water-soluble polymer (s), preferably one or more a plurality of material (s) from the group (optionally acetalised) polyvinyl alcohol (PVAL), Polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof, most preferably (optionally acetalized) polyvinyl alcohol (PVAL).
  • PVAL polyvinyl alcohol
  • the Injection molding composition comprises a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 Mol%.
  • the injection molding composition comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol -1 , preferably from 11,000 to 90,000 gmol -1 , more preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 is located.
  • the inventive method can be carried out with particular advantage, if the proportion the water-soluble polymer in the injection molding compound is high.
  • the entire Injection molding compound only from the water-soluble polymers and optionally excipients (see above).
  • methods according to the invention are preferred in which the injection molding compound mentioned Polymers in amounts of at least 50% by weight, preferably of at least 70% by weight, particularly preferably of at least 80% by weight and in particular of at least 90% by weight, each based on the weight of the injection molding compound contains.
  • the dimensionally stable hollow body produced by injection molding does not have walls which are closed on all sides and is open on at least one of its sides - in the case of a spherical or elliptical body in the region of a part of its shell.
  • One or more washing-active, cleaning-active or rinse-active preparation (s) are / are introduced through the remaining opening into the compartment (s) formed inside the dimensionally stable hollow body (s). This is also done in a known per se way, for example in the context of known from the confectionery industry manufacturing process; It is also possible to proceed in several steps.
  • a one-step procedure is particularly preferred if, in addition to solid preparations, preparations comprising liquid components (dispersions or emulsions, suspensions) or even gaseous component-containing preparations (foams) are to be incorporated into the detergent, cleaning agent or rinsing agent portions in the hollow bodies ,
  • one or more detergent-active, cleaning-active or rinse-active preparation (s) are filled into compartments which are preferably concentric or coaxial and are arranged concentrically or coaxially with one another or partially or completely surrounding each other Brought compartments.
  • compartments which partially or completely surround each other, preferably the compartments arranged concentrically or coaxially, in addition to one or more other compartment (s) filled with one or more washing-active, cleaning-active or flushing preparation (s) in the dimensionally stable are hollow body or contained alone in this.
  • This can - as already described above - by applying a "Cover" on the still open (n-th) surface of the dimensionally stable hollow body or - in spherical or elliptical hollow bodies - by applying a corresponding partial spherical shell or partial elliptical shell to happen on the opening.
  • the application may preferably by way of Gluing, preferably with a water-soluble adhesive, fusing, welding or also according to other types of bonding known to the person skilled in the art.
  • the water solubility of the walls / compartments surrounding the phases can be be set so that each pass 5 to 10 minutes after opening a compartment, until the content of the next compartment is released.
  • phase 2 is omitted and their content distributed to the phases 1 (protease) and 3 (soda, alkali carriers) and, in a further simplification, in addition to phase 2, phase 4 will also be omitted, Perfume, optical brightener and Soil Repellent are added to the Phase 3 and the fabric softener is dosed in a separate product.
  • Example 1 Polyvinyl alcohol granules (Vinex® 2019 from the company Texas Polymers) were used on a hydraulic Screw injection molding machine of the company Arburg melted and in simple tools with Hot runner nozzle injected.
  • Example 2 a trochoidal shell with three corrugated Partitions and a peripheral edge made in Example 2 a hemisphere with a circumferential stacking approach and a border.
  • the mold shells prepared in the manner described above were introduced into water and measured time to disintegration or to complete dissolution: Temperature [° C] 20 30 40 50 60 Decay after [min] 12 7 5 4 2 complete resolution after [min] 18 11 8th 6 4
  • Polyvinyl alcohol granules (Vinex® 2019 from the company Texas Polymers) were used on a hydraulic Screw injection molding machine of the company Arburg melted and in simple tools with Hot runner nozzle injected, wherein the shell is in the form of a hemisphere with a circumferential Stacking neck and a border showed.
  • a half-shell was treated with a low-water commercial liquid detergent (Persil® gel, Commercial product of the Applicant) and filled with a polyvinyl alcohol film from Greensol locked.
  • a second half-shell was made with an extruded, bleach-containing Heavy duty detergent (Persil® Megaperls®, commercial product of the applicant) filled and connect also sealed with a PVAI film.
  • the two part-hollow body in the closed Envelopes (A) and (B) were then glued together using Klatkleber.

Claims (39)

  1. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage contenue dans un ou plusieurs corps creux de forme stable, à savoir, c'est à dire déjà autonomes avant le remplissage avec un ou plusieurs composants à action de lavage, action de rinçage ou action de nettoyage, autoportants, ayant au moins un compartiment, comprenant
    (a) au moins une préparation à action de lavage, action de nettoyage, ou action de rinçage, issue du groupe formé par les tensio-actifs non ioniques, les zéolithes, les silicates, les carbonates, les agents de blanchiment, les activateurs de blanchiment, les stabilisants de blanchiment, les catalyseurs de blanchiment, les polymères, les co-builders, les agents d'alcalinisation, les agents d'acidification, les agents anti-redépôt, les agents protégeant l'argenterie, les colorants, les azurants optiques, les substances protégeant des UV, les adoucissants, les agents mouillants, en une quantité suffisante pour un cycle de lavage, de nettoyage, et de rinçage;
    (b) au moins une enveloppe entourant totalement ou partiellement ladite au moins une préparation selon (a) constituée d'une matière non pressée pouvant se déliter dans des conditions de lavage, de nettoyage ou de rinçage, conférant la stabilité de forme au(x) corps creux; et
    (c) une ou plusieurs parois, qui séparent spatialement l'un de l'autre des composants ou préparations, identiques ou différents, à action de lavage, à action de nettoyage ou action de rinçage.
  2. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage selon la revendication 1, comprenant un corps creux de forme stable, constitué d'au moins une enveloppe entourant partiellement ou totalement une préparation à action de lavage, à action de nettoyage ou à action de rinçage, enveloppe constituée d'une matière non pressée pouvant se déliter dans des conditions de lavage, de nettoyage ou de rinçage, avec au moins un compartiment, le ou les compartiments contenant une ou plusieurs préparations à action de lavage, à action de nettoyage ou à action de rinçage.
  3. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage selon la revendication 2, comprenant deux ou plusieurs compartiments contenant une ou plusieurs préparations à action de lavage, à action de nettoyage ou à action de rinçage, qui sont disposés, l'un entourant l'autre.
  4. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage selon la revendication 1, comprenant deux ou plusieurs corps creux de forme stable, constitués d'une enveloppe entourant totalement ou partiellement une préparation à action de lavage, à action de nettoyage ou à action de rinçage, constituée d'une ou de plusieurs matières non pressées, pouvant se déliter dans des conditions de lavage, de nettoyage ou de rinçage, avec au moins un compartiment chacun, le ou les compartiments contenant une ou plusieurs préparations à action de lavage, à action de nettoyage, ou à action de rinçage.
  5. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage selon la revendication 4, dans laquelle les deux ou plusieurs corps creux de forme stable sont constitués de plusieurs matières non pressées pouvant se déliter dans des conditions de lavage, de nettoyage ou de rinçage.
  6. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage sous forme d'un corps creux au moins partiellement rempli, divisé en au moins deux compartiments, déjà autonome avant le remplissage avec un ou plusieurs composants, à action de lavage, à action de rinçage, ou à action de nettoyage, autoportant, comprenant
    (a) une préparation à action de lavage, de nettoyage ou de rinçage, issue du groupe formé par les tensio-actifs non ioniques, les zéolithes, les silicates, les carbonates, les agents de blanchiment, les activateurs de blanchiment, les stabilisants de blanchiment, les catalyseurs de blanchiment, les enzymes, les polymères, les co-builders, les agents d'alcalinisation, les agents d'acidification, les agents anti-redépôt, les agents protégeant l'argenterie, les colorants, les azurants optiques, les substances protégeant des UV, les adoucissants, les agents mouillants, en une quantité suffisante pour un cycle de lavage, de nettoyage et de rinçage, laquelle préparation est entourée par une enveloppe (A), qui est constituée totalement ou partiellement d'une matière non pressée pouvant se déliter dans des conditions de lavage, de nettoyage ou de rinçage et conférant une stabilité de forme au(x) corps creux;
    (b) une préparation supplémentaire à action de lavage, de nettoyage ou de rinçage, laquelle est entourée par une enveloppe (B) qui est constituée totalement ou partiellement d'une matière non pressée pouvant se déliter dans les conditions de lavage, de nettoyage ou de rinçage et conférant une stabilité de forme au(x) corps creux;
    (c) éventuellement d'autres préparations à action de lavage, de nettoyage ou de rinçage, lesquelles sont entourées éventuellement par des enveloppes qui sont constituées totalement ou partiellement d'une matière non pressée pouvant se déliter dans les conditions de lavage, nettoyage ou de rinçage et conférant une stabilité de forme au(x) corps creux;
    (d) éventuellement d'autres préparations à action de lavage, de nettoyage ou de rinçage, sous forme solide de forme stable,
    caractérisée en ce que la portion d'agent de lavage, de nettoyage ou de rinçage, est formée par assemblage de l'enveloppe (A) et de l'enveloppe (B).
  7. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage selon la revendication 6, caractérisée en ce que les enveloppes (A) et (B) ainsi qu'éventuellement d'autres enveloppes, sont constituées éventuellement à raison de 20 à 90%, de préférence de 30 à 80%, et en particulier de 40 à 70% de leur surface, d'une ou de plusieurs parois de forme stable, séparant spatialement l'un de l'autre des composants ou préparations, identiques ou différents, à action de lavage, à action de nettoyage, ou à action de rinçage, tandis que le reste est formé par une feuille hydrosoluble.
  8. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage selon l'une quelconque des revendications 6 ou 7, caractérisée en ce que les enveloppes (A) et (B) ainsi qu'éventuellement d'autres enveloppes sont assemblées de sorte que la surface non formée par une partie éventuellement présente (d), de la portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage, est constituée, à raison d'au moins 80%, de préférence d'au moins 90% et en particulier exclusivement, d'une matière non pressée conférant une stabilité de forme au(x) corps creux.
  9. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage selon l'une quelconque des revendications 6 à 8, caractérisée en ce qu'au moins une préparation à action de lavage, de nettoyage ou de rinçage, existe sous forme liquide dans les enveloppes (A) ou (B).
  10. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage selon l'une quelconque des revendications 6 à 9, caractérisée en ce qu'au moins une enveloppe est transparente ou translucide, où l'épaisseur de paroi de la paroi totalement ou partiellement constituée d'une matière non pressée pouvant se déliter dans les conditions de lavage, de nettoyage ou de rinçage et conférant une stabilité de forme au(x) corps creux, est de 100 à 5 000 µm, de préférence de 200 à 3 000 µm, de manière particulièrement préférée de 300 à 2 000 µm et en particulier de 500 à 1 500 µm.
  11. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage selon l'une quelconque des revendications 6 à 10, caractérisée en ce que les enveloppes (A) et (B) sont formées à partir d'une demi-coque façonnée par injection, fermée par une feuille, l'épaisseur de paroi des demi-coques des enveloppes (A) et (B) étant de 100 à 1 000 µm, de préférence de 150 à 700 µm, et en particulier de 250 à 500 µm, et l'épaisseur de la feuille de l'enveloppe (A) étant de 10 à 200 µm, de préférence de 20 à 100 µm et en particulier de 40 à 80 µm, et l'épaisseur de la feuille de l'enveloppe (B) étant de 20 à 250 µm, de préférence de 40 à 200 µm, et en particulier de 60 à 150 µm.
  12. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage selon la revendication 11, caractérisée en ce que la feuille des enveloppes (A) et (B) est constituée de polymères thermoplastiques, la feuille de l'enveloppe (B) se dissolvant dans la lessive d'application, à retardement ou plus lentement que la feuille de l'enveloppe (A).
  13. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage selon l'une quelconque des revendications 11 ou 12, caractérisée en ce que l'assemblage des enveloppes (A) et (B) se réalise avec une colle fusible hydrosoluble, de sorte que la portion se délite dans la lessive d'application en l'espace de 60 secondes, de préférence en l'espace de 30 secondes, de sorte que la feuille des enveloppes (A) ou (B) vient en contact avec la lessive d'application.
  14. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage selon l'une quelconque des revendications 11 à 13, caractérisée en ce que l'enveloppe (A) contient une composition d'agent de lavage de base, riche en tensio-actifs non ioniques, de préférence un agent de lavage liquide, tandis que l'enveloppe (B) contient de préférence une composition ayant une autre utilité, en particulier une composition de blanchiment et/ou une composition enzymatique et/ou une préparation de parfum et/ou une composition inhibitrice de coloration, de grisaillement ou de dureté, et/ou une composition d'adoucissant.
  15. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage selon l'une ou plusieurs des revendications 1 à 14, dans laquelle le ou les corps creux de forme stable comprennent un ou plusieurs polymères hydrosolubles, de préférence une matière issue du groupe formé par le poly(alcool vinylique) (PVAL) (éventuellement acétalisé), la polyvinylpyrrolidone, le poly(oxyde d'éthylène), la gélatine, les dérivés de cellulose et leurs mélanges, de manière particulièrement préférée le poly(alcool vinylique) (PVAL) (éventuellement acétalisé).
  16. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage selon l'une ou plusieurs des revendications 1 à 14, dans laquelle le ou les corps creux de forme stable comprennent une ou plusieurs matières issues du groupe formé par les polymères contenant de l'acide acrylique, les polyacrylamides, les polymères d'oxazoline, les poly(sulfonate de styrène)s, les polyuréthanes, les polyesters, et les polyéthers et leurs mélanges.
  17. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage selon la revendication 6, dans laquelle le ou les corps creux de forme stable sont constitués de plusieurs matières, de préférence de matières similaires ayant des propriétés différentes;
  18. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage, selon l'une ou plusieurs des revendications 4 à 8, dans laquelle deux ou plusieurs corps creux de forme stable, présentent une forme différente.
  19. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage, selon l'une ou plusieurs des revendications 4 à 9, dans laquelle les deux ou plusieurs corps creux de forme stable forment un assemblage dissociable, sont liés de préférence les uns aux autres, de façon dissociable, par collage, soudure, fusion ou agrafage.
  20. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage, selon l'une ou plusieurs des revendications 1 à 10, dans laquelle la ou les parois, lesquelles séparent spatialement l'un de l'autre des composants ou préparations, identiques ou différents, à action de lavage, à action de nettoyage ou à action de rinçage, constituent un ou des dispositifs inhibant une réduction d'activité d'au moins un composant d'un composant à action de lavage, à action de nettoyage ou à action de rinçage.
  21. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage, selon l'une ou plusieurs des revendications 1 à 10, dans laquelle la ou les parois, lesquelles séparent spatialement l'un de l'autre des composants ou préparations, identiques ou différents, à action de lavage, à action de nettoyage ou à action de rinçage, constituent un ou des dispositifs déterminant la qualité et/ou la quantité de la libération de composants d'une préparation à action de lavage, à action de nettoyage ou à action de rinçage.
  22. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage, selon la revendication 12, dans laquelle la ou les parois, lesquelles séparent spatialement l'un de l'autre des composants ou préparations identiques ou différents, à action de lavage, à action de nettoyage ou à action de rinçage, constituent un ou des dispositifs commandant au moyen de paramètres physico-chimiques, la libération d'au moins un composant d'une préparation à action de lavage, à action de nettoyage ou à action de rinçage dans une lessive de lavage, de nettoyage ou de rinçage, de préférence un ou des dispositifs commandant la libération au moyen d'un délitement au bout d'une certaine durée, à une certaine température, à un certain pH, à une certaine force ionique, du fait d'une certaine stabilité mécanique et/ou d'une certaine perméabilité.
  23. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage, selon l'une ou plusieurs des revendications 1 à 10, dans laquelle la ou les parois, lesquelles séparent spatialement l'un de l'autre des composants ou préparations, identiques ou différents, à action de lavage, à action de nettoyage ou à action de rinçage, constituent un ou des dispositifs commandant l'activité d'au moins un composant d'une préparation à action de lavage, à action de nettoyage ou à action de rinçage.
  24. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage, selon la revendication 14, dans laquelle la ou les parois, lesquelles séparent spatialement l'un de l'autre des composants ou préparations, identiques ou différents, à action de lavage, à action de nettoyage ou à action de rinçage, constituent un ou des dispositifs fournissant un effet de libération contrôlée ou bien un ou des dispositifs pouvant être délités, de préférence un ou des dispositifs présentant ou générant des perforations.
  25. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage, selon l'une ou plusieurs des revendications 1 à 15, dans laquelle la ou les parois, lesquelles séparent spatialement l'un de l'autre des composants ou préparations, identiques ou différents, à action de lavage, à action de nettoyage ou à action de rinçage, contiennent une partie ou la quantité totale d'au moins un composant d'au moins une préparation à action de lavage, à action de nettoyage ou à action de rinçage.
  26. Portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage, selon l'une ou plusieurs des revendications 1 à 19, comprenant ladite au moins une préparation, de préférence plusieurs préparations à action de lavage, à action de nettoyage ou à action de rinçage, sous une ou plusieurs formes issues du groupe formé par les poudres, les granulés, les extrudats, les pastilles, les perles, les comprimés, les tablettes, les bagues, les blocs, les briquettes, les solutions, les masses fondues, les gels, les suspensions, les dispersions, les émulsions, les mousses, et les gaz.
  27. Procédé de fabrication d'une portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage, contenue dans un ou plusieurs corps creux de forme stable, avec au moins un compartiment, selon l'une quelconque des revendications 1 à 20, comprenant les étapes où l'on fabrique d'une manière connue en elle-même un ou plusieurs corps creux de forme stable, c'est à dire déjà autonomes avant le remplissage avec un ou plusieurs composants à action de lavage, à action de rinçage ou à action de nettoyage, autoportants, les procédés se déroulant avec compression pour la fabrication du ou des corps creux étant exclus, ce ou ces corps creux étant munis d'une ou plusieurs parois, lesquelles séparent spatialement l'un de l'autre des composants ou préparations, identiques ou différents, à action de lavage, à action de nettoyage, ou à action de rinçage, et les compartiments sont remplis avec au moins une préparation à action de lavage, à action de nettoyage ou à action de rinçage, issue du groupe formé par les tensio-actifs non ioniques, les zéolithes, les silicates, les carbonates, les agents de blanchiment, les activateurs de blanchiment , les stabilisants de blanchiment, les catalyseurs de blanchiment, les polymères, les co-builders, les agents d'alcalinisation, les agents d'acidification, les agents anti-redépôt, les agents protégeant l'argenterie, les colorants, les azurants optiques, les substances protégeant des UV, les adoucissants, les agents mouillants, en une quantité suffisante pour un cycle de lavage, de nettoyage et de rinçage, et éventuellement, les corps creux de forme stable sont refermés par la suite par formation d'une enveloppe partielle ou complète autour de la ou des préparations à action de lavage, à action de nettoyage ou à action de rinçage.
  28. Procédé de fabrication d'une portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage, contenue dans un corps creux au moins partiellement rempli, divisé en au moins deux compartiments, comprenant les étapes :
    (i) la fabrication de corps creux de forme stable, c'est à dire déjà autonomes avant le remplissage avec un ou plusieurs composants à action de lavage, à action de rinçage ou à action de nettoyage, autoportants, comprenant éventuellement une ou plusieurs parois, lesquelles séparent spatialement l'un de l'autre, des composants ou préparations; à action de lavage, à action de nettoyage ou à action de rinçage, identiques ou différents;
    (ii) le remplissage des corps creux ou des compartiments avec des préparations à action de lavage, à action de nettoyage ou à action de rinçage, issues du groupe formé par les tensio-actifs non ioniques, les zéolithes, les silicates, les carbonates, les agents de blanchiment, les activateurs de blanchiment , les stabilisants de blanchiment, les catalyseurs de blanchiment, les polymères, les co-builders, les agents d'alcalinisation, les agents d'acidification, les agents anti-redépôt, les agents protégeant l'argenterie, les colorants, les azurants optiques, les substances protégeant des UV, les adoucissants, les agents mouillants, en une quantité suffisante pour un cycle de lavage, de nettoyage et de rinçage;
    (iii) la fermeture des corps creux de forme stable en formant des enveloppes fermées (A), (B), ainsi qu'éventuellement d'autres enveloppes fermées, autour de la ou des préparations à action de lavage, à action de nettoyage ou à action de rinçage;
    (iv) l'assemblage des enveloppes fermées (A) et (B) ainsi qu'éventuellement d'autres enveloppes, et/ou d'autres préparations à action de lavage, à action de nettoyage ou à action de rinçage, sous forme solide de forme stable, pour obtenir une portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage.
  29. Procédé selon la revendication 28, caractérisé en ce que l'étape (i) comprend un procédé de moulage par injection, qui est réalisé de préférence à une pression comprise entre 100 et 5 000 bars, de préférence entre 500 et 2 500 bars, de manière particulièrement préférée entre 750 et 1 500 bars, et en particulier entre 1000 et 1 250 bars, et de préférence à des températures comprises entre 100 et 250°C, de préférence entre 120 et 200°C, et en particulier entre 140 et 180°C.
  30. Procédé selon l'une quelconque des revendications 28 ou 29, caractérisé en ce que les corps creux ou les compartiments dans l'étape (ii) sont remplis avec des préparations à action de lavage, à action de nettoyage ou à action de rinçage, à raison de 20 à 100%, de préférence de 30 à 95%, de manière particulièrement préférée de 40 à 90%, et en particulier de 50 à 85% de leur volume.
  31. Procédé selon l'une quelconque des revendications 28 à 30, caractérisé en ce que la fermeture des corps creux se réalise à l'aide d'un scellage avec une feuille hydrosoluble, la feuille présentant une épaisseur de 1 à 150 µm, de préférence de 2 à 100 µm, de manière particulièrement préférée de 5 à 75 µm, et en particulier de 10 à 50 µm.
  32. Procédé selon l'une quelconque des revendications 27 à 31, caractérisé en ce que l'assemblage des enveloppes (A) et (B) fermées, ainsi qu'éventuellement d'autres enveloppes et/ou d'autres préparations à action de lavage, à action de nettoyage ou à action de rinçage, sous forme solide de forme stable pour obtenir une portion d'agent de lavage, d'agent de nettoyage ou d'agent de rinçage dans l'étape (iv), se réalise au moyen d'un scellage à froid, d'un collage avec des colles fusibles hydrosolubles, d'un collage avec des solutions de colle, ou d'un assemblage mécanique.
  33. Procédé selon la revendication 27, dans lequel la fabrication du ou des corps creux de forme stable se réalise par emboutissage, moulage ou moulage par injection.
  34. Procédé selon la revendication 27, dans lequel le ou les corps creux de forme stable, comprenant éventuellement une ou plusieurs parois, lesquelles séparent spatialement l'un de l'autre des composants ou des préparations, identiques ou différents, à action de lavage, à action de nettoyage ou à action de rinçage, sont fabriquées, en étant fermées de façon incomplète, le ou les compartiments formés dans le ou les corps creux incomplètement fermés, sont remplis avec au moins une préparation à action de lavage, à action de nettoyage ou à action de rinçage, et éventuellement le ou les corps creux sont fermés en formant une enveloppe partielle ou complète de ladite au moins une préparation à action de lavage, à action de nettoyage ou à action de rinçage.
  35. Procédé selon la revendication 34, dans lequel des corps creux non sphériques de forme stable, présentant n surfaces frontières, sont fabriqués en tant qu'ébauches ayant (n-1) surfaces et éventuellement une ou plusieurs parois, lesquelles séparent spatialement l'un de l'autre des composants ou préparations, identiques ou différents, à action de lavage, à action de nettoyage ou à action de rinçage, sont fabriqués au moyen d'un moulage par injection, le ou les compartiments formés dans les ébauches sont remplis avec au moins une préparation à action de lavage, à action de nettoyage ou à action de rinçage, et l'ébauche remplie est complètement fermée en appliquant la énième surface frontière du ou des corps creux.
  36. Procédé selon la revendication 27, dans lequel une ou plusieurs préparations à action de lavage, à action de nettoyage ou à action de rinçage, remplissent des compartiments s'entourant mutuellement complètement, de préférence disposés de façon concentrique ou coaxiale l'un par rapport à l'autre, ou sont placées sous forme de compartiments disposés de façon concentrique ou coaxiale l'un par rapport à l'autre, et celles-ci, éventuellement conjointement avec une ou plusieurs préparations à action de lavage, à action de nettoyage ou à action de rinçage, sont introduites dans un corps façonné de forme stable, fabriqué séparément, et ce dernier est éventuellement fermé complètement.
  37. Procédé de lavage, en particulier procédé pour le lavage en machine dans une machine à laver ordinaire du commerce, comprenant les étapes où
    on introduit une portion d'agent de lavage selon l'une quelconque des revendications 1 à 20 dans la machine à laver, en particulier dans le compartiment de rinçage ou le tambour de lavage;
    on règle les conditions de lavage souhaitées; et
    lorsque ces conditions se présentent, on ajoute la ou les préparations à action de lavage de la portion d'agent de lavage dans la lessive de lavage, et celle-ci est mise en contact avec la charge à laver.
  38. Procédé de nettoyage, comprenant les étapes où
    l'on introduit une portion d'agent de nettoyage selon l'une quelconque des revendications 1 à 20 dans la lessive de nettoyage;
    on règle les conditions de nettoyage souhaitées; et
    lorsque ces conditions se présentent, on ajoute la ou les préparations à action de nettoyage de la portion d'agent de nettoyage dans la lessive de nettoyage, et celle-ci est mise en contact avec la charge à nettoyer.
  39. Procédé de rinçage, en particulier procédé pour le rinçage en machine dans un lave-vaisselle ordinaire du commerce, comprenant les étapes, où
    l'on introduit une portion d'agent de rinçage selon l'une quelconque des revendications 1 à 20 dans le lave-vaisselle, en particulier dans le compartiment de rinçage, ou dans son volume de rinçage,
    on règle les conditions de rinçage souhaitées; et
    lorsque ces conditions se présentent, on ajoute la ou les préparations à action de rinçage de la portion d'agent de rinçage dans la lessive de rinçage, et celle-ci est mise en contact avec la charge à rincer.
EP01967120A 2000-07-14 2001-07-04 Corps creux compartimentes contenant une dose d'un produit de lavage, de nettoyage ou de rincage Revoked EP1305396B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05014861A EP1586631B1 (fr) 2000-07-14 2001-07-04 Corps creux compartimentés comprenant une dose d' un produit de lavage, de mnettoyage ou de rincage

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
DE2000133827 DE10033827A1 (de) 2000-07-14 2000-07-14 Kompartiment-Hohlkörper
DE10033827 2000-07-14
DE10048448 2000-09-29
DE2000148448 DE10048448A1 (de) 2000-07-14 2000-09-29 Kompartiment-Hohlkörper II
DE2000158647 DE10058647A1 (de) 2000-07-14 2000-11-25 Kompartiment- Hohlkörper III
DE10058647 2000-11-25
DE10107878 2001-02-20
DE2001107878 DE10107878A1 (de) 2000-07-14 2001-02-20 "Kompartiment-Hohlkörper IV"
PCT/EP2001/007633 WO2002006431A2 (fr) 2000-07-14 2001-07-04 Corps creux a compartiment

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP05014861A Division EP1586631B1 (fr) 2000-07-14 2001-07-04 Corps creux compartimentés comprenant une dose d' un produit de lavage, de mnettoyage ou de rincage

Publications (2)

Publication Number Publication Date
EP1305396A2 EP1305396A2 (fr) 2003-05-02
EP1305396B1 true EP1305396B1 (fr) 2005-11-02

Family

ID=27437838

Family Applications (2)

Application Number Title Priority Date Filing Date
EP01967120A Revoked EP1305396B1 (fr) 2000-07-14 2001-07-04 Corps creux compartimentes contenant une dose d'un produit de lavage, de nettoyage ou de rincage
EP05014861A Revoked EP1586631B1 (fr) 2000-07-14 2001-07-04 Corps creux compartimentés comprenant une dose d' un produit de lavage, de mnettoyage ou de rincage

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP05014861A Revoked EP1586631B1 (fr) 2000-07-14 2001-07-04 Corps creux compartimentés comprenant une dose d' un produit de lavage, de mnettoyage ou de rincage

Country Status (8)

Country Link
US (2) US7417019B2 (fr)
EP (2) EP1305396B1 (fr)
JP (1) JP2004504443A (fr)
AT (2) ATE350462T1 (fr)
AU (1) AU2001287580A1 (fr)
DE (2) DE50111830D1 (fr)
ES (2) ES2279467T3 (fr)
WO (1) WO2002006431A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102000594A (zh) * 2010-11-26 2011-04-06 大连理工大学 可见光光催化剂银和磷酸银的制备方法及其应用

Families Citing this family (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3365978B2 (ja) * 1999-07-15 2003-01-14 株式会社神戸製鋼所 半導体デバイス電極用Ａｌ合金薄膜及び半導体デバイス電極用Ａｌ合金薄膜形成用のスパッタリングターゲット
DE10040724A1 (de) * 2000-08-17 2002-03-07 Henkel Kgaa Mechanisch stabile, flüssig formulierte Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen
US6414016B1 (en) * 2000-09-05 2002-07-02 Sucampo, A.G. Anti-constipation composition
DE10110886A1 (de) * 2001-03-07 2002-09-26 Henkel Kgaa Wasch- und/oder Reinigungsmittel
DE10149718A1 (de) * 2001-10-09 2003-04-17 Henkel Kgaa Portionierte Wasch-, Spül-oder Reinigungsmittel in flexiblen wasserlöslichen Behältern
DE10162644A1 (de) * 2001-12-20 2003-07-10 Henkel Kgaa Soda-Silikat-Compounds als Hüllmaterial
DE10253214A1 (de) * 2002-11-15 2004-06-03 Henkel Kgaa Portionierte Mittel mit unterschiedlichen Bestandteilen
US20050152932A1 (en) * 2003-06-12 2005-07-14 Valery Normand Non-crystalline perfume or flavor delivery system
DE10338043A1 (de) * 2003-08-19 2004-12-02 Henkel Kgaa Verfahren zur Herstellung von Wasch-oder Reinigungsmitteln
DE102004018790B4 (de) * 2004-04-15 2010-05-06 Henkel Ag & Co. Kgaa Wasserlöslich umhüllte Bleichmittelteilchen
DE102004030318B4 (de) * 2004-06-23 2009-04-02 Henkel Ag & Co. Kgaa Mehrkammer-Pouch
DE102004039472A1 (de) * 2004-08-14 2006-03-02 Henkel Kgaa Verfahren zur Herstellung portionierter Wasch- oder Reinigungsmittel
ES2340798T3 (es) * 2005-02-17 2010-06-09 The Procter And Gamble Company Composicion para el cuidado de tejidos.
BRPI0608295A2 (pt) * 2005-03-10 2009-12-08 Reckitt Benckiser Nv processo para o preparo de uma embalagem contendo uma composição compactada e embalagem obtida por este processo
MX2007013748A (es) * 2005-05-04 2008-01-28 Johnson Diversey Inc Sistema de lavado de loza que contiene bajos niveles de tensoactivo.
DE102005045440A1 (de) * 2005-09-22 2007-04-05 Henkel Kgaa Portionierte Wasch- oder Reinigungsmittelzusammensetzung
GB0523336D0 (en) 2005-11-16 2005-12-28 Reckitt Benckiser Uk Ltd Injection moulding
US20070111914A1 (en) * 2005-11-16 2007-05-17 Conopco, Inc., D/B/A Unilever, A Corporation Of New York Environmentally friendly laundry method and kit
US7612031B2 (en) * 2005-12-15 2009-11-03 Kimberly-Clark Worldwide, Inc. Health-and-hygiene appliance comprising a dispersible component and a releasable component disposed adjacent or proximate to said dispersible component; and processes for making said appliance
DE102006013614A1 (de) * 2006-03-22 2007-09-27 Henkel Kgaa Wasch- oder Reinigungsmitteldosiereinheit
GB0700925D0 (en) * 2007-01-18 2007-02-28 Reckitt Benckiser Nv Dosage element and a method of manufacturing a dosage element
EP2108041A1 (fr) 2007-01-18 2009-10-14 Reckitt Benckiser N.V. Élément de dosage et procédé de fabrication d'un élément de dosage
US7824741B2 (en) 2007-08-31 2010-11-02 Micron Technology, Inc. Method of forming a carbon-containing material
DE102007059968A1 (de) * 2007-12-11 2009-06-18 Henkel Ag & Co. Kgaa Reinigungsmittel
GB0811399D0 (en) * 2008-06-20 2008-07-30 Edwards David B Cushion Pack
DE102009027164A1 (de) * 2009-06-24 2010-12-30 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
WO2012021761A1 (fr) 2010-08-12 2012-02-16 Church & Dwight Co., Inc. Sachet de détergent ayant des propriétés améliorées
GB201015277D0 (en) 2010-09-14 2010-10-27 Xeros Ltd Novel cleaning method
US8778862B2 (en) 2012-05-22 2014-07-15 S.C. Johnson & Son, Inc. Concentrated cleaner in water-dissolvable pouch
DE102012214608A1 (de) * 2012-08-16 2014-02-20 Henkel Ag & Co. Kgaa Wasserlösliche Verpackung mit Bittermittel II
US9273273B2 (en) * 2013-03-15 2016-03-01 Illinois Tool Works, Inc. Vehicle wash pod
US10808210B2 (en) 2013-03-15 2020-10-20 Monosol, Llc Water-soluble film for delayed release
CN105143425B (zh) * 2013-03-15 2019-04-09 蒙诺苏尔有限公司 用于延迟释放的水溶性膜
CA2913731C (fr) 2013-06-04 2021-05-25 Monosol Llc Solutions d'etancheification de films solubles dans l'eau, procedes associes et articles associes
US9099974B2 (en) * 2013-12-20 2015-08-04 Vmware, Inc. Volume redirection
EP2924105A1 (fr) * 2014-03-28 2015-09-30 The Procter and Gamble Company Article de dose unitaire soluble dans l'eau
EP2924108A1 (fr) * 2014-03-28 2015-09-30 The Procter and Gamble Company Article de dose unitaire soluble dans l'eau
JP2016108426A (ja) * 2014-12-05 2016-06-20 日本合成化学工業株式会社 水溶性フィルム及び薬剤包装体
MX2019007193A (es) 2017-01-04 2019-09-05 Church & Dwight Co Inc Un sistema y un metodo relacionado para formar un paquete de camaras multiples.
DE102018221671A1 (de) 2018-12-13 2020-06-18 Henkel Ag & Co. Kgaa Vorrichtung und Verfahren zur Herstellung einer wasserlöslichen Hülle sowie diese wasserlösliche Hülle enthaltene Wasch- oder Reinigungsmittelportionen mit viskoelastischer, festförmiger Füllsubstanz
DE102018221674A1 (de) 2018-12-13 2020-06-18 Henkel Ag & Co. Kgaa Vorrichtung und Verfahren zur Herstellung einer wasserlöslichen Hülle sowie diese wasserlösliche Hülle enthaltene Wasch- oder Reinigungsmittelportionen
EP3722404B1 (fr) * 2019-04-12 2022-03-30 Henkel AG & Co. KGaA Composition solide contenant du parfum
CN111908514B (zh) * 2020-08-12 2022-07-08 重庆邮电大学 一种碗状c掺杂磁性中空介孔纳米材料的制备方法及产品

Family Cites Families (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3234258A (en) 1963-06-20 1966-02-08 Procter & Gamble Sulfation of alpha olefins
DE2065153C3 (de) 1969-02-18 1974-04-11 Raion Yushi K.K., Tokio Mehrkomponentendetergentformlinge
JPS4831725B1 (fr) 1969-05-12 1973-10-01
DE1954244A1 (de) 1969-10-28 1971-05-06 Jan Simon Schwimmseife
US3927195A (en) 1974-01-31 1975-12-16 Lilly Industries Ltd Production of capsules
US4001211A (en) 1974-12-02 1977-01-04 The Dow Chemical Company Pharmaceutical capsules from improved thermogelling methyl cellulose ethers
DE2963759D1 (en) * 1978-02-07 1982-11-11 Economics Lab Cast detergent-containing article and method of making and using
JPS58217598A (ja) 1982-06-10 1983-12-17 日本油脂株式会社 洗剤組成物
DE3326249A1 (de) 1983-07-21 1985-01-31 Henkel Kgaa Wasch-, spuel- oder reinigungsmittelverpackung
JPS60166400A (ja) 1984-02-09 1985-08-29 ライオン株式会社 カプセル含有界面活性剤組成物
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
JPS6186933A (ja) 1984-10-03 1986-05-02 Lion Corp カプセル含有界面活性剤組成物
DE3541153A1 (de) * 1985-11-21 1987-05-27 Henkel Kgaa Mehrschichtige reinigungsmittel in schmelzblockform
DE3541147A1 (de) * 1985-11-21 1987-05-27 Henkel Kgaa Reinigungsmittelkompaktate
US4973416A (en) 1988-10-14 1990-11-27 The Procter & Gamble Company Liquid laundry detergent in water-soluble package
DE3914131A1 (de) 1989-04-28 1990-10-31 Henkel Kgaa Verwendung von calcinierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung von fettsaeureestern
DE3929973A1 (de) 1989-09-08 1991-03-14 Henkel Kgaa Haarpflegemittel
YU221490A (sh) 1989-12-02 1993-10-20 Henkel Kg. Postupak za hidrotermalnu izradu kristalnog natrijum disilikata
US5075041A (en) 1990-06-28 1991-12-24 Shell Oil Company Process for the preparation of secondary alcohol sulfate-containing surfactant compositions
GB9107100D0 (en) 1991-04-04 1991-05-22 Unilever Plc Detergent containing article
NZ244818A (en) * 1991-10-24 1994-09-27 Rhone Poulenc Agrochimie Package containing a toxic composition which comprises two compartments formed by two sheets of water-soluble dispersible material by means of a water-soluble/dispersible heat seal and a third sheet
DE4301358C2 (de) * 1992-01-30 1995-08-10 Hermann Scheler Verpackungsfreies Waschmittel, insbesondere Körper- und/oder Textilwaschmittel
DE9214065U1 (fr) 1992-10-17 1993-06-03 Dispo-Kommerz Ag, Huenenberg, Zug, Ch
FR2724388A1 (fr) 1994-09-13 1996-03-15 Negoce Et Distribution Procede et compositions thermoplastiques pour la realisation de recipients hydrosolubles et biodegradables et recipients obtenus
GB9419091D0 (en) 1994-09-22 1994-11-09 Cerestar Holding Bv Process for decreasing the build up of inorganic incrustations on textiles and detergent composition used in such process
US5759974A (en) * 1994-11-07 1998-06-02 Henkel Kommanditgesellschaft Auf Aktien Block-form cleaners for flush toilets
AU6865196A (en) 1995-08-24 1997-03-19 F. Joh. Kwizda Gesellschaft M.B.H. Dimensionally stable packages
ES2151154T3 (es) * 1996-03-22 2000-12-16 Kaercher Gmbh & Co Alfred Concentrado detergente.
EP0801107B1 (fr) 1996-04-10 1999-12-01 Kuraray Co., Ltd. Articles formés d'alcool polyvinylique
JPH1057431A (ja) 1996-08-19 1998-03-03 Kuraray Co Ltd 自然崩壊性樹脂容器
WO1999037746A1 (fr) * 1998-01-26 1999-07-29 The Procter & Gamble Company Pastille detergente multicouches
CA2236869A1 (fr) 1998-03-10 1999-09-10 Howard Kimel Emballage ou conteneur soluble
DE19831703A1 (de) 1998-07-15 2000-01-20 Henkel Kgaa Portionierte Wasch- und Reinigungsmittelzusammensetzung
JP3269638B2 (ja) * 1998-07-23 2002-03-25 花王株式会社 シート状洗濯用品
DE19834181B4 (de) 1998-07-29 2006-06-01 Reckitt Benckiser N.V. Zusammensetzung zur Verwendung in einer Waschmaschine
DE19834172A1 (de) 1998-07-29 2000-02-03 Benckiser Nv Zusammensetzung zur Verwendung in einem Wasserreservoir
DE19834180A1 (de) 1998-07-29 2000-02-03 Benckiser Nv Zusammensetzung zur Verwendung in einer Geschirrspülmaschine
EP1059350A1 (fr) 1999-06-08 2000-12-13 Greither, Peter Composition détergente encapsulée
WO2001000781A1 (fr) 1999-06-25 2001-01-04 Henkel Kommanditgesellschaft Auf Aktien Emballage-portion de matiere active
DE19961661A1 (de) 1999-06-25 2000-12-28 Henkel Kgaa Wirkstoffportionspackung
GB2352725A (en) 1999-07-30 2001-02-07 Mcbride Robert Ltd Detergent packaging
DE19941480B4 (de) 1999-09-01 2005-06-02 Henkel Kgaa Wasch- oder Reinigungsmittel-Portion mit wasserdurchlässiger Umfassung
ES2222253T3 (es) * 1999-11-17 2005-02-01 Reckitt Benckiser (Uk) Limited Recipientes solubles en agua moldeados por inyeccion.
GB2357488A (en) 1999-11-17 2001-06-27 Aquasol Ltd Capsules by injection moulding
GB2361010B (en) 2000-04-04 2002-06-12 Reckitt & Colmann Prod Ltd Washing capsules
DE10010760A1 (de) * 2000-03-04 2001-09-20 Henkel Kgaa Mehrphasige Wasch- und Reinigungsmittelformkörper mit nicht-gepreßten Anteilen
GB2361687A (en) 2000-04-28 2001-10-31 Procter & Gamble Layered water soluble pouch for detergents
AU2001254824A1 (en) 2000-05-12 2001-11-20 Unilever Plc Unit dose cleaning product

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102000594A (zh) * 2010-11-26 2011-04-06 大连理工大学 可见光光催化剂银和磷酸银的制备方法及其应用
CN102000594B (zh) * 2010-11-26 2012-05-16 大连理工大学 可见光光催化剂银和磷酸银的制备方法及其应用

Also Published As

Publication number Publication date
DE50107923D1 (de) 2005-12-08
JP2004504443A (ja) 2004-02-12
ES2279467T3 (es) 2007-08-16
DE50111830D1 (de) 2007-02-15
AU2001287580A1 (en) 2002-01-30
ES2252286T3 (es) 2006-05-16
EP1586631A3 (fr) 2005-10-26
US20080312123A1 (en) 2008-12-18
EP1305396A2 (fr) 2003-05-02
EP1586631A2 (fr) 2005-10-19
ATE308606T1 (de) 2005-11-15
US7601679B2 (en) 2009-10-13
US7417019B2 (en) 2008-08-26
US20040029764A1 (en) 2004-02-12
ATE350462T1 (de) 2007-01-15
EP1586631B1 (fr) 2007-01-03
WO2002006431A2 (fr) 2002-01-24
WO2002006431A3 (fr) 2002-05-30

Similar Documents

Publication Publication Date Title
EP1305396B1 (fr) Corps creux compartimentes contenant une dose d'un produit de lavage, de nettoyage ou de rincage
EP1194523B1 (fr) Portion de detergent ou nettoyant
EP1299517B1 (fr) Produits de lavage pour lave-vaisselle a utilite supplementaire
WO2003099985A2 (fr) Tablettes a dosage dans le compartiment a detergent
EP1563052B1 (fr) Procede pour produire des corps moules detergents et nettoyants garnis ii
WO2004046297A1 (fr) Procede pour produire des corps moules detergents et nettoyants garnis
DE19932765A1 (de) Befüllte Wasch- und Reinigungsmittelformkörper
DE10066035B4 (de) Kompartiment-Hohlkörper
DE10062582A1 (de) Befüllte Wasch- und Reinigungsmittelformkörper
DE19941480B4 (de) Wasch- oder Reinigungsmittel-Portion mit wasserdurchlässiger Umfassung
WO2001007560A1 (fr) Portion d'agent de lavage ou de nettoyage et emballage pour agent de lavage ou de nettoyage
DE10215601B4 (de) Wasserlöslicher Behälter sowie Verfahren zu seiner Herstellung und Verwendung desselben
EP1238054B2 (fr) Fraction de produit de lavage, de produit de rinçage ou de produit de nettoyage a liberation du principe actif regulee par des enzymes
EP1888736B1 (fr) Unite de dosage de produit de lavage ou de nettoyage
DE19941266B4 (de) Formkörper mit speziell geformter Kavität, Verfahren zu dessen Herstellung und Wasch- und Reinigungsverfahren unter Einsatz dieses Formkörpers
DE19939992A1 (de) Wasch- oder Reinigungsmittelformkörper mit befülltem Hohlvolumen
DE10253214A1 (de) Portionierte Mittel mit unterschiedlichen Bestandteilen
DE20023763U1 (de) Kompartiment-Hohlkörper
EP1081218A2 (fr) Corps moulé avec un remplissage de cavité de forme spéciale
DE10327878A1 (de) Beschichtete plastische Silikate
DE20023759U1 (de) Kompartiment-Hohlkörper
DE10233832A1 (de) MGSM mit speziell konfektionierten Bleichaktivatoren
DE20023761U1 (de) Kompartiment-Hohlkörper
DE20023760U1 (de) Kompartiment-Hohlkörper
WO2003054133A1 (fr) Composes de silicate de soude en tant que materiaux enveloppants

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: RO SI

17P Request for examination filed

Effective date: 20030107

17Q First examination report despatched

Effective date: 20040223

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051102

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051102

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051102

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

REF Corresponds to:

Ref document number: 50107923

Country of ref document: DE

Date of ref document: 20051208

Kind code of ref document: P

26 Opposition filed

Opponent name: RECKITT BENCKISER (UK) LIMITED

Effective date: 20051121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060202

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060202

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060202

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20060130

NLR1 Nl: opposition has been filed with the epo

Opponent name: RECKITT BENCKISER (UK) LIMITED

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060403

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2252286

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060731

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060731

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060731

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060731

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060704

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 20060731

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: HENKEL AG & CO. KGAA

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051102

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060704

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051102

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: RECKITT BENCKISER (UK) LIMITED

Effective date: 20051121

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

REG Reference to a national code

Ref country code: DE

Ref legal event code: R103

Ref document number: 50107923

Country of ref document: DE

Ref country code: DE

Ref legal event code: R064

Ref document number: 50107923

Country of ref document: DE

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20110629

Year of fee payment: 11

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20110727

Year of fee payment: 11

27W Patent revoked

Effective date: 20110610

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Effective date: 20110610

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20110817

Year of fee payment: 11

Ref country code: DE

Payment date: 20110629

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20110729

Year of fee payment: 11

REG Reference to a national code

Ref country code: DE

Ref legal event code: R107

Ref document number: 50107923

Country of ref document: DE

Effective date: 20120119