EP1586631B1 - Corps creux compartimentés comprenant une dose d' un produit de lavage, de mnettoyage ou de rincage - Google Patents

Corps creux compartimentés comprenant une dose d' un produit de lavage, de mnettoyage ou de rincage Download PDF

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Publication number
EP1586631B1
EP1586631B1 EP05014861A EP05014861A EP1586631B1 EP 1586631 B1 EP1586631 B1 EP 1586631B1 EP 05014861 A EP05014861 A EP 05014861A EP 05014861 A EP05014861 A EP 05014861A EP 1586631 B1 EP1586631 B1 EP 1586631B1
Authority
EP
European Patent Office
Prior art keywords
detergent
acid
active
cleaning
washing
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
EP05014861A
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German (de)
English (en)
Other versions
EP1586631A3 (fr
EP1586631A2 (fr
Inventor
Henriette Dr. Weber
Sandra Dr. Hoffmann
Wilfried Dr. Rähse
Dieter Dr. Jung
Frank Dr. Meier
Christian Dr. Block
Rolf Dr. Bayersdörfer
Markus Dr. Semrau
Karl-Martin Faeser
Paul Dr. Birnbrich
Dieter Dr. 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.)
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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=EP1586631(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
Publication of EP1586631A2 publication Critical patent/EP1586631A2/fr
Publication of EP1586631A3 publication Critical patent/EP1586631A3/fr
Application granted granted Critical
Publication of EP1586631B1 publication Critical patent/EP1586631B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • 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 contained in dimensionally stable hollow bodies with at least one compartment.
  • the invention also relates to processes for the preparation of such washing, cleaning or detergent portions containing compartment hollow body.
  • the invention further relates to washing, cleaning and rinsing processes in which the detergent, cleaning agent and dishwashing detergent preparations are dosed in dimensionally stable hollow bodies with one or more separate compartments.
  • the earlier patent application DE 198 31 703 discloses a portioned detergent or cleaner composition in a bag of water-soluble film, in particular in a bag of (optionally acetalized) polyvinyl alcohol (PVAL), wherein at least 70 wt .-% of the particles of the washing or detergent preparation particle sizes> 800 microns have.
  • PVAL polyvinyl alcohol
  • Such bags or “pouches” are indeed very consumer friendly and facilitated the dosing, but are not in all cases the most suitable form for dosing detergent.
  • Detergent and rinse aid preparations especially when solid and liquid washing, cleaning or rinse-active preparations are to be dosed side by side.
  • such pouches do not permit the incorporation of detergent, cleaning agent or rinsing agent preparations into the detergent, cleaning agent or detergent portion in unstable or readily volatile phases.
  • the document DE-A 20 65 153 describes multi-component surfactant moldings consisting of an outer shell of sodium silicate and detergent components enclosed therein.
  • the silicate shell is made by compression molding into two hemispheres which, after filling the amount of detergent components sufficient for a wash, are combined and bonded to form the molded article. The process is extremely impractical and does not result in useful detergent portions.
  • the document DE-A 20 07 413 describes detergent moldings of a core of one or more detergent component (s) and a shell of press-formed, predominantly of sodium metal silicate existing shell material.
  • the compression of the shell material into half shells and the filling and welding of the half shells to the finished blank require a complex technology, and many of the blanks break before they go 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 detergent, rinsing agent or cleaning agent components and an optionally provided with an additional coating core of another detergent, detergent or detergent component.
  • the preparation can be made in this case only in a complicated, multi-step process, only a solid core can be incorporated into the tablet wrap, if not premature release of the tablet should be initiated from the inside.
  • the European application EP 0 593 952 A1 (Dispo-Commerce AG) describes water-soluble bags for the release of treatment agents into the washing liquid of an automatic washing machine or dishwashing machine.
  • the invention had the object of providing detergent, cleaning or Spolffen preparations are available in which volatile as well as less volatile washing active, active cleaning or rinse active components can be assembled or mechanically unstable components can be incorporated without them - for example when pressed into moldings - be compromised in terms of their integrity.
  • the invention was further based on the object, detergent, rotatesmittel- or Separate detergent components spatially from each other and still prepare them in the same detergent, detergent or detergent portion, with the aim of a mass transfer or mutual impairment, which may be associated with loss of activity, as low as possible to keep.
  • the term "detergent, cleaning agent or detergent portion” is understood as meaning a quantity of a detergent, cleaning agent or rinsing agent which is sufficient for a washing, cleaning or rinsing process taking place in an aqueous phase.
  • This can be, for example, a machine washing, cleaning or rinsing process, as is carried out with commercially available washing machines or dishwashers.
  • this term is also understood to mean a hand washing cycle (performed, for example, in a hand basin or in a bowl) or a dishwashing process carried out by hand or another process of washing or cleaning.
  • the preferred Detergent, detergent or detergent portions used in automatic washing, cleaning or rinsing operations.
  • detergent or cleaning agent or detergent partial portion is understood to mean a partial amount of a detergent or cleaning agent or detergent portion which is in a phase separate from other detergent or cleaning agent or detergent portions is in spatial communication with other detergent or detergent or detergent part portions of the same detergent or detergent or detergent portion, for example, in a separate compartment in a dimensionally stable hollow body according to the invention, and which is prepared by suitable measures so that they separated from other detergent or detergent or detergent part portions of the same detergent or detergent or detergent portion into the liquor and optionally dissolved or suspended in it.
  • a detergent or detergent or detergent partial portion may contain the same ingredients as another detergent or detergent or detergent portion of the same detergent or detergent or detergent portion;
  • two detergent or cleaning agent or detergent partial portions of the same detergent or cleaning agent or detergent portion preferably contain different ingredients, in particular different detergent-active, cleaning-active or rinse-active preparations.
  • the detergent 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 contain only detergent-active, cleaning-active or rinse-active preparations of a particular composition. According to the invention, however, it is preferred that several, usually at least two, washing active, cleaning active or rinse active preparations of different composition in the detergent or detergent or detergent portions are included.
  • the composition may be (qualitatively) different with regard to 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 washing-active, cleaning-active or rinse-active preparation. It is particularly preferred that the components are adapted in terms of nature and concentration to the tasks that have to meet the detergent or detergent or detergent partial portions in the washing, cleaning or rinsing.
  • washing-active or cleaning-active or rinse-active preparation is understood to mean all conceivable substances of relevance in connection with a washing or cleaning or rinsing process. These are primarily the actual detergents or detergents or dishwashing detergents with their individual components explained in the further course of the description. These include active ingredients such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builders (inorganic and organic builders), bleaches (such as peroxy bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, specialty polymers (for example, those with cobuilder properties), grayness inhibitors, dyes and fragrances (perfumes), without the term being limited to these substance groups.
  • active ingredients such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builders (inorganic and organic builders), bleaches (such as peroxy bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, specialty polymers (for example, those with co
  • washing-active or cleaning-active or rinse-active preparations is also understood to mean washing auxiliaries and cleaning auxiliaries or rinse aids.
  • these are optical brighteners, UV protectants, so-called Soil Repellents, ie polymers which counteract re-soiling of fibers or hard surfaces (including dishes), as well as silver protectants, colorants and decolorizing agents.
  • Laundry-treating agents such as fabric softener or dishwashing detergent additives such as rinse aid are also considered according to the invention as detergent-active or as detergent-active or as dishwashing active preparations.
  • the detergent, cleaning agent or detergent portions are contained in a hollow body having a plurality of chambers.
  • 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 shape and size are in accordance with the later use, ie use in a washing, cleaning or rinsing process, in particular in conventional washing machines or dishwashers.
  • Conceivable hollow bodies in spherical, ellipsoidal, cubic, cuboid, trapezoidal, conical or pyramid or Trochoidform; cuboidal or trochoidal hollow body have inventively well 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 dispensing compartment of a commercial washing machine or dishwasher, in the laundry entraining nets or bags o. ⁇ . Can be entered.
  • Particularly preferred embodiments of the inventive detergent, cleaning agent or detergent portions do not exceed a length (longest axis) of 10 cm, while the sizes of the width and the height are significantly lower, for example 1 to 5 cm.
  • dimensionally stable hollow body is understood according to the invention as meaning that the moldings containing the detergent, cleaning agent or detergent portions have an intrinsic dimensional stability which enables them, under customary conditions of preparation, storage, transport and handling To provide the consumer with a structure which is stable against breakage and / or pressure and does not coincide, and which does not change over a longer period even under the conditions mentioned. According to the invention, it does not influence whether this structural stability results from the properties of the dimensionally stable hollow body resulting from various parameters mentioned below alone or from the presence of compartmentalizing devices. In preferred embodiments of the invention, even the dimensionally stable hollow body itself have a sufficient intrinsic dimensional stability, since this has an advantageous effect on the mobility in machines in the manufacture of the hollow body and the filling during the preparation of detergent, detergent or detergent portions of the invention ,
  • the pressure resistance of the dimensionally stable hollow body according to the invention is measured in the (per se conventional) way so that unfilled and possibly provided with compartmentalization devices hollow body with films or lids are closed and applied to this hollow body at room temperature an internally applied, steadily increasing vacuum is until the hollow body begins to collapse.
  • the intrinsic dimensional stability of the hollow bodies should be particularly preferably such that in such vacuum collapse tests unfilled and optionally provided with Kompartiment michs wornen hollow body collapse does not begin before reaching a vacuum of 900 mbar, preferably from 750 mbar and in particular from 500 mbar ,
  • the hollow bodies used according to the invention fundamentally differ from films or so-called "pouches", as they are also used to provide detergents, cleaning agents or rinsing agents.
  • the dimensionally stable hollow bodies according to the invention also differ from (subsequently applied to moldings) coatings:
  • the hollow bodies according to the invention represent an independent, self-supporting coating, which as a rule already prior to filling with one or more wash-active, rinse-active or cleaning-active components (n) exists and is then filled.
  • coatings are applied to existing moldings (eg, compacts, granules, extrudates, etc.) and then dried or cured; they form only then an envelope 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 be at most in an amount of 350 g / (m 2. 24 h), preferably to be possible, more preferably only in an amount in the range of a maximum of 100 g /, even more preferably in (m 2 ⁇ 24 h) Amount of a maximum of 50 g / (m 2 .24 h).
  • Embodiments of the detergent, cleaning agent or rinsing agent portions in the dimensionally stable hollow bodies which are particularly preferred according to the invention also take account of the fact that the portions contained in the hollow bodies are of particular advantage-though not mandatory-at a certain point in time-preferably controllable-water solubility of the hollow body material the washing, cleaning or rinsing process or on reaching a certain pH or a certain ionic strength of the wash liquor or due to other controllable events or conditions in the aqueous liquor can be fed.
  • the quality of the material as well as its quantity / strength directly influence these solubility properties.
  • materials for the hollow bodies which-based on a certain wall thickness, which determines the stability-dissolve at certain temperatures, pH values, ionic strengths, or after a certain residence time in the aqueous liquor.
  • a release process can capture the hollow body as a whole or only a part thereof, so that parts of the hollow body solve when setting a certain parameter combination, while other parts are not yet (but later) or not at all.
  • the latter can be achieved by different quality of the material as well as by different amounts of material (thickness of the wall) or different geometries of the hollow body. For example, it is possible to impede the access of water by the hollow body geometry and thus delay the dissolution process.
  • the walls of the hollow body can be made of materials of different water solubility, for example of polyvinyl alcohols (PVAL) with different residual acetate content. This leads to the formation of perforated walls, which allow water to penetrate into the hollow body and / or escape of the dissolved or undissolved ingredients from the hollow body.
  • PVAL polyvinyl alcohols
  • the materials of the walls of the dimensionally stable hollow body consist of a washing-active, cleaning-active or flushing active substance, for which PVAL is an example as a builder, or contain such.
  • washing active, cleaning active or active ingredients that are only present in small amounts in the preparations and their uniform incorporation is therefore not unproblematic, 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 dissolves at the stage of the washing, cleaning or rinsing, in which the active ingredient is just needed, incorporated and released when dissolving the material of the wall at the right time in the fleet.
  • fragrances which are desired in the final stage of the washing or cleaning or rinsing process, but also optical brighteners, UV protectants, dyes and other detergent-active, cleaning-active or rinse-active preparations.
  • optical brighteners UV protectants
  • dyes dyes and other detergent-active, cleaning-active or rinse-active preparations.
  • the walls of the dimensionally stable hollow body containing the detergent, detergent or detergent portions consist of different materials, so have a heterogeneous structure.
  • a polymer material forming the wall of the hollow body islands could be dispersed from a foreign material insoluble in the polymer, for example from another polymer (having 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 polyacrylates, cellulose esters, cellulose ethers such as carboxymethylcellulose.
  • Such a structure may be associated in particularly preferred embodiments of the invention with the advantage that the other substance dissolves faster in water than the polymer, which allows penetration of water into the hollow body and thereby accelerated release of washing active, flushing or cleaning active components of the Portion contributes.
  • the entire dimensionally stable hollow body is dissolved faster in such a packaging than a molded body made of a pure polymer material.
  • the walls of the hollow bodies can be made up of layers of two or more polymers form, which can be selected in particularly preferred embodiments so that they complement each other optimally in terms of their properties (stability, heat resistance, water solubility, gas barrier properties, etc.).
  • the hollow body comprises in its interior several compartments, so chambers.
  • a chamber or such a compartment is usually limited by walls (in only one compartment, these are the walls of the hollow body) limited space.
  • Within the walls of the dimensionally stable hollow body according to the invention are several rooms. These are formed by the fact that individual rooms are delimited by walls, which are referred to in the context of the present invention as "compartmentalizing facilities" and spatially separate the same or different washing active, rinse active or cleaning active components or preparations.
  • the chamber or compartment is wholly or partially, advantageously completely, surrounded by the enclosure of a non-compressed material which can be disintegrated under washing, cleaning or rinsing conditions, which forms the wall of the dimensionally stable hollow body.
  • one or more detergent-active, cleaning-active or rinse-active preparation is / are contained.
  • a compartment advantageously contains a plurality of detergent-active, detergent-active or rinse-active preparations; However, the case of the presence of only one such preparation in a compartment or in a chamber is also conceivable.
  • the dimensionally stable hollow body according to the invention contains in its interior several compartments or chambers, each containing one or more washing active, cleaning active or rinse active preparation (s). Examples of these are cuboidal or trochoidal dimensionally stable hollow bodies, the two, three or four or even more compartments, each containing one or more detergent-active, detergent-active or rinse-active preparation (s).
  • a great advantage of this embodiment of the invention is that the various detergent-active, cleaning-active or rinse-active preparations can be distributed to the compartments as best for the specific requirements.
  • components that adversely affect each other in their effectiveness for example, enzymes, alkali, bleach, etc.
  • components that adversely affect each other in their effectiveness for example, enzymes, alkali, bleach, etc.
  • components that adversely affect each other in their effectiveness for example, enzymes, alkali, bleach, etc.
  • due to the state of aggregation - would mix together (for example, solid and liquid components), spatially separated.
  • the size and shape of the individual compartments within a dimensionally stable hollow body is not critical and can be largely tailored to the needs of the individual case.
  • larger compartments may be provided for certain washing-active, cleansing-active or rinse-active preparations or mixtures thereof which are present in a larger amount than for preparations which are present only in small quantities.
  • mixtures of certain preparations which are provided at the beginning of the washing, cleaning or rinsing process and present in specific amounts, can be spatially separated from other components or components required in other quantities and arranged in compartments of a different size become.
  • a detergent, detergent or detergent portion contained in a dimensionally stable hollow body with a plurality of compartments two or more compartments comprising one or more detergent-active, detergent-active or rinse-active preparation (s) are enclosed by the hollow body, which are arranged enclosing each other.
  • the compartments with the detergent-active, cleaning-active or rinse-active preparation (s) are thus not arranged next to one another or above or below one another in the hollow body, but enclosing one another, for example more or less concentrically ("onion model") or more or less coaxially (“ Multi-layered rod model ”) or in such a way that the innermost compartment is completely surrounded by the next outer, possibly completely again from the following, etc.
  • the washing-active, cleaning-active or rinsing-active substances can be distributed over the compartments, that the components required first in the washing, cleaning or rinsing process are contained in the outermost compartment which is first exposed to water or liquor while (later) required component (s) in (a) further inside compartment (s) is / are and / or are protected against the ingress of water by the more external compartments / are.
  • the internal compartments are completely enclosed by the outer; a partial enclosure is also within the scope of the present invention.
  • the dimensionally stable hollow body one or more water-soluble (s) polymer (s), preferably one or more materials from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL)
  • PVAL polyvinyl alcohol
  • the dimensionally stable hollow body (s) to comprise one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof comprises / comprise.
  • the enclosing surrounding the at least one detergent-active, rinse-active or cleaning-active preparation consists of a non-compressed material which gives dimensional stability to the hollow body.
  • non-pressed material is understood to mean a material which is not produced by compressing (for example) washing-active, rinsing-active or cleaning-active components or preparations to give a pressed body, as in the prior art, into which other washing-active, flushing or cleaning active components or preparations are embedded, but by injection molding
  • the above information on the materials of dimensionally stable hollow bodies apply accordingly.
  • the compartmentalizing devices within the dimensionally stable hollow bodies are made of the same materials as the hollow bodies themselves. This allows the one-piece production in one process step and makes the production process particularly economical.
  • the compartmentation device (s) is one (or more) an activity reduction of at least one component of a detergent-active, detergent-active or rinse-active preparation inhibiting device (s). Examples of these are all the cases in which components of washing-active, cleaning-active or dishwashing preparations are spatially separated from one another, taking into account a mutual impairment of their activity.
  • the compartmentalizing devices should then have properties that meet these requirements, for example, be substantially impervious to water vapor to keep bleach free of moisture, or should be acid or alkali free to protect enzymes from premature decomposition.
  • the compartmentation device (s) is / are a device (s) that determines the quality and / or quantity of the release of components of a detergent-active, detergent-active, or rinse-active preparation.
  • either components of the washing-active, cleaning-active or rinsing-active preparations can advantageously be dispensed into the liquor at different times of the washing, cleaning or rinsing process (qualitative control), or different amounts of certain (qualitatively identical) preparations can be put into the fleet (quantitative control).
  • a dimensionally stable hollow body for example, several compartments whose walls have a different solubility (or temperature of dissolution) in water or in the liquor.
  • the compartments contain (washing, cleaning, rinsing) active components for the first, second and possibly further (washing, cleaning, rinsing) courses, which have different compositions, and these at different times or at different temperatures the washing, cleaning or rinsing free.
  • the dimensionally stable hollow bodies can have walls and compartmentalizing devices, for example only, in which materials are incorporated which detach at different temperatures or under different other boundary conditions.
  • small holes form in the compartment walls first, which allow only a weak mass transfer between individual compartments and the outside environment and thus deliver only small amounts of a washing-active, cleaning-active or rinse-active preparation into the liquor; under others, later settable Conditions, the holes or pores are enlarged because in other conditions soluble wall components dissolve; Larger holes allow larger amounts of substance to be exchanged between the interior of the compartment (s) and the outside environment (ie, the liquor) and thus adjust the desired higher concentrations of the detergent-active, cleaning-active, or rinse-active preparation in the liquor.
  • the compartmentalizing device (s) is / are the activity of at least one component of a detergent-active, detergent-active or rinse-active preparation-controlling device (s).
  • a detergent-active, detergent-active or rinse-active preparation-controlling device This embodiment is particularly useful in those cases where it is necessary is that the release of one or more active ingredients is a washing active, cleaning active or rinse-active preparation with a given kinetics in the washing, cleaning or rinsing liquor.
  • a particular example is a so-called "controlled release" release, which can be controlled according to the parameters given above on the properties of the wall of the dimensionally stable hollow body and / or the Kompartiment michss drivenen. In this way, a destructive effect of the liquor or alone of the water on the active substance can be reduced and the substance can be actively released into the liquor for a longer time.
  • one or more compartmentalizing device (s) contain a part or the total amount of at least one component of at least one detergent-active, cleaning-active or rinse-active preparation.
  • This can be achieved with particular advantage by incorporating one or more component (s) of at least one detergent-active, cleaning-active or rinse-active preparation into the material of the compartmenting device. Examples of such substances have been mentioned above in connection with the stable void forming material (s) and include (but are not limited to) components contained in relatively small amounts in the detergent, detergent or rinse portions Therefore, it is relatively difficult to incorporate into large mass mixtures of washing-active, cleaning-active or dishwashing preparations.
  • a further, likewise preferred embodiment of the invention consists in that one or more compartmentalizing device (s) consists in part or in total of at least one component of at least one washing-active, cleaning-active or rinsing-active preparation.
  • the compartmenting device is thus not only a component of the detergent, cleaning agent or detergent portion influencing the kinetics of the release, but at the same time also a component of the success of the washing process. , Cleaning or rinsing process is involved. Due to the wide variety of available materials, there are numerous examples for this embodiment; particularly preferred are compartmentalizing devices consisting of or comprising (meth) acrylic acid and its derivatives (salts, esters) comprising polymers.
  • a further preferred embodiment of the invention consists in a detergent, detergent or rinsing agent portion contained in one or more dimensionally stable hollow body (s) with a plurality of chambers, in which the dimensionally stable hollow body consists of a non-spherical hollow body having n surfaces, of which an area assumes the function of a "lid", which is the conclusion of a process for producing the detergent, detergent or detergent portions according to the invention, ie after filling the / the compartments (s) in the interior of the hollow body with one or more washing-active, cleaning-active or rinse-active preparation (s) is applied while closing the hollow body.
  • the "lid” particularly preferably consists of a material with controllable water solubility and can be bonded to the remaining hollow body by bonding, for example with a water-soluble adhesive, fusing, welding or another known method of joining materials.
  • This embodiment is particularly advantageous for producing the detergent, cleaning agent or detergent portions according to the invention, since a stepwise filling of the compartment (s) with one or more detergent-active, cleaning-active or rinse-active preparations is possible and the handling during subsequent use leads to optimum results leads, 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, cleaner or rinse aid portions according to the invention contain one or more substances from the group of surfactants, surfactant compounds, builders, bleaches, bleach activators, enzymes, foam inhibitors, dyes and fragrances and - in the case that the detergents or cleaning agents - Portions are present at least in part as shaped bodies - binding and disintegration aids. These classes of substances are described below.
  • the washing and cleaning agent portions according to the invention may contain surface-active substances from the group of anionic, nonionic, zwitterionic or cationic surfactants, with anionic surfactants being clearly preferred for economic reasons and because of their power spectrum.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • Suitable surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as, for example, from C 12-18 -monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of 2-sulfofatty acids for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Further preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, petrochemical-based straight-chain alkyl radical which has an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants including the soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • surfactants are used in the form of their magnesium salts.
  • detergent, detergent or rinse agent portions are preferred which contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 15 to 25% by weight of one or more anionic surfactant (e), in each case based on the detergent, detergent or detergent portion.
  • anionic surfactant e
  • preferred detergent, detergent or rinse agent portions according to the invention have a soap content which exceeds 0.2% by weight, based on the total weight of the detergent, detergent or rinse portion.
  • Preferred anionic surfactants to be used are the alkylbenzenesulfonates and fatty alcohol sulfates, with preferred detergent, cleaning agent or detergent portions containing 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (e), in each case based on the weight of detergent, cleaning agent or detergent portion containing
  • nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 mol Ethylene oxide (EO) per mole of alcohol used, in which the alcohol radical may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, 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 as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese Patent Application JP 58/217598 or preferably prepared according to the method described in 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.
  • linear alkyl polyglucosides that is to say alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
  • the detergent, cleaner or rinse aid portions according to the invention may preferably contain alkylpolyglycosides, with contents of the detergent and cleaner portions of APG being above 0.2% by weight, based on the total preparation, being preferred.
  • Particularly preferred detergent, cleaning agent or detergent portions contain APG in amounts of from 0.2 to 10% by weight, preferably in amounts of from 0.2 to 5% by weight and in particular in amounts of from 0.5 to 3% by weight .-%.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • 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 are usually prepared by reductive amination of a reducing sugar with ammonia, a Alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained.
  • 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 into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • anionic and nonionic surfactants it may be preferable to use not only anionic and nonionic surfactants but also cationic surfactants. Their use is preferably carried out as Wasch maybesbooster, with only small amounts of cationic surfactants are required. If cationic surfactants are used, they are preferably present in the compositions in amounts of from 0.01 to 10% by weight, in particular from 0.1 to 3.0% by weight.
  • the detergent, cleaner or rinse agent portions according to the invention are detergents
  • the amount of surfactant need not be the same in all partial portions; Rather, partial portions can be provided with relatively larger and partial portions with relatively smaller surfactant content.
  • the detergent, cleaning agent or detergent portions according to the invention are detergents
  • dishwashing detergents contain these usually one or more surfactant (s) in total amounts of 0.1 to 10 wt .-%, preferably in amounts of 0.5 to 5 wt .-%, wherein in partial portions of the detergent or detergent portions of the invention surfactants in larger or smaller amount can be included.
  • the amount of surfactant does not have to be the same in cleaning or dishwashing detergents in all partial portions; Rather, partial portions can be provided with relatively larger and partial portions with relatively smaller surfactant content.
  • builders are the most important ingredients of detergents and cleaners.
  • builders usually used in detergents, cleaning agents or dishwashing detergents can be present, in particular zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 . H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • 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 over conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction nebulization or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products are microcrystalline Have ranges of size 10 to several hundred nm, with values up to max. 50 nm and in particular up to max. 20 nm are preferred. Especially preferred are densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • a fine crystalline, synthetic and bound water-containing zeolite optionally used is preferably zeolite A and / or P.
  • Zeolite MAP eg, commercial product: Doucil A24 from Crosfield
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • Commercially available and preferably usable in the context of the present invention is, for example, a 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.
  • 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.
  • phosphates as builders possible, unless such use should not be avoided for environmental reasons.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided their use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of washing and cleaning agent portions according to the invention.
  • citric acid Succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof.
  • polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrene acids are generally significantly higher than the molecular weights specified in the context of the present invention.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molecular weights of from 2,000 to 10,000 g / mol, more preferably from 3,000 to 5,000 g / mol, may in turn be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid or of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molar mass, based on free acids, is generally from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of the detergent or cleaner portions of (co) polymeric polycarboxylates according to the invention is preferably from 0.5 to 20% by weight, in particular from 3 to 10% by weight.
  • 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
  • biodegradable polymers from more than two different monomer units for example those which are salts of the monomers as monomers, are preferred 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.
  • copolymers are those which contain as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives which, in addition to co-builder properties, also have a bleach-stabilizing action.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids having 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which is a DE of 100 owns.
  • 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 also other suitable co-builders.
  • EDDS ethylenediamine-N, N'-disuccinate
  • glycerol disuccinates and glycerol trisuccinates are also preferred. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic co-builders are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferable, especially if the washing or cleaning agent portions according to the invention also contain bleach, to use Aminoalkanphosphonate, in particular DTPMP, or to use mixtures of said phosphonates.
  • the detergents, cleaning or rinsing agents according to the invention may contain further ingredients customary in detergents, cleaners or rinsing agents from the group of bleaches, bleach activators, alkalizing agents, acidifiers, enzymes, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, Silicone oils, anti-redeposition agents, optical brighteners, grayness inhibitors, dye transfer inhibitors, decolorizing and flocculating agents, antibacterial agents 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-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonylamidoperoperuccinate; and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diper
  • chlorine or bromine-releasing substances As bleaching agents in automatic dishwashing compositions it is also possible to use chlorine or bromine-releasing substances.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • bleach activators can be incorporated into the detergent, cleaning agent or detergent portions.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • 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, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • TAED tetraacety
  • bleach catalysts may also be incorporated into the detergent, cleaner, or rinse agent portions.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, 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 can also be used as bleach catalysts.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but in particular cellulase-containing mixtures are of particular interest. Peroxidases or oxidases have also proved suitable in some cases.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules in the compositions according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • Enzymes are added according to the prior art primarily to a detergent composition, in particular a dishwashing agent, which is intended for the main rinse. Disadvantage was that the optimum effect of enzymes used limited the choice of temperature and also encountered problems in the stability of the enzymes in a strongly alkaline medium. With the washing or cleaning agent portions according to the invention, it is possible to introduce enzymes into a separate compartment and then to use them in the pre-wash and thus to use the pre-rinse cycle in addition to the main rinse for an enzyme action on contamination of the dishes.
  • the washing-active preparation or partial portion of a cleaning agent or detergent portion intended for the pre-wash cycle is particularly preferred Add enzymes and then such a preparation - more preferably - with a water-soluble at low temperature material of a dimensionally stable hollow body to protect, for example, the enzyme-containing preparation from loss of activity by environmental conditions.
  • the enzymes are more preferably optimized for use under the conditions of the pre-wash cycle, that is, for example, in cold water.
  • the detergent portions of the invention may then be when the enzyme preparations are liquid, as they are sometimes available commercially, because then a rapid effect can be expected, which already occurs in (relatively short and carried out in cold water) pre-wash.
  • the enzymes are used in solid form and they are provided with a hollow body enclosure made of a water-soluble material that is already soluble in cold water, the enzymes can unfold their effect before the main wash or main cleaning.
  • Advantage of the use of an enclosure of water-soluble material, in particular of cold water-soluble material is that the enzyme / enzymes in cold water after dissolution of the enclosure comes to effect quickly / come. Thus, their duration of action can be extended, which benefits the washing or rinsing results.
  • the detergent, cleaning agent or rinsing agent portions according to the invention also contain further additives known from the state of the art as additives for detergent preparations. These can either one or more, if necessary, all portions (washing active, cleaning active or rinsing active preparations) of detergent, detergent or detergent portions of the invention are added or - as in the co-pending patent application no. 199 29 098.9 with the Title "active ingredient portion package" described - in the water-soluble, the washing active, cleaning active or rinse-active preparations comprising materials of dimensionally stable hollow body, so for example, in the / the water-soluble wall material (s) are incorporated.
  • optical brighteners are used in the invention.
  • optical brighteners are derivatives of diaminostilbene disulfonic acid or its alkali metal salts. Suitable z. B.
  • salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or the like compounds which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group.
  • brighteners of the type of substituted diphenylstyrene may be present in the partial portions (wash-active preparations) of the washing or cleaning agent portions according to the invention, e.g.
  • alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl or 4- (4-chlorostyryl) 4 '- (2 -sulfostyryl-) biphenyl can be used.
  • 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.
  • surfactants which can influence in particular the solubility of the water-soluble wall of the dimensionally stable hollow body or the compartmenting device, but can also control its wettability and foaming on dissolution, as well as foam inhibitors, but also bitter substances accidental ingestion of such hollow body or parts of such hollow body by children can prevent.
  • dyes in particular water-soluble or water-dispersible dyes.
  • dyes Preference is given here to dyes, as they are usually used to improve the appearance of the optical product in detergents and cleaning agents and detergents.
  • the choice of such dyes is not difficult for a person skilled in the art, especially since such conventional dyes have a high storage stability and insensitivity to the other ingredients of the detergent-active, cleaning-active or rinse-active preparations and to light and no pronounced substantivity to textile fibers in order not to stain them.
  • the dyes are present in the detergent or cleaning agent or detergent portions in amounts of less than 0.01% by weight.
  • polymers which can be added to the detergent, cleaner or rinse portions in accordance with the invention are polymers.
  • these polymers are on the one hand polymers in question, which show washing or cleaning or rinsing Cobuilder properties, 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 like.
  • so-called soil repellents are also suitable as polymers, as are known to the washing and cleaning agent specialist and will be described in detail below.
  • bleach catalysts in particular bleach catalysts for automatic dishwashing detergents or detergents.
  • complexes of manganese and cobalt, especially with nitrogen-containing ligands are used.
  • silver protectants are a variety of mostly cyclic organic compounds, which are also familiar to the person skilled in the art and contribute to prevent the tarnishing of silver-containing objects in the cleaning process. Specific examples may be triazoles, benzotriazoles and their complexes with metals such as Mn, Co, Zn, Fe, Mo, W or Cu.
  • the detergent, cleaning agent or rinsing agent portions may also contain so-called soil repellents, ie polymers which are applied to fibers or hard surfaces (for example on porcelain and glass), the oil and grease wash-off properties of textiles and grease washability of porcelain and glass have a positive effect and thus specifically counteract re-soiling. This effect becomes particularly evident when a textile or a hard object (porcelain, glass) is contaminated which has already been washed several times previously with a washing or cleaning agent according to the invention which contains this oil and fat-dissolving component.
  • soil repellents ie polymers which are applied to fibers or hard surfaces (for example on porcelain and glass)
  • the oil and grease wash-off properties of textiles and grease washability of porcelain and glass have a positive effect and thus specifically counteract re-soiling. This effect becomes particularly evident when a textile or a hard object (porcelain, glass) is contaminated which has already been washed several times previously with a washing or cleaning agent according
  • nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a methoxy group content of 15 to 30% by weight and hydroxypropoxy groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether .
  • polymers of phthalic acid and / or terephthalic acid or derivatives thereof in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • the additive may also be a material of a water-soluble enclosure of the dimensionally stable hollow body or of a material of the water-soluble Compartmenting device (s) comprising or containing in the Kormpartiment (s) or one of the detergent-active, cleaning-active or rinse-active preparation (s).
  • Fragrances are added to the inventive detergent, detergent or detergent portions to improve the overall aesthetic impression of the products and to provide the consumer in addition to the technical performance (softening result) a sensory typical and distinctive product available.
  • perfume oils or perfumes individual perfume compounds can be used, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-t-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • Ethers include, for example, benzyl ethyl ether.
  • the aldehydes include, for. B. linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, purple and bourgeonal.
  • the ketones include the ionone, ⁇ -isomethylionone, and methyl cedryl ketone.
  • the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol.
  • the hydrocarbons mainly include terpenes such as limonene and pinene. Preference is given to using mixtures of different odoriferous substances which are adapted to one another in such a way that together they produce an attractive fragrance note.
  • perfume oils may also contain natural fragrance mixtures as are available from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • the content of perfumes 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 spool-active preparation (s); but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the laundry and provide a slower fragrance release for long-lasting fragrance of textiles.
  • carrier materials for example, cyclodextrins have been preserved.
  • the cyclodextrin-perfume complexes can additionally be coated with other auxiliaries.
  • the perfumes and fragrances can in principle be contained in each of the partial portions (washing-active or cleaning-active or rinse-active preparations) of the detergent, cleaning agent or rinsing agent portions according to the invention. However, it is particularly preferred that they are in a detergent in a provided for the post-wash cycle or fabric conditioning portion detergent portion or in a detergent, especially in a dishwashing detergent in a provided for the rinse or rinse cycle part-detergent portion, special partial-detergent portion, are included.
  • the detergent, cleaner or detergent portions according to the invention contain wash-active, cleaning-active or rinse-active preparations in a dimensionally stable hollow body in such quantities that they are sufficient for a washing, cleaning or rinsing process.
  • a dosage of two units is possible under special conditions (heavily soiled, eg heavily greased laundry, heavily harnessed dishes).
  • a detergent, cleaning agent or detergent portion contained in a dimensionally stable hollow body comprises the at least one, preferably the several, wash-active, cleaning-active or rinse-active preparation (s) in one or more forms from the group of powders, granules, extrudates, pellets, beads, tablets, tabs, rings, blocks, briquettes, solutions, melts, gels, suspensions, dispersions, emulsions, foams and gases.
  • the shape of the washing-active, cleaning-active or rinse-active preparation contained in one or more compartments of the dimensionally stable hollow body is therefore not limited, as long as the hollow body is in the intended state
  • the detergent, detergent or rinse agent portions disclosed herein consist of an outer mold containing multiple fillings.
  • the hollow mold is divided by partitions into several compartments, whereby several fillings can be present within the same hollow body separated from each other.
  • no demands are placed on the fillings, so that both solid and liquid phases (systems) can be portioned.
  • the invention also provides filled hollow bodies, which consist only partially of a disintegratable under washing, cleaning or rinsing conditions, the / the hollow body (s) dimensional stability imparting, non-pressed material according to the claims, while the other parts of the enclosure is not necessarily dimensionally stable must be in the sense defined above.
  • a preferred embodiment provides for the provision of open, dimensionally stable hollow molds ("shells"), which are filled and later closed, closing with a film having particular significance.
  • the film, which closes the opening of the shell is applied to the opening and adherent to the edges, which can be done for example by sticking, partial melting or by chemical reaction.
  • the closing film can of course also be a laminate of a plurality of differently composed films, the opening of the shell can be released at certain times in the washing and cleaning cycle via different compositions of individual film layers.
  • Preferred film materials are the polymers known from the prior art. Particular preference is given to films of a polymer having a molecular weight of between 5000 and 500,000 daltons, preferably between 7,500 and 250,000 daltons, and in particular between 10,000 and 100,000 daltons. With regard to the media into which detergents and cleaners are customarily incorporated, particular preference is given to portions according to the invention in which the film consists of a water-soluble polymer.
  • Such preferred polymers may be of synthetic or natural origin. If polymers are used on a native or partnative basis as film material, preferred film materials are selected from one or more substances from the group of 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 constituents: 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 is unsubstituted (see formula I) and in the C6 position having a galactose radical substituted (see formula (II)) mannose units in ⁇ -D (1 ⁇ 4) linkage.
  • 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 1350-13500 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.
  • the structural properties are also highly dependent on the degree of polymerization; For example, the fruit pectins in the dried state form asbestos-like fibers, whereas the flax pectins form fine, granular powders.
  • the pectins are prepared by extraction with dilute acids mainly from the inner parts of citrus fruit peel, Obstresten or sugar beet pulp.
  • 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.
  • Suitable nonionic organic film materials are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • 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.
  • 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 Contain 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
  • GCS carboxymethyl starch
  • amino starches amino starches.
  • 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 soluble in water at room temperature in excess of 2.5% by weight.
  • the vinyl ester polymers are vinyl ester-accessible polymers having the grouping of the formula (IV) as a characteristic building block of the macromolecules.
  • the vinyl acetate polymers (R CH 3) with polyvinyl acetates, as by far the most important representatives of the greatest industrial importance.
  • Cellulose ethers can be described by the general formula (V) R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula (III) is -CH 2 CH 2 CH 2 -OH or -CH 2 CH 2 -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide).
  • Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose reacted with the etherifying reagent or how many moles of the etherifying agent were attached on average to an anhydroglucose unit.
  • Hydroxyethylcelluloses are water-soluble from a DS of about 0.6 or an MS of about 1.
  • Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS), respectively.
  • Hydroxyethyl and - propylcelluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propylcelluloses soluble in cold and hot water and in some (hydrous) organic solvents, but insoluble in most (anhydrous) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.
  • 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 present invention covers homopolymers 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 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%, So still contain a residual content of acetyl groups.
  • the polyvinyl alcohols are characterized by 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 highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
  • Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable.
  • the water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
  • the coatings off Polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • the film consists of a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol -% is.
  • 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 most preferably between about 260 to about 1500.
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant).
  • Mowiol ® Commercially, for example under the trade name Mowiol ® (Clariant).
  • particularly suitable polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88 and 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 suitable is the acrylic resin commercially available as 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 US Pat cited prior art can be found.
  • 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 US Pat cited prior art can be found.
  • Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium as they are commercially available under the name Merquat ® 2001 N, are inventively particularly preferred amphopolymers.
  • amphoteric polymers are for example sold under the names Amphomer ® and Amphomer ® LV-71 (DELFT NATIONAL) available octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.
  • Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts are preferred zwitterionic polymers.
  • Further suitable zwitterionic polymers are Methacroylethylbetain / methacrylate copolymers, which are commercially available under the name Amersette ® (AMERCHOL).
  • Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture with other copolymerizable compounds on polyalkylene glycols are obtained by homogeneous-phase polymerization by subjecting the polyalkylene glycols to the monomers of vinyl esters, esters of acrylic acid or methacrylic acid, in The presence of free radical initiator stirs.
  • 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 alcohols of low molecular weight, ie 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.
  • Polymers of ethylene glycol which are of general formula VII H- (O-CH 2 -CH 2 ) n -OH (VII) satisfy, where n can assume values between 1 (ethylene glycol) and several thousand.
  • 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 are, for example, under the trade name Carbowax ® PEG 200 (Union Carbide), Emkapol ® 200 (ICI Americas), Lipoxol ® 200 MED (Huls America), polyglycol ® E-200 (Dow Chemical), Alkapol ® PEG 300 (Rhone -Poulenc), Lutrol ® E300 (BASF) and the corresponding trade names with higher numbers.
  • the polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000.
  • the nonionic monomers may be of very different types and of these preferred are: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allylaurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.
  • the non-ionic monomers may equally be of very different types, among which particularly preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the grafting polymers.
  • 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 of saccharin.
  • terpolymers comprise monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyl esters of the formula IX: wherein R 3 is -H or -CH 3 , R 2 is -CH 3 or -CH (CH 3 ) 2 and R 1 is -CH 3 or a saturated straight or branched C 1-6 alkyl radical and the sum of the carbon atoms in the radicals R 1 and R 2 is preferably 7, 6, 5, 4, 3 or 2.
  • polycarboxylates / polycarboxylic acids are suitable as film materials in the case of the anionic polymers.
  • Useful organic film materials are, for example, the polycarboxylic acids which can be used in the form of their sodium salts but also in free form.
  • Polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass 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 weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Your molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 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 preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives Particular preference is given to polyaspartic acids or their salts and derivatives.
  • polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • polymers are cationic polymers.
  • the cationic polymers the permanent cationic polymers are preferred.
  • "permanently cationic” refers to polymers which have a cationic group, irrespective of the pH of the agent (ie both the film and the remaining portion). 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 and polymeric dimethyldiallylammonium salts and their copolymers.
  • Cationic cellulose derivatives, in particular the commercial product Polymer® JR 400, are very particularly preferred cationic polymers. Irrespective of the chemical composition of the film, washing, cleaning or rinsing agent portions according to the invention are preferred, which are characterized in that the film which forms part of the enclosure (A) or (B) has a thickness of 1 to 150 ⁇ m, preferably from 2 to 100 ⁇ m, particularly preferably from 5 to 75 ⁇ m and in particular from 10 to 50 ⁇ m.
  • a washing, cleaning or rinsing agent portion according to the invention comprises two areas in which different ingredients can be contained or different release mechanisms and dissolution kinetics can be realized.
  • the composition of the enclosure and thus also of the film must be matched to the filling in order to prevent premature destruction of the film or loss of active substance through the enclosure. This is required in the incorporation of solid substances in the compartments only to a minor extent (chemical incompatibilities), so that preferred washing, cleaning or detergent portions in at least one compartment further active ingredient in particulate form, preferably in powdered, granular, extruded, pelleted , prilled, flaky or tableted.
  • the enclosed by the film enclosure can be completely filled with washing, cleaning or rinse-active preparation. But it is also possible to fill the respective mold only partially before closing in order to allow in this way a movement of the filled particles or liquids within the mold. Particularly when filling with regularly shaped larger particles, attractive visual effects can be realized. Washing, cleaning or rinsing agent portions are preferred in which the volume ratio of the space enclosed by the film and the further enclosure to the washing, cleaning or rinsing active preparation contained in this space is 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 1: 1 volume ratio means that the mold is completely filled.
  • the / the hollow body (s) dimensional stability imparting, not pressed Material according to the claims and the sheet material may be predetermined at the time the washing or rinse-active preparation is released.
  • the film can be virtually instantaneously soluble, so that the washing, cleaning or rinse-active preparation is dosed at the beginning of the washing or cleaning cycle in the washing or cleaning liquor.
  • the shape of the "shell” can be chosen freely, with certain geometric shapes such as hemispheres have proven to be preferred for aesthetic reasons. But also box shapes or sargdeckelä Ober shaped shells are inventively feasible.
  • the "shell” may have an edge that has only the material thickness, but it may also have a web edge, which serves as a larger adhesive and sealing surface for the film.
  • the "shell” is made by injection molding from water-soluble thermoplastics. In this method, any partitions for the later formation of several compartments can be mitverspritzt already. Also, the production of the "shell” by a melt casting of suitable materials (see below) is preferred.
  • the filling of the filled trays with film takes place by adherent connection with their edges, which can be done for example by gluing, partial melting or by chemical reaction.
  • the covering film may be tightly sealed in subdivided trays not only at the edges of the outer shell periphery, but also with the upper edge of the inner septa, so that a tight seal of the compartments is also ensured against each other.
  • the covering film can also be designed so that different prefabricated film areas come to rest over the different compartments so as to influence the disintegration kinetics in aqueous solution and thus the release of the individual preparations from the compartments.
  • This liquid must be chosen so that it does not attack the materials of the envelope.
  • Non-aqueous solutions, suspensions, dispersions or emulsions have proven to be useful here.
  • the enclosure is transparent or at least translucent, to make the aesthetic appeal of liquid filling visible from the outside.
  • washing, cleaning or rinsing agent portions are particularly preferred in which at least one enclosure is transparent or translucent, wherein the wall thickness of wholly or partially disintegratable from a under washing, cleaning or rinsing conditions, the / the hollow body (n ) Form stability-imparting, non-pressed material 100 to 5000 .mu.m, preferably 200 to 3000 .mu.m, more preferably 300 to 2000 .mu.m and in particular 500 to 1500 microns amounts.
  • 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.
  • One of these preparations, as stated above, is liquid.
  • the second preparation is firm. It is particularly preferred in this case to fill the second cavity with a powdery to granular preparation.
  • thermoplastic polymers can be processed into dimensionally stable hollow bodies by this process, in particular, if appropriate, into dimensionally stable hollow bodies which contain devices for compartmentalizing in their interior.
  • the injection molding of suitable materials is carried out according to known methods 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, especially 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 molding, injecting the polymer at high temperature and high pressure, cooling the injection-molded molding, Opening the mold and removing the molded blank.
  • Other optional steps such as the application of release agents, the Demoulding, etc. are known in the art and can be carried out according to known technology.
  • the detergent, detergent or rinse agent portions disclosed herein consist of an outer mold containing one or more fillings.
  • the hollow mold can be divided by partitions into several compartments, whereby several fillings can be present within the same hollow body separated from each other.
  • no demands are placed on the fillings, so that both solid and liquid phases (systems) can be portioned.
  • the simultaneous portioning of several different fillings requires hollow bodies comprising compartmentalizing means.
  • the preparation of such hollow bodies from several contiguous compartments encounters difficulties with conventional methods.
  • the present application discloses a process for producing such hollow bodies and the detergent, cleaning agent or detergent portions which can be produced therefrom.
  • a hollow body is injection-molded, which has one or more chambers for receiving washing, rinsing or cleaning-active preparations.
  • Injection molding of suitable materials is carried out according to per se known procedures at high pressures and temperatures with the steps of closing the mold connected to the extruder for injection, injecting the polymer at high temperature and pressure, cooling the injection molded article, opening the mold and removing the mold shaped blank. Further optional steps, such as the application of release agents, demolding, etc., are known to the person skilled in the art and can be carried out according to technology known per se.
  • the advantages of the procedure of producing the dimensionally stable hollow body by injection molding are the mature technology of this procedure, the high flexibility in terms of usable materials, the ability to obtain exactly desired wall thicknesses s of the molded or dimensionally stable hollow body and the possibility in one High reproducibility step of producing a dimensionally stable hollow body having one or more integral compartmentalizing means.
  • step (i) is carried out 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.
  • step (i) is carried out at temperatures between 100 and 250.degree. C., preferably between 120 and 200.degree. C. and in particular between 140 and 180.degree.
  • 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 wall should on the one hand be chosen so thin that a rapid dissolution or disintegration is achieved and the ingredients are released quickly into the application fleet, but also a certain minimum thickness is required to give the mold the desired stability, in particular dimensional stability.
  • dimensionally stable hollow body is understood according to the invention that the detergent body, detergent or detergent portions containing moldings have a self-stability, which enables them, under normal conditions of manufacture, storage, transport and handling by the In the present invention, it does not influence whether this structural stability results from the properties of the product resulting from various parameters mentioned below
  • the dimensionally stable hollow body has a sufficient Elgen dimensional stability, which would be advantageous to the mobility in machines during the manufacture of the hollow body and the filling end of the production of detergent, detergent or detergent portions of the invention.
  • the pressure resistance of the dimensionally stable hollow body according to the invention is measured in the (per se conventional) way so that unfilled and possibly provided with compartmentalization devices hollow body with films or lids are closed and applied to this hollow body at room temperature an internally applied, steadily increasing vacuum is until the hollow body begins to collapse.
  • the intrinsic dimensional stability of the hollow bodies should be particularly preferably such that in such vacuum collapse tests unfilled and optionally provided with Kompartiment michs wornen hollow body collapse does not begin before reaching a vacuum of 900 mbar, preferably from 750 mbar and in particular from 500 mbar ,
  • the hollow bodies used according to the invention fundamentally differ from films or so-called "pouches", as they are also used to provide detergents, cleaning agents or rinsing agents.
  • the dimensionally stable hollow bodies according to the invention also differ from (subsequently applied to moldings) coatings:
  • the hollow bodies according to the invention represent an independent, self-supporting coating which, as a rule, already before being filled with one or more washing-active, rinsing-active or cleaning-active components (n) exists and is then filled.
  • coatings are applied to existing moldings (eg, compacts, granules, extrudates, etc.) and then dried or cured; they form only then an envelope surrounding the molding.
  • hollow bodies are produced in step (i) in which collapse does not commence before reaching a vacuum of 250 mbar, preferably of 100 mbar and in particular of 20 mbar.
  • the wall thickness of the enclosure (b) produced in step (i) is 100 to 5000 ⁇ m, preferably 200 to 3000 ⁇ m, particularly preferably 300 to 2000 ⁇ m and in particular 500 to 1500 ⁇ m.
  • MFI flow index
  • 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 ,
  • Polymers are particularly suitable as materials for the hollow body to be produced in step (i), preference being given to processes according to the invention in which the encapsulation (b) produced in step (i) comprises one or more materials from the group of acrylic acid-containing Polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof.
  • the enclosure (b) prepared in step (i) comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalised) polyvinyl alcohol (PVAL), Polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).
  • PVAL polyvinyl alcohol
  • PVAL Polyvinylpyrrolidone
  • 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 available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups.
  • the polyvinyl alcohols are characterized by 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 highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
  • Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable.
  • the water solubility can be achieved by post-treatment 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, but allow water vapor to pass through.
  • the hollow bodies consist of a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol -% is.
  • 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 most preferably between about 260 to about 1500.
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant).
  • Mowiol ® Commercially, for example under the trade name Mowiol ® (Clariant).
  • particularly suitable polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88 and Mowiol ® 8-88.
  • polyvinyl alcohols 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 KK ).
  • the hollow body may contain plasticizing aids. This may be advantageous in particular when polyvinyl alcohol or partially hydrolyzed polyvinyl acetate has been selected as the material for the hollow bodies.
  • the proportion of plasticizer (based on the polymer) is usually up to 15 wt .-%, with values between 5 and 10 wt.% Are preferred.
  • Glycerol, triethanolamine, ethylene glycol, propylene glycol, diethylene or dipropylene glycol, diethanolamine and methyldiethylamine have proved particularly suitable as plasticizing auxiliaries.
  • mold release additives are important auxiliary substances that can be used in the injection molding compositions. From the groups of fatty substances and the finely divided substances while in the present invention, in particular stearic acid and / or stearates and fumed silicas have (Aerosil ®), talcum, and proven.
  • 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.
  • 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-dodecanol (lauryl alcohol), 1-tridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (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 demolding additives are C 10-30 fatty alcohols, preferably C 12-24 fatty alcohols with particular preference for 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 alkaline saponification, already carried out in the last century, led directly to alkali salts (soaps), today only large quantities of water are used for cleavage, which cleave the fats into glycerine and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage.
  • 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), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanic acid (melissic acid) and unsaturated secies 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-octadecadienoic acid (l
  • tridecanoic acid pentadecanoic acid, margaric acid, nonadecanoic acid, erucic acid, elaeostearic acid and arachidonic acid
  • Such mixtures are, for example, coconut oil fatty acid (about 6% by weight C 8 , 6% by weight C 10 , 48% by weight).
  • Tallow fatty acid (about 3% by weight C 14 , 26% by weight C 16 , 2% by weight C 16 , 2% by weight C 17 , 17% by weight C 18 , 44% by weight C 18 , 3 wt .-% C 18 , 1 wt .-% C 18 ''' ), hardened tallow fatty acid (about 2 wt .-% C 14 , 28 wt .-% C 16 , 2 wt .-% C 17 , 63 wt .-% C 18 , 1 wt .-% C 18 ' ), technical oleic acid (about 1 wt .-% C 12 , 3 wt .-% C 14 , 5 wt .-% C 16 , 6 wt % 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 ''' ) ,
  • the fatty acid esters which can be used are the esters of fatty acids with alkanols, diols or polyols, with fatty acid polyol esters being preferred.
  • Suitable fatty acid polyol esters are mono- or diesters of fatty acids with certain polyols.
  • the fatty acids which are esterified with the polyols are preferably saturated or unsaturated fatty acids having 12 to 18 carbon atoms, for example lauric acid, myristic acid, palmitic acid or stearic acid, preferably using the technically occurring mixtures of the fatty acids, for example those of coconut, Palm kernel or tallow derived acid mixtures.
  • acids or mixtures of acids having 16 to 18 carbon atoms such as tallow fatty acid are suitable for esterification with the polyhydric alcohols.
  • Suitable polyols which are esterified with the abovementioned fatty acids are, for the purposes of the present invention, sorbitol, trimethylolpropane, neopentyl glycol, ethylene glycol, polyethylene glycols, glycerol and polyglycerols.
  • Preferred embodiments of the present invention provide that glycerine is used as the polyol esterified with fatty acid (s). Accordingly, fatty substances from the group of fatty alcohols and fatty acid glycerides are preferred as mold release additives. Particularly preferred demulsifying additives are fatty substances from the group of fatty alcohols and fatty acid monoglycerides. Examples of such fatty substances which are preferably used are glycerol monostearic acid esters or glycerol monopalmitic acid esters.
  • antioxidants include, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • the material for the mold, the wall thickness and the size of the mold are chosen so that the hollow body dissolves in still water of 20 ° C in less than 300 seconds, preferably 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 ingredients dissolve under the conditions of use within the period of application.
  • the release of the ingredients of at least one compartment should preferably be done in less than 300 seconds, especially less than 60 seconds. This can be done by using disintegration aids, by sealing a compartment with a thin, water-soluble film, by dissolving a "stopper" occluding an opening, or by other means.
  • a further subject of the present invention is therefore an injection molding process for hollow bodies which comprise such polymers, ie a process for the production of hollow bodies by injection molding, which is characterized in that the injection molding compound comprises one or more water-soluble polymer (s), preferably one or a plurality of material (s) from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).
  • PVAL polyvinyl alcohol
  • PVAL polyvinylpyrrolidone
  • the injection molding composition comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol -% is.
  • the injection molding composition comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 g / mol -1 , preferably from 11,000 to 90,000 gmol -1 , particularly preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 .
  • the processes according to the invention can be carried out with particular advantage if the proportion of water-soluble polymers in the injection-molding composition is high.
  • the entire injection molding compound consists only of the water-soluble polymers and optionally excipients (see above).
  • 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.
  • a washing-active, cleaning-active or rinse-active preparations is / are filled into the compartments formed in the interior of the dimensionally stable hollow body. 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 ,
  • the washing-active, cleaning-active or rinse-active preparation (s) are filled into compartments which are surrounded, preferably concentrically or coaxially with one another.
  • the dimensionally stable hollow body containing in its interior one or more washing-active, cleaning-active or rinsing-active preparations in a compartment or distributed in several compartments is sealed, thus sealing the preparations in its interior.
  • the water solubility of the walls / compartmentation devices surrounding the phases can be adjusted so that 5 to 10 minutes pass each time one compartment is opened until the contents of the next compartment are released.
  • Simplified forms of the detergent portion can be prepared by omitting the phase 2 and distributing its contents to the phases 1 (protease) and 3 (soda, alkali carrier) and, in a further simplification, in addition to phase 2, also the phase 4, perfume, optical brightener and Soil Repellent Phase 3 are added and the fabric softener is dosed in a separate product.
  • incompatible washing-active, cleaning-active or rinse-active preparations or their components can be spatially separated and can not react with one another due to the lack of a common contact surface, in particular no reaction which impairs the activity of the respective preparation.
  • open to the expert for the combination of previously considered incompatible substances in detergent, detergent or detergent formulations new formulation options. Due to the spatial separation of the individual components, it is possible to optimize the technological functions of the individual components independently of each other, without any fear of influencing the components.
  • the detergent, entertek- or detergent portions contained in the hollow bodies with one or more compartments promise a consistent and prefabricated dosage with all the required or desired components for the entire washing, cleaning or rinsing. Dosing does not occur during dosing, nor do you fear fouling of the product, contact with active ingredients or accidents due to ingestion of active ingredients.
  • the dosage is carried out in one step, and the solubility of the enclosure or the hollow body material for release of the ingredients is carried out reliably according to predetermined or predetermined kinetics, so that significantly improve the washing, cleaning or dishwashing results, compared with powdered or compressed Moldings of the same composition without compartmentalized separation of the components.
  • Example 1 Polyvinyl alcohol granules (Vinex ® 2019 Fa. Texas polymer) was melted on a hydraulic screw-injection molding machine from the company. Arburg and injected into Simple tools with hot runner nozzle. In Example 1, a trochoidal shell with three corrugated partitions and a peripheral edge was prepared, in Example 2 a hemisphere with a circumferential stacking approach and an edge.
  • 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 Fa. Texas polymer) was melted on a hydraulic screw-injection molding machine from the company. Arburg and injected into Simple tools with hot runner nozzle, wherein the shell having the shape of a hemisphere with a circumferential stacking tab and an edge.

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Claims (11)

  1. Portion d'agent de lavage, de nettoyage ou de rinçage contenue dans un corps creux à forme stable, présentant plusieurs chambres, comprenant
    (a) au moins une composition liquide active en lavage, en nettoyage ou en rinçage ainsi qu'au moins une composition solide active en lavage, nettoyage ou rinçage, qui sont séparées l'une de l'autre dans l'espace;
    (b) au moins une enveloppe entourant totalement ou partiellement les compositions selon (a) en un matériau moulé par injection, désintégrable dans les conditions de lavage, de nettoyage ou de rinçage, conférant une stabilité de forme au(x) corps creux ; et
    (c) une ou plusieurs parois, qui sépare(nt) les composants ou compositions identiques ou différent(e)s, actif(ve)s en lavage, nettoyage ou rinçage les un(e)s des autres dans l'espace.
  2. Portion d'agent de lavage, de nettoyage ou de rinçage selon la revendication 1, comprenant deux chambres ou plus, contenant une ou plusieurs compositions actives en lavage, nettoyage ou rinçage qui sont disposées en s'entourant l'une l'autre.
  3. Portion d'agent de lavage, de nettoyage ou de rinçage selon l'une ou plusieurs des revendications 1 ou 2, dans laquelle le/les corps creux à forme stable comprend/comprennent un ou plusieurs polymères solubles dans l'eau, de préférence un matériau du groupe formé par le poly(alcool vinylique) (PVAL) (le cas échéant acétalisé), la polyvinylpyrrolidone, le poly(oxyde d'éthylène), la gélatine, la cellulose, et leurs dérivés et leurs mélanges, de manière particulièrement préférée du poly(alcool vinylique) (PVAL) (le cas échéant acétalisé).
  4. Portion d'agent de lavage, de nettoyage ou de rinçage selon l'une ou plusieurs des revendications 1 à 3, dans laquelle le/les corps creux à forme stable comprend/comprennent un ou plusieurs matériaux du groupe formé par les polymères contenant de l'acide acrylique, les polyacrylamides, les polymères d'oxazoline, les polystyrènesulfonates, les polyuréthanes, les polyesters et les polyéthers et leurs mélanges.
  5. Portion d'agent de lavage, de nettoyage ou de rinçage selon l'une ou plusieurs des revendications 1 à 4, dans laquelle une ou plusieurs parois contiennent une partie ou la quantité totale d'au moins un composant d'au moins une composition active en lavage, nettoyage ou rinçage.
  6. Portion d'agent de lavage, de nettoyage ou de rinçage selon l'une ou plusieurs des revendications 1 à 5, comprenant au moins une, de préférence plusieurs, compositions actives en lavage, nettoyage ou rinçage du groupe formé par les agents tensioactifs anioniques, non ioniques, cationiques et amphotères, les substances de type builder, les agents de blanchiment, les activateurs de blanchiment, les stabilisateurs de blanchiment, les catalyseurs de blanchiment, les enzymes, les polymères, les cobuilders, les agents d'alcalinisation, les agents d'acidification, les agents d'anti-redépôt, les agents de protection de l'argent, les colorants, les azurants optiques, les substances de protection contre les UV, les adoucisseurs, les agents de rinçage, en une quantité suffisante pour un processus de lavage, de nettoyage et de rinçage.
  7. Portion d'agent de lavage, de nettoyage ou de rinçage selon l'une ou plusieurs des revendications 1 à 6, caractérisée en ce que la composition solide active en lavage, nettoyage ou rinçage est choisie dans le groupe formé par les poudres, les granulés, les extrudats, les pellets, les billes, les comprimés, les tablettes, les anneaux, les blocs, les briquettes.
  8. Procédé de lavage, en particulier procédé pour le lavage en machine d'une machine à lessiver usuelle du commerce, comprenant les étapes dans lesquelles
    - on introduit une portion d'agent de lavage selon l'une quelconque des revendications 1 à 7 dans la machine à lessiver, en particulier dans le compartiment à détergent ou dans le tambour de lavage ;
    - on règle les conditions de lavage souhaitées ; et
    - lors de l'apparition de ces conditions, on introduit la/les composition(s) active(s) en lavage de la portion d'agent de lavage dans le bain de lavage et on met ce dernier en contact avec les objets à laver.
  9. Procédé de nettoyage, comprenant les étapes dans lesquelles
    - on introduit une portion d'agent de nettoyage selon l'une quelconque des revendications 1 à 7 dans le bain de nettoyage;
    - on règle les conditions de nettoyage souhaitées ; et
    - lors de l'apparition de ces conditions, on introduit la/les composition(s) active(s) en nettoyage de la portion d'agent de nettoyage dans le bain de nettoyage et on met ce dernier en contact avec les objets à nettoyer.
  10. Procédé de rinçage, en particulier procédé pour le rinçage en machine dans un lave-vaisselle usuel du commerce, comprenant les étapes dans lesquelles
    - on introduit une portion d'agent de rinçage selon l'une quelconque des revendications 1 à 7 dans le lave-vaisselle, en particulier dans son compartiment à détergent ou sa chambre de rinçage ;
    - on règle les conditions de rinçage souhaitées ; et
    - lors de l'apparition de ces conditions, on introduit la/les composition(s) active(s) en rinçage de la portion d'agent de rinçage dans le bain de rinçage et on met ce dernier en contact avec les objets à rincer.
  11. Procédé de production d'une portion d'agent de lavage, de nettoyage ou de rinçage selon l'une quelconque des revendications 1 à 7, comprenant les étapes
    (i) de production d'un corps creux à forme stable, comprenant une ou plusieurs parois par moulage par injection;
    (ii) de remplissage des chambres avec des compositions actives en lavage, nettoyage ou rinçage.
EP05014861A 2000-07-14 2001-07-04 Corps creux compartimentés comprenant une dose d' un produit de lavage, de mnettoyage ou de rincage Revoked EP1586631B1 (fr)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
DE10033827 2000-07-14
DE2000133827 DE10033827A1 (de) 2000-07-14 2000-07-14 Kompartiment-Hohlkörper
DE2000148448 DE10048448A1 (de) 2000-07-14 2000-09-29 Kompartiment-Hohlkörper II
DE10048448 2000-09-29
DE10058647 2000-11-25
DE2000158647 DE10058647A1 (de) 2000-07-14 2000-11-25 Kompartiment- Hohlkörper III
DE2001107878 DE10107878A1 (de) 2000-07-14 2001-02-20 "Kompartiment-Hohlkörper IV"
DE10107878 2001-02-20
EP01967120A EP1305396B1 (fr) 2000-07-14 2001-07-04 Corps creux compartimentes contenant une dose d'un produit de lavage, de nettoyage ou de rincage

Related Parent Applications (1)

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

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EP1586631A2 EP1586631A2 (fr) 2005-10-19
EP1586631A3 EP1586631A3 (fr) 2005-10-26
EP1586631B1 true EP1586631B1 (fr) 2007-01-03

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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

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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

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US (2) US7417019B2 (fr)
EP (2) EP1305396B1 (fr)
JP (1) JP2004504443A (fr)
AT (2) ATE308606T1 (fr)
AU (1) AU2001287580A1 (fr)
DE (2) DE50111830D1 (fr)
ES (2) ES2279467T3 (fr)
WO (1) WO2002006431A2 (fr)

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Publication number Publication date
AU2001287580A1 (en) 2002-01-30
ES2279467T3 (es) 2007-08-16
DE50107923D1 (de) 2005-12-08
US7601679B2 (en) 2009-10-13
ATE350462T1 (de) 2007-01-15
WO2002006431A3 (fr) 2002-05-30
US20040029764A1 (en) 2004-02-12
DE50111830D1 (de) 2007-02-15
JP2004504443A (ja) 2004-02-12
US7417019B2 (en) 2008-08-26
ES2252286T3 (es) 2006-05-16
ATE308606T1 (de) 2005-11-15
US20080312123A1 (en) 2008-12-18
EP1586631A3 (fr) 2005-10-26
EP1305396A2 (fr) 2003-05-02
EP1305396B1 (fr) 2005-11-02
WO2002006431A2 (fr) 2002-01-24
EP1586631A2 (fr) 2005-10-19

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