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 in dimensionally stable hollow bodies are contained with at least one compartment.
• the invention also relates to methods of making such washing, cleaning or rinse agent portions containing compartment hollow body.
• the invention relates to washing, cleaning and Rinsing processes in which the detergent, cleaning agent and dishwashing detergent preparations in dimensionally stable hollow bodies with one or more separate compartment (s) dosed become.
• the older patent application DE 198 31 703 discloses a portioned detergent or cleaner preparation in a bag of water-soluble Film, in particular in a bag of (optionally acetalized) polyvinyl alcohol (PVAL), wherein at least 70% by weight of the particles of the detergent or cleaner composition Have particle sizes> 800 microns.
• PVAL polyvinyl alcohol
• the document DE-A 20 65 153 describes surfactant shaped bodies comprising several components, those made of an outer shell of sodium silicate and enclosed therein Detergent components exist.
• the silicate shell is formed by compression molding in two Hemispheres made after filling the sufficient for a wash amount of Detergent components are assembled and connected to the molding.
• the Process is extremely impractical and does not result in useful detergent portions.
• the document DE-A 20 07 413 describes detergent moldings from a core of one or several detergent component (s) and a shell of press-molded, predominantly made Sodium metal silicate existing shell material.
• the 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 from a made by compression molding, consisting of two equal halves tablet of one or more detergent, rinse or detergent components and a optionally provided with an additional envelope core of another Detergent, detergent or cleaner component.
• a solid core can be incorporated into the tablet wrapper, if not premature release of the tablet should be initiated from within.
• the invention was based on the object, detergent, cleaning agent or detergent preparations in which volatile as well as less volatile washing active, cleaning active or rinse active components can be assembled or mechanically unstable components can be incorporated without them - For example, when pressed into moldings - impaired in terms of their integrity become.
• the invention was further based on the object, detergent, rotatesmittel- or Detergent components spatially separate from each other and still in the same Make up detergent, detergent or detergent portion, with the aim of a Substance exchange or mutual interference, which may result in losses of Activity may be as low as possible.
• one detergent, detergent or detergent portions in dimensionally stable hollow bodies with one or more separate compartment (s) can fill and thus provide dosages of the respective remedies that are opposite compact or bagged preparations have application advantages.
• the invention further relates to a process for producing one in one or more dimensionally stable hollow body (s) containing at least one compartment detergent, Detergent or detergent portion according to the above and detailed below Description comprising the steps of using one or more known methods produces several dimensionally stable (s) hollow body, wherein running under compression process for Manufacture of / the hollow body (s) are excluded, this (s) hollow body optionally with one or more device (s) for compartmentalizing the dimensionally stable Hollow body (s) and the compartment (s) with at least one washing-active, filled active cleaning or rinse-active preparation and optionally subsequently the dimensionally stable hollow body to form a partial or complete enclosure to include the detergent-active, cleaning-active or rinse-active preparation (s).
• detergent, detergent or detergent portion is used in the context of present invention for a taking place in an aqueous phase washing, Cleaning or rinsing sufficient amount of detergent, cleaning agent or detergent understood. This can be, for example, a machine washing, cleaning or flushing, as it is with commercial washing machines or Dishwashers is performed. According to the invention, however, this term is used also a (for example, in the hand basin or in a bowl performed) Hand wash or hand-carried dishwashing or other process of washing or cleaning understood. According to the invention, the preferred Detergent, detergent or detergent portions in automatic washing, Cleaning or rinsing used.
• detergent or detergent or detergent partial portion is in within the scope of the present invention, a subset of a detergent or cleaning agent or Detergent portion understood in one of other detergent or Detergent or detergent part-portions separated phase in spatial communication with other detergent or detergent or detergent partial portions of the same Detergent or detergent or detergent portion is present, for example, in one Separate compartment in a dimensionally stable hollow body according to the invention, and by appropriate measures are prepared so that they are separated from other detergents or Detergent or detergent portion portions of the same detergent or cleaning agent or Rinsing agent portion added to the liquor and optionally dissolved or suspended in it can be.
• a detergent or detergent or detergent partial portion the same ingredients as another detergent or cleaner portion same detergent or cleaning agent or detergent portion contain; but preferably contain two detergent or detergent or detergent partial portions same detergent or cleaning agent or detergent portion different ingredients, especially different washing active, cleaning active or rinse-active preparations.
• the detergents or cleaning agent or detergent portions contain measured amounts of at least one washing active, cleaning active or rinse active Preparation, usually measured amounts of several washing active, cleaning active or rinse-active preparations. It is possible that the portions only wash active, contain cleaning-active or rinse-active preparations of a particular composition. However, according to the invention it is preferred that several, usually at least two, Wash-active, cleaning-active or rinse-active preparations of different Composition in the detergent or detergent or detergent portions are included.
• the composition may be in terms of the concentration of the individual Components of the washing-active, cleaning-active or rinsing-active preparation (quantitative) and / or with regard to the nature of the individual components of the washing-active, cleaning-active or rinse-active preparation (qualitatively). It is particularly preferred that the Components are adapted in terms of nature and concentration to the tasks that the Detergent or detergent or detergent partial portions in the washing, cleaning or Have to fulfill flushing.
• washing-active or cleaning-active or rinse-active preparation are used in the In the context of the present invention preparations of all conceivable, in connection with understood a washing or cleaning or rinsing relevant substances. This are primarily the actual detergents or cleaners or dishwashing detergents with theirs in the further course of the description explained in more detail individual components.
• Active substances such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), Builders (inorganic and organic builders), bleaches (such as for example, peroxo bleach and chlorine bleach), bleach activators, Bleach stabilizers, bleach catalysts, enzymes, special polymers (for example those with cobuilder properties), grayness inhibitors, dyes and fragrances (perfumes), without the term being limited to these substance groups.
• washing active or cleaning active or active Preparations but also detergents and cleaning aids or rinse aids Understood.
• these are optical brighteners, UV protection substances, so-called Soil Repellents, ie polymers that reshuffle fibers or hard surfaces (including dishes), as well as silver protectants, colorants and Dye removers.
• laundry treatment agents such as fabric softener or dishwashing detergent additives Like rinse aid according to the invention as washing active or as cleaning active or considered as active ingredient preparations.
• the detergent, cleaning agent or detergent portions are in one or more dimensionally stable hollow body (s) having at least one compartment.
• the exact shape of the hollow body is just as critical in this context as its size; The only requirement in this regard is that the shape and size comply with the later use, so use in a washing, cleaning or Rinsing process, especially in conventional washing machines or dishwashers.
• Hollow body in spherical, ellipsoidal, cubic, cuboid, trapezoidal, conical or pyramidal or Trochoidform; Cuboid or trochoid-shaped hollow body have the invention best proven and can therefore be used with advantage.
• the size of the hollow body is in preferred embodiments of the invention such that the Hollow body in the Ein Hughes screening a commercial washing machine or Dishwasher, in in the laundry running nets or bags o. ⁇ . Entered can be.
• Particularly preferred embodiments of the invention Detergent, detergent or detergent portions exceed a length (longest Axis) of 10 cm not, while the sizes of the width and height are much lower, for example, at 1 to 5 cm.
• dimensionally stable hollow body is understood according to the invention that the Detergent, detergent or detergent portions containing moldings an inherent dimensional stability which enables them, under normal conditions of manufacture, the Storage, transport and handling by the consumer against breakage and / or pressure to have stable, non-coincident structure, which is also among the conditions not changed for a long time. It is according to the invention without Influence, whether this structural stability out of due to various mentioned below Parameter-yielding properties of the dimensionally stable hollow body alone or (even) from the Presence of compartmentation devices and / or (also) from the filling with washing-active, cleaning-active or rinse-active preparations results. In preferred Embodiments of the invention already have the dimensionally stable hollow body itself sufficient inherent dimensional stability, as this is beneficial to the mobility in machines in the manufacture of the hollow body and the filling during the production of Detergent, detergent or detergent portions according to the invention.
• the pressure resistance of the dimensionally stable hollow body according to the invention is in the (se usual) way measured so that unfilled and optionally with compartmentalizing facilities provided hollow body with films or lids are closed and on these hollow bodies at room temperature an internally applied, steadily increasing vacuum is applied until the hollow body begins to collapse.
• the inherent shape stability of Hollow body should more preferably be such that in such vacuum collapse tests unfilled and optionally provided with compartmentalization hollow body collapse not before reaching a vacuum of 900 mbar, preferably 750 mbar and in particular from 500 mbar begins.
• the invention differ used hollow body fundamentally of films or so-called "pouches", as to Provision of detergents, detergents or detergents also used become.
• the hollow bodies according to the invention provide an independent, self-supporting Envelope, which usually already before filling with one or more washing active, rinse active or cleaning active component (s) exists and then is filled.
• coatings are applied to existing moldings (eg. Compacts, granules, extrudates, etc.) applied and then dried or cured; she only then form 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 preferably be at most in an amount of 350 g / (m 2 ⁇ 24 h), more preferably only in an amount within a range of at most 100 g / (m 2 ⁇ 24 h), still more preferably in one Amount of a maximum of 50 g / (m 2 x 24 h).
• the detergent Take into account cleaning agent or detergent portions in the dimensionally stable hollow bodies also, that with particular advantage - although not mandatory - in the hollow bodies Portions contained by a - preferably controllable - water solubility of Hollow body material at a certain time of washing, cleaning or Rinsing process or when reaching a certain pH or a certain ionic strength of the wash liquor or due to other controllable events or Conditions can be fed into the aqueous liquor.
• the quality of the material like its quantity, too, has a direct influence on these solubility properties.
• a release process can capture the hollow body as a whole or only a part thereof, so that parts of the hollow body when setting a certain Solve parameter combination, while other parts are not yet (but later) or not solve it at all.
• the latter can be due to different quality of the material as well by different amounts of material (thickness of the wall) or different Geometries of the hollow body can be achieved. For example, it is possible through the Hollow body geometry to complicate the access of water and thus the dissolution process delay.
• the walls of the Hollow body of different thickness are very thin and thus at the thinner places to allow earlier release.
• the walls of the hollow body of materials of different Solubilization of water for example from Polyvinalalkoholen (PVAL) with different residual acetate content. This leads to the formation of perforated walls, the one Ingress of water into the hollow body and / or leakage of the dissolved or the allow undissolved ingredients from the hollow body.
• PVAL Polyvinalalkoholen
• a active, active cleaning or active washing active ingredient for which PVAL as a builder an example is, or contain such.
• Detergents, detergents or active ingredients that are active only in small quantities in the Preparations are present and their uniform incorporation therefore not is unproblematic in the material of the wall of the hollow body or in a part of the material the wall of the hollow body, for example one which is in the state of washing, Purification or rinse triggers, in which just the active ingredient is needed, incorporated and release the material of the wall at the right time into the fleet.
• fragrances that in the last phase of the washing or Cleaning or rinsing are desired, but also optical brighteners, UV-protective substances, Dyes and other washing active, cleaning active or rinse active Preparations.
• optical brighteners UV-protective substances
• Dyes and other washing active, cleaning active or rinse active Preparations.
• the basic principle of incorporation of such (usually in small Incorporated into) components in the materials that surround the detergent, Detergent or detergent portions form, is the parallel pending Patent Application 199 29 098.9 of the Applicant entitled "active ingredient portion package" to the disclosure of which is incorporated herein by reference in its entirety is included in the present application.
• the walls of the dimensionally stable hollow body containing the detergent, detergent or detergent portions contain, consist of different materials, so have a heterogeneous structure.
• a wall of the hollow body forming polymer material could islands be dispersed from a non-soluble in the polymer foreign material, for example from another polymer (with different water solubility) or even one completely another substance (for example, an inorganic or organic substance).
• water-soluble salts such as sodium sulfate, sodium chloride, Sodium carbonate, calcium carbonate, etc .
• organic acids such as citric acid, Tartaric acid, adipic acid, phthalic acid, etc .
• 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 construction may be associated with the advantage in particularly preferred embodiments of the invention be that the other substance dissolves faster in water than the polymer, what a Penetration of water in the hollow body allows and thereby accelerated Release of washing-active, rinse-active or cleaning-active components of the portion contributes.
• the entire dimensionally stable hollow body is in such a packaging dissolved faster than a molding of a pure polymer material.
• the walls of the hollow bodies from layers of two or more polymers form, which can be selected in particularly preferred embodiments so that their properties (stability, heat resistance, water solubility, Gas barrier properties, etc.) optimally complete.
• a detergent, Detergent or detergent portion a dimensionally stable hollow body of at least one a washing-active, cleaning-active or rinse-active preparation wholly or partly surrounding enclosure from one under washing, cleaning or rinsing conditions disintegratable, non-compressed material having at least one compartment, wherein the / Compartment (s) one or more washing active, cleaning active or rinse active Preparation (s) contains / contain.
• the one hollow body comprises at least one compartment, a chamber inside of him.
• a chamber or compartment is usually through walls (in just one compartment, these are the walls of the Hollow body) limited space.
• the invention may also be several rooms. These can either be through be formed that individual rooms are separated by walls from each other in the frame be referred to as "compartmentalizing devices" of the present invention and the same or different washing active, rinse active or cleaning active components or separate preparations spatially from each other, or that different washing-active, rinse-active or cleaning-active components or compositions directly to each other but do not mix with each other.
• the chamber or the Compartment is wholly or partly, advantageously completely, surrounded by the enclosure from a disintegrate under washing, cleaning or rinsing conditions, not pressed material forming the wall of the dimensionally stable hollow body.
• the compartment or in the chamber is / are one or more washing active, cleaning active or rinse active Preparation (s) included.
• the invention includes Compartment advantageously several washing active, cleaning active or rinse active preparations; However, the case of the presence of just one is also conceivable Preparation in a compartment or in a chamber.
• a particularly preferred embodiment of the invention contains the dimensionally stable Hollow body in its interior several compartments or chambers, each one or contain several washing active, cleaning active or rinse active preparation (s).
• Examples for this purpose are cuboid or trochoid-shaped dimensionally stable hollow body, the two, three or four or even more compartments, each containing one or more wash-active, detergent-active or rinse-active preparation (s).
• a big advantage of this Embodiment of the invention is that the various washing-active, detergent-active or rinse-active preparations are distributed to the compartments so can, as it is best for the special requirements.
• the size and shape of the individual compartments within a dimensionally stable hollow body is not critical and can be focused largely on the needs of the case.
• certain detergent-active, cleaning-active or rinse-active preparations or Mixtures thereof which are present in larger quantities, provided larger compartments are used as preparations that are present only in small quantities.
• mixtures of certain preparations, which are provided at the beginning of the washing, cleaning or rinsing and in certain Quantities are present, required by other or in other quantities required components be spatially separated and arranged in compartments of other sizes.
• one in a dimensionally stable hollow body with at least one, preferably a plurality of compartment (s) contained detergent, Detergent or detergent portion will be two or more, one or more wash-active, cleansing or rinse-active preparation (s) containing compartments of the hollow body, which are arranged enclosing each other.
• the compartments with the washing-active, cleaning-active or rinse-active preparation (s) are therefore in the Hollow body not juxtaposed or arranged over / under each other, but each other enclosing, for example, more or less concentric (“onion model") or more or less coaxially (“multilayer rod model”) or such that the innermost compartment is completely surrounded by the next outer, this possibly completely again of the following, etc.
• the washing-active, detergent-active or rinse-active substances distributed to the compartments so that the in the washing, cleaning or rinsing process as the first required components in the am
• the most external compartments are the first to be exposed to water or fleet, while (a) later required component (s) in (one) further inside compartment (s) is / are arranged and before the entry of water through the outer compartments are protected.
• the invention relates to a detergent, Detergent or detergent portion containing two or more dimensionally stable hollow body at least one washing-active, cleaning-active or rinsing-active preparation wholly or partially surrounding enclosure of one or more under washing, cleaning or Rinsing conditions of disintegratable, non-pressed material (s) with at least one each Compartment, the compartment (s) having one or more wash-active, detergent-active or rinse-active preparation (s).
• the size, shape and arrangements of the / the compartment (s) and the at least a washing-active, cleaning-active or rinse-active preparation should be designed as well as in the context of the embodiments described above, d. H. it can be in a dimensionally stable Hollow body one or more compartments of any shape and size, each with one or more a plurality of detergent-active, cleaning-active or rinse-active preparation (s). In the present case, however, several such dimensionally stable hollow body are common present.
• the two or more dimensionally stable hollow body made of several different materials or (optionally similar) materials with different properties that - with special Advantage - are disintegratable under washing, cleaning or rinsing conditions.
• Materials of the hollow body (s) include, but are not limited to, one or a plurality of water-soluble polymer (s), preferably one or more materials from the group (optionally acetalated) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, Gelatin, cellulose, and their derivatives and mixtures thereof, more preferred (optionally acetalated) polyvinyl alcohol (PVAL).
• the dimensionally stable hollow body (s) contains one or more materials from the group Acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, Polyurethanes, polyesters and polyethers and mixtures thereof include / include.
• the at least one wash-active, rinse-active or cleaning-active preparation surrounding enclosure of the hollow body dimensional stability giving, not pressed material By “non-pressed” material according to the invention understood a material that is not - as in the prior art - by pressing (For example) wash-active, rinse-active or cleaning-active components or Preparations is made to obtain a compact, then others embedded washing active, rinse active or cleaning active components or preparations but by any other molding techniques, as detailed below be explained. By way of example, thermoforming, casting, injection molding, sintering, etc. are mentioned. at Inorganic materials, which can also be used, can also be cast a preferred method of preparation.
• the two or more dimensionally stable hollow body made of two or more different materials may be selected from the materials listed above, but also may include other materials.
• the walls of these hollow body of two or more similar materials such as materials from the same monomer building blocks, however Materials with different properties, exist. Examples of this can be similar Materials with different molecular weight (and thus different solubility), PVAL materials with different degrees of acetalization (and thus different Solubility or different solution temperature in water), materials with different proportion of grafted co-monomers o. ⁇ . Be.
• these dimensionally stable hollow body different have geometric shape. This can be advantageous to different Dissolution behavior or different kinetics of the release of the in the compartment (s) lead the detergent contained in the hollow body detergent, detergent or detergent portion.
• Detergent or detergent portions in which the two or more dimensionally stable Hollow body a - particularly preferred, but not necessarily releasable - form composite.
• One Composite of two or more dimensionally stable hollow bodies can with particular advantage be used if either detergent, detergent or detergent portions of different composition should be dosed (eg, heavy duty detergent and Colored fabrics; in the latter example bleaching components are not or not in the same concentration desired as in the former; the bleach containing hollow body could then be removed by the user, if colorful laundry should be washed) or if - For example, for small amounts of laundry or dishes - only a partial dose of in dimensionally stable hollow bodies contained detergent or detergent portion used should.
• Such a composite could be particularly preferred by gluing, fusing, Welding or clamping the dimensionally stable hollow body are produced; one Mechanical clamping also allowed for easy release of the composite.
• Especially preferred embodiments are such composite hollow body in an aqueous environment again detachable from each other, for example by using a water-soluble adhesive; This could ensure that an automatic washing, cleaning or Rinsing process used composite completely dissolved and with the washing, cleaning or Rinse liquor is withdrawn from the machine.
• the above information on the materials of dimensionally stable hollow body accordingly.
• the compartmentalization facilities within the dimensionally stable hollow body made of the same materials as the hollow body itself one-piece production in one process step and makes the manufacturing process especially economical.
• the compartmentalization device (s) is / are one (or more) an activity reduction of at least one component a washing-active, cleaning-active or rinse-active preparation inhibiting Device (s).
• a washing-active, cleaning-active or rinse-active preparation inhibiting Device examples include all the cases where components are washing-active, cleaning-active or rinse-active preparations, taking into account a mutual Disruption of their activity spatially separated.
• the Compartmentalization facilities should then have properties that include this Requirements, for example essentially impermeable to To be water vapor to keep bleach free of moisture, or acid or acid alkali-free to protect enzymes from premature decomposition.
• Such inhibition of a Activity reduction not only contributes directly to a better activity of the respective protected Component, but also allows to reduce the amounts of such components, since a surplus is no longer required in anticipation of the usual loss of activity.
• the Compartmentalizing device (s) one) the quality and / or quantity of the release of Components of a washing-active, cleaning-active or rinse-active preparation determining institution (s).
• a dimensionally stable hollow body for example, several compartments on whose walls a different solubility (or temperature of dissolution) in water or in the fleet.
• the compartments contain (washing, cleaning, rinsing) active Components for the first, second and possibly further (washing, cleaning, rinsing) Gears that have different compositions and set these different times or at different temperatures of the washing, cleaning or rinsing free.
• the dimensionally stable hollow body for example only - Have walls and compartmentalization facilities, incorporated into the materials are, who are at different temperatures or under different others Solve boundary conditions.
• small ones first form Holes that show only weak mass transfer between individual compartments and the Outdoor environment allow and therefore only small amounts of a washing active, cleaning active or flushing preparation into the liquor; under others, later settable Conditions will increase the holes or pores, because in other conditions release soluble wall components; larger holes allow larger amounts of material between the interior of the compartment (s) and the outside environment (ie the fleet) and thus the desired higher concentrations of the washing-active, cleaning active or rinse-active preparation can be adjusted in the fleet.
• the compartmentalization device (s) is / are (a) the activity of at least one component of a detergent, cleaning-active or rinse-active preparation controlling device (s).
• a detergent, cleaning-active or rinse-active preparation controlling device s.
• These Embodiment is particularly useful in cases where it is necessary is that the release of one or more drugs a washing active, cleaning active or rinse-active preparation with a given kinetics in the washing, cleaning or Rinsing carried out.
• a particular example is a so-called "controlled release" release, which, according to the parameters given above, determine the properties of the wall of the dimensionally stable hollow body and / or the compartmentation devices can be controlled. On This way can be a destructive influence of the fleet or alone of the water on the active Substance decreases and the substance is actively released into the liquor over a longer period of time become.
• one or several compartmentalizing device a part or the total amount at least a component of at least one washing active, cleaning active or rinse active Preparation contains / contains.
• this can be achieved in that one or more component (s) of at least one washing active, cleaning active or rinse-active preparation incorporated into the material of the compartmentalizing device will be.
• Such substances have already been mentioned above the mentioned forming the stable hollow body material and include (but are not limited to) components that are in relatively small amounts in the detergent, Detergent or detergent portions are included and therefore relatively poor in large mass mixtures of washing-active, cleaning-active or dishwashing preparations work in.
• a very simple training succeeds in the materials of Compartmentalization facilities, and from these also manages a reliable, controllable Release during the washing, cleaning or rinsing process.
• By a suitable choice of Materials can also be released with "controlled release" kinetics.
• compartmentalizing device in part or in total of at least one Component of at least one detergent-active, cleaning-active or rinse-active preparation consist. This is preferred because it does not make the compartmentalization device only a kinetics of release affecting or even controlling component of Detergent, detergent or detergent portion according to the invention, but at the same time as a component of the success of the washing, cleaning or Rinsing process is involved. Due to the wide choice of available Materials for this embodiment are numerous examples; are particularly preferred Compartmentalizing devices derived from (meth) acrylic acid and its derivatives (salts, esters) comprehensive polymers include or include.
• Compartmentalization device from an interface between two contiguous components of a washing active, cleaning active or rinse active Preparation or an interface between two adjoining washing-active, cleaning-active or rinse-active preparations.
• This can be preferred Embodiments of the invention for example, be the case when washing-active, cleaning-active or rinse-active preparations by means of suitable measures, for example formed into structures by co-extruding, press-forming or rolling several components whose components have solidified interfaces to adjacent components. In these cases, activity-reducing or otherwise adverse effects of washing-active, cleaning-active or rinse-active preparations are minimized or even be excluded.
• a further preferred embodiment of the invention consists in a in one or a plurality of dimensionally stable hollow body (s) with at least one compartment contained Detergent, detergent or detergent portion in which the dimensionally stable hollow body a n limiting surfaces, non-spherical hollow body consists of which a surface assumes the function of a "cover", which concludes a Process for producing the detergent, cleaning agent or detergent portions according to the invention, d. H. after filling the compartment (s) inside the hollow body with one or more washing-active, cleaning-active or rinsing-active preparation (s), is applied under closing of the hollow body.
• the "lid” is particularly preferred made of a material with controllable water solubility and can with the remaining hollow body gluing, for example with a water-soluble adhesive, fusing, Welding or another known method for connecting Materials are connected.
• This embodiment is for producing the Detergent, detergent or detergent portions according to the invention particularly advantageous because a gradual filling of the / the compartments with one or more washing active, active cleaning or rinse-active preparation is possible and handling leads to optimal results in later use, especially one Reliable control of the access of water or aqueous liquor to the interior of the dimensionally stable hollow body or the outlet of washing-active, cleaning-active or rinse-active preparation from the interior of the hollow body.
• the detergent, cleaning or rinsing agent portions according to the invention contain one or more substances from the group of surfactants, surfactant compounds, builders, Bleaching agents, bleach activators, enzymes, foam inhibitors, dyes and fragrances, and - in the case that the detergent or cleaner portions at least partially as a shaped body present - binding and disintegration aids.
• surfactants surfactant compounds
• builders Bleaching agents
• bleach activators enzymes
• foam inhibitors dyes and fragrances
• the washing and Detergent portions surfactants from the group of anionic, nonionic, zwitterionic or cationic surfactants containing anionic surfactants for economic reasons and because of their range of services are clearly preferred.
• anionic surfactants for example, those of the sulfonate type and sulfates are used.
• Suitable surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as, for example, from C 12-18 -monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained.
• alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• esters of 2-sulfofatty acids for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
• sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
• fatty acid glycerol esters are the mono-, di- and triesters and their mixtures to understand how they in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or obtained 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 with 6 to 22 carbon atoms, for example the caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.
• Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
• C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
• 2,3-alkyl sulfates prepared, for example, according to U.S. Patents 3,234,258 or 5,075,041, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
• EO ethylene oxide
• Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
• Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or 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 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 in the form of their sodium or potassium salts, especially in the form of the sodium salts.
• surfactants are used in the form of their magnesium salts.
• detergent, cleaning agent or detergent portions preferably, the 5 to 50 wt .-%, preferably 7.5 to 40 wt .-% and in particular 15 to 25 wt .-% of one or more anionic surfactant (s), each based on the detergent, detergent or detergent portion.
• 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 alone nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, as described, for example, in Japanese Patent Application JP 58/217598 are described or preferably after in the international Patent Application WO-A-90/13533.
• alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
• APG alkyl polyglycosides
• Usable alkylpolyglycosides satisfy the general formula RO (G) z , in which R is a linear or branched, in particular in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
• the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
• the detergent, cleaning agent or detergent portions according to the invention can preferably contain alkylpolyglycosides, wherein contents of the washing and cleaning agent portions to APG over 0.2 wt .-%, based on the total preparation are preferred.
• Particularly preferred detergent, detergent or detergent portions contain APG in amounts of 0.2 to 10 wt .-%, preferably in amounts of 0.2 to 5 wt .-% and in particular in amounts of 0.5 to 3 wt .-%.
• Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide may be suitable.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.
• polyhydroxy fatty acid amides of the formula (I) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
• R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
• R 1 is a linear, branched or cyclic alkyl radical or an aryl radical
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy- or N-aryloxy-substituted compounds can then be converted 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 also to use cationic surfactants.
• Their use is preferably as Washing power booster, with only small amounts of cationic surfactants required. If cationic surfactants are used, they are preferred in amounts of 0.01 to 10 wt .-%, in particular from 0.1 to 3.0 wt .-%.
• inventive detergent, cleaning agent or Detergent portions are detergent
• the amount of surfactant does not have to be the same in all partial portions; rather, partial portions with relatively larger and partial portions are provided with relatively smaller surfactant content.
• inventive detergent, cleaning agent or Detergent portions are detergent, especially dishwashing detergent
• the amount of surfactant must also at Cleaning or dishwashing detergents should not be the same in all partial portions; rather, you can Partial portions with relatively larger and partial portions with relatively smaller surfactant content be provided.
• builders are the most important ingredients of Detergents and cleaners.
• cleaning agent or Detergent portions can usually be used in detergents, detergents or Be contained scavengers used builders, especially zeolites, silicates, Carbonates, organic cobuilders and - where no ecological prejudices against their use exist - 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, preferred values for x 2, 3 or 4 are.
• Such crystalline layered silicates are described, for example, in European Patent Application EP-A-0 164 514.
• Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
• both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 ⁇ yH 2 O are preferred, with ⁇ -sodium disilicate being obtainable for example by the method / described in the international patent application WO-A-91 08,171th
• amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
• the dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
• the term "amorphous” is also understood to mean "X-ray amorphous”.
• the silicates do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle.
• the silicate particles may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments.
• densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are especially preferred.
• a fine crystalline, synthetic and bound water-containing zeolite optionally used is preferably zeolite A and / or P.
• Zeolite MAP eg, commercial product: Doucil A24 from Crosfield
• zeolite X is particularly preferred as the P-type zeolite.
• zeolite X is particularly preferred as the P-type zeolite.
• zeolite X is particularly preferred as the P-type zeolite.
• mixtures of A, X and / or P are also suitable, however, are zeolite X and mixtures of A, X and / or P.
• zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2 - 2.5) SiO 2 • (3.5-5.5) H 2 O can be described.
• Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
• detergents also a use of the well-known phosphates as builders possible, if such use is not for environmental reasons should be avoided.
• Particularly suitable are the sodium salts of orthophosphates, the pyrophosphates and in particular the tripolyphosphates.
• Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, wherein among polycarboxylic acids such carboxylic acids be understood that carry more than one acid function.
• these are Citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if their Use for environmental reasons is not objectionable, as well as mixtures of these.
• Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
• the Acids themselves can be used.
• the acids have besides their builder effect typically also the property of an acidifying component and thus also serve for Adjustment of a lower and milder pH of washing and cleaning agent portions according to the invention.
• polymeric polycarboxylates are suitable. These are, for example, the Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.
• the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrene acids are generally significantly higher than the molecular weights specified in the context of the present invention.
• Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, this group may again, the short-chain polyacrylates may be preferred, the molecular weights of 2,000 to 10,000 g / mol, more preferably from 3,000 to 5,000 g / mol.
• copolymeric polycarboxylates in particular those of acrylic acid Methacrylic acid or acrylic acid or methacrylic acid with maleic acid.
• copolymeric polycarboxylates in particular those of acrylic acid Methacrylic acid or acrylic acid or methacrylic acid with maleic acid.
• acrylic acid with maleic acid have proven to be suitable, containing 50 to 90% by weight.
• Your relative molecular weight, based to free acids is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
• the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution be used.
• the content of the washing or cleaning agent portions according to the invention of (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight, in particular 3 to 10 wt .-%.
• the polymers may also be allyl sulfonic acids, such as For example, allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
• allyl sulfonic acids such as For example, allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
• biodegradable polymers of more than two are also preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.
• copolymers are those which as monomers preferably acrolein and Acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
• builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors.
• Particularly preferred Polyaspartic acids or their salts and derivatives, in addition to co-builder properties also have a bleach-stabilizing effect.
• polyacetals obtained by reaction of dialdehydes can be obtained with Polyolcarbonklaren, the 5 to 7 carbon atoms and at least Have 3 hydroxy groups.
• Preferred polyacetals are selected from dialdehydes such as glyoxal, Glutaraldehyde, terephthalaldehyde and mixtures thereof and from Polyolcarbon Textren such Gluconic acid and / or glucoheptonic acid.
• dextrins for example oligomers or Polymers of carbohydrates obtained by partial hydrolysis of starches can.
• the hydrolysis can be carried out by conventional, for example acid or enzyme catalyzed Procedures are performed.
• they are hydrolysis products average molecular weights in the range of 400 to 500,000 g / mol.
• DE dextrose equivalent
• 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.
• Ethylenediamine disuccinate is another suitable co-builder.
• This is ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts.
• EDDS ethylenediamine-N, N'-disuccinate
• glycerol disuccinates and Glycerol trisuccinates are also preferred. Suitable amounts are zeolithissen and / or silicate-containing Formulations at 3 to 15 wt .-%.
• organic co-builders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be present in lactone form and which at least 4 carbon atoms and at least one hydroxy group and contain a maximum of two acid groups.
• phosphonates these are in particular hydroxyalkane or aminoalkanephosphonates.
• Aminoalkane phosphonates are preferably ethylenediamine tetramethylene phosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question.
• the neutral reacting sodium salts are preferably in the form of the neutral reacting sodium salts, e.g. when Hexasodium salt of EDTMP or as hepta- and octasodium salt of DTPMP used.
• Builder is used from the class of phosphonates preferably HEDP.
• the Aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may, especially if the washing or Detergent portions also contain bleach, preferably, aminoalkanephosphonates, in particular DTPMP, use or mixtures of the said phosphonates use.
• the inventive Detergents, cleaning agents or dishwashing detergents in washing, cleaning or rinsing agents conventional ingredients from the group of bleaches, bleach activators, alkalizers, Acidifiers, enzymes, fragrances, perfume carriers, fluorescers, dyes, Foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, Grayness inhibitors, color transfer inhibitors, decolorizer and flekcen agents, contain antibacterial substances and corrosion inhibitors.
• sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
• Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
• bleaching agents from the group of organic bleaching agents.
• Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
• peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
• Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxy-caproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-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 may also be used or bromine-releasing substances are used.
• suitable chlorine or bromine releasing materials include, for example, heterocyclic N-bromo- and N-chloroamides, for example, trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or Dichloroisocyanuric acid (DICA) and / or salts thereof with cations such as potassium and sodium in Consideration.
• DICA Dichloroisocyanuric acid
• Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
• bleach activators When washing, cleaning or rinsing at temperatures of 60 ° C and below one
• bleach activators may be incorporated into the detergent, Detergent or detergent portions are incorporated.
• bleach activators can Compounds which, under perhydrolysis conditions, are aliphatic peroxycarboxylic acids preferably 1 to 10 C-atoms, in particular 2 to 4 C-atoms, and / or optionally substituted perbenzoic acid, can be used. Suitable substances are those which and / or N-acyl groups of said C atom number and / or optionally substituted Wear benzoyl groups.
• polyacylated alkylenediamines in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
• TAED Tetraacetylethylenediamine
• bleach catalysts in the detergent, detergent or detergent portions may also so-called bleach catalysts in the detergent, detergent or detergent portions be incorporated.
• These substances are bleach-enhancing Transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru - or Mo-salicene complexes or carbonyl complexes.
• Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are usable as bleach catalysts.
• Enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof in question. Particularly suitable are from bacterial strains or Fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Preferably, subtilisin-type proteases and in particular Proteases derived from Bacillus lentus.
• Enzyme mixtures for example from protease and amylase or protease and lipase or Protease and cellulase or cellulase and lipase or protease, amylase and lipase or protease, lipase and cellulase, but especially cellulase-containing mixtures of special interest.
• Peroxidases or oxidases have in some cases as proved suitable.
• the enzymes can be adsorbed on carriers and / or in coating substances be embedded to protect them against premature decomposition.
• the proportion of enzymes, enzyme mixtures or enzyme granules in the compositions of the invention for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-% amount.
• Enzymes are in the prior art primarily a detergent formulation added, in particular added to a dishwashing detergent, for the main rinse is determined. Disadvantage was that the optimum effect of enzymes used the Temperature selection limited and also problems in the stability of the enzymes in the strong alkaline environment occurred. With the washing or cleaning agent portions according to the invention it is possible to introduce enzymes into a separate compartment and then this also to be used in the pre-wash cycle and thus the pre-wash cycle in addition to the main wash cycle to be used for an enzyme action on soiling of the items to be washed.
• the one intended for the preliminary rinse cycle detergent-active preparation or partial portion of a detergent or detergent portion Add enzymes and then such a preparation - more preferably - with a Already at low temperature water-soluble material of a dimensionally stable hollow body include, for example, the enzyme-containing preparation before a loss of effect Protect environmental conditions.
• the enzymes are further preferred for use below the conditions of the pre-wash, so for example in cold water, optimized.
• the detergent portions of the invention may then be when the Liquid enzyme preparations are available, as they are sometimes sold commercially, because then a rapid effect can be expected, which is already in the (relatively short and cold Water performed) pre-rinse occurs. Even if - as usual - the enzymes in solid Form are used and this with a hollow body enclosure of a water-soluble Material are already soluble in cold water, the enzymes can already before the main wash cycle or main cleaning cycle unfold their effect.
• Advantage of Use of an enclosure of water-soluble material, in particular of cold water-soluble material is that the enzyme / enzymes in cold water after dissolution the enclosure quickly comes to effect / come. This can their effect time be extended, which benefits the washing or rinsing result.
• the detergent, cleaner or detergent portions according to the invention contain According to a particularly preferred embodiment, further additives, as known from the State of the art as additives for detergent or dishwashing detergent preparations are known. These can either one or more, if necessary, too all partial portions (washing-active, cleaning-active or rinse-active preparations) of Detergent, detergent or detergent portions according to the invention added or as described in co-pending patent application no. 199 29 098.9 entitled "Active ingredient portion pack" - into 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) be 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-morpholinol, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar compounds which, instead of the morpholino group, have a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
• brighteners of the type of substituted Diphenylstyryle in the partial portions (washing active preparations) of the washing or cleaning agent portions according to the invention be included, for.
• UV protection substances are substances that are released during the washing process or in the subsequent fabric softening process in the wash liquor and that accumulate accumulatively on the fiber, in order then to achieve a UV protection effect. Suitable are the products marketed under the name Tinosorb R Ciba Specialty Chemicals.
• additives which are preferred in specific embodiments are surfactants which in particular the solubility of the water-soluble wall of the dimensionally stable hollow body or influence the compartmenting device, but also their wettability and can control foaming on dissolution, as well as foam inhibitors, as well Bitter substances, the accidental ingestion of such hollow bodies or parts thereof Hollow body can be prevented by children.
• dyes in particular water-soluble or water-dispersible dyes.
• Preferred here are dyes, as they to improve the visual appearance of products in detergents and cleaning agents and Rinsing agents are usually used.
• the selection of such dyes prepares the Expert no difficulties, especially since such conventional dyes a high Storage stability and insensitivity to the other ingredients of the detergent, cleaning active or rinse-active preparations and against light and no pronounced Have substantivity to textile fibers so as not to stain them.
• the dyes are According to the invention in the detergent or detergent or detergent portions in Levels of less than 0.01 wt .-% present.
• the detergent, cleaning or Detergent portions can be added are polymers.
• these polymers come on the one hand polymers in question, the washing or cleaning or rinsing Cobuilder properties show, for example, polyacrylic acids, also modified Polyacrylic acids or corresponding copolymers.
• Another group of polymers are Polyvinyl pyrrolidone and other grayness inhibitors, such as copolymers of Polyvinylpyrrolidone, cellulose ethers and the like.
• Soil Repellents in question, as they Detergents and cleaning agents are known in the art and in detail below to be discribed.
• bleach catalysts especially bleach catalysts for automatic dishwashing or laundry detergents.
• complexes of the Manganese and cobalt, especially with nitrogen-containing ligands are used.
• silver protectants are a variety of mostly cyclic organic compounds, the Also addressed to this person skilled in the art and help to startup prevent silver-containing objects in the cleaning process. Specific Examples may include triazoles, benzotriazoles and their complexes with metals such as Mn, Co, Zn, Fe, Mo, W or Cu.
• the detergent, detergent or Detergent portions also contain so-called.
• Soil repellents ie polymers based on fibers or hard surfaces (for example, on porcelain and glass) raise the oil and Fettauswaschles from textiles and the Fettabwaschles porcelain and glass positive influence and thus specifically counteract re-soiling. This effect will especially clear when a textile or a hard object (porcelain, glass) is dirty is, the / before several times with a washing or Detergent containing this oil and fat dissolving component was washed.
• nonionic Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a share of Methoxy groups from 15 to 30 wt .-% and hydroxypropoxy groups from 1 to 15 wt .-%, in each case based on the nonionic cellulose ether, as well as those of the prior Technically known polymers of phthalic acid and / or terephthalic acid or of their Derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and the terephthalic acid polymers.
• additives are the inventive detergent, cleaning or Detergent portions in amounts of at most 30 wt .-%, preferably 2 to 20 wt .-%, added.
• the additive may also be a material of a water-soluble Surrounding the dimensionally stable hollow body or a material of the water-soluble Compartmentalizing device (s) that carry out the or one of the washing-active (s), detergent-active or rinse-active preparation (s) comprises or in which Kormpartiment (s) stops.
• the polymer material for the wall of the hollow body or for the Compartmentalization device (s) either in its weight increase, so the depot effect, which is achieved according to the invention to exploit, or in addition to the additives mentioned to keep at least partially in the remaining detergent preparation. This is but less preferred.
• Fragrances are the detergent, cleaner or detergent portions of the invention added to improve the overall aesthetic appearance of the products and the consumer in addition to the technical performance (softening result) a sensory to provide typical and distinctive product.
• perfume oils or Fragrances can be used individual fragrance compounds, such as synthetic products of the ester, ether, aldehyde, ketone, alcohol and type 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.
• To the ethers include, for example, benzyl ethyl ether.
• the aldehydes include, for. B. linear Alkanals of 8 to 18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lileal and Bourgeonal.
• the ketones include the ionone, ⁇ -isomethylionone, and methyl cedryl ketone.
• To the Alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and Terpineol.
• the hydrocarbons mainly include terpenes such as limonene and pinene. Preference is given to using mixtures of different odoriferous substances which thus interact with one another are coordinated that they produce an appealing scent together.
• perfume oils may also contain natural perfume mixtures, as from plant sources are accessible. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
• the content of fragrances is in the range up to 2 wt .-% of the total Detergent, detergent or detergent portion.
• the fragrances can be added directly to the detergent-active, cleaning-active or rinse-active (s) Preparation (s) are incorporated; but it can also be beneficial to the fragrances To apply carriers that strengthen the adhesion of the perfume on the laundry and by a Slower fragrance release provide for long-lasting fragrance of textiles.
• Support materials for example, cyclodextrins have been proven.
• the can Cyclodextrin-perfume complexes are additionally coated with other excipients.
• the fragrances and fragrances can basically be used in any of the partial portions (washing-active or detergent-active or rinse-active preparations) of the detergent composition according to the invention, Detergent or detergent portions may be included. However, it is particularly preferred that they are in a detergent in a post-wash or fabric conditioner provided part-detergent portion or in a detergent, especially in one Dishwashing detergent, in a part-detergent portion intended for rinsing or rinsing, special partial-detergent portion, are included.
• Detergent, cleaning agent or rinsing agent portions according to the invention contain in a dimensionally stable hollow body with at least one compartment one or more wash-active, cleansing or rinse-active preparations in quantities such that they are suitable for a washing, cleaning or rinsing sufficient.
• a dosage Two units under special conditions (heavily soiled, eg strong greasy laundry; heavily harnessed dishes) possible.
• one in or several dimensionally stable hollow body with at least one compartment contained Detergent, detergent or detergent portion which at least one, preferably the a plurality of detergent-active, cleaning-active or rinse-active preparation (s) in one or more several forms from the group of powders, granules, extrudates, pellets, pearls, tablets, Tabs, rings, blocks, briquettes, solutions, melts, gels, suspensions, dispersions, Emulsions, foams and gases.
• the shape of one or more compartments of the dimensionally stable hollow body contained washing active, cleaning active or rinse active So preparation is no limit, as long as the hollow body in the intended Use way.
• the detergent, cleaning agent or detergent portions disclosed herein consist of an outer mold containing one or more fillings.
• the mold divided by partitions into several compartments, creating several fillings may be present separately within the same hollow body.
• the invention also provides filled hollow body, which only partially from a sub Washing, cleaning or rinsing conditions of disintegratable hollow body (s) Form stability conferring, not pressed material, while the remaining parts of the Enclosure does not necessarily have to be dimensionally stable in the sense defined above.
• a preferred embodiment provides the provision of open, dimensionally stable molds ("Shells"), which are filled and sealed later, closing with a film is of particular importance.
• the term "enclosure” characterizes the wall a body that completely surrounds a washing, cleaning or purging preparation.
• This body inside which the washing, cleaning or rinsing active preparation is present, can be completely or partially from a washing, cleaning or Rinsing conditions disintegratable, the / the hollow body (s) dimensional stability imparting, not consist of pressed material.
• the term “hollow body” in the context of the present invention the body, the from enclosure and contents (according to washing, cleaning or rinsing preparation) is formed.
• the term “hollow body” includes both the individual parts (a) or (b) in the sense the invention as well as the entire agent according to the invention, by joining the Parts (a) and (b) is formed.
• that of the enclosure (A) is enclosed washing, cleaning or rinse-active preparation as a macroscopic object as well (filled) "hollow body” in the sense of the present invention as the washing, Cleaning or rinsing agent portion.
• the latter is characterized in that they has at least two spatially separated areas, the different Fillings may contain. These spatially separated areas are "Compartments" within the meaning of the present invention.
• a four-compartment hollow body it is possible to the part-hollow body, which are enclosed by the enclosures (A) and (B), so that they are each subdivided into two compartments, but it is also possible only the part-hollow body enclosed by the enclosure (A) or by the enclosure (B) to divide three compartments.
• the number of possibilities naturally increases with the number the total compartments - at the same time the complexity in the production increases, so in particular, portions according to the invention having two, three and four compartments are preferred.
• compartments can not only by subdivision of the part-hollow body, by the Enclosures (A) and (B) are enclosed, be configured. It is according to the invention additionally possible, further partial hollow bodies, which of enclosures (C), (D), (E), (F) etc. enclosed with the enclosing of the enclosures (A) and (B) part-hollow bodies to unite to the total portion.
• a preferred embodiment provides for the provision of open, dimensionally stable molds ("shells"), which are filled and sealed later, wherein the closing with a film is of particular importance.
• inventive Washing, cleaning or detergent portions preferred in which the enclosures (A) and (B) and optionally further enclosures to 20 to 90%, preferably to 30 to 80% and in particular from 40 to 70% of their surface of dimensionally stable, optionally one or several devices (s) for compartmentalizing comprehensive shells, while the Rest is formed by a water-soluble film.
• the partial hollow body is accordingly produced by producing an open shell any shape, filling this shell and then sealing with a foil produced.
• a foil produced Through targeted selection of the materials that make up shell and foil, the dissolution kinetics and thus the release of the filling can be controlled.
• closure is to be understood in the context of the present invention that the film, which closes the opening of the shell (s), is adhesively bonded to the edges of the shell.
• the film which closes the opening of the shell, is applied to the opening and adherent connected with their edges, which for example by gluing, partial melting or by chemical reaction.
• the closing film can of course also a laminate of several be differently composite films, on different compositions individual layers of film, the opening of the shell at certain times in the washing and cleaning cycle are released.
• Preferred film materials are the polymers known from the prior art. Particularly preferred are films of a polymer having a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons and in particular between 10,000 and 100,000 daltons. With regard to the media, in the detergents and cleaners are usually introduced, in particular portions according to the invention are preferred, in which the film consists of a water-soluble polymer.
• Such preferred polymers may be of synthetic or natural origin. Become Polymers on a native or partnative basis are used as the film material, so are preferred Film materials selected from one or more substances of the group carrageenan, Guar, pectin, xanthan, cellulose and their derivatives, starch and its derivatives as well Gelatin.
• Carrageenan is a named after the Irish coastal town of Carragheen, educated and similar to Agar built extract of North Atlantic, belonging to the Floridean red algae.
• the carrageenan precipitated from the algae's hot water extract is a colorless to sand-colored powder with molecular weights of 100,000-800,000 and a sulphate content of about 25%, which is very slightly soluble in warm water.
• Carrageenan has three main components:
• the yellow-forming f-fraction consists of D-galactose-4-sulfate and 3,6-anhydro- ⁇ -D-galactose, which are alternately glycosidically linked in the 1,3- and 1,4-positions (Agar, in contrast, contains 3,6-anhydro- ⁇ -L-galactose).
• the non-gelling I fraction is composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues and is readily soluble in cold water.
• the i-carrageenan composed of D-galactose-4-sulfate in 1,3-bond and 3,6-anhydro-aD-galactose-2-sulfate in 1,4-bond is both water-soluble and gel-forming.
• Other types of carrageenan are also denoted by Greek letters: ⁇ , ⁇ , y, ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ .
• the type of cations present K, NH 4, Na, Mg, Ca
• Semisynthetic products which contain only one type of ion and can also be used as film materials in the context of the present invention are also called Carrag (h) eenates.
• Guar also known as guar flour, which can be used as a film material in the context of the present invention, is an off-white powder obtained by grinding the endosperm of guar bean (Cyamopsis tetragonobolus).
• the main constituent of guar is up to about 85% by weight of the dry substance guar gum (guar gum, cyamopsis gum); Secondary components are proteins, lipids and cellulose.
• Guaran itself is a polygalactomannan, ie a polysaccharide whose linear chain of unsubstituted (see formula I) and in the C6 position with a galactose radical substituted (see formula (II) mannose units in ⁇ -D- (1 ⁇ 4 ) Link is established.
• the ratio of I: II is about 2: 1; the II units are not strictly alternating, contrary to initial assumptions, but arranged in pairs or triplets in the polygalactomannan molecule.
• Data on the molecular weight of the guaran vary with values of about 2.2 ⁇ 10 5 -2.2 ⁇ 10 6 g / mol, depending on the degree of purity of the polysaccharide - the high value was determined on a highly purified product - significant and correspond to about 1350 -13,500 sugar units / macromolecule. Guaran is insoluble in most organic solvents.
• the pectins which can likewise be used as film material, are high molecular weight glycosidic plant substances which are very widespread in fruits, roots and leaves.
• the pectins consist essentially of chains of 1,4- ⁇ -glycoside-linked galacturonic acid units, the acid groups of which are esterified to 20-80% with methanol, using between highly esterified (> 50%) and low-esterified pectins ( ⁇ 50%). different.
• 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 obtained by extraction with dilute acids mainly from the inner Proportions of citrus fruit peel, Obstresten or sugar beet pulp produced.
• 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 obtained by partial hydrolysis of starches can be obtained.
• the hydrolysis can by customary, for example acid or enzyme-catalyzed process can be performed.
• it is Hydrolysis products with average molecular weights in the range of 400 to 500,000 g / mol.
• DE dextrose equivalent
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents capable of producing at least one alcohol function of the Oxidize 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 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 at Room temperature in water to more than 2.5 wt .-% are soluble.
• the films may be made of any of the aforementioned polymers, it However, mixtures or multilayer coatings of the polymers can also be used be used.
• the polymers are described in more detail below.
• 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 technical 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 are soluble in cold and hot water as well as 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 context of the present invention 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 known as white-yellowish powder or granules with Degrees of polymerization in the range of about 100 to 2500 (molecular weights 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. Characterized are the Polyvinyl alcohols from the manufacturer by indicating the degree of polymerization of the Starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
• Polyvinyl alcohols are soluble in water and a few strongly depending on the degree of hydrolysis polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); from (chlorinated) hydrocarbons, esters, fats and oils they are not attacked. Polyvinyl alcohols are classified as toxicologically harmless and are biological at least partially degradable. The water solubility can be achieved by post-treatment Aldehydes (acetalization), by complexation with Ni or Cu salts or by Reduce 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 pass water vapor.
• gases such as oxygen, nitrogen, helium, Hydrogen, carbon dioxide, but pass water vapor.
• the film consists of a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mole%.
• Polyvinyl alcohols of a certain molecular weight range are preferably used in the film, with portions according to the invention being preferred in which the film consists of a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol -1 , preferably from 11,000 to 90,000 gmol -1 , more preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 .
• the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and more particularly between about 260 to about 1500.
• polyvinyl alcohols described above are widely available commercially, for example, under the trademark Mowiol® (Clariant).
• Mowiol® Cosmetically, for example, under the trademark Mowiol® (Clariant).
• Polyvinyl alcohols which are particularly suitable for the purposes of the invention 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 which can be used according to the invention is the acrylic resin obtainable under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters.
• Amphomer® is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters.
• amphopolymers are composed of unsaturated carboxylic acids (for example acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (for example acrylamidopropyltrimethylammonium chloride) and, if appropriate, further ionic or nonionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the state cited therein Technique are to be taken.
• unsaturated carboxylic acids for example acrylic and methacrylic acid
• cationically derivatized unsaturated carboxylic acids for example acrylamidopropyltrimethylammonium chloride
• further ionic or nonionic monomers as described, for example, in German Offenlegungsschrift 39 29 973 and the state cited therein Technique are to be taken.
• Terpolymers of acrylic acid, methyl acrylate and Methacrylamidopropyltrimoniumchlorid as they are commercially available under the name Merquat®2001 N, according to the invention are
• amphoteric polymers are, for example, the octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers available under the names Amphomer® and Amphomer® LV-71 (DELFT NATIONAL).
• Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copoly-merisate and their alkali and ammonium salts are preferred zwitterionic polymers.
• suitable Zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are disclosed in US Pat the name Amersette® (AMERCHOL) are commercially available.
• 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 polymerization in the heat in homogeneous phase characterized in that the Polyalkylene glycols in the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid, in the presence of free radical initiator.
• 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 low molecular weight aliphatic alcohols, 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.
• n can assume values between 1 (ethylene glycol) and several thousand.
• Technically common is the indication of the average relative molecular weight following the indication "PEG”, so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210.
• polyethylene glycols for example, under the trade name Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HUBS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone -Poulenc), Lutrol® E300 (BASF) and the corresponding trade name with higher numbers.
• the polyethylene glycol used has a molecular weight between 200 and more Million, preferably between 300 and 30,000.
• the nonionic monomers may be of very different types and among these the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, Allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.
• the nonionic monomers can equally be of very different types, among these, particularly preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, Maleic acid, acrylic acid and methacrylic acid are contained in the graft polyamides.
• crosslinking agents used are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho, meta- and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose having 2 to 5 allyl groups per molecule saccharin.
• 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 are suitable as film materials in the case of the anionic polymers / Polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins which are described below.
• Useful organic film materials are, for example, those in the form of their sodium salts but also usable in free form polycarboxylic acids.
• polymeric polycarboxylates for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 500 to 70,000 g / mol.
• the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
• Suitable polymers are, in particular, polyacrylates which preferably have a molecular mass of 2000 to 20,000 g / mol. Because of their superior solubility, this can be Group again the short-chain polyacrylates, the molecular weights of 2000 to 10,000 g / mol, and particularly preferably from 3000 to 5000 g / mol, have to be preferred.
• copolymeric polycarboxylates in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
• copolymeric polycarboxylates in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
• acrylic acid with maleic acid have proven to be suitable, containing 50 to 90% by weight.
• Your molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
• the polymers may also be allyl sulfonic acids, such as For example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
• allyl sulfonic acids such as For example, allyloxybenzenesulfonic acid and methallylsulfonic acid
• Particularly preferred as sheet materials are also biodegradable polymers more than two different monomer units, for example, those as monomers Salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or the monomers used as salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.
• copolymeric film materials are those which are preferably used as monomers Acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
• film materials are polymeric aminodicarboxylic acids, their To name salts or their precursors.
• polyacetals which by reaction of Dialdehydes with Polyolcarbonklaren, which 5 to 7 C-atoms and at least 3 Hydroxyl groups can be obtained.
• Preferred polyacetals are made Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Polyolcarboxylic 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 regardless of the pH of the agent (ie both the film and the remaining portion) one have cationic group. These are usually polymers that are quaternary Nitrogen atom, for example in the form of an ammonium group.
• Preferred cationic polymers are, for example
• 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.
• the Foil which forms part of the enclosure (A) or (B) has a thickness of 1 to 150 ⁇ m, preferably from 2 to 100 ⁇ m, more preferably from 5 to 75 ⁇ m and in particular from 10 to 50 microns, has.
• a washing, cleaning or washing detergent portion comprises two areas that contain different ingredients or different Release mechanisms and dissolution kinetics can be realized.
• the one in one Compartment containing active substance may be any aggregate state or any To accept the form of performance.
• Preferred washing, cleaning or rinsing agent portions contain the further active substance in at least one compartment in liquid, gel-like, pasty or solid form, see below.
• the enclosure closed by the film can be completely filled with washing, cleaning or rinse-active preparation to be filled. But it is also possible, the respective mold to fill only partially before closing, in this way a movement of the to allow filled particles or liquids within the mold. Especially at The filling with regularly shaped larger particles can be attractive optical Realize effects. Washing, cleaning or rinsing agent portions are preferred here, where the volume ratio of the through the film and the further enclosure enclosed space to the washing, cleaning or rinsing active contained in this room Preparation 1: 1 to 100: 1, preferably 1.1: 1 to 50: 1, particularly preferably 1.2: 1 to 25: 1 and in particular 1.3: 1 to 10: 1. In this terminology, a volume ratio of 1: 1, that the mold is completely filled.
• the / the hollow body (s) dimensional stability imparting, not pressed Material and the film material, the time at which the washing or Spülin preparation is released be predetermined.
• the film be virtually instantaneously soluble, so that the washing, cleaning or rinse-active preparation the same is metered into the washing or cleaning liquor at the beginning of the washing or cleaning cycle (or as soon as the film comes into contact with the washing, cleaning or rinsing liquor, i.e. in Cases in which the portion according to the invention has no film on its outer surface, after the falling apart of the portion in the partial hollow body (A) or (B)).
• the shape of the "shell” can be chosen freely, with certain geometric Shapes such as hemispheres for aesthetic reasons proved to be preferred to have. But also box shapes or coffin-like shaped trays are can be realized according to the invention.
• the "shell” may have an edge that only the Material thickness, but it can also have a web edge which can be used as a larger adhesive and sealing surface for the film is used.
• Invention is the "shell” by injection molding of water-soluble thermoplastics produced. In this process, possible partitions for later education Several compartments are already sprayed. Also the production of the "shell” after a melt casting process of suitable materials (see below) is preferred.
• the closing of the filled trays with foil is carried out by adherent connection with their Edges, such as by gluing, partial melting or by chemical Reaction can take place.
• the cover film can not only at the subdivided shells Rims of the outer shell circumference be tightly sealed, but also with the upper Edge of the inner partitions, so that a tight seal of the compartments also is guaranteed against each other.
• the covering film can also be designed so that differently prepared film areas over the different compartments come to rest, so the disintegration kinetics in aqueous solution and thus the Release of the individual preparations from the compartments.
• the enclosures (A) and (B) and possibly further enclosures and / or further Ingredients of the portions of the invention form in their entirety the Washing, cleaning or washing detergent portion according to the invention. It is preferred that the enclosures (A) and (B) and possibly further enclosures joined together in that the surface not formed by an optionally present part (d) is Washing, cleaning or detergent portion to at least 80%, preferably at least 90% and in particular exclusively from the hollow body (s) giving shape stability, not pressed material.
• the separately manufactured part-hollow body are joined together so that only a small part (in a particularly preferred case no part at all) of the surface of the Washing, cleaning or detergent portion according to the invention is formed by film. Rather, the "outer skin" of the washing, cleaning or Detergent portion for the most part (in particularly preferred cases: completely) off the non-pressed material which imparts dimensional stability to the hollow body.
• washing, cleaning or rinsing agent portions contain washing, cleaning or rinse-active preparations. These can be used in any form of packaging in be contained in the part-hollow bodies or compartments. Particularly preferred washing, Cleaning or rinsing agent portions are characterized in that at least one washing, cleaning or rinsing active preparation in the enclosures (A) or (B) in liquid Form is present.
• This liquid must be chosen so that they do not cover the materials of the envelope attacks.
• the coating is transparent, or at least is translucent to the aesthetic appeal of the liquid filling visible from the outside to be let.
• inventive washing, cleaning or detergent portions particularly preferred in which at least one enclosure is transparent or translucent is, wherein the wall thickness of the wholly or partly from a washing under, cleaning or Rinsing conditions disintegratable, the / the hollow body (s) dimensional stability imparting, not pressed material 100 to 5000 microns, preferably 200 to 3000 microns, more preferably 300 to 2000 microns and in particular 500 to 1500 microns.
• the washing, cleaning or rinsing agent portions according to the invention have at least two areas in which washing, cleaning or rinsing active preparation is located.
• these preparations are preferably liquid.
• the second Preparation may also be a liquid (optionally different composition) But it is also possible to use here solids of any packaging. Especially it is preferred in this case, the second cavity with a powdery to granular Preparation to fill.
• the washing, cleaning or rinsing agent portions according to the invention can preferably be used for the separation of incompatible active ingredients by their division into a plurality of separate regions.
• the table below gives a non-limiting overview of possible drugs and their division into different compartments. It was additionally specified in which packaging the corresponding preparation is contained in the partial hollow body.
• the partial hollow body which washing, cleaning or rinse-active preparation in the Contain enclosures (A) or (B) are combined with each other to the detergent according to the invention, Detergent or detergent portion combined.
• This is not according to the invention bound to connect only two partial hollow bodies. Rather, it is also possible other partial hollow body, which washing, cleaning or rinse-active preparation in further Enclosing enclosures (C) or (D), etc., append.
• partial hollow bodies are preferred, which have flat connecting surfaces.
• part-hollow body which washing, cleaning or Spüline preparation in the enclosures (A) and (B) included, with further washing,
• cleaning, cleaning or Spüline preparation in the enclosures (A) and (B) included, with further washing To combine cleaning or rinse-active preparations in solid, dimensionally stable form.
• the joining of partial hollow bodies with tablets is particularly advantageous proved.
• the portions according to the invention are in particular suitable, various washing, cleaning or rinse-active preparations from the To release enclosures (A) or (B) at different times.
• This controlled Release of certain preparations is used in the washing, cleaning or rinsing process of Achieving improved results.
• the release from the enclosures (A) or (B) can either be achieved at different times that the parts of the respective enclosure, which from the hollow body dimensional stability-conferring material exist, have different resolution or Ddsintegrations horren. This is For example, by selecting the material thickness possible.
• Washing, cleaning or rinsing agent portions are preferred in which the Envelopes (A) and (B) made of a foil-sealed injection-molded half-shell are formed, wherein the wall thickness of the half-shells of the enclosures (A) and (B) 100 bis 1000 microns, preferably 150 to 700 microns and in particular 250 to 500 microns and the Thickness of the film of the enclosure (A) 10 to 200 .mu.m, preferably 20 to 100 .mu.m and is in particular 40 to 80 ⁇ m and the thickness of the film of the enclosure (B) is 20 to 250 ⁇ m, preferably 40 to 200 microns and especially 60 to 150 microns.
• the wall thickness of the half-shells of the enclosures (A) and (B) 100 bis 1000 microns, preferably 150 to 700 microns and in particular 250 to 500 microns and the Thickness of the film of the enclosure (A) 10 to 200 .mu.m, preferably 20 to 100 .mu
• the injection molding process can be facilitated adding external plasticizers (e.g., glycerine) to the polymers or "internally" used plasticized polymers.
• external plasticizers e.g., glycerine
• either the film of the enclosure (B) thicker chosen and / or the film can be chemically modified to make it easier to dissolve.
• Washing, cleaning or rinsing agent portions according to the invention are preferred in which the Foil of the enclosures (A) and (B) consists of thermoplastic polymers, wherein the film the enclosure (B) in the application liquor is slower or more delayed than the film the enclosure (A).
• a polyvinyl alcohol film is suitable, which is in 20 ° C dissolves sufficiently quickly, while for the enclosure (B) in such a case a film with slower dissolution kinetics at 20 ° C is selected, for example, one with a better solubility above 40 ° C or 50 or 60 ° C.
• washing, cleaning or detergent portions are thereby characterized in that the compound of the closed enclosures (A) and (B) with a water-soluble hot melt adhesive takes place, so that the portion in the application liquor within of 60 s, preferably within 30 s, so disintegrated that the film of the closed Enclosures (A) or (B) gets contact to the application fleet.
• the filling of the partial hollow body (A) or (B) can be chosen completely arbitrary, wherein numerous examples are already described above. Particularly preferred are in the In the context of the present invention, washing, cleaning or rinsing agent portions in which the closed enclosure (A) a non-sensible base detergent composition, preferably a liquid detergent, while the closed enclosure (B) preferably a further benefit composition, especially one Bleaching compositions and / or an enzyme composition and / or a Perfume preparation and / or a discoloration, graying or Hardness inhibitor composition and / or a softener composition.
• a non-sensible base detergent composition preferably a liquid detergent
• the closed enclosure (B) preferably a further benefit composition, especially one Bleaching compositions and / or an enzyme composition and / or a Perfume preparation and / or a discoloration, graying or Hardness inhibitor composition and / or a softener composition.
• the ingredients for the above preparations are detailed above described.
• the above principle also for Adapt cleaning agents, for example for automatic dishwashing detergents, in which the enclosed enclosure (A) a builder-rich detergent composition contains, while the closed enclosure (B) is preferably a composition with further benefit, in particular a rinse aid composition and / or a Enzyme composition and / or a perfume preparation and / or a Complexing agent composition and / or a polymer composition.
• step (i) comprises an injection molding process, preferably at a pressure of between 100 and 5,000 bar, preferably between 500 and 2500 bar, more preferably between 750 and 1500 bar and in particular between 1000 and 1250 bar and preferably at temperatures between 100 and 250 ° C, preferably between 120 and 200 ° C and in particular between 140 and 180 ° C, is performed.
• the individual hollow body are preferably not completely filled.
• the Hollow bodies or compartments in step (ii) to 20 to 100%, preferably to 30 to 95%, particularly preferably from 40 to 90% and in particular from 50 to 85% of its volume washing, cleaning or rinsing active preparations are filled.
• the sealing of the hollow body by sealing with a water-soluble film takes place, wherein the film 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.
• inventive Preferred method in which the compound of the enclosures (A) and (B) and optionally further enclosures and / or further washing, cleaning or rinsing active Preparations in solid, dimensionally stable form for the washing, cleaning or rinsing agent portion in Step (iv) by cold sealing, bonding with water-soluble hot melt adhesives, bonding done with adhesive solutions or mechanical connection.
• the partial hollow bodies with adhesion agents.
• adhesion agents can be used substances that the surfaces, to which they are applied, impart sufficient adhesion ("stickiness") to it the partial hollow body permanently adhere to each other.
• adhesion agents can be used substances that the surfaces, to which they are applied, impart sufficient adhesion ("stickiness") to it the partial hollow body permanently adhere to each other.
• step iv) as a primer melting one or several substances are used with a melting range of 40 ° C to 75 ° C, are therefore preferred.
• the Schmelz supportivearia Solidification behavior on the other hand, however, the material properties in the solidified area at ambient temperature. Since the adhered part-hollow body When transporting or storage should hold together permanently, the bond must a high stability against, for example, occurring during packaging or transport shock loads exhibit.
• the bonding agents should therefore either at least partially elastic or have at least plastic properties in order to impact on a occurring elastic or plastic deformation to respond and not to break.
• the adhesion agents should have a melting range (solidification range) in such a temperature range, in which the partial hollow body or the preparations contained in them not too high thermal Be exposed to stress. On the other hand, however, the melting range must be sufficient be high to still provide effective adhesion at least slightly elevated temperature.
• the coating substances preferably have a melting point above 30 ° C.
• the Width of the melting range of the primer also has an immediate effect on the Procedure:
• the provided with primer part-hollow body must in the following Process step are brought into contact with the / the other part-hollow body (s) - In the meantime, the adhesion must not be lost. After the sticking together should the Adhesion should be reduced as quickly as possible to avoid unnecessary loss of time or Caking and stagnation in subsequent process steps or handling and Avoid packaging. In the case of the use of melts, the reduction of the Adherence by cooling (for example, blowing cold air) are supported.
• adhesion promoters do not have a sharply defined melting point show how it usually occurs in pure, crystalline substances, but one under Circumstances have several degrees Celsius melting range.
• the adhesion promoters preferably have a melting range of between about 45 ° C and about 75 ° C is located. This means in the present case that the melting range within the specified temperature interval occurs and does not denote the width of the melting range.
• the width of the melting region is at least 1 ° C, preferably about 2 to about 3 ° C.
• waxes are usually met by so-called waxes.
• “Waxing” is understood to mean a number of natural or artificial substances found in the Melt above 40 ° C without decomposition and just above the melting point are relatively low-viscosity and non-stringy. They have a strong temperature-dependent Consistency and solubility.
• the waxes are divided into three groups, the natural waxes, chemical modified waxes and the synthetic waxes.
• Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, japan wax, esparto wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, Shellac wax, spermaceti, lanolin (woolwax), or raffia fat, mineral waxes such as ceresin or Ozokerite (ground wax), or petrochemical waxes such as petrolatum, paraffin waxes or Microcrystalline waxes.
• vegetable waxes such as candelilla wax, Carnauba wax, japan wax, esparto wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax
• animal waxes such as beeswax, Shellac wax, spermaceti, lanolin (woolwa
• the chemically modified waxes include, for example, hard waxes such as Montanester waxes, Sassol waxes or hydrogenated jojoba waxes.
• synthetic waxes are usually polyalkylene waxes or Polyalkylene glycol waxes understood. It is also possible to use compounds as adhesion promoters other substance classes meeting the stated softening requirement. Suitable synthetic compounds are, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG) available, proved. Also suitable are synthetically produced waxes from lower Carboxylic acids and fatty alcohols, for example dimyristyl tartrate, under the name Cosmacol® ETLP (Condea) is available. Conversely, synthetic or semi-synthetic ones are also used Esters of lower alcohols can be used with fatty acids from natural sources.
• Tegin® 90 Goldschmidt
• a glycerol monostearate palmitate a glycerol monostearate palmitate.
• shellac For example, shellac KPS Dreiring-SP (Kalkhoff GmbH) according to the invention as a primer used.
• wax alcohols are higher molecular weight, water-insoluble Fatty alcohols with usually about 22 to 40 carbon atoms.
• the waxy alcohols come for example in the form of wax esters of higher molecular weight fatty acids (wax acids) as Main ingredient of many natural waxes.
• wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
• the adhesion promoter in step iv) may optionally also contain wool wax alcohols, including triterpenoid and Steroidal alcohols, such as lanolin, understands, for example, under the Trade name Argowax® (Pamentier & Co) is available. Also at least proportionately as Component of the adhesion promoter can be used in the context of the present invention Fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.
• wool wax alcohols including triterpenoid and Steroidal alcohols, such as lanolin, understands, for example, under the Trade name Argowax® (Pamentier & Co) is available.
• Component of the adhesion promoter can be used in the context of the present invention Fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.
• the adhesion promoters should have the lowest possible water solubility, even in water with increased Temperature, exhibit a temperature-independent release of the enveloped To avoid active substances as much as possible.
• the adhesion promoters to be applied in process step iv) can be pure substances or Be substance mixtures. In the latter case, the melt may vary in amounts Contain adhesion promoters and excipients.
• the principle described above is for the delayed release of the in step iv) adhered part-hollow body from each other at a given time, for example in the cleaning cycle of a dishwasher and can be used particularly advantageously when rinsing in the main rinse at a lower temperature (for example, 55 ° C), so that the Active substance from the adhesive layer only in the rinse cycle at higher temperatures (about 70 ° C) is released.
• a lower temperature for example, 55 ° C
• the said principle can also be reversed to the effect that the partial hollow body is not Delayed, but accelerated to be resolved from each other.
• This can be in the invention Achieve process in a simple manner in that as a primer in step iv) not Lcaptivateverzögerer, but release accelerators are used, so that the partial hollow body not slower, but faster.
• Adhesion agent readily soluble in water.
• the water solubility of the primer can be determined by certain Additives can be significantly increased, for example, by incorporating easily soluble Salts or effervescent systems.
• the release acceleration can also be achieved by certain geometric factors or get supported. Detailed comments can be found below.
• Suitable adhesion promoters for the accelerated release are, in particular, the above mentioned synthetic waxes from the group of polyethylene glycols and polypropylene glycols.
• PEG and PPG are of course also Other substances can be used provided they have a sufficiently high water solubility and a Melting point above 30 ° C.
• step iv) of the process according to the invention other Substances are applied as adhesion promoters.
• Suitable for this purpose for example concentrated salt solutions which, after application of the active ingredients by crystallization or Evaporation / evaporation can be converted into an adhesion-promoting salt crust. It can Of course, supersaturated solutions are used or solutions of salts in Solvent mixtures.
• adhesion promoters in step iv) are solutions or suspensions of water-soluble or -dispersible polymers, preferably polycarboxylates.
• water-soluble or -dispersible polymers preferably polycarboxylates.
• adhesion promoters are solutions of water-soluble substances the group (acetalated) polyvinyl alcohol, polyvinylpyrrolidone, gelatin and mixtures thereof. These substances have already been described above as Folienmatertialien.
• adhesion promoter to preferably the edge region of the closed part-hollow body can be done in different ways. It is possible, for example, the sealed part-hollow body in the dipping process on one side with adhesive to wet and then place in the cavity. This technique is technologically easy to implement, But there is a risk that the adhesive wets the entire film and thus possibly a provided controlled by the film controlled release difficult.
• the amount of Adhesive can in this variant by variation of the rheological characteristics of the Adhesion promoters are controlled.
• adhesion promoter apply consists of the surfaces to be wetted (usually the edges of the partial hollow body) to pass adhesive metering systems. This succeeds by Adhesive agent metering nozzles, impregnated with adhesion promoters brushes or nonwovens or by Rollers. The latter method design is particularly easy to implement.
• the bonding agent when joining two partial hollow bodies with their flat surfaces do not apply to the bonding surface, but only Apply "primer points" at the edge or at the corners. These are the Water access when used immediately exposed, so that the two partial hollow body separate faster. Become in this way two partial hollow body with square Contact surface connected together, the bonding agent does not have on all four edges be applied. It can rather for even faster separation of the compound contribute to apply only at the four corners adhesion points. For even faster Separation can be dispensed with individual adhesion promoter points, so that for example only two diagonally opposite contact corners are provided with adhesion promoter.
• the process for the preparation of the invention in one or more dimensionally stable Hollow body (s) containing at least one compartment detergent, cleaning agent or Detergent portion is carried out in ways known per se in that one in a first Step produces one or more dimensionally stable (s) hollow body.
• This can be, for example done by deep drawing, pouring (for example, from the confectionery industry known or modified methods), injection molding, sintering or casting (for example) inorganic mixtures.
• In the preparation of the dimensionally stable hollow body according to the invention are under pressing proceeding process for the preparation of the / the hollow body (s) except.
• thermoforming of polymers by thermoforming are known from the prior art Technique known as such.
• a plate or sheet of a polymer is by means of a Stamp and die existing thermoforming press at elevated temperature to the desired blank formed from a dimensionally stable polymer.
• Disadvantage of this Procedure for the present case of producing a hollow body is the fact that during removal of the blank, a vacuum in the interior of the hollow body is formed by Blowing a gas must be lifted. This will be the otherwise technical simple deep drawing press consuming.
• thermoforming dimensionally stable hollow body with Compartmentalizing facilities are not produced in one step.
• blanks for dimensionally stable hollow body also are prepared by pouring the polymer into appropriately prepared molds.
• the Process variant of the casting not only allows the use of fusible polymers as Wall materials, but also other fusible substances.
• the production of the outer molds can process economy by so-called Casting techniques are carried out, and it is precisely this technology maximum flexibility in terms of processing to the mold and in terms of the material systems used allows. All casting techniques common is the transformation of a flowable mixture, the is solidified under suitable conditions.
• the production of the open hollow mold comprises informing a deformable, preferably flowable mixture or such a substance and the solidification to a dimensionally stable mold.
• Solidify indicates in the context of the present invention any curing mechanism made of a formable, preferably flowable Mixture or such a substance or such a mass at room temperature provides solid body without pressing or Kompaktier modifier are necessary.
• Freezing in the The meaning of the present invention is therefore, for example, the curing of melts of at room temperature solid substances by cooling.
• Solidification processes in the sense of present application are also the curing of formable masses by time delayed water binding, by evaporation of solvents, by chemical Reaction, crystallization, etc., and the reactive curing of flowable powder mixtures stable hollow bodies. As stated above, tabletting, pelleting, Briquetting operations, etc., so pressing method, not in this category.
• methods according to the invention are preferred in which the open Hollow form due to delayed water binding, by cooling below the melting point, by evaporation of solvents, by crystallization, by chemical reaction (s), especially polymerization, by changing the rheological properties e.g. by altered shear, by sintering or by radiation hardening, in particular by UV, Alpha beta or gamma rays.
• the open Molded and produced e.g. is stored until filling.
• the Steps i) and ii) of the method according to the invention are also carried out simultaneously, by filling a mold "in situ", ie directly during its production.
• a mold "in situ" ie directly during its production.
• This is in particular in the manufacture of molds of self-solidifying masses (e.g. Cooling below the melting point or by time-delayed water binding) simple feasible by passing through a two-fluid nozzle, which is built like a Daniell'scher Hahn, inside the filling and outside the material for the mold are metered into a mold.
• This "one-shot" process described in detail below, allows the economic Production of large quantities of moldings.
• steps i) and ii) are carried out simultaneously.
• step step by step so that, for example, hollow bodies are produced and subsequently filled Technology includes the possibility of the formulation of the filled in step ii) washing or To change detergent without having to adapt the process. Especially at Detergents or cleaning agents which are not or not readily dosed via two-fluid nozzles, We recommend this procedure. Also methods in which steps i) and ii) Accordingly, are preferred embodiments of the present invention.
• the shell production comprises informing one formable mixture, which is during or after informing to open Mold solidifies ("solidifies").
• the formable mixture which also consists of a single Substance may consist, in the form of a powder, a liquid, a gel, a Melt, etc., depending on the composition of one or more of the above mentioned solidification mechanisms come to fruition.
• melts From procedural economic Sichet are particularly preferred melts, as they are by easy cooling solidify below the melting point and generally easy to process are. Therefore erfindungsffleße method are particularly preferred in which the production the open mold in step i) takes place by solidification of a melt, wherein the melt is made of a material whose melting point is in the range of 40 to 1000 ° C, preferably from 42.5 to 500 ° C, more preferably from 45 to 200 ° C and especially from 50 to 160 ° C, lies.
• Substances which are particularly suitable for carrying out this variant of the process according to the invention are, for example, polyethylene glycols H- (O-CH 2 -CH 2 ) n -OH where the degree of polymerization n can assume values between about 30 and several thousand.
• polyethylene glycols there are various nomenclatures that can lead to confusion.
• 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.
• PEG polyethylene glycol having a relative molecular weight of about 190 to about 210.
• another nomenclature is used in which the abbreviation PEG is hyphenated and directly followed by the hyphen followed by a number corresponding to the number n in the above formula.
• polyethylene glycols for example, under the trade name Carbowax® PEG (Union Carbide), Emkapol® (ICI Americas), Lipoxol® (HÜLS America), Polyglycol® E (Dow Chemical), Alkapol® PEG (Rhone-Poulenc), Lutrol® E (BASF).
• Carbowax® PEG Union Carbide
• Emkapol® ICI Americas
• Lipoxol® HÜLS America
• Polyglycol® E Denst Chemical
• Alkapol® PEG Rohone-Poulenc
• Lutrol® E BASF
• the molar masses of preferred polyethylene glycols are in the range between 1500 and 35,000 daltons, preferably between 2000 and 30,000 Da, more preferably between 3,000 and 25,000 Da and in particular between 4,000 and 20,000 Da.
• PPG polypropylene glycols
• n can also assume values between about 30 and several thousand.
• the molecular weights preferably to be used PPG applies analogous to what said for PEG.
• the polyethylene or polypropylene glycols in mixture with other substances are used as shell material.
• Particularly suitable additives to the polyalkylene glycols are polymers or polymer mixtures, wherein the polymer or at least 50% by weight of the polymer mixture is selected from graft copolymers, which are obtainable by grafting (a) polyalkylene oxides with (b) vinyl acetate. These polymers will be described in more detail below.
• Graft copolymers are obtainable by grafting a polyalkylene oxide with vinyl acetate, wherein the acetate groups of the vinyl acetate may be partially saponified.
• polyalkylene oxides in particular polymers with ethylene oxide, propylene oxide and butylene oxide units with polyethylene oxide being preferred.
• the preparation of the graft copolymers is achieved, for example, by dissolving the Polyalkylene oxides in vinyl acetate and continuous or discontinuous polymerization after Addition of a polymerization initiator, or by semi-continuous polymerization in which a part of the polymerization mixture of polyalkylene oxide, vinyl acetate and Polymerization initiator is heated to polymerization temperature, after which the rest of the polymerizing mixture is added.
• the graft copolymers can also be characterized be obtained that presents polyalkylene oxide er55mt on the polymerization temperature and vinyl acetate and polymerization initiator either at once, by batch or preferably continuously adds.
• step i) melts of polyalkylene glycols which comprise at least one polymer obtainable by grafting (a) polyalkylene oxides having a molecular weight of 1500 to 70,000 gmol -1 with (b) vinyl acetate in a weight ratio of (a) :( b) from 100: 1 to 1: 5, wherein the acetate groups are optionally saponified up to 15%.
• the molecular weight of the polyalkylene oxides contained in the graft copolymers is 2,000 to 50,000 gmol -1 , preferably 2,500 to 40,000 gmol -1 , particularly preferably 3,000 to 20,000 gmol -1 and in particular 4,000 to 10,000 gmol -1 .
• the proportion of individual monomers of the melt added graft copolymers vary.
• Polymers are preferred in which the vinyl acetate content of 1 to 60 wt .-%, preferably 2 to 50 Wt .-%, particularly preferably 3 to 40 wt .-% and in particular 5 to 25 wt .-%, respectively based on the graft copolymer is.
• a graft copolymer which is particularly preferred in the context of the present invention is based on a polyethylene oxide having an average molar mass of 6000 gmol -1 (corresponding to 136 ethylene oxide units) which contains about 3 parts by weight of vinyl acetate per part by weight of polyethylene oxide.
• This polymer which has an average molecular weight of about 24,000 gmol -1 , is commercially sold by BASF under the name Sokalan® HP22.
• Another class of substances which is outstandingly suitable as a material for the open mold are aliphatic and aromatic dicarboxylic acids which can be melted individually, in mixture with one another or also mixed with other substances and processed according to the invention.
• Particularly preferred dicarboxylic acids are summarized in the table below: Common name IUPAC name Melting point [° C] oxalic acid ethanedioic 101.5 malonic propanedioic 135 Succinic acid Butandiklare 185 glutaric pentanedioic 97 adipic acid hexanedioic 153 pimelic heptanedioic 105 azelaic acid nonanedioic 106 sebacic decanedioic 134.5 dodecanedioic 128 maleic (Z) -Butendiklare 130-139 fumaric acid (E) -Butendiklare 287 sorbic acid 2,4-Hexadiendiklare 134 phthalic
• carboxylic acids and their salts are also suitable as materials for the production of the open mold.
• Citric acid and trisodium citrate as well as salicylic acid and glycolic acid have proven to be suitable for this class of substances.
• fatty acids preferably having more than 10 carbon atoms, and their salts as material for the open mold.
• hexanoic acid caproic acid
• heptanoic acid capnonic 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 the unsaturated secties 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-oct
• Such mixtures are for example coconut oil (about 6 wt .-% C 8 , 6 wt .-% C 10 , 48 wt .-% C 12 , 18 wt .-% C 14 , 10 wt .-% C 16 , 2 wt % C 18 , 8% by weight C 18 ' , 1% by weight C 18 " ), palm kernel oil fatty acid (about 4% by weight C 8 , 5% by weight C 10 , 50% by weight C 12 , 15 wt .-% C 14 , 7 wt .-% C 16 , 2 wt .-% C 18 , 15 wt .-% C 18 ' , 1 wt .-% C 18 " ), tallow fatty acid (ca.
• % C 16 ' 1% by weight C 17 , 2% by weight C 18 , 70% by weight C 18' , 10% by weight C 18 " , 0.5% by weight C 18 ''' ), technical palmitic / stearic acid (about 1 wt .-% C 12 , 2 wt .-% C 14 , 45 wt .-% C 16 , 2 wt .-% C 17 , 47 wt .-% C 18 , 1 wt .-% C 18 ' ) and soybean oil fatty acid (about 2 wt .-% C 14 , 15 Wt% C 16 , 5 wt% C 18 , 25 wt% C 18 ' , 45 wt% C 18 " , 7 wt% C 18''' ),
• the abovementioned carboxylic acids are technically largely derived from native fats and Oils obtained by hydrolysis. While already in the past century Alkaline saponification carried out directly to the alkali salts (soaps) will become today used industrially for cleavage only water containing the fats in glycerol and the free ones Fatty acids splits. For example, industrially applied methods are cleavage in the Autoclave or continuous high-pressure cleavage. The Alkalimetallslaze the The above-mentioned carboxylic acids or carboxylic acid mixtures can be optionally in mixture with other materials - use for the production of the open mold.
• suitable materials which can be processed via the state of the melt to open molds are hydrogencarbonates, in particular the alkali metal hydrogencarbonates, especially sodium and potassium bicarbonate, and the hydrogen sulfates, in particular alkali metal hydrogen sulfates, especially potassium hydrogen sulfate and / or sodium hydrogen sulfate.
• the eutectic mixture of potassium bisulfate and sodium bisulfate, which consists of 60% by weight of NaHSO 4 and 40% by weight of KHSO 4 has also proved to be particularly suitable.
• Suitable materials for the open mold, which in step i) of process according to the invention can be processed over the state of the melt are Sugar.
• sugar in the context of the present invention single and Multiple sugars, ie monosaccharides and oligosaccharides, in which 2 to 6 monosaccharides acetal-like interconnected. "Sugars” are within the scope of the present invention ie monosaccharides, disaccharides, trisaccharides, tetra-, penta- and hexasaccharides.
• Monosaccharides are linear polyhydroxy aldehydes (aldoses) or polyhydroxy ketones (Ketoses). They usually have a chain length of five (pentoses) or six (Hexoses) carbon atoms. Monosaccharides with more (heptoses, octoses etc.) or fewer (tetrosen) C atoms are relatively rare. Some monosaccharides have one large number of asymmetric C atoms. For a hexose with four asymmetric C atoms this results in a number of 24 stereoisomers. The orientation of the OH group on Most-numbered asymmetric C atom in the Fischer projection divides the monosaccharides in D- and L-configured rows.
• monosaccharides which can be used as sugar are For example, the tetroses D (-) - erythrose and D (-) - threose and D (-) - erythrulose, the Pentoses D (-) - ribose, D (-) - ribulose, D (-) - arabinose, D (+) - xylose, D (-) - xylulose and D (-) - lyxose and the hexoses D (+) - allose, D (+) - altrose, D (+) - glucose, D (+) - mannose, D (-) - gulose, D (-) - idose, D (+) - galactose, D (+) - talose, D (+) - psicose, D (-) - fructose, D (+) - sorbose and D (-)
• D-glucose D-galactose
• D-mannose D-fructose
• L-arabinose D-xylose
• D-ribose 2-deoxy-D-ribose
• Disaccharides are composed of two simple linked by glycosidic linkage Monosaccharide molecules (D-glucose, D-fructose u.a.) constructed. Is the glycosidic Binding between the acetalic carbon atoms (1 for aldoses and 2 for ketoses) Both monosaccharides, so it is fixed in both the ring shape; the sugars do not show any Mutarotation, do not react with ketone reagents and no longer have a reducing effect (Fehling negative: trehalose or sucrose type).
• sucrose cane sugar, sucrose
• trehalose lactose
• lactulose lactose
• maltose malt sugar
• cellobiose degradation product of cellulose
• Gentobiose Melibiose, Turanose and others.
• Trisaccharides are carbohydrates that are linked together from 3 glycosidically Monosaccharides are constructed and for which one occasionally also the incorrect designation Triosen encounters. Trisaccharides are relatively rare in nature, examples are Gentianose, Kestose, maltotriose, melecitose, raffinose, and as an example of aminosugar containing Trisaccharides streptomycin and validamycin.
• Tetrasaccharides are oligosaccharides with 4 monosaccharide units. Examples of these Compound class are stachyose, lychnose (galactose-glucose-fructose-galactose) and Secalose (from 4-fructose units).
• sugar from the saccharides Group glucose, fructose, saccharose, cellubiose, maltose, lactose, lactulose, ribose and their mixtures used.
• urea the diamide of carbonic acid, which is sometimes referred to as carbamide and can be described by the formula H 2 N-CO-NH 2 .
• Urea forms colorless, odorless crystals of density 1.335, which melt at 133 ° C.
• Urea is soluble in water, methanol, ethanol and glycerol with neutral reaction.
• urea is highly suitable as a material for the mold.
• polyethylene and polypropylene glycols, fragrances, dyes, etc. can be melted together with the urea in high amounts and processed into an open mold without impairing the mechanical and haptic properties of the mold.
• additives in the melts When processing the melts to the open mold, it may be advantageous Add additives in the melts.
• disintegration aids in addition to the aesthetic
• reinforcing fibers or liquid binders have proven particularly suitable.
• Disintegration aids are described in detail above; as reinforcing fibers come for example natural or synthetic polymer fibers are used.
• microcrystalline Cellulose is suitable as an additive.
• melt in Step i) one or more substances from the groups of the carboxylic acids, Carboxylic anhydrides, dicarboxylic acids, dicarboxylic acid anhydrides, bicarbonates, Hydrogen sulfates, polyethylene glycols, polypropylene glycols, sodium acetate trihydrate and / or Urea in amounts of at least 40 wt .-%, preferably at least 60 wt .-% and in particular at least 80 wt .-%, each based on the melt contains.
• the solidification of the formable mixtures may be due to different mechanisms the time-delayed water binding, the evaporation of solvents, crystallization, chemical reaction (s), in particular polymerization, change the rheological properties e.g. by altered shearing of the mass (s), as well as the Radiation curing by UV, alpha-beta or gamma rays as the most important Hardening mechanisms in addition to the already mentioned cooling below the melting point are called.
• the preferred method is the Solidification due to delayed water binding.
• the time-delayed water binding can in hereseits in different ways will be realized.
• a shaping processing with low pressure is then no longer possible, and there are handling stable Hollow body in front.
• the staggered water binding can for example also take place in that one salts containing hydrated water which, when the temperature increases, are in their own water of crystallization solve, work into the masses. If the temperature drops later, the water of crystallization will be restored bound, resulting in a loss of molding processability with simple means and leads to a solidification of the masses.
• the swelling of natural or synthetic polymers as a time-delayed water binding mechanism can also be used within the scope of the process according to the invention.
• mixtures of unswollen polymer and suitable swelling agent for example water, diols, glycerol, etc.
• suitable swelling agent for example water, diols, glycerol, etc.
• the most important mechanism of curing by time-delayed water binding is the use of a combination of water and anhydrous or low-raw materials that hydrate slowly.
• preferred ingredients of the molds are, for example, phosphates, carbonates, silicates and zeolites.
• the starting materials for the mold are from 10 to 95% by weight, preferably from 15 to 90% by weight, particularly preferably from 20 to 85% by weight and in particular from 25 to 80% by weight anhydrous Containing substances which by hydration in a hydrate form with a melting point below 120 ° C, preferably below 100 ° C and especially below 80 ° C pass.
• the deformable properties can by adding plasticizing aids such Polyethylene glycols, polypropylene glycols, waxes, paraffins, nonionic surfactants, etc. to be influenced. Further information on the mentioned substance classes can be found further above.
• Raw materials preferably to be used in the production of the open molds come from the group of phosphates, with alkali metal phosphates being particularly preferred. These Substances are used in the production in anhydrous or low-form and the desired plastic or deformable properties of the masses with water and set optional plasticizing aids. After the shaping processing then takes place the curing of the molded molds by hydration of the phosphates.
• the mixtures used to prepare the molds contain Phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate), in amounts of 20 to 80 wt .-%, preferably from 25 to 75% by weight, in particular from 30 to 70% by weight, in each case based on their weight.
• Phosphate preferably alkali metal phosphate (s), particularly preferably pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate)
• the amount should be added water whose water binding capacity does not exceed the content of To keep hollow body low on free water.
• the Weight ratio of phosphate (s) to water in the mixtures for preparing the Hollow forms less than 1: 0.3, preferably less than 1: 0.25 and in particular less than 1: 0.2.
• ingredients that may be included instead of or in addition to phosphates are carbonates and / or bicarbonates, the alkali metal salts and below especially the potassium and / or sodium salts are preferred.
• the weight ratio of carbonate (s) and / or Hydrogen carbonate (s) to water in the mixtures for producing the molds smaller than 1: 0.2, preferably less than 1: 0.15 and in particular less than 1: 0.1.
• silicates which, instead of or in addition to the said phosphates and / or Carbonates / bicarbonates may be included are silicates, wherein the Alkali metal silicates and especially the amorphous and / or crystalline potassium and / or sodium disilicates are preferred. Again, with respect to the water content of Masses the above.
• the weight ratio of water to certain ingredients in According to the invention preferably given to hollow bodies to be processed mixtures.
• To the processing of this water is preferably bound in the form of water of hydration, so that the hollow molds produced in step i) preferably have a significantly lower content have free water.
• Preferred molds are substantially anhydrous, i. in a state where the content of liquid, i. not in the form of water of hydration and / or water of constitution present water below 2 wt .-%, preferably below 1 Wt .-% and in particular even less than 0.5 wt .-%, each based on the moldings, is.
• water can essentially only be used chemically and / or physically bonded form or as part of the present as solid raw materials or Compounds, but not as a liquid, solution or dispersion in the end products of Step i) are present.
• the hollow bodies at the end of Manufacturing process total of a water content of not more than 15 wt .-%, so this water is not in liquid free form, but chemically and / or is physically bound, and it is particularly preferred that the content of not at Zeolite and / or water bound to silicates in the solid premix not more than 10 Wt .-% and in particular not more than 7 wt .-% is.
• particularly preferred molds not only possess a very small proportion of free water, but are preferably even in the Able to bind more free water.
• the water content is the molds 50 to 100% of the calculated water binding capacity.
• the water binding capacity is the ability of a substance (here: the mold) to absorb water in chemically stable form and ultimately indicates how much water in the form of stable hydrates of a substance or a shaped body can be bound.
• the value WBV can be used for all hydrate-forming substances used in the invention Hollow molds to be used for processing mixtures are calculated. About the percentage of these substances then gives the total water binding capacity the recipe. In preferred molds, the water content is then between 50 and 100% of this calculated value.
• the water content of the molds and the ratio of water to certain Raw materials can also provide information about the absolute water content of the invention to processing mixtures are made.
• particularly preferred methods has / show the serving for the production of molds mixtures during processing a water content of 2.5 to 30 wt .-%, preferably from 5 to 25 wt .-% and in particular from 7.5 to 20 wt .-%, each based on the mass on.
• process variants according to the invention are preferred in which the production of the open mold in step i) takes place by time-delayed water binding, the solidifying composition, based on its weight, 10 to 95 wt .-%, preferably 15 to 90 wt .-%, particularly preferably Contains 20 to 85 wt .-% and in particular 25 to 80 wt .-% of anhydrous substances which cure by hydration.
• solutions or dispersions of the desired ingredients can be prepared in one or more suitable, readily volatile solvent (s) which, after the shaping processing step, release and harden the solvent (s).
• suitable solvents are, for example, lower alkanols, aldehydes, ethers, esters, etc., the selection of which is carried out depending on the further composition of the mixtures to be processed.
• Particularly suitable solvents for such processes are 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 and the acetic acid esters of the abovementioned alcohols, in particular ethyl acetate.
• the evaporation of the solvents mentioned can be due to the shaping subsequent heating, or be accelerated by air movement. Also Combinations of the measures mentioned are suitable for this purpose, for example blowing the hollow body with hot or hot air.
• step i) methods according to the invention are preferred in which the production of the open Hollow mold in step i) is carried out by evaporation of solvents, wherein the solidifying Weight based on their weight 1 to 50 wt .-%, preferably 2 to 40 wt .-% and in particular 5 to 30 wt .-% vaporizable solvent.
• the method may be based on crystallization.
• the crystallization as the solidification underlying mechanism can be used by, for example, melting crystalline substances as the basis of one or more serving formable processed mixtures. After processing, such systems go in a higher order state, in turn, to cure the entire formed hollow body leads.
• the crystallization can also be characterized by crystallization supersaturated solution.
• Supersaturation is within the scope of the present invention the term for a metastable state in which in a closed system there is more of a substance than is needed to saturate.
• An example by Supercooling supersaturated solution thus contains more solute than in the should contain thermal equilibrium. The excess of dissolved substance can pass through Inoculate with germs or dust particles or by shaking the system for crystallization to be brought.
• the term "supersaturated" always at a temperature of 20 ° C.
• the present invention means the maximum amount of a Substance that can absorb the solvent at a certain temperature, i. the Proportion of the solute in a solution saturated at the temperature in question. contains a solution more solute than they do at a given temperature thermodynamic equilibrium (e.g., in solvent evaporation), so they are called oversaturated. By seeding with germs can cause the excess as BodenMech the now only saturated solution precipitates.
• One in relation to a substance saturated solution is able to dissolve other substances (for example, one can in one saturated sodium chloride solution still dissolve sugar).
• the state of supersaturation can be, as described above, by cooling a Solution as long as the solute in the solvent at higher temperatures is more soluble.
• Other ways to get supersaturated solutions are For example, combining two solutions, their ingredients to another substance which does not precipitate immediately (prevented or delayed precipitation reactions). Of the latter mechanism is as basis for the formation of according to the invention especially suitable for processing mixtures.
• the state of supersaturation in the context of present invention on the saturated solution at 20 ° C.
• solutions which have a temperature above 20 ° C
• the state of supersaturation can easily be achieved.
• Process according to the invention in which the solidifying by crystallization Mixture when processing a temperature between 35 and 120 ° C, preferably between 40 and 110 ° C, more preferably between 45 and 90 ° C and in particular between 50 and 80 ° C, are preferred in the context of the present invention. Since the hollow body produced usually stored neither at elevated temperatures nor be applied later at these elevated temperatures, the cooling of the leads Mixture for precipitating the content of solute from the supersaturated solution passing over the saturation limit at 20 ° C was contained in the solution.
• the supersaturated solution can be divided on cooling into a saturated solution and a soil body. It is but also possible that through recrystallization and hydration phenomena the supersaturated Solution solidifies on cooling to a solid. This is the case, for example certain hydrate-containing salts dissolve on heating in their water of crystallization.
• supersaturated solutions which are formed by mechanical action or Seed addition to a solid - the salt containing water as at room temperature thermodynamically stable state - solidify.
• this phenomenon is known of sodium thiosulfate pentahydrate and sodium acetate trihydrate, in particular the latter hydrazine-containing salt in the form of the supersaturated solution in the inventive method is advantageously used.
• the previously supersaturated solution after the Solidified to a solid by heating to the temperature at which the supersaturated solution was formed can not be reconverted into a supersaturated solution. This is for example, in the case of the phosphonates mentioned the case.
• the supersaturated solution used as the basis of the solidifying mixture can - like mentioned above - obtained in several ways and then after optional admixture further ingredients are processed according to the invention.
• Another way is to use a non-supersaturated solution with a gas or a solution further liquid or solution, so that the solute in the solution to a poorly soluble substance reacts or dissolves in the mixture of solvents worse.
• Combining two solutions, each containing two substances, which together a less soluble substance is also a method of production supersaturated solutions as long as the less soluble material does not precipitate instantaneously.
• also preferred methods are characterized characterized in that serving as the basis of the solidifying mixture supersaturated Solution is made by combining two or more solutions. Examples of such Ways to produce supersaturated solutions are discussed below.
• Preferred processes according to the invention are characterized in that the supersaturated aqueous solution by combining an aqueous solution of one or more acidic Ingredients of detergents and cleaners, preferably from the group of Surfactant acids, the builder acids and the complexing acids, and an aqueous Alkali solution, preferably an aqueous alkali metal hydroxide solution, in particular an aqueous Sodium hydroxide solution is obtained.
• the phosphonates take in the context of the present invention a outstanding position.
• the supersaturated aqueous solution by combining an aqueous Phosphonkland with Concentrations above 45 wt .-%, preferably above 50 wt .-% and in particular Above 55 wt .-%, each based on the phosphonic acid solution and an aqueous Sodium hydroxide solution with concentrations above 35 wt .-%, preferably above 40 Wt .-% and in particular above 45 wt .-%, each based on the Sodium hydroxide solution.
• co-builders such as co-builders, soil repellents or soil-release polymers used should be.
• co-builders may be selected, for example, from the groups of Polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, Dextrins etc. come. These classes of substances have been described above.
• Another mechanism according to which the hardening of the solidifying mixture (s) in the Frame of the method according to the invention can be done by changing the rheological properties taking place curing.
• the sintering provides the provision of an in the shape of the later hollow body preformed particle heap, which under the influence external conditions (temperature, radiation, reactive gases, liquids, etc.) into one compact hollow body part is transferred.
• Examples of sintering processes are those from the state known in the art production of moldings by microwaves or the Radiation curing.
• Another preferred sintering process for producing hollow bodies is the reactive one Sintering.
• the starting components are shaped and then solidified by reacting a component A and a component B with each other be brought, wherein the components A and B mixed with the starting components, applied thereto or added after informing.
• the components A and B react under Solidification of the individual ingredients together.
• the formed reaction product from the Components A and B connect the individual output components such that a solid, relatively break-resistant hollow body is obtained.
• the starting components are mixed with the component A or before they are brought into shape with it.
• compounds of component A are the alkali metal hydroxides, in particular NaOH and KOH, alkaline earth hydroxides, in particular Ca (OH) 2 , alkali metal silicates organic or inorganic acids such as citric acid, or acidic salts such as hydrogen sulfate, anhydrous hydratable salts or hydrated water-containing salts such as soda , Acetates, sulfates, alkali metal, wherein the aforementioned compounds, if possible, can also be used in the form of their aqueous solutions.
• the component B is selected such that it reacts with the component A without exerting higher pressures or substantial increase in temperature to form a solid to solidify the other existing starting components.
• Examples of compounds of component B are CO 2 , NH 3 , water vapor or spray, hydrated water-containing salts, which optionally react with the present as component A anhydrous salts by hydrate migration, hydrates forming anhydrous salts with the hydrate water-containing salts of the component A react under hydrate migration, SO 2 , SO 3 , HCl, HBr, silicon halides such as SiCl 4 or Kiselklareester S (OR) x R ' 4-x .
• the starting components are mixed or coated with compounds of component A and then admixed with the compounds of component B. It has proven to be particularly suitable if the compounds of component B are gaseous.
• the shaped starting components (hereinafter referred to as preforms) can then either be gassed in a simple manner or introduced into a gas atmosphere.
• a particularly preferred combination of the components A and B are concentrated solutions of the alkali metal hydroxides, in particular NaOH and KOH, and alkaline earth hydroxides, such as Ca (OH) 2 , or alkali metal silicates as component A and CO 2 as component B.
• the starting components are first shaped, ie they are usually filled in a die having the external shape of the hollow body to be produced.
• the starting components are preferably in powdery to granular form.
• they are mixed or coated with the component A.
• it has proved to be preferable to easily press the starting components, for example by hand or with a die at a pressure below the above values, especially below 100 N / cm 2 . It is also possible to compress the premix by vibration (knock compaction).
• a preform may e.g. offset with this be so that the gas flows through it. This procedure allows a uniform hardening of the molding within a short time.
• a preform is placed in an atmosphere of the reactive Gas introduced.
• This variant is easy to perform. It is possible to hollow body which have a hardness gradient, i. Hollow body, only a tougher Surface have up to hollow bodies that are fully cured.
• a preform or the premix can also be under overpressure with the reactive gas be implemented.
• This variant of the method has the advantage that the surface quickly under Forming a hard shell hardens, the curing process is already stopped here or as described above about increasing cure levels may also be complete hardened moldings are produced.
• the above process variants can also be combined by first reactive gas flows through the preform to displace air. Then sets one preform of a gas atmosphere at atmospheric pressure. By the reaction between The gas and the second component gas is automatically sucked into the molding.
• the present invention is not the Starting mixture but a preform already brought in shape with the component A. coated and then reacted with the component B. It cures up on the surface of the preform located layer, while in the core of the loose or slightly dense structure is maintained.
• Such hollow bodies are characterized by a particularly good decay behavior.
• process variants are preferred in which the production of open mold in step i) by sintering, wherein the flowable mixture by Temperature action or chemical reaction is solidified.
• Wall thicknesses of 100 to 6000 microns preferably from 120 to 4000 microns, more preferably from 150 to 3000 microns and in particular from 200 to 2500 microns, wherein wall thicknesses below 2000 microns are again preferred.
• step i) The production of the mold in step i) can be done with different techniques, the depend in part on the type of solidification mechanism. In the simplest case, a filled flowable mixture in a suitable mold, allowed to harden there and then demoulded.
• the disadvantage here is the design of the form, as the desired Wall thickness of the resulting hollow body rapid filling of complicated geometries not allow.
• the solidifying mixture may be filled into a mold which is merely a cavity is trained. If you let the mixture solidify there, you would get a compact Body, no mold. By suitable process management can be ensured that the mixture first solidifies on the wall of the mold. Turn the shape to one For a certain period of time t, the excess mixture flows off leaving a lining the form, which itself represents a mold, which is removed after complete solidification can be. As already mentioned, the filling can also take place before demolding; also a filling during the solidification process is possible.
• Preferred embodiments of the present invention are therefore methods in which Step i) an open die filled with the flowable shell material and after a Time t between 0 and 5 minutes the excess mass is emptied.
• the die can be filled only partially.
• the mixture is in these cases pressed with a matching stamp on the wall of the die, where they are to Hollow body solidifies.
• This variant of the method constitutes, as it were, an intermediate form between the "Abg screentechnik” and the casting technique in negative forms of the hollow body is.
• Corresponding Method in which in step i) an open mold with the flowable shell material filled and the material pushed through a stamp on the walls of the mold and so on Mold is made, are therefore also preferred.
• Particularly advantageous in this Process management also known as the "cold stamp method” is the ability to To produce large quantities with precisely defined wall thickness of the hollow body. moreover the process is largely insensitive to fluctuating flow properties and also applicable to higher viscosity mixtures.
• the molds are during or after the preparation with washing or Cleaning agent filled.
• washing or Cleaning agent filled are all ready-made washing or Detergents in liquid, pasty, gelatinous, powdered, extruded, granulated, pelleted, scaly or tableted form are introduced into the mold. It is however, it is not necessary to fill in a finished washing or cleaning agent, but rather can also individual detergent or detergent ingredients or precursors thereof in the Hollow body to be filled.
• Powders bicarbonates, silicates, potash, soda, zeolites, polymers (PEG, maleic acid-polyacrylic acid copolymer salts, Citric acid, citrates, sugar, soap, disintegration aid and Disintegrants, sulphates, phosphates, perborates, carboxymethylcellulose (CMC), LAS powder (linear alkylbenzenesulfonates), FAS powder (fatty alcohol sulfates).
• PEG maleic acid-polyacrylic acid copolymer salts
• Citric acid citrates
• sugar, soap disintegration aid and Disintegrants
• sulphates phosphates, perborates
• LAS powder linear alkylbenzenesulfonates
• FAS powder fatty alcohol sulfates
• Pastes surfactant pastes (LAS paste, aqueous FAS paste), water glass
• tower powder spray agglomerates
• LAS compounds LAS compounds
• FAS compounds FAS compounds
• TAED Percarbonate
• enzyme extrudates crude extrudate
• nonionic surfactant compounds tower powder (spray agglomerates), LAS compounds, FAS compounds, TAED, Percarbonate, enzyme extrudates, crude extrudate, nonionic surfactant compounds
• Liquids Polymer solutions (maleic acid-polyacrylic acid copolymer salts in aqueous Solutions), phosphonate solutions (aqueous), perfume oils, enzyme solutions, chlorine bleach, Hydrogen peroxide solutions, cationic surfactant solutions, nonionic surfactants
• the liquids can also be present as gel (due to higher active substance concentrations or by adding thickeners, e.g. Tixogel® (Süd-Chemie)).
• the solids can also are processed as solutions or suspensions containing liquids as compounds in bound form.
• the open mold can be closed. This is included liquid or pasty fillings necessary to prevent the filling from leaking before use to prevent. For fillings that remain adherent in the mold, the closing the shape is omitted, if desired. But a closure can also in such Cases may be indicated for aesthetic reasons.
• the optional closing of the mold can be done in different ways. at Moldings with bung hole this can for example by inserting a matching part be closed. Open molds in the form of hollow bodies without undercuts can be closed with foil or after filling with further material for the mold be poured over. The optional sealing with foils will be described below.
• the film which closes the opening (s) of the mold (s) is applied to the surface of the mold Molded and adhesively bonded thereto, which for example by gluing, partial melting or by chemical reaction can take place. It is possible the slide Apply to all surfaces of the mold (ie not just over the opening) and adherent connect with this, so that the film has a coating, a "coating" of the whole Forming body.
• Preferred washing and Detergent portions are, however, characterized in that the film is not the enclosing the entire molded body.
• the film is only applied so that it performs a function, ie. closing the Mold is used.
• the closing film can of course also a laminate of several be differently composite films, on different compositions individual film layers, the opening of the mold at certain times in the Washing and cleaning gear to be released.
• a thickness of 1 to 150 .mu.m preferably from 2 to 100 .mu.m, especially preferably from 5 to 75 ⁇ m and in particular from 10 to 50 ⁇ m.
• the active substance contained in the mold can be any state of aggregation or accept any form of performance.
• Preferred washing or cleaning agent portions contain the other active substance in liquid, gel, pasty or solid form.
• the closed by the film mold can completely with other active substance be filled. But it is also possible, the mold only partially closed before closing fill, in this way, a movement of the filled particles or liquids within to allow the mold. Especially when filling with regularly shaped larger ones Particles can be realized sexy optical effects.
• preferred washing or cleaning agent portions preferred in which the Volume ratio of the space enclosed by the film and the hollow body to the active substance contained in this space 1: 1 to 100: 1, preferably 1.1: 1 to 50: 1, particularly preferably 1.2: 1 to 25: 1 and in particular 1.3: 1 to 10: 1.
• Terminology means a volume ratio of 1: 1, that the mold completely filled is.
• washing or cleaning agent portions prepared according to the invention are preferred here, in which the weight ratio of hollow body to that in the through the film and the Hollow body enclosed space contained active substance 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1.
• weight ratio defined above is the ratio of the mass of unfilled hollow body to the mass of the filling. The mass of the film is at this Calculation not included.
• the film can be virtually instantaneously soluble, so that in the mold active substance at the beginning of the washing or cleaning cycle into the washing or cleaning liquor is metered.
• the film may be so poorly soluble that only the molding is dissolved and the active substance contained in the mold thereby is released.
• the filled hollow body can also by Applying a melt, solution, emulsion or dispersion of the aforementioned Foil materials are closed.
• the occlusive layer forms from the Melt, solution, emulsion or dispersion by cooling or evaporation of the Solvent, i. the occlusive "foil" is produced on the mold.
• This alternative can be used with completely filled molds, while only partially filled molds are suitably closed in other ways, provided that a "mobility" of the content value sets, for example, as a special incentive to buy.
• the hollow body in step i) can also be prepared so that they come with a further filled hollow body connected and can be closed in this way.
• Such bodies are of two half-shells assembled forms without undercuts, which have an equatorial plane. The latter does not necessarily have to be arranged centrally, but may for example also in the upper or lower third, fourth, fifth, etc. lie. This procedure is facilitated if the hollow bodies produced in step i) Have flange. Alternatively, the adhesion of the molded parts to each other even over the Limiting edges of the opening surfaces done.
• processes are also preferred which has the Hohlfom flange parts and in step iii) by welding with a another mold is closed.
• the melt is then via heated and / or insulated piping systems the dosing supplied; parallel to this, the individual casting molds are at the desired temperature preheated or cooled.
• the liquid melt is metered into the mold cavities, wherein these be filled to the upper edge of the die.
• the mold cavities usually run several identically designed Casting molds pass the casting machine and are filled.
• the filled forms After leaving the derr Casting machine (or passing the dosing head), the filled forms either fed to a cooling line or as long as bewgt or "parked” until the melt from the outside begins to stiffen.
• the substance-dependent cooling time Essential for the later wall thickness of the forming shell to be formed among other things, the substance-dependent cooling time.
• the mold is turned once from top to bottom or turned upside down, so that the not yet solidified and excess melt from the Form expires in a waiting collection reservoir for return to the process.
• the adhesive Shell formation can be assisted by an eccentric motion of the mold, with the Centrifugal forces the still flowing melt evenly to the mold surface transport and provide for the formation of a shell with uniform wall thickness. Also a degassing of the melt by vibration of the mold may possibly be necessary.
• the formation of the shell can be completed by a cooling.
• the edge of the mold projecting shell residue can be cut off using knives or thermo rolls.
• the formed shell mold is then filled and the filling later optionally cooled.
• the shape is completely or depending on the desired type of closing only partially filled.
• a sealing barrier are applied (especially in liquid fillings), which consists of a substance which has a lower melting point than the shell material and is good can be sprayed.
• the tight closure of the mold can then by filling with the filling provided mold shell with the melt for the shell material.
• the solidification to the finished Shaped body can also be promoted by passing through a cooling section.
• the moldings are removed from the mold in a mold discharge station. This is the form of Turned downwards so that the formed molding down to a conveyor belt can fall or be dropped. This Entfromungs Republic can by twisting / twisting the Form or by impact on the back are supported.
• the moldings produced according to the invention can, as already mentioned, be of any desired form and size are made and combine a high aesthetic appeal with great technical flexibility and the possibility of different product benefits such as realize controlled-release concepts.
• Another object of the present invention are portioned washing or Detergent with a detergent composition which at least partially comprises solidified material and characterized in that the enclosure has a wall thickness of 100 to 6000 ⁇ m and consists of a material, which by delayed water binding, by cooling below the melting point, by evaporation of solvents, by crystallization, by chemical reaction (s), especially polymerization, by changing the rheological properties e.g. by altered shear, by sintering or by radiation hardening, in particular by UV, Alpha beta or gamma rays.
• the mechanism by which the formation of the mold can be made were discussed earlier described in detail. These explanations also apply to the enclosure of the Detergents or cleaning agents according to the invention.
• the term "at least partly of solidified material" indicates that at least part of the surface of the Detergent composition of solidified material in the sense of includes the above definition.
• the part not covered by solidified material can either otherwise (e.g., covered with film, see above) or direct Own contact with the atmosphere.
• the detergent composition is poured into a mold are here Pre-portioned detergents or cleaners according to the invention are preferred in which the Surrounding at least 50%, preferably at least 60%, more preferably at least 70% and in particular at least 80% of the surface of the portioned agent covered.
• portioned detergents or cleaning agents are preferred in which the ratio of masses of containment and content in the range of 10: 1 to 1: 1000, preferably from 2: 1 to 1: 100, more preferably from 1: 1 to 1:50 and in particular from 1: 5 to 1:25, lies.
• melts are particularly suitable.
• portioned detergents or cleaners according to the invention are those preferred in which the enclosure consists of a material whose melting point in Range from 40 to 250 ° C.
• portioned detergents or cleaning agents are certain substances, the top described in detail here, especially suitable as enclosing.
• preferred portioned detergents or cleaning agents are characterized characterized in that the enclosure comprises one or more substances from the groups of Dicarboxylic acids, dicarboxylic anhydrides, bicarbonates, hydrogen sulfates and / or Urea in amounts of at least 40 wt .-%, preferably at least 60 wt .-% and in particular at least 80 wt .-%, each based on the mass of the enclosure containing.
• the at least partially enclosed in the enclosure washing or Detergent composition may be described in detail in any of the above Form present.
• Portioned detergents or cleaners, in which the laundry or household detergent Detergent composition in liquid, pasty, gelatinous or particulate form or in the form of a suspension or emulsion and completely from the enclosure is therefore another preferred embodiment of the present invention Invention.
• thermoplastic polymers can be excellent for dimensionally stable hollow bodies, in particular by this method optionally to dimensionally stable hollow bodies, which in their interior facilities for Compartmentalize included, processed.
• the injection molding of suitable materials is carried out according to known procedures at high pressures and temperatures, For example, at temperatures between 100 and 220 ° C, especially devishalöb of 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, especially at about 1,400 bar, with the steps of closing the to the extruder for Injection molding attached mold, injecting the polymer at high temperature and high pressure, cooling of the injection-molded molding, opening the mold and removing the shaped blank.
• Other optional steps such as the application of release agents, the Demolding etc. are known in the art and can according to known technology be performed.
• the detergent, cleaning agent or detergent portions disclosed herein are made from an outer mold containing one or more fillings.
• the mold divided by partitions into several compartments, creating several fillings may be present separately within the same hollow body.
• the simultaneous portioning of several different fillings requires hollow body, which include compartmentalizing devices.
• the production of such hollow body Several contiguous compartments encounter conventional methods Difficulties.
• the present application discloses a method for producing such Hollow body and the detergent, detergent or detergent portions which can be produced therefrom.
• a hollow body is injection-molded, which one or more rooms for Has washing, rinsing or cleaning active preparations.
• the injection molding suitable materials is carried out according to known procedures at high pressures and temperatures with the steps of closing the to the extruder for injection molding connected mold, injection of the polymer at high temperature and high pressure, Cooling of the injection-molded molding, opening the mold and removing the molded Blank.
• Other optional steps such as the application of release agents, demolding, etc. are known in the art and can be carried out according to known technology become.
• step (i) is carried out at a pressure of between 100 and 5000 bar, preferably between 500 and 2500 bar, more preferably between 750 and 1500 bar and in particular between 1000 and 1250 bar performed.
• the temperature of the material to be injection molded is preferably above the Melting or softening point of the material and thus depends on the nature of Materials for the hollow body from.
• step (i) at temperatures between 100 and 250 ° C, preferably between 120 and 200 ° C and in particular between 140 and 180 ° C, carried out.
• 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 be chosen so thin that a rapid resolution or Disintegration is achieved and the ingredients quickly released into the application fleet be, but also a certain minimum thickness is required to the mold To give stability, in particular dimensional stability.
• dimensionally stable hollow body is understood according to the invention that the Detergent, detergent or detergent portions containing moldings an inherent dimensional stability which enables them, under normal conditions of manufacture, the Storage, transport and handling by the consumer against breakage and / or pressure to have stable, non-coincident structure, which is also among the conditions not changed for a long time. It is according to the invention without Influence, whether this structural stability out of due to various mentioned below Parameter-yielding properties of the dimensionally stable hollow body alone or (even) from the Presence of compartmentation devices and / or (also) from the filling with washing-active, cleaning-active or rinse-active preparations results. In preferred Embodiments of the invention already have the dimensionally stable hollow body itself sufficient inherent dimensional stability, as this is beneficial to the mobility in machines in the manufacture of the hollow body and the filling during the production of Detergent, detergent or detergent portions according to the invention.
• the pressure resistance of the dimensionally stable hollow body according to the invention is in the (se usual) way measured so that unfilled and optionally with compartmentalizing facilities provided hollow body with films or lids are closed and on these hollow bodies at room temperature an internally applied, steadily increasing vacuum is applied until the hollow body begins to collapse.
• the inherent shape stability of Hollow body should more preferably be such that in such vacuum collapse tests unfilled and optionally provided with compartmentalization hollow body collapse not before reaching a vacuum of 900 mbar, preferably 750 mbar and in particular from 500 mbar begins.
• the invention differ used hollow body fundamentally of films or so-called "pouches", as to Provision of detergents, detergents or detergents also used become.
• the hollow bodies according to the invention provide an independent, self-supporting Envelope, which usually already before filling with one or more washing active, rinse active or cleaning active component (s) exists and then is filled.
• coatings are applied to existing moldings (eg. Compacts, granules, extrudates, etc.) applied and then dried or cured; she only then form an envelope surrounding the molding.
• hollow bodies are produced in step (i) which does not collapse before reaching a vacuum of 250 mbar, preferably from 100 mbar and in particular from 20 mbar begins.
• Preferred methods of the invention are therefore characterized in that the Wall thickness of the enclosure produced in step (i) (b) 100 to 5000 .mu.m, preferably 200 to 3000 .mu.m, more preferably 300 to 2000 .mu.m and in particular 500 to 1500 .mu.m is.
• MFI flow index
• the dimensionally stable hollow body produced by injection molding is not at all Sides closed walls and is on at least one of its sides - at one spherical or elliptical body in the area of part of its shell - open due to production. Through the remaining opening is / in the inside of the dimensionally stable hollow body formed compartment (s) one or more washing active, detergent-active or rinse-active preparation (s) filled. This also happens on itself known way, for example in the context of known from the confectionery industry Production method; It is also possible to proceed in several steps.
• a one-step procedure is particularly preferred if in addition to fixed Preparations also preparations containing liquid components (dispersions or Emulsions, suspensions) or even gaseous components comprising preparations (Foams) in the detergent, detergent or detergent portions in the hollow bodies to be incorporated.
• step (i) As materials for the hollow body to be produced in step (i), it is possible in particular Polymers, preference being given to processes according to the invention in which the processes described in step (i) produced enclosure (b) one or more materials from the group acrylic acid-containing Polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters and polyethers and mixtures thereof.
• water-soluble polymers as material for the hollow body.
• methods have proven which are characterized in that in step (i) prepared enclosure (b) one or more water-soluble polymer (s), preferably a Material from the group (optionally acetalised) polyvinyl alcohol (PVAL), Polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and their Mixtures, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).
• PVAL polyvinyl alcohol
• polyvinyl alcohols are particularly preferred as coating materials.
• Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure in small proportions (about 2%) also structural units of the type contain.
• polyvinyl alcohols which are known as white-yellowish powder or granules with Degrees of polymerization in the range of about 100 to 2500 (molecular weights 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. Characterized are the Polyvinyl alcohols from the manufacturer by indicating the degree of polymerization of the Starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
• Polyvinyl alcohols are soluble in water and a few strongly depending on the degree of hydrolysis polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); from (chlorinated) hydrocarbons, esters, fats and oils they are not attacked. Polyvinyl alcohols are classified as toxicologically harmless and are biological at least partially degradable. The water solubility can be achieved by post-treatment Aldehydes (acetalization), by complexation with Ni or Cu salts or by Reduce 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 pass water vapor.
• gases such as oxygen, nitrogen, helium, Hydrogen, carbon dioxide, but pass water vapor.
• 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 especially 82 to 88 mol%.
• Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the hollow bodies, preference being given to processes according to the invention in which the hollow bodies produced in step (i) consist of a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol -1 , preferably from 11,000 to 90,000 gmol -1 , more preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 .
• the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and more particularly between about 260 to about 1500.
• polyvinyl alcohols described above are widely available commercially, for example, under the trademark Mowiol® (Clariant).
• Mowiol® Cosmetically, for example, under the trademark Mowiol® (Clariant).
• Polyvinyl alcohols which are particularly suitable for the purposes of the invention are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88 and Mowiol® 8-88.
• polyvinyl alcohols suitable as material for the hollow mold are ELVANOL® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei K.K.).
• the hollow body Plasticizing aids included. This can be particularly advantageous if as a material were selected for the hollow body polyvinyl alcohol or partially hydrolyzed polyvinyl acetate.
• the proportion of plasticizer (based on the polymer) is usually up to 15 Wt .-%, with values between 5 and 10 wt .-% are preferred.
• plasticizer In particular, glycerol, triethanolamine, ethylene glycol, propylene glycol, diethylene or dipropylene glycol, diethanolamine and methyldiethylamine proven.
• mold release additives are important auxiliary substances that are used in the Injection molding compounds can be used. From the groups of fatty substances and the finely divided substances have in the context of the present invention in particular Stearic acid and / or stearates and fumed silicas (Aerosil®) and talc proven.
• the proportion of Entformungszu effects (based on the polymer) is usually up to 5 Wt .-%, with values between 0.5 and 2.5 wt .-% are preferred.
• demolding additives substances come in particular from the Group of fatty substances.
• fatty substances are included in the context of this application Normal temperature (20 ° C) liquid to solid substances from the group of fatty alcohols, the Fatty acids and the fatty acid derivatives, in particular the fatty acid esters understood.
• Reaction products of fatty alcohols with alkylene oxides are within the scope of the present invention Application to the surfactants (see above) and are not fatty substances in the context of the invention.
• Fats can be inventively preferred fatty alcohols and fatty alcohol mixtures, Fatty acids and fatty acid mixtures, fatty acid esters with alkanols or diols or polyols, Use 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-
• the invention also Guerbet alcohols and oxo alcohols, for example C 13-15 oxoalcohols or mixtures of C 12- 18 alcohols with C 12-14 alcohols easily be used 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 the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage. For example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc.
• Fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), 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-oc
• tridecanoic acid pentadecanoic acid, margaric acid, nonadecanoic acid, erucic acid, elaeostearic acid and arachidonic acid can be used.
• Such mixtures are for example coconut oil (about 6 wt .-% C 8 , 6 wt .-% C 10 , 48 wt .-% C 12 , 18 wt .-% C 14 , 10 wt .-% C 16 , 2 wt % C 18 , 8% by weight C 18 ' , 1% by weight C 18 " ), palm kernel oil fatty acid (about 4% by weight C 8 , 5% by weight C 10 , 50% by weight C 12 , 15 wt .-% C 14 , 7 wt .-% C 16 , 2 wt .-% C 18 , 15 wt .-% C 18 ' , 1 wt .-% C 18 " ), tallow fatty acid (ca.
• % C 16 ' 1% by weight C 17 , 2% by weight C 18 , 70% by weight C 18' , 10% by weight C 18 " , 0.5% by weight C 18 ''' ), technical palmitic / stearic acid (about 1 wt .-% C 12 , 2 wt .-% C 14 , 45 wt .-% C 16 , 2 wt .-% C 17 , 47 wt .-% C 18 , 1 wt .-% C 18 ' ) and soybean oil fatty acid (about 2 wt .-% C 14 , 15 Wt% C 16 , 5 wt% C 18 , 25 wt% C 18 ' , 45 wt% C 18 " , 7 wt% C 18''' ).
• fatty acid esters the esters of fatty acids with alkanols, diols or polyols can be use, with FettTexrepolyolester are preferred.
• fatty acid polyol esters mono- or diesters of fatty acids with certain polyols into consideration.
• the fatty acids with the Polyols are esterified, are preferably saturated or unsaturated fatty acids with 12 up to 18 carbon atoms, for example lauric acid, myristic acid, palmitic acid or stearic acid, wherein preferably the technically occurring mixtures of the fatty acids are used, For example, derived from coconut, palm kernel or tallow fatty 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.
• polyols the are esterified with the fatty acids mentioned above, come within the Sorbitol, trimethylolpropane, neopentyl glycol, ethylene glycol, Polyethylene glycols, glycerol and polyglycerols into consideration.
• Preferred embodiments of the present invention provide that as a polyol with Fatty acid (s) is esterified, glycerol is used. Consequently, as demolding additives Fatty substances from the group of fatty alcohols and fatty acid glycerides are preferred. Especially preferred Entformungszu accounts are fatty substances from the group of fatty alcohols and Fatty acid monoglycerides. Examples of such preferred fatty substances used are glycerol monostearic acid esters or glycerol monopalmitinklareester.
• antioxidants may contain.
• This class of compounds includes, for example, substituted phenols, hydroquinones, Brenzatechnine 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 chosen so that the hollow body in unmoved Water of 20 ° C in less than 300 seconds, preferably in less than 60 seconds dissolves or releases the ingredients of the filling. It is not necessary that the entire body spontaneously dissolves. Rather, it is enough if all the ingredients within the application period under the conditions of use. For usual Washing or rinsing processes this means temperatures of 20 ° C and above, mechanical Exposure and times of less than 200 minutes, preferably less than 60 minutes, especially under 20 minutes.
• the release of the ingredients of at least one However, compartment should preferably be in less than 300 seconds, especially in less than 60 seconds. This can be achieved by using disintegration aids, by sealing a compartment with a thin, water-soluble film, through Resolution of a "plug" closing an opening or otherwise respectively.
• the production of injection-molded hollow body, wherein the injection molding material is water-soluble Containing polymers is not described in the prior art.
• Another item The present invention is therefore an injection molding process for hollow bodies, such Comprise polymers, ie a process for the production of hollow bodies by injection molding, characterized in that the injection molding compound contains one or more water-soluble (s) Polymer (s), preferably one or more material (s) from the group (optionally acetalated) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, Cellulose, and their derivatives and mixtures thereof, particularly preferably (optionally acetalated) polyvinyl alcohol (PVAL).
• PVAL polyvinyl alcohol
• the injection molding composition comprises a polyvinyl alcohol whose degree of hydrolysis 70 to 100 Mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and especially 82 to 88 mol%.
• the injection molding composition comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol -1 , preferably from 11,000 to 90,000 gmol -1 , more preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 is located.
• the inventive method can be carried out with particular advantage, if the Proportion of water-soluble polymers in the injection molding compound is high.
• the entire injection molding compound only from the water-soluble polymers and optionally Auxiliaries (see above).
• methods according to the invention are preferred in which the Injection molding compound, the said polymers in amounts of at least 50 wt .-%, preferably of at least 70% by weight, more preferably of at least 80% by weight, and in particular of at least 90% by weight, in each case based on the weight of Injection molding compound containing.
• the dimensionally stable hollow body produced by injection molding is not at all Sides closed walls and is on at least one of its sides - at one spherical or elliptical body in the area of part of its shell - open due to production. Through the remaining opening is / in the inside of the dimensionally stable hollow body formed compartment (s) one or more washing active, detergent-active or rinse-active preparation (s) filled. This also happens on itself known way, for example in the context of known from the confectionery industry Production method; It is also possible to proceed in several steps.
• a one-step procedure is particularly preferred if in addition to fixed Preparations also preparations containing liquid components (dispersions or Emulsions, suspensions) or even gaseous components comprising preparations (Foams) in the detergent, detergent or detergent portions in the hollow bodies to be incorporated.
• the method according to the invention will / become one or more detergent, detergent or dishwashing active preparation (s) in surrounding, preferably concentric or coaxial with each other Compartments filled or arranged in the form concentric or coaxial with each other or partially or completely surrounding compartments.
• These will, optionally together with one or more washing active, cleaning active or rinse-active preparation (s), in a separately prepared dimensionally stable shaped body brought in.
• the partially or completely surrounding each other Compartments, preferably arranged concentrically or coaxially to each other Compartments, in addition to one or more others, with one or more in the detergent-containing or rinse-active preparation (s) filled compartment (s) in the dimensionally stable hollow body are present or contained alone in this.
• one or more washing-active, detergent-active or rinse-active preparation in a compartment-containing or in Formally stable hollow bodies containing distributed over several compartments closed and so the Preparation (s) sealed inside.
• This can - as already described above - by Applying a "lid" on the still open (n-th) surface of the dimensionally stable hollow body or -
• For spherical or elliptical hollow bodies by applying a corresponding partial spherical shell or partial ellipse shell done on the opening.
• the application can preferably by way of bonding, preferably with a water-soluble adhesive, fusing, welding or otherwise, to a person skilled in the art Known ways of connecting done.
• the water solubility of the walls / compartments surrounding the phases can be set so that every 5 to 10 minutes after opening a compartment pass until the contents of the next compartment are released.
• Simplified forms of detergent portion can be prepared by the Phase 2 is omitted and their contents on the phases 1 (protease) and 3 (soda, Alkali carrier) is distributed, and that in a further simplification in addition to the phase 2 and the Phase 4 is omitted, perfume, optical brightener and Phase 3 Soil Repellent be slammed and the fabric softener is dosed in a separate product.
• the detergent, detergent or detergent portions according to the invention are solved in an advantageous manner the tasks. So can be incompatible wash-active, cleaning-active or rinse-active preparations or their components spatially separate and can not due to the lack of a common contact area React reactions with each other, in particular no activity of the respective preparation debilitating reaction. This leads - especially at elevated drug concentrations - to an increased storage stability of the detergent, detergent or detergent portions, to an improved washing performance due to the lack of activity loss and to Saving of active substance, since earlier due to the expected loss of activity to be used excess of active substance in the detergent, detergent or Detergent portions according to the invention can be omitted.
• the in the hollow bodies with one or several compartments contained detergent, makesmittek- or detergent portions promise a consistent and pre-packaged dosage with all for the entire washing, cleaning or rinsing required or desired Components.
• the dosage is done in one step, and the solubility of the enclosure or the hollow body material to release the Ingredients are reliable according to predetermined or predetermined kinetics, so that the Clearly improve washing, cleaning or rinsing results compared to powdered ones Means or compressed moldings of the same composition without compartmentalized Separation of the components.
• Example 1 Polyvinyl alcohol granules (Vinex® 2019 from the company Texas Polymers) were used on a hydraulic Screw injection molding machine of the company Arburg melted and in simple tools with Hot runner nozzle injected.
• Example 2 a trochoidal shell with three corrugated Partitions and a peripheral edge made in Example 2 a hemisphere with a circumferential stacking approach and a border.
• the mold shells prepared in the manner described above were introduced into water and measured time to disintegration or to complete dissolution: Temperature [° C] 20 30 40 50 60 Decay after [min] 12 7 5 4 2 complete resolution after [min] 18 11 8th 6 4
• Polyvinyl alcohol granules (Vinex® 2019 from the company Texas Polymers) were used on a hydraulic Screw injection molding machine of the company Arburg melted and in simple tools with Hot runner nozzle injected, wherein the shell is in the form of a hemisphere with a circumferential Stacking neck and a border showed.
• a half-shell was treated with a low-water commercial liquid detergent (Persil® Gel, commercial product of the Applicant) and filled with a polyvinyl alcohol film of the company Greensol closed.
• a second half-shell was made with an extruded, bleach-containing Heavy duty detergent (Persil® Megaperls®, commercial product of the Applicant) filled and also plugged with a PVAI film.
• the two part-hollow body in the closed enclosures (A) and (B) were then glued together using Klatkleber.

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