EP1586631B1 - Hollow bodies with compartments comprising a portion of washing, cleaning or rinsing agent - Google Patents

Abstract

Portions (A) of laundry, dish-washing or other detergent in dimensionally-stable hollow molding(s) with at least one compartment comprise: (a) at least one detergent formulation (I); (b) that is (partly) surrounded by an uncompressed material (II) that gives the molding dimensional stability and can disintegrate; and (c) optionally partition(s) dividing the molding(s) into compartments. Independent claims are also included for: (a) portions (B) of laundry and other detergents in the form of hollow moldings sub-divided into not less than 2 (partly) filled compartments surrounded by (I); (b) portions (C) of laundry and other detergents (partly) comprising solidified material; (c) methods of producing portions of detergents in hollow moldings with compartment(s); and (d) a method of producing hollow moldings.

Description

The present invention relates to washing, cleaning or rinsing agent portions which are contained in dimensionally stable hollow bodies with at least one compartment. The invention also relates to processes for the preparation of such washing, cleaning or detergent portions containing compartment hollow body. The invention further relates to washing, cleaning and rinsing processes in which the detergent, cleaning agent and dishwashing detergent preparations are dosed in dimensionally stable hollow bodies with one or more separate compartments.

The prior art extensively describes that detergents, cleaning agents or dishwashing detergents have hitherto usually been made available to the consumer in the form of spray-dried or granulated solid products or as liquid goods. Following the consumer's desire for convenient dosing options, products in pre-portioned form have become established in the market in addition to the two classic variants mentioned above and are also extensively described in the prior art. There are descriptions of washing, cleaning or rinsing agents in the form of compressed molded articles, ie tablets, blocks, briquettes, rings and the like, as well as packaged in bags portions of solid and / or liquid detergents, cleaners or detergents.

In the case of single-dose quantities of detergents or cleansers packed in sachets in the market, bags of water-soluble film have prevailed. These make a tearing of the packaging by the consumer unnecessary. In this way, a convenient dosing of a single, for a washing or cleaning course sized portion by inserting the bag directly into the washing machine or dishwasher, especially in their Einspülkammer, or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or in the hand-washing or -spülbecken, possible. The bag surrounding the detergent, detergent or detergent portion dissolves without residue when a certain temperature is reached. Also in bags of water-soluble film packaged detergents and cleaners are described in the art in large numbers. Thus, the earlier patent application DE 198 31 703 discloses a portioned detergent or cleaner composition in a bag of water-soluble film, in particular in a bag of (optionally acetalized) polyvinyl alcohol (PVAL), wherein at least 70 wt .-% of the particles of the washing or detergent preparation particle sizes> 800 microns have. Such bags or "pouches" are indeed very consumer friendly and facilitated the dosing, but are not in all cases the most suitable form for dosing detergent. Detergent and rinse aid preparations, especially when solid and liquid washing, cleaning or rinse-active preparations are to be dosed side by side. Furthermore, such pouches do not permit the incorporation of detergent, cleaning agent or rinsing agent preparations into the detergent, cleaning agent or detergent portion in unstable or readily volatile phases.

The document DE-A 20 65 153 describes multi-component surfactant moldings consisting of an outer shell of sodium silicate and detergent components enclosed therein. The silicate shell is made by compression molding into two hemispheres which, after filling the amount of detergent components sufficient for a wash, are combined and bonded to form the molded article. The process is extremely impractical and does not result in useful detergent portions.

The document DE-A 20 07 413 describes detergent moldings of a core of one or more detergent component (s) and a shell of press-formed, predominantly of sodium metal silicate existing shell material. The compression of the shell material into half shells and the filling and welding of the half shells to the finished blank require a complex technology, and many of the blanks break before they go into the washing process.

The documents DE-A 198 34 181, DE-A 198 34 180 and DE-A 198 34 172 describe detergent, dishwashing or cleaning / decalcifying agent preparations of a tablet made by compression molding, consisting of two equal halves from one or more detergent, rinsing agent or cleaning agent components and an optionally provided with an additional coating core of another detergent, detergent or detergent component. Apart from the fact that the preparation can be made in this case only in a complicated, multi-step process, only a solid core can be incorporated into the tablet wrap, if not premature release of the tablet should be initiated from the inside.

The European application EP 0 593 952 A1 (Dispo-Commerce AG) describes water-soluble bags for the release of treatment agents into the washing liquid of an automatic washing machine or dishwashing machine.

The subject of US patent application US 4,973,416 (Procter & Gamble) are metering units for textile cleaning in the form of liquid-filled water-soluble bags.

Detergent packages comprising enclosing water-soluble bags are described in European patent application EP 132 726 A2 (Henkel).

Hollow floats are described in German Offenlegungsschrift DE 1 954 244 (Jan Simon).

The invention had the object of providing detergent, cleaning or Spolmittel preparations are available in which volatile as well as less volatile washing active, active cleaning or rinse active components can be assembled or mechanically unstable components can be incorporated without them - for example when pressed into moldings - be compromised in terms of their integrity. The invention was further based on the object, detergent, Reinigungsmittel- or Separate detergent components spatially from each other and still prepare them in the same detergent, detergent or detergent portion, with the aim of a mass transfer or mutual impairment, which may be associated with loss of activity, as low as possible to keep. This would also have the advantage that the storage stability of detergent, cleaning agent or detergent preparations could be significantly increased and also the levels of active substance could be reduced in some cases, as in the prior art in their calculation due to an expected loss of activity individual Components always overdosing had to be provided.

Surprisingly, it has now been found that one can fill detergent, detergent or detergent portions in dimensionally stable hollow body with one or more separate compartment (s) and thus can provide dosages of the respective agent, compared to compact moldings or bagged preparations preparations in terms of application Have advantages.

1. (a) wenigstens eine flüssige waschaktive, reinigungsaktive oder spülaktive Zubereitung sowie mindestens eine feste waschaktive, reinigungsakfive oder spülaktive Zubereitung, welche räumlich voneinander getrennt sind;
2. (b) wenigstens eine die Zubereitungen nach (a) ganz oder teilweise umgebende Umfassung aus einem unter Wasch-, Reinigungs- oder Spülbedingungen desintegrierbaren, dem/den Hohlkörper(n) Formstabilität verleihenden, spritzgegossenen Material; und
3. (c) eine oder mehrere Wände, welche gleiche oder verschiedene waschaktive, reinigungsaktive oder spülaktive Komponenten oder Zubereitungen räumlich voneinander trennt/trennen.

The invention relates to a washing agent, cleaning agent or detergent portion contained in a dimensionally stable hollow body with a plurality of chambers

1. (a) at least one liquid detergent-active, cleaning-active or rinse-active preparation and at least one solid washing-active, cleansing-active or rinse-active preparation, which are spatially separated from one another;
2. (B) at least one of the preparations according to (a) completely or partially surrounding enclosure of a disintegratable under washing, cleaning or rinsing conditions, the / the hollow body (s) dimensional stability imparting, injection-molded material; and
3. (c) one or more walls which spatially separate / separate the same or different detergent-active, cleaning-active or rinse-active components or preparations.

• man eine Waschmittel-Portion nach der obigen und der nachfolgenden detaillierten Beschreibung in die Waschmaschine, insbesondere in deren Einspülkammer oder Waschtrommel, eingibt;
• man die gewünschten Waschbedingungen einstellt; und
• bei Eintreten dieser Bedingungen die waschaktive(n) Zubereitung(en) der Waschmittel-Portion in die Waschflotte freigesetzt und diese mit dem zu waschenden Gut in Kontakt gebracht werden.

The invention also relates to a washing process, in particular to a method of machine washing in a commercial washing machine, comprising the steps of

• one enters a detergent portion according to the above and the following detailed description in the washing machine, in particular in their Einspülkammer or washing drum;
• to set the desired washing conditions; and
• when these conditions occur, the wash-active preparation (s) of the detergent portion are released into the wash liquor and these are brought into contact with the product to be washed.

• man eine Reinigungsmittel-Portion nach der obigen und der nachfolgenden detaillierten Beschreibung in die Reinigungsflotte eingibt;
• man die gewünschten Reinigungsbedingungen einstellt; und
• bei Eintreten dieser Bedingungen die reinigungsaktive(n) Zubereitung(en) der Reinigungsmittel-Portion in die Reinigungsflotte freigesetzt und diese mit dem zu reinigenden Gut in Kontakt gebracht werden.

The invention also relates to a cleaning method comprising the steps of

• one enters a detergent portion according to the above and the following detailed description in the cleaning liquor;
• you set the desired cleaning conditions; and
• when these conditions occur, the cleaning-active preparation (s) of the cleaning agent portion are released into the cleaning liquor and brought into contact with the material to be cleaned.

• man eine Spülmittel-Portion nach der obigen und der nachfolgenden detaillierten Beschreibung in die Geschirrspülmaschine, insbesondere in deren Einspülkammer oder in deren Spülraum eingibt;
• man die gewünschten Spülbedingungen einstellt; und
• bei Eintreten dieser Bedingungen die spülaktive(n) Zubereitung(en) der Spülmittel-Portion in die Spülflotte freigesetzt und diese mit dem zu spülenden Gut in Kontakt gebracht werden.

The invention also relates to a rinsing method, in particular to a method of machine rinsing in a commercial dishwashing machine, comprising the steps of

• one enters a detergent portion according to the above and the following detailed description in the dishwasher, in particular in the Einspülkammer or in the washing compartment;
• to set the desired rinsing conditions; and
• when these conditions occur, the rinse-active preparation (s) of the detergent portion are released into the rinsing liquor and brought into contact with the product to be rinsed.

In the context of the present invention, the term "detergent, cleaning agent or detergent portion" is understood as meaning a quantity of a detergent, cleaning agent or rinsing agent which is sufficient for a washing, cleaning or rinsing process taking place in an aqueous phase. This can be, for example, a machine washing, cleaning or rinsing process, as is carried out with commercially available washing machines or dishwashers. According to the invention, however, this term is also understood to mean a hand washing cycle (performed, for example, in a hand basin or in a bowl) or a dishwashing process carried out by hand or another process of washing or cleaning. According to the invention, the preferred Detergent, detergent or detergent portions used in automatic washing, cleaning or rinsing operations.

In the context of the present invention, the term "detergent or cleaning agent or detergent partial portion" is understood to mean a partial amount of a detergent or cleaning agent or detergent portion which is in a phase separate from other detergent or cleaning agent or detergent portions is in spatial communication with other detergent or detergent or detergent part portions of the same detergent or detergent or detergent portion, for example, in a separate compartment in a dimensionally stable hollow body according to the invention, and which is prepared by suitable measures so that they separated from other detergent or detergent or detergent part portions of the same detergent or detergent or detergent portion into the liquor and optionally dissolved or suspended in it. In this case, a detergent or detergent or detergent partial portion may contain the same ingredients as another detergent or detergent or detergent portion of the same detergent or detergent or detergent portion; However, two detergent or cleaning agent or detergent partial portions of the same detergent or cleaning agent or detergent portion preferably contain different ingredients, in particular different detergent-active, cleaning-active or rinse-active preparations.

According to the invention, the detergent or cleaning agent or detergent portions contain measured amounts of at least one washing-active, cleaning-active or rinse-active preparation, usually measured amounts of several washing-active, cleaning-active or rinse-active preparations. It is possible that the portions contain only detergent-active, cleaning-active or rinse-active preparations of a particular composition. According to the invention, however, it is preferred that several, usually at least two, washing active, cleaning active or rinse active preparations of different composition in the detergent or detergent or detergent portions are included. The composition may be (qualitatively) different with regard to the concentration of the individual components of the washing-active, cleaning-active or rinse-active preparation (quantitatively) and / or with regard to the nature of the individual components of the washing-active, cleaning-active or rinse-active preparation. It is particularly preferred that the components are adapted in terms of nature and concentration to the tasks that have to meet the detergent or detergent or detergent partial portions in the washing, cleaning or rinsing.

For the purposes of the present invention, the term "washing-active or cleaning-active or rinse-active preparation" is understood to mean all conceivable substances of relevance in connection with a washing or cleaning or rinsing process. These are primarily the actual detergents or detergents or dishwashing detergents with their individual components explained in the further course of the description. These include active ingredients such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builders (inorganic and organic builders), bleaches (such as peroxy bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, specialty polymers ( for example, those with cobuilder properties), grayness inhibitors, dyes and fragrances (perfumes), without the term being limited to these substance groups.

However, the term "washing-active or cleaning-active or rinse-active preparations" is also understood to mean washing auxiliaries and cleaning auxiliaries or rinse aids. Examples of these are optical brighteners, UV protectants, so-called Soil Repellents, ie polymers which counteract re-soiling of fibers or hard surfaces (including dishes), as well as silver protectants, colorants and decolorizing agents. Laundry-treating agents such as fabric softener or dishwashing detergent additives such as rinse aid are also considered according to the invention as detergent-active or as detergent-active or as dishwashing active preparations.

According to the detergent, cleaning agent or detergent portions are contained in a hollow body having a plurality of chambers. The exact shape of the hollow body is just as critical in this context as its size; The only requirement in this regard is that shape and size are in accordance with the later use, ie use in a washing, cleaning or rinsing process, in particular in conventional washing machines or dishwashers. Conceivable hollow bodies in spherical, ellipsoidal, cubic, cuboid, trapezoidal, conical or pyramid or Trochoidform; cuboidal or trochoidal hollow body have inventively well proven and can therefore be used with advantage.

The size of the hollow body is in preferred embodiments of the invention such that the hollow body in the dispensing compartment of a commercial washing machine or dishwasher, in the laundry entraining nets or bags o. Ä. Can be entered. Particularly preferred embodiments of the inventive detergent, cleaning agent or detergent portions do not exceed a length (longest axis) of 10 cm, while the sizes of the width and the height are significantly lower, for example 1 to 5 cm.

The term "dimensionally stable hollow body" is understood according to the invention as meaning that the moldings containing the detergent, cleaning agent or detergent portions have an intrinsic dimensional stability which enables them, under customary conditions of preparation, storage, transport and handling To provide the consumer with a structure which is stable against breakage and / or pressure and does not coincide, and which does not change over a longer period even under the conditions mentioned. According to the invention, it does not influence whether this structural stability results from the properties of the dimensionally stable hollow body resulting from various parameters mentioned below alone or from the presence of compartmentalizing devices. In preferred embodiments of the invention, even the dimensionally stable hollow body itself have a sufficient intrinsic dimensional stability, since this has an advantageous effect on the mobility in machines in the manufacture of the hollow body and the filling during the preparation of detergent, detergent or detergent portions of the invention ,

The pressure resistance of the dimensionally stable hollow body according to the invention is measured in the (per se conventional) way so that unfilled and possibly provided with compartmentalization devices hollow body with films or lids are closed and applied to this hollow body at room temperature an internally applied, steadily increasing vacuum is until the hollow body begins to collapse. The intrinsic dimensional stability of the hollow bodies should be particularly preferably such that in such vacuum collapse tests unfilled and optionally provided with Kompartimentierungseinrichtungen hollow body collapse does not begin before reaching a vacuum of 900 mbar, preferably from 750 mbar and in particular from 500 mbar , In this respect, the hollow bodies used according to the invention fundamentally differ from films or so-called "pouches", as they are also used to provide detergents, cleaning agents or rinsing agents. These collapse already at a pressure which is only slightly below the atmospheric pressure. In a similar manner, however, the dimensionally stable hollow bodies according to the invention also differ from (subsequently applied to moldings) coatings: The hollow bodies according to the invention represent an independent, self-supporting coating, which as a rule already prior to filling with one or more wash-active, rinse-active or cleaning-active components (n) exists and is then filled. In contrast, coatings are applied to existing moldings (eg, compacts, granules, extrudates, etc.) and then dried or cured; they form only then an envelope surrounding the molding.

According to the invention, it is particularly preferred if the walls of the hollow bodies used according to the invention continue to form a good diffusion barrier in the same way as the devices for compartmentalization which are to be explained in detail below, in particular for substances which are detrimentally active in washing, detergent or dishwashing active preparations, in particular gaseous substances and especially water vapor. A diffusion of water vapor should be at most in an amount of 350 g / (m ^2. 24 h), preferably to be possible, more preferably only in an amount in the range of a maximum of 100 g /, even more preferably in (m ² · 24 h) Amount of a maximum of 50 g / (m ² .24 h).

Embodiments of the detergent, cleaning agent or rinsing agent portions in the dimensionally stable hollow bodies which are particularly preferred according to the invention also take account of the fact that the portions contained in the hollow bodies are of particular advantage-though not mandatory-at a certain point in time-preferably controllable-water solubility of the hollow body material the washing, cleaning or rinsing process or on reaching a certain pH or a certain ionic strength of the wash liquor or due to other controllable events or conditions in the aqueous liquor can be fed. The quality of the material as well as its quantity / strength directly influence these solubility properties. Particular preference is given to materials for the hollow bodies, which-based on a certain wall thickness, which determines the stability-dissolve at certain temperatures, pH values, ionic strengths, or after a certain residence time in the aqueous liquor. In this case, such a release process can capture the hollow body as a whole or only a part thereof, so that parts of the hollow body solve when setting a certain parameter combination, while other parts are not yet (but later) or not at all. The latter can be achieved by different quality of the material as well as by different amounts of material (thickness of the wall) or different geometries of the hollow body. For example, it is possible to impede the access of water by the hollow body geometry and thus delay the dissolution process. In another preferred embodiment, it is possible to make walls of the hollow body of different thicknesses (nevertheless of the same material) and thus to allow earlier dissolution at the thinner locations. In likewise preferred embodiments, the walls of the hollow body can be made of materials of different water solubility, for example of polyvinyl alcohols (PVAL) with different residual acetate content. This leads to the formation of perforated walls, which allow water to penetrate into the hollow body and / or escape of the dissolved or undissolved ingredients from the hollow body.

It is also possible that the materials of the walls of the dimensionally stable hollow body consist of a washing-active, cleaning-active or flushing active substance, for which PVAL is an example as a builder, or contain such. In the latter case, for example, washing active, cleaning active or active ingredients that are only present in small amounts in the preparations and their uniform incorporation is therefore not unproblematic, in the material of the wall of the hollow body or in a part of the material of the wall of the hollow body, for example one which dissolves at the stage of the washing, cleaning or rinsing, in which the active ingredient is just needed, incorporated and released when dissolving the material of the wall at the right time in the fleet. An example of this may be fragrances which are desired in the final stage of the washing or cleaning or rinsing process, but also optical brighteners, UV protectants, dyes and other detergent-active, cleaning-active or rinse-active preparations. The basic principle of the incorporation of such (usually in small amounts) incorporated components in the materials which form the enclosure of detergent, detergent or detergent partitions, the applicant's patent application WO 01/00781 A 1 entitled "active ingredient" Portion pack ", published on 4.01.01.

In a particular embodiment of the invention, it is also possible that the walls of the dimensionally stable hollow body containing the detergent, detergent or detergent portions, consist of different materials, so have a heterogeneous structure. For example, in a polymer material forming the wall of the hollow body, islands could be dispersed from a foreign material insoluble in the polymer, for example from another polymer (having different water solubility) or even from a completely different substance (for example, an inorganic or organic substance). Examples of these are water-soluble salts such as sodium sulfate, sodium chloride, sodium carbonate, calcium carbonate, organic acids such as citric acid, tartaric acid, adipic acid, phthalic acid; Sugars such as maltoses, dextrose, sorbitol, etc .; zeolites; silicates; crosslinked, for example weakly crosslinked polymers such as polyacrylates, cellulose esters, cellulose ethers such as carboxymethylcellulose. Such a structure may be associated in particularly preferred embodiments of the invention with the advantage that the other substance dissolves faster in water than the polymer, which allows penetration of water into the hollow body and thereby accelerated release of washing active, flushing or cleaning active components of the Portion contributes. Overall, the entire dimensionally stable hollow body is dissolved faster in such a packaging than a molded body made of a pure polymer material. Similarly, it is possible for the walls of the hollow bodies to be made up of layers of two or more polymers form, which can be selected in particularly preferred embodiments so that they complement each other optimally in terms of their properties (stability, heat resistance, water solubility, gas barrier properties, etc.).

The hollow body comprises in its interior several compartments, so chambers. Such a chamber or such a compartment is usually limited by walls (in only one compartment, these are the walls of the hollow body) limited space. Within the walls of the dimensionally stable hollow body according to the invention are several rooms. These are formed by the fact that individual rooms are delimited by walls, which are referred to in the context of the present invention as "compartmentalizing facilities" and spatially separate the same or different washing active, rinse active or cleaning active components or preparations. The chamber or compartment is wholly or partially, advantageously completely, surrounded by the enclosure of a non-compressed material which can be disintegrated under washing, cleaning or rinsing conditions, which forms the wall of the dimensionally stable hollow body. In the compartment or in the chamber, one or more detergent-active, cleaning-active or rinse-active preparation (s) is / are contained. In most embodiments of the invention, a compartment advantageously contains a plurality of detergent-active, detergent-active or rinse-active preparations; However, the case of the presence of only one such preparation in a compartment or in a chamber is also conceivable.

The dimensionally stable hollow body according to the invention contains in its interior several compartments or chambers, each containing one or more washing active, cleaning active or rinse active preparation (s). Examples of these are cuboidal or trochoidal dimensionally stable hollow bodies, the two, three or four or even more compartments, each containing one or more detergent-active, detergent-active or rinse-active preparation (s). A great advantage of this embodiment of the invention is that the various detergent-active, cleaning-active or rinse-active preparations can be distributed to the compartments as best for the specific requirements. Thus, components that adversely affect each other in their effectiveness (for example, enzymes, alkali, bleach, etc.) or otherwise - for example, due to the state of aggregation - would mix together (for example, solid and liquid components), spatially separated. On the other hand, it is possible to spatially separate components which should optimally be released into the respective liquor at different times of the washing, cleaning or rinsing process and to introduce them into the liquor at the optimum time.

The size and shape of the individual compartments within a dimensionally stable hollow body is not critical and can be largely tailored to the needs of the individual case. For example, larger compartments may be provided for certain washing-active, cleansing-active or rinse-active preparations or mixtures thereof which are present in a larger amount than for preparations which are present only in small quantities. In other embodiments of the invention that can be used with advantage, mixtures of certain preparations, which are provided at the beginning of the washing, cleaning or rinsing process and present in specific amounts, can be spatially separated from other components or components required in other quantities and arranged in compartments of a different size become.

In a particularly preferred embodiment of a detergent, detergent or detergent portion contained in a dimensionally stable hollow body with a plurality of compartments, two or more compartments comprising one or more detergent-active, detergent-active or rinse-active preparation (s) are enclosed by the hollow body, which are arranged enclosing each other. The compartments with the detergent-active, cleaning-active or rinse-active preparation (s) are thus not arranged next to one another or above or below one another in the hollow body, but enclosing one another, for example more or less concentrically ("onion model") or more or less coaxially (" Multi-layered rod model ") or in such a way that the innermost compartment is completely surrounded by the next outer, possibly completely again from the following, etc. In such a case, the washing-active, cleaning-active or rinsing-active substances can be distributed over the compartments, that the components required first in the washing, cleaning or rinsing process are contained in the outermost compartment which is first exposed to water or liquor while (later) required component (s) in (a) further inside compartment (s) is / are and / or are protected against the ingress of water by the more external compartments / are. In the context of this embodiment, it is not necessary that the internal compartments are completely enclosed by the outer; a partial enclosure is also within the scope of the present invention.

It corresponds to a preferred embodiment, when the dimensionally stable hollow body one or more water-soluble (s) polymer (s), preferably one or more materials from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL)

In a further, likewise preferred embodiment, it is advantageous in accordance with the invention for the dimensionally stable hollow body (s) to comprise one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof comprises / comprise.

• Mischungen aus 50 bis 100 % Polyvinylalkohol oder Poly(vinylalkohol - co - vinylacetat) mit Molekulargewichten im Bereich von 10.000 bis 200.000 g/mol und Acetatgehalten von 0 bis 30 Mol-%; diese können Verarbeitungszusätze wie Weichmacher (Glycerin, Sorbit, Wasser, PEG usw.), Gleitmittel (Stearinsäure und andere Mono-, Di- und Tricarbonsäuren), sogenannte "Slipmittel" (z. B. "Aerosil"), organische und anorganische Pigmente, Salze, Blasformmittel (Citronensäure-Natriumbicarbonat-Mischungen) enthalten;
• Acrylsäure-haltige Polymere, wie z. B. Copolymere, Terpolymere oder Tetrapolymere, die mindestens 20 % Acrylsäure enthalten und ein Molekulargewicht von 5.000 bis 500.000 g/mol besitzen; als Comonomere sind besonders bevorzugt Acrylsäureester wie Ethylacrylat, Methylacrylat, Hydroxy-ethylacrylat, Ethylhexylacrylat, Butylacrylat, und Salze der Acrylsäure wie Natriumacrylat, Methacrylsäure und deren Salze und deren Ester wie Methylmethacrylat, Ethylmethacrylat, Trimethylammoniummethylmethacrylatchlorid (TMAEMC), Methacrylat-amidopropyl-trimethylammoniumchlorid (MAPTAC). Weitere Monomere wie Acrylamid, Styrol, Vinylacetat, Maleinsäureanhydrid, Vinylpyrrolidon sind ebenfalls mit Vorteil verwendbar;
• Polyalkylenoxide, bevorzugt Polyethylenoxide mit Molekulargewichten von 600 bis 100.000 g/mol und deren durch Pfropfcopolymerisation mit Monomeren wie Vinylacetat, Acrylsäure und deren Salzen und deren Estern, Methacrylsäure und deren Salzen und deren Estern, Acrylamid, Styrol, Styrolsulfonat und Vinylpyrrolidon modifizierte Derivate (Beispiel: Poly-(ethylenglykol - graft - vinylacetat). Der Polyglykol-Anteil sollte 5 bis 100 Gew.% betragen, der Pfropfanteil sollte 0 bis 95 Gew.-% betragen; letzterer kann aus einem oder aus mehreren Monomeren bestehen. Besonders bevorzugt ist ein Pfropfanteil von 5 bis 70 Gew.%; dabei sinkt die Wasserlöslichkeit mit dem Pfropfanteil;
• Polyvinylpyrrolidon (PVP) mit einem Molekulargewicht von 2.500 bis 750.000 g/mol;
• Polyacrylamid mit einem Molekulargewicht von 5.000 bis 5.000.000 g/mol;
• Polyethyloxazolin und Polymethyloxazolin mit einem Molekulargewicht von 5.000 bis 100.000 g/mol;
• Polystyrolsulfonate und deren Copolymere mit Comonomeren wie Ethyl-(meth-)acrylat, Methyl(meth-)acrylat, Hydroxyethyl(meth-)acrylat, Ethylhexyl(meth-)acrylat, Butyl(meth)acrylat und den Salzen der (Meth-) Acrylsäure wie Natrium-(meth-)acrylat, Acrylamid, Styrol, Vinylacetat, Maleinsäureanhydrid, Vinylpyrrolidon; der Comonomer-Gehalt sollte 0 bis 80 Mol-% betragen, und das Molekulargewicht sollte im Bereich von 5.000 bis 500.000 g/mol liegen;
• Polyurethane, insbesondere die Umsetzungsprodukte von Diisocyanaten (z. B. TMXDI) mit Polyalkylenglykolen, insbesondere Polyethylenglykolen des Molekulargewichts 200 bis
• 35.000, oder mit anderen difunktionellen Alkoholen zu Produkten mit Molekulargewichten von 2.000 bis 100.000 g/mol;
• Polyester mit Molekulargewichten von 4.000 bis 100.000 g/mol, basierend auf Dicarbonsäuren (z. B. Terephthalsäure, Isophthalsäure, Phthalsäure, Sulfoisophthalsäure, Oxalsäure, Bernsteinsäure, Suffobemsteinsäure. Glutarsäure, Adipinsäure, Sebacinsäure usw.) und Diolen (z. B. Polyethylenglykole, beispielsweise mit Molekulargewichten von 200 bis 35.000 g/mol);
• Celluloseether/ester, z. B. Celluloseacetate, Cellulosebutyrate, Methylcellulose, Hydroxypropylcellulose, Hydroxyethylcellulose, Methylhydroxypropylcellulose usw.;
• Polyvinylmethylether mit MoleKulargewichten von 5.000 bis 500.000 g/mol.

With particular advantage, one or more materials may be cited from the following illustrative but non-limiting list:

• Mixtures of 50 to 100% polyvinyl alcohol or poly (vinyl alcohol-co-vinyl acetate) having molecular weights in the range of 10,000 to 200,000 g / mol and acetate contents of 0 to 30 mol%; these may include processing additives such as plasticizers (glycerine, sorbitol, water, PEG, etc.), lubricants (stearic acid and other mono-, di- and tricarboxylic acids), so-called "slip agents" (eg "Aerosil"), organic and inorganic pigments, Salts, blowing agents (citric acid-sodium bicarbonate mixtures);
• Acrylic acid-containing polymers, such as. Copolymers, terpolymers or tetrapolymers containing at least 20% of acrylic acid and having a molecular weight of from 5,000 to 500,000 g / mol; Particularly preferred comonomers are acrylic esters such as ethyl acrylate, methyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, butyl acrylate, and salts of acrylic acid such as sodium acrylate, methacrylic acid and their salts and their esters such as methyl methacrylate, ethyl methacrylate, trimethylammonium methylmethacrylate chloride (TMAEMC), methacrylate-amidopropyltrimethylammonium chloride (MAPTAC ). Other monomers such as acrylamide, styrene, vinyl acetate, maleic anhydride, vinyl pyrrolidone are also useful with advantage;
• Polyalkylene oxides, preferably polyethylene oxides having molecular weights of 600 to 100,000 g / mol and their derivatives by graft copolymerization with monomers such as vinyl acetate, acrylic acid and their salts and their esters, methacrylic acid and its salts and their esters, acrylamide, styrene, styrenesulfonate and vinylpyrrolidone modified derivatives (Example: The amount of polyglycol should be from 5 to 100% by weight, and the amount of grafting should be from 0 to 95% by weight, the latter consisting of one or more monomers, a grafting portion being particularly preferred from 5 to 70% by weight, the water solubility decreasing with the grafting portion;
• Polyvinylpyrrolidone (PVP) having a molecular weight of 2,500 to 750,000 g / mol;
• Polyacrylamide having a molecular weight of 5,000 to 5,000,000 g / mol;
• Polyethyloxazoline and polymethyloxazoline having a molecular weight of 5,000 to 100,000 g / mol;
• Polystyrenesulfonates and their copolymers with comonomers such as ethyl (meth) acrylate, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, butyl (meth) acrylate and the salts of (meth) acrylic acid such as sodium (meth) acrylate, acrylamide, styrene, vinyl acetate, maleic anhydride, vinylpyrrolidone; the comonomer content should be 0 to 80 mol%, and the molecular weight should be in the range of 5,000 to 500,000 g / mol;
• Polyurethanes, in particular the reaction products of diisocyanates (eg TMXDI) with polyalkylene glycols, in particular polyethylene glycols of molecular weight 200 to
• 35,000, or with other difunctional alcohols to products with molecular weights from 2,000 to 100,000 g / mol;
• Polyesters having molecular weights of 4,000 to 100,000 g / mol, based on dicarboxylic acids (eg terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid, oxalic acid, succinic acid, succinic acid, glutaric acid, adipic acid, sebacic acid etc.) and diols (eg polyethylene glycols, for example, with molecular weights of 200 to 35,000 g / mol);
• Cellulose ethers / esters, eg. Cellulose acetates, cellulose butyrates, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, methyl hydroxypropyl cellulose, etc .;
• Polyvinyl methyl ether with molecular weights of 5,000 to 500,000 g / mol.

According to the invention, the enclosing surrounding the at least one detergent-active, rinse-active or cleaning-active preparation consists of a non-compressed material which gives dimensional stability to the hollow body. According to the invention, "non-pressed" material is understood to mean a material which is not produced by compressing (for example) washing-active, rinsing-active or cleaning-active components or preparations to give a pressed body, as in the prior art, into which other washing-active, flushing or cleaning active components or preparations are embedded, but by injection molding

For the materials that make up the devices for compartmentalization, the above information on the materials of dimensionally stable hollow bodies apply accordingly. With regard to a reliable and simple method of production, in a preferred embodiment of the invention, the compartmentalizing devices within the dimensionally stable hollow bodies are made of the same materials as the hollow bodies themselves. This allows the one-piece production in one process step and makes the production process particularly economical.

In principle, however, it is also possible to select the materials of the devices for compartmentalizing independently of the materials of the dimensionally stable hollow bodies. This has the advantage that special requirements in terms of properties, such as water solubility, the compartmentation facilities can be taken into account.

In a preferred embodiment of the invention, the compartmentation device (s) is one (or more) an activity reduction of at least one component of a detergent-active, detergent-active or rinse-active preparation inhibiting device (s). Examples of these are all the cases in which components of washing-active, cleaning-active or dishwashing preparations are spatially separated from one another, taking into account a mutual impairment of their activity. The compartmentalizing devices should then have properties that meet these requirements, for example, be substantially impervious to water vapor to keep bleach free of moisture, or should be acid or alkali free to protect enzymes from premature decomposition. Such inhibition of activity reduction not only directly contributes to a better activity of the particular protected component, but also allows to reduce the amounts of such components, since an excess is no longer required in anticipation of the otherwise usual loss of activity. In other particularly preferred embodiments of the present invention, the compartmentation device (s) is / are a device (s) that determines the quality and / or quantity of the release of components of a detergent-active, detergent-active, or rinse-active preparation. In cases in which the compartmentalizing devices have such a function, either components of the washing-active, cleaning-active or rinsing-active preparations can advantageously be dispensed into the liquor at different times of the washing, cleaning or rinsing process (qualitative control), or different amounts of certain (qualitatively identical) preparations can be put into the fleet (quantitative control).

In the former case, a dimensionally stable hollow body, for example, several compartments whose walls have a different solubility (or temperature of dissolution) in water or in the liquor. The compartments contain (washing, cleaning, rinsing) active components for the first, second and possibly further (washing, cleaning, rinsing) courses, which have different compositions, and these at different times or at different temperatures the washing, cleaning or rinsing free.

In the second exemplary case, the dimensionally stable hollow bodies can have walls and compartmentalizing devices, for example only, in which materials are incorporated which detach at different temperatures or under different other boundary conditions. For example, small holes form in the compartment walls first, which allow only a weak mass transfer between individual compartments and the outside environment and thus deliver only small amounts of a washing-active, cleaning-active or rinse-active preparation into the liquor; under others, later settable Conditions, the holes or pores are enlarged because in other conditions soluble wall components dissolve; Larger holes allow larger amounts of substance to be exchanged between the interior of the compartment (s) and the outside environment (ie, the liquor) and thus adjust the desired higher concentrations of the detergent-active, cleaning-active, or rinse-active preparation in the liquor.

• die Zeit, d. h. der Ablauf einer bestimmten Zeit, in der die Wände der formstabilen Hohlkörper und/oder die Kompartimentierungs-Einrichtungen mit einem bestimmten Medium, beispielsweise mit einer wäßrigen Flotte, in Kontakt stehen, wobei eine zuverlässige Zeitsteuerung eine lineare Lösungskinetik voraussetzt;
• die Temperatur, d. h. das Erreichen eines bestimmten Temperaturwertes im Verlauf des Temperaturprofils des Wasch-, Reinigungs- oder Spülvorgangs; die Steuerung über die Temperatur stellt insbesondere bei Geschirrspülmitteln wegen der mit jeder Stufe des Spülvorgangs steigenden Temperatur eine zuverlässige und damit bevorzugte Ausführungsform dar;
• der pH-Wert, d. h. die Einstellung eines bestimmten pH-Wertes im Verlauf eines Wasch-, Reinigungs- oder Spülvorgangs durch Komponenten der waschaktiven, reinigungsaktiven oder spülaktiven Zubereitung oder das Verlassen eines bestimmten pH-Wertes nach Zerfall einer den pH-Wert beeinflussenden oder bestimmenden Komponente;
• die Ionenstärke;
• die mechanische Stabilität, welche - in Abhängigkeit von der Zeit, von der Temperatur oder von anderen Parametern - ein die Desintegration bestimmender Faktor sein kann;
• die Permeabilität für eine bestimmte - vornehmlich gasförmige oder flüssige - Komponente; usw..

Possible "switches" of the release of the components by the compatibilizers are, in particularly preferred embodiments, physicochemical parameters which bring about the disintegration of the compartmentalizing devices and / or the walls of the dimensionally stable hollow bodies. Examples thereof, which should not be construed as limiting, are

• the time, ie the passage of a certain time in which the walls of the dimensionally stable hollow body and / or the compartmentalization devices in contact with a certain medium, for example with an aqueous liquor, wherein a reliable timing requires a linear solution kinetics;
• the temperature, ie the achievement of a certain temperature value in the course of the temperature profile of the washing, cleaning or rinsing process; the control over the temperature represents a reliable and therefore preferred embodiment, in particular for dishwashing detergents, because of the rising temperature with each stage of the flushing process;
• the pH value, ie the setting of a specific pH value during the course of a washing, cleaning or rinsing process by components of the detergent-active, cleaning-active or rinse-active preparation or the leaving of a specific pH value after decomposition of a pH influencing or determining agent Component;
• the ionic strength;
• the mechanical stability, which - depending on time, temperature or other parameters - may be a factor determining disintegration;
• the permeability for a particular - primarily gaseous or liquid - component; etc..

The aforementioned parameters are only examples that are not intended to limit the invention.

In a further preferred embodiment of the invention, the compartmentalizing device (s) is / are the activity of at least one component of a detergent-active, detergent-active or rinse-active preparation-controlling device (s). This embodiment is particularly useful in those cases where it is necessary is that the release of one or more active ingredients is a washing active, cleaning active or rinse-active preparation with a given kinetics in the washing, cleaning or rinsing liquor. A particular example is a so-called "controlled release" release, which can be controlled according to the parameters given above on the properties of the wall of the dimensionally stable hollow body and / or the Kompartimentierungsseinrichtungen. In this way, a destructive effect of the liquor or alone of the water on the active substance can be reduced and the substance can be actively released into the liquor for a longer time.

It is a further preferred embodiment of the invention that one or more compartmentalizing device (s) contain a part or the total amount of at least one component of at least one detergent-active, cleaning-active or rinse-active preparation. This can be achieved with particular advantage by incorporating one or more component (s) of at least one detergent-active, cleaning-active or rinse-active preparation into the material of the compartmenting device. Examples of such substances have been mentioned above in connection with the stable void forming material (s) and include (but are not limited to) components contained in relatively small amounts in the detergent, detergent or rinse portions Therefore, it is relatively difficult to incorporate into large mass mixtures of washing-active, cleaning-active or dishwashing preparations. A very simple incorporation succeeds in the materials of Kompartimentierungs facilities, and from these also manages a reliable, controllable release during the washing, cleaning or rinsing process. By suitable choice of materials, the release can also be carried out with "controlled release" kinetics.

A further, likewise preferred embodiment of the invention consists in that one or more compartmentalizing device (s) consists in part or in total of at least one component of at least one washing-active, cleaning-active or rinsing-active preparation. This is preferred because the compartmenting device is thus not only a component of the detergent, cleaning agent or detergent portion influencing the kinetics of the release, but at the same time also a component of the success of the washing process. , Cleaning or rinsing process is involved. Due to the wide variety of available materials, there are numerous examples for this embodiment; particularly preferred are compartmentalizing devices consisting of or comprising (meth) acrylic acid and its derivatives (salts, esters) comprising polymers.

A further preferred embodiment of the invention consists in a detergent, detergent or rinsing agent portion contained in one or more dimensionally stable hollow body (s) with a plurality of chambers, in which the dimensionally stable hollow body consists of a non-spherical hollow body having n surfaces, of which an area assumes the function of a "lid", which is the conclusion of a process for producing the detergent, detergent or detergent portions according to the invention, ie after filling the / the compartments (s) in the interior of the hollow body with one or more washing-active, cleaning-active or rinse-active preparation (s) is applied while closing the hollow body. The "lid" particularly preferably consists of a material with controllable water solubility and can be bonded to the remaining hollow body by bonding, for example with a water-soluble adhesive, fusing, welding or another known method of joining materials. This embodiment is particularly advantageous for producing the detergent, cleaning agent or detergent portions according to the invention, since a stepwise filling of the compartment (s) with one or more detergent-active, cleaning-active or rinse-active preparations is possible and the handling during subsequent use leads to optimum results leads, in particular to a reliable control of the access of water or aqueous liquor to the interior of the dimensionally stable hollow body or the outlet of washing active, cleaning active or rinse-active preparation from the interior of the hollow body.

The detergent, cleaner or rinse aid portions according to the invention contain one or more substances from the group of surfactants, surfactant compounds, builders, bleaches, bleach activators, enzymes, foam inhibitors, dyes and fragrances and - in the case that the detergents or cleaning agents - Portions are present at least in part as shaped bodies - binding and disintegration aids. These classes of substances are described below.

To develop the washing performance, the washing and cleaning agent portions according to the invention may contain surface-active substances from the group of anionic, nonionic, zwitterionic or cationic surfactants, with anionic surfactants being clearly preferred for economic reasons and because of their power spectrum.

As 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. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of 2-sulfofatty acids (ester sulfonates), for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Further preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, petrochemical-based straight-chain alkyl radical which has an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . 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.

Further 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. 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. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts. In a further embodiment of the invention, surfactants are used in the form of their magnesium salts.

In the context of the present invention, detergent, detergent or rinse agent portions are preferred which contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 15 to 25% by weight of one or more anionic surfactant (e), in each case based on the detergent, detergent or detergent portion.

When selecting the anionic surfactants that are used in the detergent, cleaner and rinse portions according to the invention, the freedom from formulation no restrictions to be met in the way. However, 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 As 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. In particular, however, 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). In addition to these nonionic surfactants, 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.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese Patent Application JP 58/217598 or preferably prepared according to the method described in international patent application WO-A-90/13533.

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). 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.

Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

The detergent, cleaner or rinse aid portions according to the invention may preferably contain alkylpolyglycosides, with contents of the detergent and cleaner portions of APG being above 0.2% by weight, based on the total preparation, being preferred. Particularly preferred detergent, cleaning agent or detergent portions contain APG in amounts of from 0.2 to 10% by weight, preferably in amounts of from 0.2 to 5% by weight and in particular in amounts of from 0.5 to 3% by weight .-%.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (I)

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which are usually prepared by reductive amination of a reducing sugar with ammonia, a Alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propxylierte Derivate dieses Restes. [Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.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. [Z] is preferably obtained by reductive amination of 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.

Furthermore, it may be preferable to use not only anionic and nonionic surfactants but also cationic surfactants. Their use is preferably carried out as Waschleistungsbooster, with only small amounts of cationic surfactants are required. If cationic surfactants are used, they are preferably present in the compositions in amounts of from 0.01 to 10% by weight, in particular from 0.1 to 3.0% by weight.

In the cases in which the detergent, cleaner or rinse agent portions according to the invention are detergents, these usually contain one or more surfactants in total amounts of from 5 to 50% by weight, preferably in amounts of 10 to 35 wt .-%, wherein in partial portions of the detergent portions of the invention surfactants may be contained in greater or smaller amount. In other words: the amount of surfactant need not be the same in all partial portions; Rather, partial portions can be provided with relatively larger and partial portions with relatively smaller surfactant content.

In the cases in which the detergent, cleaning agent or detergent portions according to the invention are detergents, in particular dishwashing detergents, contain these usually one or more surfactant (s) in total amounts of 0.1 to 10 wt .-%, preferably in amounts of 0.5 to 5 wt .-%, wherein in partial portions of the detergent or detergent portions of the invention surfactants in larger or smaller amount can be included. In other words, the amount of surfactant does not have to be the same in cleaning or dishwashing detergents in all partial portions; Rather, partial portions can be provided with relatively larger and partial portions with relatively smaller surfactant content.

In addition to the washing-active substances, builders are the most important ingredients of detergents and cleaners. In the detergent, detergent or rinse aid portions according to the invention, builders usually used in detergents, cleaning agents or dishwashing detergents can be present, in particular zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} ^. H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European Patent Application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ -yH ₂ O are preferred, and β-sodium disilicate can be obtained, for example, by the method described in International Patent Application WO-A-91/08171.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay over conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction nebulization or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that in X-ray diffraction experiments, the silicates do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products are microcrystalline Have ranges of size 10 to several hundred nm, with values up to max. 50 nm and in particular up to max. 20 nm are preferred. Especially preferred are densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

A fine crystalline, synthetic and bound water-containing zeolite optionally used is preferably zeolite A and / or P. Zeolite MAP (eg, commercial product: Doucil A24 from Crosfield) is particularly preferred as the P-type zeolite. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ O (1-n) K ₂ O. 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 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, in detergents, a use of the well-known phosphates as builders possible, unless such use should not be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided their use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acids themselves can also be used. In addition to their builder effect, the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of washing and cleaning agent portions according to the invention. In particular, in this context, citric acid, Succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof.

As builder further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70,000 g / mol.

In the context of the present invention, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrene acids are generally significantly higher than the molecular weights specified in the context of the present invention.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molecular weights of from 2,000 to 10,000 g / mol, more preferably from 3,000 to 5,000 g / mol, may in turn be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid or of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molar mass, based on free acids, is generally from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of the detergent or cleaner portions of (co) polymeric polycarboxylates according to the invention is preferably from 0.5 to 20% by weight, in particular from 3 to 10% by weight.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer. In particular, biodegradable polymers from more than two different monomer units, for example those which are salts of the monomers as monomers, are preferred Acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymers are those which contain as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives which, in addition to co-builder properties, also have a bleach-stabilizing action.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids having 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which is a DE of 100 owns. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2,000 to 30,000 g / mol. A preferred dextrin is described in British Patent Application 94 19 091.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Also suitable is an oxidized oligosaccharide. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are also other suitable co-builders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Other useful organic co-builders are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

Another class of substances with co-builder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroalkane phosphonates, the 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH = 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octasodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferable, especially if the washing or cleaning agent portions according to the invention also contain bleach, to use Aminoalkanphosphonate, in particular DTPMP, or to use mixtures of said phosphonates.

In addition, all compounds capable of forming complexes with alkaline earth metal ions can be used as co-builders.

In addition to the constituents surfactant and builder, the detergents, cleaning or rinsing agents according to the invention may contain further ingredients customary in detergents, cleaners or rinsing agents from the group of bleaches, bleach activators, alkalizing agents, acidifiers, enzymes, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, Silicone oils, anti-redeposition agents, optical brighteners, grayness inhibitors, dye transfer inhibitors, decolorizing and flocculating agents, antibacterial agents and corrosion inhibitors.

Among the compounds serving as bleaches in water H ₂ O ₂ , 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. When cleaning or bleaching preparations for automatic dishwashing are prepared, it is also possible to use bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the 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-α-naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-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-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid ) can be used.

As bleaching agents in automatic dishwashing compositions it is also possible to use chlorine or bromine-releasing substances. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

In order to achieve an improved bleaching effect during washing, cleaning or rinsing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the detergent, cleaning agent or detergent portions. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to or in place of the conventional bleach activators, so-called bleach catalysts may also be incorporated into the detergent, cleaner, or rinse agent portions. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. Enzyme mixtures, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but in particular cellulase-containing mixtures are of particular interest. Peroxidases or oxidases have also proved suitable in some cases. The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation. The proportion of the enzymes, enzyme mixtures or enzyme granules in the compositions according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

Enzymes are added according to the prior art primarily to a detergent composition, in particular a dishwashing agent, which is intended for the main rinse. Disadvantage was that the optimum effect of enzymes used limited the choice of temperature and also encountered problems in the stability of the enzymes in a strongly alkaline medium. With the washing or cleaning agent portions according to the invention, it is possible to introduce enzymes into a separate compartment and then to use them in the pre-wash and thus to use the pre-rinse cycle in addition to the main rinse for an enzyme action on contamination of the dishes.

Thus, according to the invention, the washing-active preparation or partial portion of a cleaning agent or detergent portion intended for the pre-wash cycle is particularly preferred Add enzymes and then such a preparation - more preferably - with a water-soluble at low temperature material of a dimensionally stable hollow body to protect, for example, the enzyme-containing preparation from loss of activity by environmental conditions. The enzymes are more preferably optimized for use under the conditions of the pre-wash cycle, that is, for example, in cold water.

Advantageously, the detergent portions of the invention may then be when the enzyme preparations are liquid, as they are sometimes available commercially, because then a rapid effect can be expected, which already occurs in (relatively short and carried out in cold water) pre-wash. Even if - as usual - the enzymes are used in solid form and they are provided with a hollow body enclosure made of a water-soluble material that is already soluble in cold water, the enzymes can unfold their effect before the main wash or main cleaning. Advantage of the use of an enclosure of water-soluble material, in particular of cold water-soluble material is that the enzyme / enzymes in cold water after dissolution of the enclosure comes to effect quickly / come. Thus, their duration of action can be extended, which benefits the washing or rinsing results.

According to a particularly preferred embodiment, the detergent, cleaning agent or rinsing agent portions according to the invention also contain further additives known from the state of the art as additives for detergent preparations. These can either one or more, if necessary, all portions (washing active, cleaning active or rinsing active preparations) of detergent, detergent or detergent portions of the invention are added or - as in the co-pending patent application no. 199 29 098.9 with the Title "active ingredient portion package" described - in the water-soluble, the washing active, cleaning active or rinse-active preparations comprising materials of dimensionally stable hollow body, so for example, in the / the water-soluble wall material (s) are incorporated.

A preferred group of additives used in the invention are optical brighteners. Can be used here, the usual in detergents optical brightener. These are added as an aqueous solution or as a solution in an organic solvent of the polymer solution, which is converted into the wall of the dimensionally stable hollow body, or are added to a portion (washing active preparation) of a detergent or cleaning agent in solid or liquid form. Examples of optical brighteners are derivatives of diaminostilbene disulfonic acid or its alkali metal salts. Suitable z. B. salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or the like compounds which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group. In addition, brighteners of the type of substituted diphenylstyrene may be present in the partial portions (wash-active preparations) of the washing or cleaning agent portions according to the invention, e.g. For example, the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl or 4- (4-chlorostyryl) 4 '- (2 -sulfostyryl-) biphenyl. Mixtures of the aforementioned brightener can be used.

Another group of additives which is preferred according to the invention are UV protection substances. These 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.

Other conceivable additives which are preferred in specific embodiments are surfactants which can influence in particular the solubility of the water-soluble wall of the dimensionally stable hollow body or the compartmenting device, but can also control its wettability and foaming on dissolution, as well as foam inhibitors, but also bitter substances accidental ingestion of such hollow body or parts of such hollow body by children can prevent.

Another group of additives which is preferred according to the invention are dyes, in particular water-soluble or water-dispersible dyes. Preference is given here to dyes, as they are usually used to improve the appearance of the optical product in detergents and cleaning agents and detergents. The choice of such dyes is not difficult for a person skilled in the art, especially since such conventional dyes have a high storage stability and insensitivity to the other ingredients of the detergent-active, cleaning-active or rinse-active preparations and to light and no pronounced substantivity to textile fibers in order not to stain them. According to the invention, the dyes are present in the detergent or cleaning agent or detergent portions in amounts of less than 0.01% by weight.

Another class of additives which can be added to the detergent, cleaner or rinse portions in accordance with the invention are polymers. Among these polymers are on the one hand polymers in question, which show washing or cleaning or rinsing Cobuilder properties, so for example polyacrylic acids, and modified polyacrylic acids or corresponding copolymers. Another group of polymers are polyvinylpyrrolidone and other grayness inhibitors, such as copolymers of Polyvinylpyrrolidone, cellulose ethers and the like. According to a further embodiment of the invention, so-called soil repellents are also suitable as polymers, as are known to the washing and cleaning agent specialist and will be described in detail below.

Another group of additives are bleach catalysts, in particular bleach catalysts for automatic dishwashing detergents or detergents. Here are used complexes of manganese and cobalt, especially with nitrogen-containing ligands.

Another preferred group of additives within the meaning of the invention are silver protectants. These are a variety of mostly cyclic organic compounds, which are also familiar to the person skilled in the art and contribute to prevent the tarnishing of silver-containing objects in the cleaning process. Specific examples may be triazoles, benzotriazoles and their complexes with metals such as Mn, Co, Zn, Fe, Mo, W or Cu.

As further additives according to the invention, the detergent, cleaning agent or rinsing agent portions may also contain so-called soil repellents, ie polymers which are applied to fibers or hard surfaces (for example on porcelain and glass), the oil and grease wash-off properties of textiles and grease washability of porcelain and glass have a positive effect and thus specifically counteract re-soiling. This effect becomes particularly evident when a textile or a hard object (porcelain, glass) is contaminated which has already been washed several times previously with a washing or cleaning agent according to the invention which contains this oil and fat-dissolving component. Examples of preferred oil and fat dissolving components include nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a methoxy group content of 15 to 30% by weight and hydroxypropoxy groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether , As well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

All of these additives are added to the inventive detergent, cleaning agent or detergent portions in amounts of at most 30% by weight, preferably 2 to 20% by weight. As already stated, the additive may also be a material of a water-soluble enclosure of the dimensionally stable hollow body or of a material of the water-soluble Compartmenting device (s) comprising or containing in the Kormpartiment (s) or one of the detergent-active, cleaning-active or rinse-active preparation (s). To obtain the balance of the formulation, it is therefore possible for the skilled person to increase the polymer material for the wall of the hollow body or for the Kompartimentseinrichtung (s) either in its weight, so as to exploit the depot effect, which is achieved according to the invention , or else to keep the said additives additionally at least partially in the remaining detergent-active preparation. However, this is less preferred.

Fragrances are added to the inventive detergent, detergent or detergent portions to improve the overall aesthetic impression of the products and to provide the consumer in addition to the technical performance (softening result) a sensory typical and distinctive product available. As perfume oils or perfumes, individual perfume compounds can be used, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-t-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. Ethers include, for example, benzyl ethyl ether. The aldehydes include, for. B. linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, purple and bourgeonal.

The ketones include the ionone, α-isomethylionone, and methyl cedryl ketone. The alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include terpenes such as limonene and pinene. Preference is given to using mixtures of different odoriferous substances which are adapted to one another in such a way that together they produce an attractive fragrance note. Such perfume oils may also contain natural fragrance mixtures as are available from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are nutmeg oil, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.

Usually, the content of perfumes in the range up to 2 wt .-% of the total detergent, detergent or detergent portion.

The fragrances can be incorporated directly into the detergent-active, cleaning-active or spool-active preparation (s); but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the laundry and provide a slower fragrance release for long-lasting fragrance of textiles. As such carrier materials, for example, cyclodextrins have been preserved. The cyclodextrin-perfume complexes can additionally be coated with other auxiliaries.

The perfumes and fragrances can in principle be contained in each of the partial portions (washing-active or cleaning-active or rinse-active preparations) of the detergent, cleaning agent or rinsing agent portions according to the invention. However, it is particularly preferred that they are in a detergent in a provided for the post-wash cycle or fabric conditioning portion detergent portion or in a detergent, especially in a dishwashing detergent in a provided for the rinse or rinse cycle part-detergent portion, special partial-detergent portion, are included. They must therefore according to the invention of a water-insoluble only in the conditions (especially at the temperature) of Nachwaschgangs or Nachspülgangs, at the conditions (especially at the temperature) of the previous washes or rinses water-insoluble material of the dimensionally stable hollow body and the compartmentalizing device ( en). According to the invention this is feasible, for example, with a detergent, cleaning agent or detergent portion comprising several compartments in a dimensionally stable hollow body.

The detergent, cleaner or detergent portions according to the invention contain wash-active, cleaning-active or rinse-active preparations in a dimensionally stable hollow body in such quantities that they are sufficient for a washing, cleaning or rinsing process. Of course, a dosage of two units (hollow body) is possible under special conditions (heavily soiled, eg heavily greased laundry, heavily harnessed dishes).

In a particularly preferred embodiment of the invention, a detergent, cleaning agent or detergent portion contained in a dimensionally stable hollow body comprises the at least one, preferably the several, wash-active, cleaning-active or rinse-active preparation (s) in one or more forms from the group of powders, granules, extrudates, pellets, beads, tablets, tabs, rings, blocks, briquettes, solutions, melts, gels, suspensions, dispersions, emulsions, foams and gases. The shape of the washing-active, cleaning-active or rinse-active preparation contained in one or more compartments of the dimensionally stable hollow body is therefore not limited, as long as the hollow body is in the intended state

Use way. It is to be regarded as a significant advantage of the invention that for the first time the use of fluid phases in detergent, detergent or detergent portions is possible and a suitable for the administration of such fluid phases detergent, detergent or detergent portion is provided , Thus, in the compartments of a hollow body, liquids, gels, gases or foams may be closed alone or together with solid constituents in one or more compartments and, in use, brought into contact with the objects to be washed, cleaned or rinsed. This achieves a new freedom in the preparation of detergents, cleaning agents or dishwashing detergents.

The detergent, detergent or rinse agent portions disclosed herein consist of an outer mold containing multiple fillings. The hollow mold is divided by partitions into several compartments, whereby several fillings can be present within the same hollow body separated from each other. In addition to the compatibility with the material of the mold, no demands are placed on the fillings, so that both solid and liquid phases (systems) can be portioned.

The invention also provides filled hollow bodies, which consist only partially of a disintegratable under washing, cleaning or rinsing conditions, the / the hollow body (s) dimensional stability imparting, non-pressed material according to the claims, while the other parts of the enclosure is not necessarily dimensionally stable must be in the sense defined above. A preferred embodiment provides for the provision of open, dimensionally stable hollow molds ("shells"), which are filled and later closed, closing with a film having particular significance.

The film, which closes the opening of the shell is applied to the opening and adherent to the edges, which can be done for example by sticking, partial melting or by chemical reaction.

The closing film can of course also be a laminate of a plurality of differently composed films, the opening of the shell can be released at certain times in the washing and cleaning cycle via different compositions of individual film layers.

Preferred film materials are the polymers known from the prior art. Particular preference is given to films of a polymer having a molecular weight of between 5000 and 500,000 daltons, preferably between 7,500 and 250,000 daltons, and in particular between 10,000 and 100,000 daltons. With regard to the media into which detergents and cleaners are customarily incorporated, particular preference is given to portions according to the invention in which the film consists of a water-soluble polymer.

Such preferred polymers may be of synthetic or natural origin. If polymers are used on a native or partnative basis as film material, preferred film materials are selected from one or more substances from the group of carrageenan, guar, pectin, xanthan, cellulose and its derivatives, starch and its derivatives, and gelatin.

Carrageenan is a named after the Irish coastal town of Carragheen, educated and similar to Agar built extract of North Atlantic, belonging to the Floridean red algae. The carrageenan precipitated from the algae's hot water extract is a colorless to sand-colored powder with molecular weights of 100,000-800,000 and a sulphate content of about 25%, which is very slightly soluble in warm water. Carrageenan has three main constituents: the yellow-forming f- fraction consists of D-galactose-4-sulfate and 3,6-anhydro-α-D-galactose, which are alternately glycosidically linked in the 1,3- and 1,4-positions (Agar, in contrast, contains 3,6-anhydro-α-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: α, β, γ, μ, ν, ξ, π, ω, χ. Also, the type of cations present (K, NH _4, Na, Mg, Ca) affects the solubility of the carrageenans. Semisynthetic products which contain only one type of ion and can also be used as film materials in the context of the present invention are also called Carrag (h) eenates.

Guar, also known as guar flour, which can be used as a film material in the context of the present invention, is an off-white powder obtained by grinding the endosperm of guar bean (Cyamopsis tetragonobolus). The main constituent of guar is up to about 85% by weight of the dry substance guar gum (guar gum, cyamopsis gum); Secondary components are proteins, lipids and cellulose. Guaran itself is a polygalactomannan, ie a polysaccharide whose linear chain is unsubstituted (see formula I) and in the C6 position having a galactose radical substituted (see formula (II)) mannose units in β-D (1 → 4) linkage.

The ratio of I: II is about 2: 1; the II units are not strictly alternating, contrary to initial assumptions, but arranged in pairs or triplets in the polygalactomannan molecule. Data on the molecular weight of the guaran vary with values of about 2.2 × 10 ⁵ -2.2 × 10 ⁶ g / mol, depending on the degree of purity of the polysaccharide - the high value was determined on a highly purified product - significant and correspond to about 1350-13500 sugar units / macromolecule. Guaran is insoluble in most organic solvents.

Obst-Pektin enthält 95%, Rüben-Pektin bis 85% Galacturonsäure. Die Molmassen der verschiedenen Pektine variieren zwischen 10000 und 500000. Auch die Struktureigenschaften sind stark vom Polymerisationsgrad abhängig; so bilden z.B. die Obst-Pektine in getrocknetem Zustand asbestartige Fasern, die Flachs-Pektine dagegen feine, körnige Pulver.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-α-glycoside. connected galacturonic acid units whose acid groups are esterified to 20-80% with methanol, with a distinction between highly esterified (> 50%) and low-esterified pectins (<50%). The pectins have a leaflet structure and are thus in the middle of starch and cellulose molecules. Their macromolecules still contain some glucose, galactose, xylose and arabinose and have weakly acidic properties.

Fruit pectin contains 95%, beet pectin to 85% galacturonic acid. The molecular weights of the various pectins vary between 10,000 and 500,000. The structural properties are also highly dependent on the degree of polymerization; For example, the fruit pectins in the dried state form asbestos-like fibers, whereas the flax pectins form fine, granular powders.

The pectins are prepared by extraction with dilute acids mainly from the inner parts of citrus fruit peel, Obstresten or sugar beet pulp.

Also 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 β-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 β-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.

In addition to cellulose and cellulose derivatives, it is also possible to use (modified) dextrins, starch and starch derivatives as film materials.

Suitable nonionic organic film materials are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.

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 α-glycosidically. Starch is composed of two components of different molecular weight: about 20-30% straight-chain amylose (MW 50,000-150,000) and 70-80% branched-chain amylopectin (MW 300,000-2,000,000); Amounts of lipids, phosphoric acid and Contain cations. While the 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. In addition to pure starch, 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.
Among the proteins and modified proteins, gelatin as a sheet material has an outstanding importance. 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.

1. a) wasserlöslichen nichtionischen Polymeren aus der Gruppe der
   • a1) Polyvinylpyrrolidone,
   • a2) Vinylpyrrolidon/Vinylester-Copolymere,
   • a3) Celluloseether
2. b) wasserlöslichen amphoteren Polymeren aus der Gruppe der
   • b1) Alkylacrylamid/Acrylsäure-Copolymere
   • b2) Alkylacrylamid/Methacrylsäure-Copolymere
   • b3) Alkylacrylamid/Methylmethacrylsäure-Copolymere
   • b4) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymere
   • b5) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymere
   • b6) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere
   • b7) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymere
   • b8) Copolymere aus
     • b8i) ungesättigten Carbonsäuren
     • b8ii) kationisch derivatisierten ungesättigten Carbonsäuren
     • b8iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
3. c) wasserlöslichen zwitterionischen Polymeren aus der Gruppe der
   • c1) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
   • c2) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
   • c3) Methacroylethylbetain/Methacrylat-Copolymere
4. d) wasserlöslichen anionischen Polymeren aus der Gruppe der
   • d1) Vinylacetat/Crotonsäure-Copolymere
   • d2) Vinylpyrrolidon/Vinylacrylat-Copolymere
   • d3) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere
   • d4) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen
   • d5) gepropften und vernetzten Copolymere aus der Copolymerisation von
     • d5i) mindesten einem Monomeren vom nicht-ionischen Typ,
     • d5ii) mindestens einem Monomeren vom ionischen Typ,
     • d5iii) von Polyethylenglycol und
     • d5iv) einem Vernetzter
   • d6) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere:
     • d6i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
     • d6ii) ungesättigte Carbonsäuren,
     • d6iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols
   • d7) Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester
   • d8) Tetra- und Pentapolymere aus
     • d8i) Crotonsäure oder Allyloxyessigsäure
     • d8ii) Vinylacetat oder Vinylpropionat
     • d8iii) verzweigten Allyl- oder Methallylestern
     • d8iv) Vinylethern, Vinylesterrn oder geradkettigen Allyl- oder Methallylestern
   • d9) Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinymethylether, Acrylamid und deren wasserlöslicher Salze
   • d10) Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in α-Stellung verzweigten Monocarbonsäure
5. e) wasserlöslichen kationischen Polymeren aus der Gruppe der
   • e1) quaternierten Cellulose-Derivate
   • e2) Polysiloxane mit quaternären Gruppen
   • e3) kationischen Guar-Derivate
   • e4) polymeren Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure
   • e5) Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats
   • e6) Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere
   • e7) quaternierter Polyvinylalkohol
   • e8) unter den INCl-Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 angegeben Polymere.

Other polymers which can be used as film materials are synthetic polymers which are preferably water-swellable and / or water-soluble. Such synthetic-based polymers can be "tailored" for the desired film permeability during storage and dissolution of the film when used. Particularly preferred film materials are selected from a polymer or polymer mixture, wherein the polymer or at least 50 wt .-% of the polymer mixture is selected from

1. a) water-soluble nonionic polymers from the group of
   • a1) polyvinylpyrrolidones,
   • a2) vinylpyrrolidone / vinyl ester copolymers,
   • a3) cellulose ethers
2. b) water-soluble amphoteric polymers from the group of
   • b1) alkylacrylamide / acrylic acid copolymers
   • b2) alkylacrylamide / methacrylic acid copolymers
   • b3) alkylacrylamide / methylmethacrylic acid copolymers
   • b4) Alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
   • b5) Alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
   • b6) Alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
   • b7) Alkylacrylamide / Alkymethacrylate / Alkylaminoethylmethacrylate / Alkylmethacrylate Copolymers
   • b8) copolymers
     • b8i) unsaturated carboxylic acids
     • b8ii) cationically derivatized unsaturated carboxylic acids
     • b8iii) optionally further ionic or nonionic monomers
3. c) water-soluble zwitterionic polymers from the group of
   • c1) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts
   • c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts
   • c3) Methacroylethylbetaine / methacrylate copolymers
4. d) water-soluble anionic polymers from the group of
   • d1) vinyl acetate / crotonic acid copolymers
   • d2) vinylpyrrolidone / vinyl acrylate copolymers
   • d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
   • d4) graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols
   • d5) grafted and crosslinked copolymers from the copolymerization of
     • d5i) at least one nonionic type monomer,
     • d5ii) at least one ionic-type monomer,
     • d5iii) of polyethylene glycol and
     • d5iv) a networked one
   • d6) copolymers obtained by copolymerization of at least one monomer of each of the following three groups:
     • d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
     • d6ii) unsaturated carboxylic acids,
     • d6iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 -alcohols
   • d7) terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester
   • d8) tetra- and pentapolymers from
     • d8i) crotonic acid or allyloxyacetic acid
     • d8ii) vinyl acetate or vinyl propionate
     • d8iii) branched allyl or methallyl esters
     • d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
   • d9) Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts
   • d10) terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic α-branched monocarboxylic acid
5. e) water-soluble cationic polymers from the group of
   • e1) quaternized cellulose derivatives
   • e2) polysiloxanes with quaternary groups
   • e3) cationic guar derivatives
   • e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid
   • e5) Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate
   • e6) vinylpyrrolidone-methoimidazolinium chloride copolymers
   • e7) quaternized polyvinyl alcohol
   • e8) polymers specified under the INCl designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

Water-soluble polymers in the context of the invention are those polymers which are soluble in water at room temperature in excess of 2.5% by weight.

• Polyvinylpyrrolidone, wie sie beispielsweise unter der Bezeichnung Luviskol^® (BASF) vertrieben werden. Polyvinylpyrrolidone sind bevorzugte nichtionische Polymere im Rahmen der Erfindung.

The films may be made of any of the above-mentioned polymers, but it can also be used mixtures or multilayered layer structures of the polymers. The polymers are described in more detail below. Water-soluble polymers preferred according to the invention are nonionic. Suitable nonionic polymers are, for example:

• Polyvinylpyrrolidones, as sold for example under the name Luviskol ^® (BASF). Polyvinylpyrrolidones are preferred nonionic polymers in the invention.

die durch radikalische Polymerisation von 1-Vinylpyrrolidon nach Verfahren der Lösungs- oder Suspensionspolymerisation unter Einsatz von Radikalbildnern (Peroxide, Azo-Verbindungen) als Initiatoren hergestellt werden. Die ionische Polymerisation des Monomeren liefert nur Produkte mit niedrigen Molmassen. Handelsübliche Polyvinylpyrrolidone haben Molmassen im Bereich von ca. 2500-750000 g/mol, die über die Angabe der K-Werte charakterisiert werden und - K-Wert-abhängig - Glasübergangstemperaturen von 130-175° besitzen. Sie werden als weiße, hygroskopische Pulver oder als wäßrige. Lösungen angeboten. Polyvinylpyrrolidone sind gut löslich in Wasser und einer Vielzahl von organischen Lösungsmitteln (Alkohole, Ketone, Eisessig, Chlorkohlenwasserstoffe, Phenole u.a.).

• Vinylpyrrolidon/Vinylester-Copolymere, wie sie beispielsweise unter dem Warenzeichen Luviskol^® (BASF) vertrieben werden. Luviskol^® VA 64 und Luviskol^® VA 73, jeweils Vinylpyrrolidon/Vinylacetat-Copolymere, sind besonders bevorzugte nichtionische Polymere.

Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula (III)

which are prepared by free-radical polymerization of 1-vinylpyrrolidone by the method of solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer provides only low molecular weight products. Commercially available polyvinylpyrrolidones have molecular weights in the range of about 2500-750000 g / mol, which are characterized by the specification of the K values and - K value-dependent - glass transition temperatures of 130-175 ° have. They are called white, hygroscopic powder or aqueous. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

• Vinylpyrrolidone / vinyl ester copolymers, as sold, for example, under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred non-ionic polymers.

als charakteristischem Grundbaustein der Makromoleküle. Von diesen haben die Vinylacetat-Polymere (R = CH₃) mit Polyvinylacetaten als mit Abstand wichtigsten Vertretern die größte technische Bedeutung.The vinyl ester polymers are vinyl ester-accessible polymers having the grouping of the formula (IV)

as a characteristic building block of the macromolecules. Of these, the vinyl acetate polymers (R = CH ₃₎ with polyvinyl acetates, as by far the most important representatives of the greatest industrial importance.

• Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose und Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen Culminal^® und Benecel^® (AQUALON) vertrieben werden.

The polymerization of the vinyl esters is carried out free-radically by different processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization). Copolymers of vinyl acetate with vinylpyrrolidone contain monomer units of the formulas (III) and (IV)

• Cellulose ethers, such as hydroxypropylcellulose, hydroxyethylcellulose and methylhydroxypropylcellulose, as sold, for example, under the trademarks Culminal ^® and Benecel ^® (AQUALON).

in R für H oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in Formel (III) für -CH₂CH₂CH₂-OH oder -CH₂CH₂-OH. Celluloseether werden technisch durch Veretherung von Alkalicellulose (z.B. mit Ethylenoxid) hergestellt. Celluloseether werden charakterisiert über den durchschnittlichen Substitutionsgrad DS bzw. den molaren Substitutionsgrad MS, die angeben, wieviele Hydroxy-Gruppen einer Anhydroglucose-Einheit der Cellulose mit dem Veretherungsreagens reagiert haben bzw. wieviel mol des Veretherungsreagens im Durchschnitt an eine Anhydroglucose-Einheit angelagert wurden. Hydroxyethylcellulosen sind ab einem DS von ca. 0,6 bzw. einem MS von ca. 1 wasserlöslich. Handelsübliche Hydroxyethyl- bzw. Hydroxypropylcellulosen haben Substitutionsgrade im Bereich von 0,85-1,35 (DS) bzw. 1,5-3 (MS). Hydroxyethyl- und - propylcellulosen werden als gelblich-weiße, geruch- und geschmacklose Pulver in stark unterschiedlichen Polymerisationsgraden vermarktet. Hydroxyethyl- und -propylcellulosen sind in kaltem und heißem Wasser sowie in einigen (wasserhaltigen) organischen Lösungsmitteln löslich, in den meisten (wasserfreien) organischen Lösungsmitteln dagegen unlöslich; ihre wäßrigen Lösungen sind relativ unempfindlich gegenüber Änderungen des pH-Werts oder Elektrolyt-Zusatz.Cellulose ethers can be described by the general formula (V)

R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula (III) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose reacted with the etherifying reagent or how many moles of the etherifying agent were attached on average to an anhydroglucose unit. Hydroxyethylcelluloses are water-soluble from a DS of about 0.6 or an MS of about 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS), respectively. Hydroxyethyl and - propylcelluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propylcelluloses soluble in cold and hot water and in some (hydrous) organic solvents, but insoluble in most (anhydrous) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Polyvinyl alcohols, referred to as PVAL for short, 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.

Thus, the term "polyvinyl alcohol" in the present invention covers homopolymers of vinyl alcohol, copolymers of vinyl alcohol with copolymerizable monomers or hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with copolymerizable monomers.

Commercially available polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%, So still contain a residual content of acetyl groups. The polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable. The water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The coatings off Polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Portions preferred in the context of the present invention are characterized in that the film consists of a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol -% is.

Polyvinyl alcohols of a certain molecular weight range are preferably used in the film, with portions according to the invention being preferred in which the film consists of a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , more preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

Further 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. An example of the present invention amphopolymer suitable is the acrylic resin commercially available as Amphomer ^® is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (for example acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (for example acrylamidopropyltrimethylammonium chloride) and optionally further ionic or nonionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and US Pat cited prior art can be found. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium as they are commercially available under the name Merquat ^® 2001 N, are inventively particularly preferred amphopolymers. Other suitable amphoteric polymers are for example sold under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) available octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are Methacroylethylbetain / methacrylate copolymers, which are commercially available under the name Amersette ^® (AMERCHOL).

• Vinylacetat/Crotonsäure-Copolymere, wie sie beispielsweise unter den Bezeichnungen Resyn^® (NATIONAL STARCH), Luviset^® (BASF) und Gafset^® (GAF) im Handel sind.

According to the invention suitable anionic polymers include:

• Vinyl acetate / crotonic acid copolymers, such as those sold under the names Resyn ^® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF) are commercially available.

• Vinylpyrrolidon/Vinylacrylat-Copolymere, erhältlich beispielsweise unter dem Warenzeichen Luviflex^® (BASF). Ein bevorzugtes Polymer ist das unter der Bezeichnung Luviflex^® VBM-35 (BASF) erhältliche Vinylpyrrolidon/Acrylat-Terpolymere.
• Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere, die beispielsweise unter der Bezeichnung Ultrahold^® strong (BASF) vertrieben werden.
• Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen

In addition to monomer units of the abovementioned formula (IV), these polymers also have monomer units of the general formula (VI):

[-CH (CH ₃ ) -CH (COOH) -] _n (VI)

• Vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF). A preferred polymer is the VBM-35 (BASF) under the name Luviflex ^® available vinylpyrrolidone / acrylate terpolymers.
• Acrylic acid / ethyl acrylate / N-tert.butyl acrylamide terpolymers, for example, under the name Ultrahold ^® strong (BASF).
• Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture with other copolymerizable compounds on polyalkylene glycols are obtained by homogeneous-phase polymerization by subjecting the polyalkylene glycols to the monomers of vinyl esters, esters of acrylic acid or methacrylic acid, in The presence of free radical initiator stirs.

Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid those with aliphatic alcohols of low molecular weight, ie in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are proven.

Suitable polyalkylene glycols are, in particular, polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol which are of general formula VII

H- (O-CH ₂ -CH ₂ ) _n -OH (VII)

satisfy, where n can assume values between 1 (ethylene glycol) and several thousand. For 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. For cosmetic ingredients, a different 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 formula V above. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-8, PEG-9 , PEG-10, PEG-12, PEG-14 and PEG-16. Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone -Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers.

genügen, wobei n Werte zwischen 1 (Propylenglycol) und mehreren tausend annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglycol, d.h. die Vertreter mit n=2, 3 und 4 in Formel VI.Polypropylene glycols (abbreviated PPG) are polymers of propylene glycol which are of general formula VIII

satisfy, where n can assume values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycols, ie the representatives with n = 2, 3 and 4 in formula VI.

• gepropfte und vernetzte Copolymere aus der Copolymerisation von
  1. i) mindesten einem Monomeren vom nicht-ionischen Typ,
  2. ii) mindestens einem Monomeren vom ionischen Typ,
  3. iii) von Polyethylenglycol und
  4. iv) einem Vernetzter

In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.

• grafted and crosslinked copolymers from the copolymerization of
  1. i) at least one nonionic type monomer,
  2. ii) at least one ionic-type monomer,
  3. iii) of polyethylene glycol and
  4. iv) a networked person

The polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000.

The nonionic monomers may be of very different types and of these preferred are: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allylaurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.

The non-ionic monomers may equally be of very different types, among which particularly preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the grafting polymers.

The crosslinking agents used are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose having 2 to 5 allyl groups per molecule of saccharin.

1. i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ,
2. ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ,
3. iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglycol und
4. iv) 0,1 bis 8 Gew.-% eines Vernetzers, wobei der Prozentsatz des Vernetzers durch das Verhältnis der Gesamtgewichte von i), ii) und iii) ausgebildet ist.
   • durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltene Copolymere:
     1. i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
     2. ii) ungesättigte Carbonsäuren,
     3. iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols

The grafted and crosslinked copolymers described above are preferably formed from:

1. i) from 5 to 85% by weight of at least one nonionic type monomer,
2. ii) from 3 to 80% by weight of at least one ionic-type monomer,
3. iii) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
4. iv) 0.1 to 8 wt% of a crosslinker, wherein the percentage of crosslinker is formed by the ratio of the total weights of i), ii) and iii).
   • Copolymers obtained by copolymerization of at least one monomer of each of the following three groups:
     1. i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
     2. ii) unsaturated carboxylic acids,
     3. iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 -alcohols

• Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester

Short-chain carboxylic acids or alcohols such are to be understood as having 1 to 8 carbon atoms, wherein the carbon chains of said compounds optionally interrupted by divalent hetero groups such as -O-, -NH-, -S _- may be interrupted.

• Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester

worin R³ für -H oder -CH₃, R² für -CH₃ oder -CH(CH₃)₂ und R¹ für -CH₃ oder einen gesättigten geradkettigen oder verzweigten C_1-6-Alkylrest steht und die Summe der Kohlenstoffatome in den Resten R¹ und R² vorzugsweise 7, 6, 5, 4, 3 oder 2 ist.These 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.

• Tetra- und Pentapolymere aus
  1. i) Crotonsäure oder Allyloxyessigsäure
  2. ii) Vinylacetat oder Vinylpropionat
  3. iii) verzweigten Allyl- oder Methallylestern
  4. iv) Vinylethern, Vinylesterrn oder geradkettigen Allyl- oder Methallylestern
• Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinymethylether, Acrylamid und deren wasserlöslicher Salze
• Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in α-Stellung verzweigten Monocarbonsäure.

The abovementioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight .-% allyl or Methallyletsre of formula IX.

• Tetra and pentapolymers from
  1. i) crotonic acid or allyloxyacetic acid
  2. ii) vinyl acetate or vinyl propionate
  3. iii) branched allyl or methallyl esters
  4. iv) vinyl ethers, Vinylesterrn or straight-chain allyl or methallyl esters
• Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts
• Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic α-branched monocarboxylic acid.

In particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins, which are described below, are suitable as film materials in the case of the anionic polymers.

Useful organic film materials are, for example, the polycarboxylic acids which can be used in the form of their sodium salts but also in free form. Polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Your molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer. Particularly preferred as film materials are also biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar Derivatives included.

Further preferred copolymeric film materials are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise to be mentioned as further preferred film materials polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives.

Further suitable film materials are polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further, preferably usable as film materials polymers are cationic polymers. Among the cationic polymers, the permanent cationic polymers are preferred. According to the invention, "permanently cationic" refers to polymers which have a cationic group, irrespective of the pH of the agent (ie both the film and the remaining portion). These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group.

• quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind. Die Verbindungen Celquat^® H 100, Celquat^® L 200 und Polymer JR^®400 sind bevorzugte quaternierte Cellulose-Derivate.
• Polysiloxane mit quaternären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning^® 929 Emulsion (enthaltend ein hydroxyl-aminomodifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil^®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt; diquaternäre Polydimethylsiloxane, Quatemium-80),
• Kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia^®Guar und Jaguar^® vertiebenen Produkte,
• Polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat^®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat^®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^®734 und Gafquat^®755 im Handel erhältlich.
• Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat^® angeboten werden.
• quaternierter Polyvinylalkohol

sowie die unter den Bezeichnungen

• Polyquaternium 2,
• Polyquaternium 17,
• Polyquaternium 18 und
• Polyquaternium 27

bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette. Die genannten Polymere sind dabei nach der sogenannten INCl-Nomenklatur bezeichnet, wobei sich detaillierte Angaben im CTFA International Cosmetic Ingredient Dictionary and Handbook, 5^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, finden, auf die hier ausdrücklich Bezug genommen wird.Preferred cationic polymers are, for example

• quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat L 200 and Polymer JR ^{® ®} 400 are preferred quaternized cellulose derivatives.
• Polysiloxanes with quaternary groups, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning ^® 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80),
• Cationic guar derivatives, in particular the vertiebenen under the trade names Cosmedia® ^® Guar and Jaguar ^® products,
• Polymers Dimethyldiallylammoniumsalze and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers.
• Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminomethacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially.
• Vinylpyrrolidone methoimidazolinium chloride copolymers, as offered under the name Luviquat.RTM ^®.
• quaternized polyvinyl alcohol

as well as those under the designations

• Polyquaternium 2,
• Polyquaternium 17,
• Polyquaternium 18 and
• Polyquaternium 27

known polymers with quaternary nitrogen atoms in the polymer main chain. The polymers mentioned are designated according to the so-called INCl nomenclature, details of which are found in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which reference is expressly made becomes.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers. Cationic cellulose derivatives, in particular the commercial product ^Polymer® JR 400, are very particularly preferred cationic polymers. Irrespective of the chemical composition of the film, washing, cleaning or rinsing agent portions according to the invention are preferred, which are characterized in that the film which forms part of the enclosure (A) or (B) has a thickness of 1 to 150 μm, preferably from 2 to 100 μm, particularly preferably from 5 to 75 μm and in particular from 10 to 50 μm.

In this way, a washing, cleaning or rinsing agent portion according to the invention comprises two areas in which different ingredients can be contained or different release mechanisms and dissolution kinetics can be realized.

When incorporating liquid, gelatinous or pasty active substances or mixtures of active substances, the composition of the enclosure and thus also of the film must be matched to the filling in order to prevent premature destruction of the film or loss of active substance through the enclosure. This is required in the incorporation of solid substances in the compartments only to a minor extent (chemical incompatibilities), so that preferred washing, cleaning or detergent portions in at least one compartment further active ingredient in particulate form, preferably in powdered, granular, extruded, pelleted , prilled, flaky or tableted.

The enclosed by the film enclosure can be completely filled with washing, cleaning or rinse-active preparation. But it is also possible to fill the respective mold only partially before closing in order to allow in this way a movement of the filled particles or liquids within the mold. Particularly when filling with regularly shaped larger particles, attractive visual effects can be realized. Washing, cleaning or rinsing agent portions are preferred in which the volume ratio of the space enclosed by the film and the further enclosure to the washing, cleaning or rinsing active preparation contained in this space is 1: 1 to 100: 1, preferably 1.1: 1 to 50: 1, more preferably 1.2: 1 to 25: 1 and in particular 1.3: 1 to 10: 1. In this terminology, a 1: 1 volume ratio means that the mold is completely filled.

By suitable packaging of the disintegratable under washing, cleaning or rinsing conditions, the / the hollow body (s) dimensional stability imparting, not pressed Material according to the claims and the sheet material may be predetermined at the time the washing or rinse-active preparation is released. For example, the film can be virtually instantaneously soluble, so that the washing, cleaning or rinse-active preparation is dosed at the beginning of the washing or cleaning cycle in the washing or cleaning liquor.

The shape of the "shell" can be chosen freely, with certain geometric shapes such as hemispheres have proven to be preferred for aesthetic reasons. But also box shapes or sargdeckelähnlich shaped shells are inventively feasible. The "shell" may have an edge that has only the material thickness, but it may also have a web edge, which serves as a larger adhesive and sealing surface for the film. In a preferred embodiment of the present invention, the "shell" is made by injection molding from water-soluble thermoplastics. In this method, any partitions for the later formation of several compartments can be mitverspritzt already. Also, the production of the "shell" by a melt casting of suitable materials (see below) is preferred.

The filling of the filled trays with film takes place by adherent connection with their edges, which can be done for example by gluing, partial melting or by chemical reaction. The covering film may be tightly sealed in subdivided trays not only at the edges of the outer shell periphery, but also with the upper edge of the inner septa, so that a tight seal of the compartments is also ensured against each other. In this case, the covering film can also be designed so that different prefabricated film areas come to rest over the different compartments so as to influence the disintegration kinetics in aqueous solution and thus the release of the individual preparations from the compartments.

This liquid must be chosen so that it does not attack the materials of the envelope. Non-aqueous solutions, suspensions, dispersions or emulsions have proven to be useful here. Especially when filling the partial Holhlkörper with liquid washing, cleaning or rinse-active preparation, it is preferred if the enclosure is transparent or at least translucent, to make the aesthetic appeal of liquid filling visible from the outside. Here, washing, cleaning or rinsing agent portions according to the invention are particularly preferred in which at least one enclosure is transparent or translucent, wherein the wall thickness of wholly or partially disintegratable from a under washing, cleaning or rinsing conditions, the / the hollow body (n ) Form stability-imparting, non-pressed material 100 to 5000 .mu.m, preferably 200 to 3000 .mu.m, more preferably 300 to 2000 .mu.m and in particular 500 to 1500 microns amounts.

The washing, cleaning or rinsing agent portions according to the invention have at least two areas in which washing, cleaning or rinsing active preparation is located. One of these preparations, as stated above, is liquid. The second preparation is firm. It is particularly preferred in this case to fill the second cavity with a powdery to granular preparation.

According to the invention, it is particularly preferred to effect the production of the dimensionally stable hollow body (s), which optionally has one or more devices (s) for compartmentalizing, by injection molding. In particular, thermoplastic polymers can be processed into dimensionally stable hollow bodies by this process, in particular, if appropriate, into dimensionally stable hollow bodies which contain devices for compartmentalizing in their interior. The injection molding of suitable materials is carried out according to known methods at high pressures and temperatures, for example at temperatures between 100 and 220 ° C, in particular oberhalöb the softening point of the thermoplastic, for example at 140 ° C and higher, especially at about 180 ° C, and a pressure between 500 and 2,000 bar, preferably of> 1,000 bar, in particular at about 1,400 bar, with the steps of closing the mold connected to the extruder for injection molding, injecting the polymer at high temperature and high pressure, cooling the injection-molded molding, Opening the mold and removing the molded blank. Other optional steps such as the application of release agents, the Demoulding, etc. are known in the art and can be carried out according to known technology.

The advantages of Verfahresweise the production of dimensionally stable hollow body by injection molding are in the mature technology of this procedure, the high flexibility in terms of usable materials, the ability to obtain exactly desired wall thickness s of the molding or dimensionally stable hollow body and the possibility in one High reproducibility step of producing a dimensionally stable hollow body having one or more integral compartmentalization devices.

The detergent, detergent or rinse agent portions disclosed herein consist of an outer mold containing one or more fillings. The hollow mold can be divided by partitions into several compartments, whereby several fillings can be present within the same hollow body separated from each other. In addition to the compatibility with the material of the mold, no demands are placed on the fillings, so that both solid and liquid phases (systems) can be portioned.

The simultaneous portioning of several different fillings requires hollow bodies comprising compartmentalizing means. The preparation of such hollow bodies from several contiguous compartments encounters difficulties with conventional methods. The present application discloses a process for producing such hollow bodies and the detergent, cleaning agent or detergent portions which can be produced therefrom.

1. (i) Herstellung des/der formstabilen, eine oder mehrere Wand/Wände umfassenden Hohlkörper(s) durch Spritzgießen;
2. (ii) Befüllung der Kammern mit waschaktiven, reinigungsaktiven oder spülaktiven Zubereitungen;
3. (iii) gegebenenfalls anschließendes Verschließen des/der formstabilen Hohlkörper(s) unter Ausbilden einer teilweisen oder vollständigen Umfassung um die waschaktiven, reinigungsaktiven oder spülaktiven Zubereitungen.

Another object of the invention is a process for the preparation of a detergent, detergent or detergent portion according to the invention comprising the steps

1. (i) preparation of the dimensionally stable hollow body (s) comprising one or more walls / walls by injection molding;
2. (ii) filling the chambers with detergent-active, cleaning-active or rinse-active preparations;
3. (iii) optionally subsequent sealing of the dimensionally stable hollow body (s) to form a partial or complete enclosure around the detergent-active, cleaning-active or rinse-active preparations.

For this purpose, in step (i), a hollow body is injection-molded, which has one or more chambers for receiving washing, rinsing or cleaning-active preparations. Injection molding of suitable materials is carried out according to per se known procedures at high pressures and temperatures with the steps of closing the mold connected to the extruder for injection, injecting the polymer at high temperature and pressure, cooling the injection molded article, opening the mold and removing the mold shaped blank. Further optional steps, such as the application of release agents, demolding, etc., are known to the person skilled in the art and can be carried out according to technology known per se.

The advantages of the procedure of producing the dimensionally stable hollow body by injection molding are the mature technology of this procedure, the high flexibility in terms of usable materials, the ability to obtain exactly desired wall thicknesses s of the molded or dimensionally stable hollow body and the possibility in one High reproducibility step of producing a dimensionally stable hollow body having one or more integral compartmentalizing means.

In preferred processes according to the invention, step (i) is carried out at a pressure between 100 and 5000 bar, preferably between 500 and 2500 bar, more preferably between 750 and 1500 bar and in particular between 1000 and 1250 bar.

The temperature of the material to be injection molded is preferably above the melting or softening point of the material and thus also depends on the nature of the material for the hollow body. In preferred processes according to the invention, step (i) is carried out at temperatures between 100 and 250.degree. C., preferably between 120 and 200.degree. C. and in particular between 140 and 180.degree.

The tools that receive the materials are preferably pre-tempered and have temperatures above room temperature, with temperatures between 25 and 60 ° C and in particular from 35 to 50 ° C are preferred.

Regardless of the material used for the hollow body (see below), but depending on the desired dissolution properties, the thickness of the wall can be varied. The wall should on the one hand be chosen so thin that a rapid dissolution or disintegration is achieved and the ingredients are released quickly into the application fleet, but also a certain minimum thickness is required to give the mold the desired stability, in particular dimensional stability.

The term "dimensionally stable hollow body is understood according to the invention that the detergent body, detergent or detergent portions containing moldings have a self-stability, which enables them, under normal conditions of manufacture, storage, transport and handling by the In the present invention, it does not influence whether this structural stability results from the properties of the product resulting from various parameters mentioned below The dimensionally stable hollow body has a sufficient Elgen dimensional stability, which would be advantageous to the mobility in machines during the manufacture of the hollow body and the filling end of the production of detergent, detergent or detergent portions of the invention.

The pressure resistance of the dimensionally stable hollow body according to the invention is measured in the (per se conventional) way so that unfilled and possibly provided with compartmentalization devices hollow body with films or lids are closed and applied to this hollow body at room temperature an internally applied, steadily increasing vacuum is until the hollow body begins to collapse. The intrinsic dimensional stability of the hollow bodies should be particularly preferably such that in such vacuum collapse tests unfilled and optionally provided with Kompartimentierungseinrichtungen hollow body collapse does not begin before reaching a vacuum of 900 mbar, preferably from 750 mbar and in particular from 500 mbar , In this respect, the hollow bodies used according to the invention fundamentally differ from films or so-called "pouches", as they are also used to provide detergents, cleaning agents or rinsing agents. These collapse already at a pressure that is only slightly below that Atmospheric pressure is. In a similar manner, however, the dimensionally stable hollow bodies according to the invention also differ from (subsequently applied to moldings) coatings: The hollow bodies according to the invention represent an independent, self-supporting coating which, as a rule, already before being filled with one or more washing-active, rinsing-active or cleaning-active components (n) exists and is then filled. In contrast, coatings are applied to existing moldings (eg, compacts, granules, extrudates, etc.) and then dried or cured; they form only then an envelope surrounding the molding.

In preferred processes according to the invention, hollow bodies are produced in step (i) in which collapse does not commence before reaching a vacuum of 250 mbar, preferably of 100 mbar and in particular of 20 mbar.

Preferred processes according to the invention are therefore characterized in that the wall thickness of the enclosure (b) produced in step (i) is 100 to 5000 μm, preferably 200 to 3000 μm, particularly preferably 300 to 2000 μm and in particular 500 to 1500 μm.

The use of polymers which have a flow index (MFI) below 120, preferably below 10 and in particular below 8, is preferred.

Regularly, the dimensionally stable hollow body produced by injection molding does not have walls which are closed on all sides and is open on at least one of its sides - in the case of a spherical or elliptical body in the region of a part of its shell. One or more washing-active, cleaning-active or rinse-active preparation (s) are / are introduced through the remaining opening into the compartment (s) formed inside the dimensionally stable hollow body (s). This is also done in a known per se way, for example in the context of known from the confectionery industry manufacturing process; It is also possible to proceed in several steps. A one-step procedure is particularly preferred if, in addition to solid preparations, preparations comprising liquid components (dispersions or emulsions, suspensions) or even gaseous component-containing preparations (foams) are to be incorporated into the detergent, cleaning agent or rinsing agent portions in the hollow bodies ,

Polymers are particularly suitable as materials for the hollow body to be produced in step (i), preference being given to processes according to the invention in which the encapsulation (b) produced in step (i) comprises one or more materials from the group of acrylic acid-containing Polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof.

Particularly preferred is the use of water-soluble polymers as material for the hollow body. In this case, processes have proven effective which are characterized in that the enclosure (b) prepared in step (i) comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalised) polyvinyl alcohol (PVAL), Polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten.In the context of the present invention, 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.

Commercially available polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups. The polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable. The water solubility can be achieved by post-treatment Aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or Borax reduce. The coatings of polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Preferred processes in the context of the present invention are characterized in that the hollow bodies consist of a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol -% is.

Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the hollow bodies, preference being given to processes according to the invention in which the hollow bodies produced in step (i) consist of a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , more preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

Further polyvinyl alcohols which are particularly suitable as material for the hollow bodies are shown in the following table: description Degree of hydrolysis [%] Molecular weight [kDa] Melting point [° C] Airvol ^® 205 88 15-27 230 Vinex ^® 2019 88 15-27 170 Vinex ^® 2144 88 44 - 65 205 Vinex ^® 1025 99 15-27 170 Vinex ^® 2025 88 25 - 45 192 Gohsefimer ^® 5407 30 - 28 23,600 100 Gohsefimer ^® LL02 41 - 51 17,700 100

Other suitable as a material for the mold, polyvinyl alcohols are ELVANOL ^® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ^® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK ).

To facilitate the injection molding process (ie their production), the hollow body may contain plasticizing aids. This may be advantageous in particular when polyvinyl alcohol or partially hydrolyzed polyvinyl acetate has been selected as the material for the hollow bodies. The proportion of plasticizer (based on the polymer) is usually up to 15 wt .-%, with values between 5 and 10 wt.% Are preferred. Glycerol, triethanolamine, ethylene glycol, propylene glycol, diethylene or dipropylene glycol, diethanolamine and methyldiethylamine have proved particularly suitable as plasticizing auxiliaries.

In addition to the plasticizing aids, mold release additives are important auxiliary substances that can be used in the injection molding compositions. From the groups of fatty substances and the finely divided substances while in the present invention, in particular stearic acid and / or stearates and fumed silicas have (Aerosil ^®), talcum, and proven. The proportion of demolding additives (based on the polymer) is usually up to 5 wt .-%, with values between 0.5 and 2.5 wt.% Are preferred.

Further substances which can be used as mold release additives come in particular from the group of fatty substances. For the purposes of this application, fatty substances are understood to mean liquid to solid substances from the group of the fatty alcohols, the fatty acids and the fatty acid derivatives, in particular the fatty acid esters, at normal temperature (20 ° C.). Reaction products of fatty alcohols with alkylene oxides count in the present application to the surfactants (see above) and are not fatty substances in the context of the invention. Fatty substances which can be used according to the invention are preferably fatty alcohols and fatty alcohol mixtures, fatty acids and fatty acid mixtures, fatty acid esters with alkanols or diols or polyols, fatty acid amides, fatty amines, etc.

Examples of 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-cis-9,12-octadecadiene 1-ol (linoleyl alcohol), all-cis-9,12,15-octadecatrien-1-ol (Linolenyl alcohol), 1-nonadecanol, 1-eicosanol (arachidyl alcohol), 9-cis-eicosen-1-ol (gadoleyl alcohol), 5,8,11,14-eicosatetraen-1-ol, 1-heneicosanol, 1-docosanol ( Behenyl alcohol), 1-3-cis-docosen-1-ol (erucyl alcohol), 1-3-trans-docosen-1-ol (brassidyl alcohol) and mixtures of these alcohols. According to the invention, Guerbet alcohols and oxo alcohols, for example C _13-15 oxo alcohols or mixtures of C _12-18 alcohols with C _12-14 alcohols, can also be used without problems as fatty substances. Of course, however, it is also possible to use 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.

As a mold release additive also fatty acids can be used. These are largely derived from native fats and oils by hydrolysis. While alkaline saponification, already carried out in the last century, led directly to alkali salts (soaps), today only large quantities of water are used for cleavage, which cleave the fats into glycerine and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage. 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. are preferred in the context of the present invention. The use of Fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanic acid (melissic acid) and unsaturated secies 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid ( Linolaidic acid) and 9c, 12c, 15c-octadecatenic acid (linolenic acid). Of course, tridecanoic acid, pentadecanoic acid, margaric acid, nonadecanoic acid, erucic acid, elaeostearic acid and arachidonic acid can be used. For cost reasons, it is preferred not to use the pure species, but technical mixtures of the individual acids, as they are accessible from lipolysis. Such mixtures are, for example, coconut oil fatty acid (about 6% by weight C ₈ , 6% by weight C ₁₀ , 48% by weight). C ₁₂ , 18 wt .-% C ₁₄ , 10 wt .-% C ₁₆ , 2 wt .-% C ₁₈ , 8 wt .-% C ₁₈ , 1 wt .-% C _{18 ''} ), palm kernel oil fatty acid (ca. 4 wt .-% C ₈ , 5 wt .-% C ₁₀ , 50 wt .-% 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 (about 3% by weight C ₁₄ , 26% by weight C ₁₆ , 2% by weight C ₁₆ , 2% by weight C ₁₇ , 17% by weight C ₁₈ , 44% by weight C ₁₈ , 3 wt .-% C ₁₈ , 1 wt .-% C _{18 '''} ), hardened tallow fatty acid (about 2 wt .-% C ₁₄ , 28 wt .-% C ₁₆ , 2 wt .-% C ₁₇ , 63 wt .-% C ₁₈ , 1 wt .-% C _{18 '} ), technical oleic acid (about 1 wt .-% C ₁₂ , 3 wt .-% C ₁₄ , 5 wt .-% C ₁₆ , 6 wt % C ₁₆ , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C ₁₈ , 10% by weight C ₁₈ , 0.5% by weight C _{18 '''} ) , 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% by weight C ₁₄ , 15% by weight C ₁₆ , 5% by weight C ₁₈ , 25% by weight C ₁₈ , 45% by weight C) _{18 '''} , 7 wt .-% C _18''' ).

The fatty acid esters which can be used are the esters of fatty acids with alkanols, diols or polyols, with fatty acid polyol esters being preferred. Suitable fatty acid polyol esters are mono- or diesters of fatty acids with certain polyols. The fatty acids which are esterified with the polyols are preferably saturated or unsaturated fatty acids having 12 to 18 carbon atoms, for example lauric acid, myristic acid, palmitic acid or stearic acid, preferably using the technically occurring mixtures of the fatty acids, for example those of coconut, Palm kernel or tallow derived acid mixtures. In particular, acids or mixtures of acids having 16 to 18 carbon atoms such as tallow fatty acid are suitable for esterification with the polyhydric alcohols. Suitable polyols which are esterified with the abovementioned fatty acids are, for the purposes of the present invention, sorbitol, trimethylolpropane, neopentyl glycol, ethylene glycol, polyethylene glycols, glycerol and polyglycerols.

Preferred embodiments of the present invention provide that glycerine is used as the polyol esterified with fatty acid (s). Accordingly, fatty substances from the group of fatty alcohols and fatty acid glycerides are preferred as mold release additives. Particularly preferred demulsifying additives are fatty substances from the group of fatty alcohols and fatty acid monoglycerides. Examples of such fatty substances which are preferably used are glycerol monostearic acid esters or glycerol monopalmitic acid esters.

To prevent undesirable changes to the injection molding compounds caused by the action of oxygen and other oxidative processes, these may contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates. In preferred methods of the invention, the material for the mold, the wall thickness and the size of the mold are chosen so that the hollow body dissolves in still water of 20 ° C in less than 300 seconds, preferably in less than 60 seconds or the ingredients of the Filling releases. It is not necessary that the entire body spontaneously dissolves. Rather, it is sufficient if all ingredients dissolve under the conditions of use within the period of application. For conventional washing or rinsing processes this means temperatures of 20 ° C and above, mechanical action and times of less than 200 minutes, preferably less than 60 minutes, especially less than 20 minutes. However, the release of the ingredients of at least one compartment should preferably be done in less than 300 seconds, especially less than 60 seconds. This can be done by using disintegration aids, by sealing a compartment with a thin, water-soluble film, by dissolving a "stopper" occluding an opening, or by other means.

Further details on ingredients (a) and their division into individual compartments as well as information on process steps (ii) and (iii) can be found in the above comments.

The production of injection-molded hollow bodies, wherein the injection molding composition comprises water-soluble polymers, has hitherto not been described in the prior art. A further subject of the present invention is therefore an injection molding process for hollow bodies which comprise such polymers, ie a process for the production of hollow bodies by injection molding, which is characterized in that the injection molding compound comprises one or more water-soluble polymer (s), preferably one or a plurality of material (s) from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).

As already described above, processes according to the invention are preferred in which the injection molding composition comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol -% is.

Also with regard to the molecular weight distribution applies the above; In this case, preference is given to processes according to the invention in which the injection molding composition comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 g / mol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

The processes according to the invention can be carried out with particular advantage if the proportion of water-soluble polymers in the injection-molding composition is high. Preferably, the entire injection molding compound consists only of the water-soluble polymers and optionally excipients (see above). In this case, preference is given to processes according to the invention in which the injection molding composition contains the polymers mentioned in amounts of at least 50% by weight, preferably at least 70% by weight, more preferably at least 80% by weight and in particular at least 90% by weight. , in each case based on the weight of the injection molding composition contains.

With regard to the other process parameters (pressure, temperature) as well as the preform to be preferably produced, the above applies analogously.

Regularly, the dimensionally stable hollow body produced by injection molding does not have walls which are closed on all sides and is open on at least one of its sides - in the case of a spherical or elliptical body in the region of a part of its shell. Through the remaining opening, a washing-active, cleaning-active or rinse-active preparations is / are filled into the compartments formed in the interior of the dimensionally stable hollow body. This is also done in a known per se way, for example in the context of known from the confectionery industry manufacturing process; It is also possible to proceed in several steps. A one-step procedure is particularly preferred if, in addition to solid preparations, preparations comprising liquid components (dispersions or emulsions, suspensions) or even gaseous component-containing preparations (foams) are to be incorporated into the detergent, cleaning agent or rinsing agent portions in the hollow bodies ,

In a particularly preferred embodiment of the process according to the invention, the washing-active, cleaning-active or rinse-active preparation (s) are filled into compartments which are surrounded, preferably concentrically or coaxially with one another. In a final step, the dimensionally stable hollow body containing in its interior one or more washing-active, cleaning-active or rinsing-active preparations in a compartment or distributed in several compartments is sealed, thus sealing the preparations in its interior. This can - as already described above - done by applying a "lid" on the still open (n-th) surface of the dimensionally stable hollow body or - in spherical or elliptical hollow bodies - by applying a corresponding partial spherical shell or partial ellipse shell on the opening , The application may preferably be effected by way of bonding, preferably with a water-soluble adhesive, fusion, welding or other types of bonding known to those skilled in the art.

• eine Waschmittel-Portion nach der obigen Beschreibung in die Waschma-schine, insbesondere in deren Einspülkammer oder Waschtrommel, eingibt;
• die gewünschten Waschbedingungen einstellt; und
• bei Eintreten dieser Bedingungen die waschaktive(n) Zubereitung(en) der Waschmittel-Portion in die Waschflotte gibt und diese mit dem zu waschenden Gut in Kontakt bringt.

Finally, the invention also relates to a washing method, in particular method for machine washing in a commercial washing machine, comprising the steps of

• a detergent portion as described above in the washing machine, in particular in the Einspülkammer or wash drum, inputs;
• Sets the desired washing conditions; and
• when these conditions enter the detergent-active preparation (s) of detergent portion in the wash liquor and brings this in contact with the material to be washed.

• Phase 1: anionisches Tensid, nicht-ionisches Tensid, Polycarboxylat, Citrat, Citronensäure, Phosphonate, Enzyme (ohne Protease);
• Phase 2: Soda, Alkaliträger, Protease;
• Phase 3: alkalische Builder, Zeolith, Silicate, Perborat, Percarbonat, Carboxymethylcellulose;
• Phase 4: Parfüm, optische Aufheller, Soil Repellent, Weichmacher (einschl. Esterquats).

A preferred detergent used in such a washing process comprises a plurality of "phases" contained in compartments in a dimensionally stable hollow body comprising a detergent portion according to the invention. The means for compartmentalizing, thus preferably at least one wall of each compartment, dissolves due to the inherent properties of the material forming the respective wall when certain parameters are set in water or in the aqueous liquor. The following "phases" may be mentioned as examples of a detergent according to the invention:

• Phase 1: anionic surfactant, nonionic surfactant, polycarboxylate, citrate, citric acid, phosphonates, enzymes (without protease);
• Phase 2: soda, alkali carrier, protease;
• Phase 3: alkaline builders, zeolite, silicates, perborate, percarbonate, carboxymethylcellulose;
• Phase 4: perfume, optical brightener, soil repellent, plasticizer (including ester quats).

The water solubility of the walls / compartmentation devices surrounding the phases can be adjusted so that 5 to 10 minutes pass each time one compartment is opened until the contents of the next compartment are released.

Simplified forms of the detergent portion can be prepared by omitting the phase 2 and distributing its contents to the phases 1 (protease) and 3 (soda, alkali carrier) and, in a further simplification, in addition to phase 2, also the phase 4, perfume, optical brightener and Soil Repellent Phase 3 are added and the fabric softener is dosed in a separate product.

• eine Reinigungsmittel-Portion nach der obigen detaillierten Beschreibung in die Reinigungsflotte eingibt;
• die gewünschten Reinigungsbedingungen einstellt; und
• bei Eintreten dieser Bedingungen die reinigungsaktive(n) Zubereitung(en) der Reinigungsmittel-Portion in die Reinigungsflotte gibt und diese mit dem zu reinigenden Gut in Kontakt bringt.

The invention also relates to a purification process comprising the steps of

• enters a detergent portion according to the above detailed description in the cleaning liquor;
• sets the desired cleaning conditions; and
• when these conditions occur, the cleaning-active preparation (s) of the cleaning agent portion is in the cleaning liquor and brings them into contact with the material to be cleaned.

• eine Spülmittel-Portion nach der obigen detaillierten Beschreibung in die Geschirrspülmaschine, insbesondere in deren Einspülkammer oder in deren Spülraum eingibt;
• die gewünschten Spülbedingungen einstellt; und
• bei Eintreten dieser Bedingungen die spülaktive(n) Zubereitung(en) der Spülmittel-Portion in die Spülflotte gibt und diese mit dem zu spülenden Gut in Kontakt bringt.

The invention also relates to a rinsing method, in particular a method for machine rinsing in a commercial dishwashing machine, comprising the steps of

• a detergent portion according to the above detailed description in the dishwasher, in particular in the Einspülkammer or in the washing compartment enters;
• sets the desired purge conditions; and
• when these conditions occur, the rinse-active preparation (s) of the detergent portion are in the rinsing liquor and bring them into contact with the material to be rinsed.

With the detergent, detergent or detergent portions according to the invention, the objects are achieved in an advantageous manner. Thus, incompatible washing-active, cleaning-active or rinse-active preparations or their components can be spatially separated and can not react with one another due to the lack of a common contact surface, in particular no reaction which impairs the activity of the respective preparation. This leads - especially at elevated concentrations of active ingredient - to increased storage stability of the detergent, detergent or detergent portions, to an improved due to the lack of loss of activity and washing performance Saving of active substance, since the excess of active substance to be used earlier due to the expected loss of activity can be omitted in the detergent, cleaning agent or detergent portions according to the invention. Furthermore, open to the expert for the combination of previously considered incompatible substances in detergent, detergent or detergent formulations new formulation options. Due to the spatial separation of the individual components, it is possible to optimize the technological functions of the individual components independently of each other, without any fear of influencing the components.

There are also clear advantages for the user. The detergent, Reinigungsmittek- or detergent portions contained in the hollow bodies with one or more compartments promise a consistent and prefabricated dosage with all the required or desired components for the entire washing, cleaning or rinsing. Dosing does not occur during dosing, nor do you fear fouling of the product, contact with active ingredients or accidents due to ingestion of active ingredients. The dosage is carried out in one step, and the solubility of the enclosure or the hollow body material for release of the ingredients is carried out reliably according to predetermined or predetermined kinetics, so that significantly improve the washing, cleaning or dishwashing results, compared with powdered or compressed Moldings of the same composition without compartmentalized separation of the components.

Examples: a) Injection compartments:

Polyvinyl alcohol granules (Vinex ^® 2019 Fa. Texas polymer) was melted on a hydraulic screw-injection molding machine from the company. Arburg and injected into Simple tools with hot runner nozzle. In Example 1, a trochoidal shell with three corrugated partitions and a peripheral edge was prepared, in Example 2 a hemisphere with a circumferential stacking approach and an edge.

The tool temperature was 40 ° C, the demoulding took place via an air-assisted scraper system. Further operating parameters are summarized in Table 1: <b> Table 1: </ b> Injection molding [Process step (i)] example 1 2 Injection pressure [bar] 1280 1120 Flow rate [ml / s] 50 45 Overall cycle [s] 13 13 Temperature of the material [° C] 140-160 140-160 Wall thickness [mm] 0.55 0.55

The mold shells prepared in the manner described above were introduced into water and measured time to disintegration or to complete dissolution: Temperature [° C] 20 30 40 50 60 Decay after [min] 12 7 5 4 2 complete resolution after [min] 18 11 8th 6 4

Polyvinyl alcohol granules (Vinex ^® 2019 Fa. Texas polymer) was melted on a hydraulic screw-injection molding machine from the company. Arburg and injected into Simple tools with hot runner nozzle, wherein the shell having the shape of a hemisphere with a circumferential stacking tab and an edge.

The tool temperature was 40 ° C, the demoulding took place via an air-assisted scraper system. Further operating parameters are summarized in Table 1: <b> Table 1: </ b> Injection molding [Process step (i)] Injection pressure [bar] 1120 Flow rate [ml / s] 45 Overall cycle [s] 13 Temperature of the material [° C] 140-160 Wall thickness [mm] 0.55

Claims (11)

1. Detergent portion which is present in a dimensionally stable hollow body comprising a plurality of chambers and which comprises

   (a) at least one liquid detersive formulation and at least one solid detersive formulation which are spatially separate from one another;

   (b) at least one enclosure which wholly or partly surrounds one of the formulations according to (a) and comprises an injection-molded material which can disintegrate under laundering, cleaning or washing conditions and which gives the hollow body(ies) dimensional stability; and

   (c) one or more walls which spatially separate identical or different detersive components or formulations from one another.
2. Detergent portion according to Claim 1, comprising two or more chambers which comprise one or more detersive formulations and which are disposed embracing one another.
3. Detergent portion according to one or more of Claims 1 or 2, wherein the dimensionally stable hollow body(ies) comprises/comprise one or more water-soluble polymer, preferably a material from the group consisting of (unacetalized or acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives, and mixtures thereof, more preferably (unacetalized or acetalized) polyvinyl alcohol (PVAL).
4. Detergent portion according to one or more of Claims 1 to 3, wherein the dimensionally stable hollow body(ies) comprises/comprise one or more materials from the group consisting of acrylic acid (co)polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, and polyethers, and mixtures thereof.
5. Detergent portion according to one or more of Claims 1 to 4, wherein one or more wall(s) comprises/comprise a portion or the entirety of at least one component of at least one detersive formulation.
6. Detergent portion according to one or more of Claims 1 to 5, comprising at least one, preferably two or more, detersive formulation(s) from the group consisting of anionic, nonionic, cationic, and amphoteric surfactants, builder substances, bleaches, bleach activators, bleach stabilizers, bleaching catalysts, enzymes, polymers, cobuilders, alkalifiers, acidifiers, antiredeposition agents, silver protectants, colorants, optical brighteners, UV protection substances, fabric softeners, rinse aids, in an amount sufficient for one laundering, cleaning, and washing cycle.
7. Detergent portion according to one or more of Claims 1 to 6, characterized in that the solid detersive formulation is selected from the group consisting of powders, granules, extrudates, pellets, beads, tablets, tabs, rings, blocks and briquettes.
8. Laundering process, especially process for machine laundering in a commercially customary washing machine, which comprises the steps whereby

   - a detergent portion according to one of Claims 1 to 7 is introduced into the washing machine, especially into its rinse-in compartment or washing drum;

   - the desired laundering conditions are set; and

   - when the conditions come about the detersive formulation(s) of the detergent portion is (are) released into the laundering liquor and contacted with the material to be laundered.
9. Cleaning process comprising the steps whereby

   - a detergent portion according to one of Claims 1 to 7 is introduced into the cleaning liquor;

   - the desired cleaning conditions are set; and

   - when the conditions come about the detersive formulation(s) of the detergent portion is (are) released into the cleaning liquor and contacted with the material to be cleaned.
10. Washing process, especially process for machine washing in a commercially customary dishwasher, comprising the steps whereby

    - a detergent portion according to one of Claims 1 to 7 is introduced into the dishwasher, especially into its rinse-in compartment or wash chamber;

    - the desired wash conditions are set; and

    - when the conditions come about the detersive formulation(s) of the detergent portion is (are) released into the wash liquor and contacted with the material to be washed.
11. Process for producing a detergent portion according to one of Claims 1 to 7, comprising the steps of

    (i) preparing the dimensionally stable hollow body comprising one or more wall(s) by injection-molding;

    (ii) filling the chambers compartments with detersive formulations.