DE10253213B3 - Water-soluble portion packaging with filling and process for its production - Google Patents

Abstract

Aesthetically pleasing detergent or cleaning agent portions, which combine the advantages of the compactness of tablets with those of the quick solubility of portioned systems, comprise a water-soluble coating and at least one core therein and a matrix of flowable material that at least partially surrounds the core (s) , wherein the core (s) is / are fixed to the water-soluble coating.

Description

The present invention resides the field of portioned compositions, which are preferred have washing and cleaning properties. Such washing and detergent portions include, for example, portioned portions Funds for washing textiles, portioned detergents for the machine Wash the dishes or cleaning hard surfaces, portioned bleach for use in washing machines or dishwashers, portioned water softeners or stain salts; these individual forms of offer are as follows under the term “laundry or detergent portion ". In particular The invention relates to detergent and cleaning agent portions for machine cleaning of dishes in household dishwashers be used.

Portioned washing and cleaning agents are widely described in the prior art and enjoy Consumers are becoming increasingly popular due to the simple dosage. The portioning can be done for example by transfer to achieve a compact shape or by separate packaging. in the the former case, the tableting has an outstanding role, in the latter case, predominantly in the field of detergents or cleaning agents Portions used by packaging made from water-soluble Materials are surrounded.

Tableted detergents and cleaning agents have a number of advantages over powdered ones:
They are easier to dose and handle and, due to their compact structure, have advantages for storage and transportation. Detergent tablets are consequently also extensively described in the patent literature. A problem that occurs again and again when using shaped articles which are active in washing and cleaning is the insufficient rate of disintegration and dissolution of the shaped articles under conditions of use. Since sufficiently stable, that is to say molded and break-resistant molded articles can only be produced by relatively high compression pressures, there is a strong compression of the molded article components and consequently a delayed disintegration of the molded article in the aqueous liquor and thus to a slow release of the active substances in the Washing or cleaning process. The delayed disintegration of the moldings has the further disadvantage that many detergent tablets cannot be washed in via the induction chamber of household washing machines, since the tablets do not disintegrate into secondary particles that are small enough to be washed out of the induction chamber into the washing drum to become.

This dichotomy between hardness (i.e. Manageability) and disintegration play with packaged detergent or cleaning agent portions only a subordinate role. Rather, phenomena like here occur the solubility or Disintegration of packaging in the foreground, while that packaged detergents or cleaning agents with their physical Properties only play a role if a tablet has been packed.

However, these have servings the disadvantage of not having the high degree of compactness that it has Have tablets. The filling leads from tubular bags on the one hand to a low degree of compaction, on the other hand to one technically related empty volume, so that one for a washing or cleaning cycle measured amount of a detergent or cleaning agent a larger space takes as a corresponding amount in tablet form. moreover does that Empty volume means that filled bags against mechanical influences are unstable and can burst.

In addition, filled tubular bags only slight aesthetic Stimuli. The consumer accepts this form of offer very little and does not trust the corresponding means to a high level of performance. Becomes packed in a bag only a uniform composition, multifunctional advantages of the means cannot be visualized.

In addition, there is the problem that the compared to tablets lower density of portioned packaged Compositions for space problems in dosing devices in dishwashers to lead can. Here, if necessary be dosed lower so that the portion can be applied, which leads to poorer cleaning results.

Therefore, in the prior art Packaging made from water-soluble Materials disclosed which are not in the form of tubular bags available, but produced by processes such as injection molding or deep drawing are. These more rigid bodies are infested - similar to yogurt cups and after filling locked. But if you want bigger ones in such packaging: Fill in visualization of a multi-use and with another Composition (for example a powder, a liquid or a melt), the solid can become uncontrolled separate, which leads to problems with the closure of the filled hollow body and to aesthetic Inconvenience.

Special graft polymers which are suitable as coating material for detergent or cleaning agent ingredients or as packaging material for detergent or cleaning agent are the subject of DE 100 50 958 A1 (BASF).

Portion bags for detergents made of water-soluble or water-dispersible materials are described, for example, in DE 199 45 849 A1 (Handle).

The GB 2 376 676 A (Reckitt Benckiser) finally discloses injection-molded containers made of certain water-soluble polymers, which are suitable for packaging detergents.

The present invention was now based on the task, aesthetically to provide appealing detergent or cleaning agent portions, the advantages of compactness of tablets with those of fast ones solubility of portioned systems. Larger solids ("cores"), i.e. solids, should be used become clear in their size of particulate Stand out compositions and, for example, minimum diameter Have above 2 mm, can be incorporated without it technical or aesthetic Disadvantage comes. Another task, which of the present The invention was based on the provision of a manufacturing process for such Cleaner portions.

It has now been found that cores in water soluble Portion packaging introduced and surrounded with flowable material can, if before filling with flowable material on the water soluble wrapping be fixed.

Object of the present invention is in a first embodiment a portion packaging comprising a water-soluble envelope and at least one core and a core (s) at least partially surrounding matrix of flowable material, the core (s) being / are fixed to the water-soluble coating.

• a) Herstellung einer einseitig offenen Portionsverpackung aus wasserlöslichem Material;
• b) Befüllen der Portionsverpackung mit einem oder mehreren Kernen) sowie Fixierung des Kerns bzw. der Kerne;
• c) Befüllen der Portionsverpackung mit der fließfähigen Matrix;
• d) Verschließen der Portionsverpackung.

Another object of the present invention is a method for producing water-soluble portion packaging with at least one core therein and a matrix of flowable material at least partially surrounding the core (s), characterized by the steps

• a) Production of a portion packaging open on one side from water-soluble material;
• b) filling the portion packaging with one or more cores) and fixing the core or cores;
• c) filling the portion packaging with the flowable matrix;
• d) Close the portion packaging.

In the description below of the invention, the terms “portion packaging” and “washing or detergent portion "used without there where "washing or detergent portion " other porfion packaging according to the invention should be excluded. The portion packaging according to the invention is rather suitable also for other areas of application such as crop protection agents, pharmaceuticals, Cosmetics etc.

The portion packaging according to the invention initially comprises one water-soluble Serving. This wrapping can be made from a single material or a blend of different Materials exist. In preferred portion packaging according to the invention comprises the water soluble wrapping one or more materials from the group (possibly acetalizing) Potyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinyl pyrrolidone, Polyethylene oxide, polyethylene glycol, gelatin, cellulose and their Derivatives, in particular MC, HEC, HPC, HPMC and / or CMC, and / or Copolymers and their mixtures. If necessary, the wrappings Plasticizers known to those skilled in the art are added to increase the flexibility of the material his.

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

enthalten.In the context of the present invention, polyvinyl alcohols are particularly preferred as water-soluble polymers. "Polyvinyl alcohols" (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure

which in small proportions (approx. 2%) also structural units of the type

contain.

Commercial polyvinyl alcohols as white-yellowish powders or granules with polymerizations grades in the range of approximately 100 to 2500 (molar masses of approximately 4000 to 100,000 g / mol) are offered, have degrees of hydrolysis of 98-99 and 87-89 mol%, respectively, and therefore still contain a residual content of acetyl groups. The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.

Polyvinyl alcohols are dependent on Degree of hydrolysis soluble in water and a few strongly polar organic solvents (Formamide, dimethylformamide, dimethyl sulfoxide); from (chlorinated) They do not attack hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be achieved by post-treatment with aldehydes (acetalization) Complexing with Ni or Cu salts or by treatment with dichromates, boric acid or reduce borax. Polyvinyl alcohol is largely impenetrable for gases such as Oxygen, nitrogen, helium, hydrogen, carbon dioxide, however, leaves Pass water vapor through.

Within the scope of the present invention preferred portion packs are characterized in that the water-soluble envelope is polyvinyl alcohols and / or PVAL copolymers, 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, with portion packs according to the invention being preferred in which the water-soluble envelope comprises polyvinyl alcohols and / or PVAL copolymers, the molecular weight of which is in the range from 3,500 to 100,000 gmol ^-1 , preferably from 10,000 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 degree of polymerization of such preferred Polyvinyl alcohols is between about 200 to about 2100, preferably between approximately 220 to about 1890, more preferably between about 240 to about 1680 and especially between about 260 to about 1500th

Preferred packaging according to the invention are characterized in that the water-soluble wrapping Polyvinyl alcohols and / or PVAL copolymers, their average Degree of polymerization between 80 and 700, preferably between 150 and 400, particularly preferably between 180 to 300 and / or their molecular weight ratio MG (50%) to MG (90%) between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.

In summary, portion packs according to the invention are preferred in which the wrapping comprises polyvinyl alcohols and / or PVAL copolymers 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% %, with polyvinyl alcohols and / or PVAL copolymers being preferred, whose molecular weight is in the range from 3,500 to 100,000 gmol ^-1 , preferably from 10,000 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 and particularly preferred polyvinyl alcohols and / or PVAL copolymers have an average degree of polymerization between 80 and 700, preferably between 150 and 400, particularly preferably between 180 and 300 and / or their molecular weight ratio MG (50%) to MG (90% ) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.

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 materials for the water-soluble coating can be found in the table below:

Other polyvinyl alcohols suitable as material for the water-soluble coating 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). ERKOL types from Wacker are also suitable.

die durch radikalische Polymerisation von 1-Vinytpyrrolidon 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.).Another preferred group of water-soluble polymers that can serve as a coating according to the invention are the polyvinylpyrrolidones. These are sold, for example, under the name Luviskol ^® (BASF). Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (I)

which are produced by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercially available polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol, which are characterized by the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

Also suitable are copolymers of vinylpyrrolidone with other monomers, particularly vinyl pyrrolidone / Vinyiester-Couolymere, as sold for example under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic 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 polymers accessible from vinyl esters with the grouping of the formula

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

The vinyl esters are polymerized by free radicals using different processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (I) and (II). Other suitable water-soluble polymers are the polyethylene glycols (polyethylene oxides), which are referred to as PEG for short. PEG are polymers of ethylene glycol which have the general formula (III) H- (O-CH ₂ -CH ₂ ) _n -OH (III) are sufficient, where n can have values between 5 and> 100,000.

PEGs are manufactured technically by anionic ring opening polymerization of ethylene oxide (oxirane) mostly in the presence of small amounts of water. You have depending on the reaction Molar masses in the range of approx. 200-5,000,000 g / mol, accordingly Degree of polymerization from approx. 5 to> 100,000.

The products with molar masses <approx. 25,000 g / mol are liquid at room temperature become sore as the actual polyethylene glycols, abbreviation PEG, designated. These short chain PEGs can in particular be other water soluble Polymers, e.g. Polyvinyl alcohols or cellulose ethers as plasticizers be added. The usable according to the invention at room temperature Solid polyethylene glycols are called polyethylene oxides, short marks PEOX. High molecular weight polyethylene oxides are extremely low Concentration of reactive hydroxy end groups and therefore only show still weak glycol properties.

According to the invention, golatine is also suitable as a water-soluble covering material, which is preferably used together with other polymers. Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 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 the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, particularly in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.

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

Further water-soluble polymers which are suitable as coatings according to the invention are described below:

• - cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methylhydroxypropyl cellulose, such as are for example sold under the trademark 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 (IV)

in R represents 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 cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average. Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Preferred portion packaging according to the invention are characterized in that the water-soluble wrapping Hydroxypropylmethylcellulose (HPMC) which has a degree of substitution (Average number of methoxy groups per anhydroglucose unit cellulose) from 1.0 to 2.0, preferably from 1.4 to 1.9, and a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25.

Other polymers suitable according to the invention are water-soluble amphopolymers. Ampho-polymers are amphoteric polymers, ie polymers that contain both free amino groups and free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - Contain COO ^- or -SO ₃ groups, and summarized those polymers which contain -COOH or SO ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Methacrylic acid and its simple esters. Likewise preferred amphopolymers consist of unsaturated carboxylic acids (e.g.

Acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (for example acrylamidopropyltrimethylammonium chloride) and optionally other ionic or nonionic monomers together, as can be seen, for example, in German Offenlegungsschrift 39 29 973 and the prior art cited therein. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat ^® 2001 N, are particularly preferred amphopolymers according to the invention. Other suitable amphoteric polymers are for example those available under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

• – Vinylacetat/Crotonsäure-Copolymere, wie sie beispielsweise unter den Bezeichnungen Resyn^® (NATIONAL STARCH), Luviset^® (BASF) und Gafset^® (GAF) im Handel sind. Diese Polymere weisen neben Monomereinheiten der vorstehend genannten Formel (II) auch Monomereinheiten der allgemeinen Formel (V) auf: [-CH(CH₃)-CH(COOH)-]_n (V)
• – 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 Vinylestem, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen Solche gepfropften Polymere von Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch mit anderen copolymerisierbaren Verbindungen auf Polyalkylenglycolen werden durch Polymerisation in der Hitze in homogener Phase dadurch erhalten, daß man die Polyalkylenglycole in die Monomeren der Vinylester, Ester von Acrylsäure oder Methacrylsäure, in Gegenwart von Radikalbildner einrührt. Als geeignete Vinylester haben sich beispielsweise Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinylbenzoat und als Ester von Acrylsäure oder Methacrylsäure diejenigen, die mit aliphatischen Alkcholen mit niedrigem Molekulargewicht, also insbesondere Ethanol, Propanol, Isopropanol, Butanol, 2-Butanol, 2-Methy-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, erhältlich sind, bewährt. Polypropylenglycole (Kurzzeichen PPG) sind Polymere des Propylenglycols, die der allgemeinen Formel VI
  
  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. Insbesondere können die auf Polyethylenglycole gepfropften Vinylacetatcopolymeren und die auf Polyethylenglycole gepfropften Polymeren von Vinylacetat und Crotonsäure eingesetzt werden.
• – gepropfte und vernetzte Copolymere aus der Copolymerisation von i) mindesten einem Monomeren vom nicht-ionischen Typ, ii) mindestens einem Monomeren vom ionischen Typ, iii) von Polyethylenglycol und iv) einem Vernetrter Das verwendete Polyethylenglycol weist ein Molkekulargewicht zwischen 200 und mehreren Millionen, vorzugsweise zwischen 300 und 30.000, auf. Die nicht-ionischen Monomeren können von sehr unterschiedlichem Typ sein und unter diesen sind folgende bevorzugt: Vinylacetat, Vinylstearat, Vinyllaurat, Vinylpropionat, Allylstearat, Allyllaurat, Diethylmaleat, Allylacetat, Methylmethacrylat, Cetylvinylether, Stearylvinylether und 1-Hexen. Die nicht-ionischen Monomeren können gleichermaßen von sehr unterschiedlichen Typen sein, wobei unter diesen besonders bevorzugt Crotonsäure, Allyloxyessigsäure, Vinylessigsäure, Maleinsäure, Acrylsäure und Methacrylsäure in den Pfropfpolameren enthalten sind. Als Vernetzer werden vorzugsweise Ethylenglycoldimethacrylat, Diallylphthalat, ortho-, meta- und para-Divinylbenzol, Tetraallylnxyethan und Polyallylsocharosen mit 2 bis 5Alkylgruppen pro Molekül Saccharin. Die vorstehend beschriebenen gepfropften und vernetzten Copoymere werden vorzugsweise gebildet aus: i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ, ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ, iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglycol und 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: i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesätigter Alkohole und ungesättigter Carbonsäuren, ii) ungesättigte Carbonsäuren, 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 Unter kurzkettigen Carbonsäuren bzw. Alkoholen sind dabei solche mit 1 bis 8 Kohlenstoffatomen zu verstehen, wobei die Kohlenstoffketten dieser Verbindungen gegebenenfalls durch zweibindige Heterogruppen wie -O-, -NH-, -S- unterbrochen sein können.
• – Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester Diese Terpolymere enthalten Monomereinheiten der allgemeinen Formeln (II) und (IV) (siehe oben) sowie Monomereinheiten aus einem oder mehreren Allyl- oder Methallyestem der Formel VII:
  
  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. Die vorstehend genannten Terpolymeren resultieren vorzugsweise aus der Copolymerisation von 7 bis 12 Gew.-% Crotonsäure, 65 bis 86 Gew.-%, vorzugsweise 71 bis 83 Gew.-% Vinylacetat und 8 bis 20 Gew. %, vorzugsweise 10 bis 17 Gew.-% Allyl- oder Methallyletsre der Formel VII.
• – Tetra- und Pentapolymere aus i) Crotonsäure oder Allyloxyessigsäure ii) Vinylacetat oder Vinylpropionat iii) verzweigten Allyl- oder Methallylestem 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 O-Stellung verzweigten Monocarbonsäure.

Water-soluble anionic polymers suitable according to the invention include:

• - Vinyl acetate / crotonic acid copolymers, such as those sold under the names Resyn ^® (NATIO NAL STARCH), Luviset ^® (BASF) and Gafset ^® (GAF) are on the market. In addition to monomer units of the aforementioned formula (II), these polymers also have monomer units of the general formula (V): [-CH (CH ₃ ) -CH (COOH) -] _n (V)
• - vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF). A preferred polymer is that available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymers.
• - Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, which are sold, for example, under the name Ultrahold ^® strong (BASF).
• - Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, 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 a mixture with other copolymerizable compounds on polyalkylene glycols, are characterized by Heat polymerization in a homogeneous phase is obtained by stirring the polyalkylene glycols into the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid, in the presence of radical formers. Suitable vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and as an ester of acrylic acid or methacrylic acid, those which have low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 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 available. Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula VI
  
  are sufficient, where n can take values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycol, ie the representatives with n = 2, 3 and 4 in formula VI. 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 i) at least one monomer of the non-ionic type, ii) at least one monomer of the ionic type, iii) of polyethylene glycol and iv) a crosslinker The polyethylene glycol used has a molecular weight of between 200 and several million, preferably between 300 and 30,000. The nonionic monomers can be of very different types and the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene. The non-ionic monomers can likewise be of very different types, of which crotonic acid, allyloxyacetic acid, vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are particularly preferably contained in the graft polymers. Preferred crosslinkers are ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallylnxyethane and polyallylsocharoses with 2 to 5 alkyl groups per molecule of saccharin. The grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight of at least one monomer of the nonionic type, ii) 3 to 80% by weight of at least one monomer of the ionic type, iii) 2 to 50% by weight, preferably 5 to 30% by weight of polyethylene glycol and iv) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii) is.
• Copolymers obtained by copolymerization of at least one monomer of each of the following three groups: i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, ii) unsaturated carboxylic acids, iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol. Short-chain carboxylic acids or alcohols are understood to mean those with 1 to 8 carbon atoms, the carbon chains of these compounds can optionally be interrupted by double-bonded hetero groups such as -O-, -NH-, -S-.
• Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester. These terpolymers contain monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyesters of the formula VII:
  
  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-chain 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. The above-mentioned 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 methallyletre of the formula VII.
• - Tetra- and pentapolymers of i) crotonic acid or allyloxyacetic acid ii) vinyl acetate or vinyl propionate iii) branched allyl or methallyl esters iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
• - Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts
• - Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the O position.

Further, preferably usable as a covering according to the invention Polymers are cationic polymers. Among the cationic polymers the permanently cationic polymers are preferred. As "permanent become cationic " according to the invention such Polymers referred to independently have a cationic group of pH. These are in the Rule polymers that are a quaternary Contain 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^® N 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-amino-modifiziertes 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 Polydime- thylsiloxane, Quaternium-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 INCI-Nomenklatur bezeichnet, wobei sich detaillierte Angaben im CTFA International Cosmetic Ingredient Dictionan 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, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® N 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 referred to 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, such as in particular the products marketed under the trade names Cosmedia ^® Guar and Jaguar ^® ,
• - Polymers dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available 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 dialkylaminoacrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755.
• - Vinylpyrrolidone-methoimidazolinium chloride copolymers, as are offered under the name Luviquat ^® .
• - Quaternized polyvinyl alcohol and those under the names
• - polyquaternium 2,
• - polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27

known polymers with quaternary nitrogen atoms in the main polymer chain. The polymers mentioned are designated according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionan and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which express reference is made here 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.

The coating of the washing machine according to the invention or detergent servings can be in addition to the water-soluble Polymer or the water-soluble Polymers contain other ingredients, which in particular the Improve processability of raw materials for wrapping. Here are especially plasticizers and release agents. Furthermore can Dyes and / or fragrances and optical brighteners incorporated into the water-soluble coating to be aesthetic there and / or to achieve technical effects.

According to the invention, plasticizers in particular can be: use hydrophilic, high-boiling liquids, where appropriate, even at room temperature, solids as a solution, dispersion or melt can be used. Particularly preferred Plasticizers come from the group glycol, di, tri, tetra, penta-, Hexa-, Hepta-, Octa-, Nona-, Deca-, Undeca-, Dodecaethylenglycol, Glycerin, neopentyl glycol, trimethylol propane, pentaerythritol, mono-, Di-, triglycerides, surfactants, especially nonionic surfactants, and their Mixtures.

Ethylene glycol (1,2-ethanediol, "glycol") is a colorless, viscous, sweet tasting, strongly hygroscopic liquid, which is miscible with water, alcohols and acetone and has a density of 1.113. The freezing point of ethylene glycol is at –11.5 ° C, the liquid boils at 198 ° C. Technically, ethylene glycol is made from ethylene oxide by heating with Extracted water under pressure. Promising manufacturing processes can also be used on the acetoxylation of ethylene and beyond Build hydrolysis or synthesis gas reactions.

Diethylene glycol (2,2'-oxydiethanol, digol), HO- (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -OH, is a colorless, viscous, hygroscopic, sweet-tasting liquid, density 1.12, which is -6 ° C melts and boils at 245 ° C. Diglycol is miscible in any ratio with water, alcohols, glycol ether, ketones, esters, chloroform, but not with hydrocarbons and oils. The diethylene glycol, usually called diglycol in practice, is made from ethylene oxide and ethylene glycol (ethoxylation) and is thus practically the starting link for polyethylene glycols (see above).

Glycerin is a colorless, clear, difficult to move, odorless, sweet-tasting hygroscopic liquid with a density of 1.261 that solidifies at 18.2 ° C. Glycerin was originally only a by-product of fat saponification, but is now technically synthesized in large quantities. Most technical processes start from propene, which is processed to glycerol via the intermediate stages allyl chloride, epichlorohydrin: Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO ₃ contact via the stage of the glycide.

Trimethylolpropane [TMP, Etriol, Ettriol, 1,1,1-tris (hydroxymethyl) propane] is chemically designated 2-ethyl-2-hydroxymethyl-1,3-propanediol and comes in the form of colorless, hygroscopic masses with a melting point of 57-59 ° C and one Boiling point of 160 ° C (7 hPa) in the trade. It is soluble in water, alcohol, acetone, but insoluble in aliphatic and aromatic hydrocarbons. The production takes place through Reaction of formaldehyde with butyraldehyde in the presence of alkalis.

Pentaerythritol [2,2-bis (hydroxymethyl) -1,3-propanediol, penta, PE] is a white, crystalline powder with a sweet taste that is not hygroscopic and flammable and has a density of 1.399, a melting point of 262 ° C. as well has a boiling point of 276 ° C (40 hPa). Pentaerythritol is readily soluble in boiling water, slightly soluble in alcohol and insoluble in benzene, carbon tetrachloride, ether, petroleum ether. Technically, pentaerythritol is produced by reacting formaldehyde with acetaldehyde in an aqueous solution of Ca (OH) ₂ or NaOH at 15–45 ° C. First, a mixed aldol reaction takes place, in which formaldehyde reacts as the carbonyl component and acetaldehyde as the methylene component. Due to the high carbonyl activity of formaldehyde, the reaction of acetaldehyde with itself almost does not occur. Finally, the tris (hydroxymethyl) acetaldehyde thus formed is converted into pentaerythritol and formate in a crossed Cannizzaro reaction with formaldehyde.

Mono-, di-, triglycerides are esters of fatty acids, preferably longer-chain fatty acids with glycerin, one, two or three OH groups of the glycerol being esterified, depending on the type of glyceride. As an acid component with which the glycerol in mono-, di- or triglyceri which can be used according to the invention as plasticizers which may be esterified are, 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. 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 (arachic acid), docosanic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotinic acid), triacotanoic acid (9) 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-linadic acid and linadic acid) , 12c, 15c-octadecatreic acid (linolenic acid) into consideration the native fat substances (triglycerides) or the modified native fat substances (partially hydrolyzed fats and oils) are used. Alternatively, fatty acid mixtures can also be prepared by cleaving native fats and oils and then separated, the purified fractions later being converted into mono-, di- or triglycerides. Acids are esterified with the Glacerin here, coconut oil fatty acid (in particular, about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% C _14, 10 percent .-% C _16, 2 wt .-% _C18, 8 wt .-% _C18 ', 1 wt .-% C _18' '), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt _10% C, 50 wt .-% _C12, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _C18 ', 1 wt .-% C ₁₈ ''), tallow fatty acid (approx. 3% by weight C ₁₄ , 26% by weight C ₁₆ , 2% by weight C ₁₆ ', 2% by weight C ₁₇ , 17% by weight G ₁₆ , 44% by weight C ₁₈ ', 3% by weight C ₁₈ '', 1% by weight C ₁₈ '''), hardened tallow fatty acid (approx. 2% by weight C ₁₄ , 28% by weight ₁₆ C, 2 wt .-% C ₁₇ 63 wt .-% C _{1 8,} 1 wt .-% C ₁₈ '), technical grade oleic acid (about 1 wt .-% C _{1 2,} 3 wt .-% C _14, 5 wt .-% C _16, 6 wt .-% C ₁₆ ', 1 wt .-% C _17, 2 wt .-% C ₁₈ 70 wt .-% C _18', 10 wt .-% C ₁₈ '', 0.5 wt .-% C ₁₈ '''), technical palmitic / stearic acid (about 1 wt .-% C _{1 2,} 2 wt .-% C ₁₄ 45 wt .-% C _16, 2% by weight of C ₁₇ , 47% by weight of C ₁₈ , 1% by weight of C ₁₈ ') and soybean oil fatty acid (approx. 2 wt% C ₁₄ , 15 wt% C ₁₆ , 5 wt% C ₁₈ , 25 wt% C ₁₈ ', 45 wt% C ₁₈ '', 7 wt% C ₁₈ ''').

Surfactants, in particular nonionic surfactants, are also suitable as further plasticizers. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C ₁ _ _{2 1 4} alcohols containing 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO , C _{1 2} _ _{1 8} alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _{1 2} _ _{1 4} alcohol with 3 EO and C _{1 2} _ _{1 8} alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. 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.

With particular preference as Plasticizers used nonionic surfactants that have a melting point have above room temperature. Accordingly, preferred wrappers are characterized in that as Plasticizer nonionic) surfactants) with a melting point above of 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C, be used.

Suitable nonionic surfactants, the melting or depletion points in the temperature range mentioned are, for example, low-foaming nonionic surfactants, which can be solid or highly viscous at room temperature. Become highly viscous nonionic surfactants used at room temperature, it is preferred that these a viscosity above 20 Pas, preferably above 35 Pas and in particular above Have 40 Pas. Also nonionic surfactants, which are waxy at room temperature Have consistency are preferred.

Preferred than at room temperature fixed nonionic surfactants come from the groups of alkoxylated Nonionic surfactants, especially ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PC / EO / PO) surfactants.

In a preferred embodiment The present invention is the nonionic surfactant with a Melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferred at least 15 moles, especially at least 20 moles of ethylene oxide per Mol alcohol or alkylphenol has emerged.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C _{1 8} alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide. Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, in particularly preferred processes according to the invention, ethoxylated nonionic surfactants are used which consist of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol was obtained.

The nonionic surfactant preferably has additionally Propylene oxide units in the molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or Alkylphenols additionally Have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules does this preferably more than 30% by weight, particularly preferably more than 50 % By weight and in particular more than 70% by weight of the total molar mass such non-ionic surfactants.

Further particularly preferably to be used Contains nonionic surfactants with melting points above room temperature 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethyl propane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole Trimethylolpropane.

Further preferred nonionic surfactants satisfy the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ], in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrogen chloride radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y stands for a value of at least 15.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ) kCH (OH) [CH ₂ ) _j OR ² in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula can be different. R ¹ and are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each x ³ in the above formula can be different if xz is 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula can be used R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15.

Another preferred plasticizer Substances to be used can Glycerol carbonate, propylene glycol and propylene carbonate.

Glycerol carbonate can be obtained by transesterification of ethylene carbonate or dimethyl carbonate with glycerin, ethylene glycol or methanol being obtained as by-products. Another synthetic route starts from Glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO ₂ to glycerol carbonate. Glycerol carbonate is a clear, highly mobile liquid with a density of 1.398 gcm ^-3 that boils at 125-130 ° C (0.15 mbar).

There are two of the propylene glycol Isomers, 1,3-propanediol and 1,2-propanediol. 1,3-propanediol (trimethylene glycol) is a neutral, colorless and odorless, sweet tasting liquid density 1.0597, which solidifies at -32 ° C and at 214 ° C boils. 1,3-propanediol can be produced from aerolein and Water under subsequent catalytic hydrogenation.

Technically far more important 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless Liquid, represents the density 1.0381, which solidifies at -60 ° C and boils at 188 ° C. 1,2-propanediol made from propylene oxide by water retention.

Propylene carbonate is a water-bright, easily moving liquid with a density of 1.21 gcm ^-3 , the melting point is -49 ° C, the boiling point is 242 ° C. Large quantities of propylene carbonate can also be obtained by reacting propylene oxide and CO ₂ at 200 ° C and 80 bar.

Highly disperse silicas are particularly suitable as additional additives, which are preferably in solid form at room temperature. Pyrogenic silicas such as the commercially available Aerosil ^® or precipitated silicas are available here. Particularly preferred processes according to the invention are characterized in that one or more materials from the group (preferably highly disperse) silica, dispersion powder, high molecular weight polyglycols, stearic acid and / or stearic acid salts, and / or from the group of inorganic salts such as sodium sulfate, calcium chloride and / or from the group of inclusion formers such as urea, cyclodextrin and / or from the group of superadsorbers such as (preferably crosslinked) polyacrylic acid and / or their salts such as Cabloc 5066 / CTF and mixtures thereof.

The water-soluble coating can. from the above mentioned materials or their mixtures by injection molding or Blow molding process can be obtained. The casting can be done both from the melt as well from a solution with subsequent Drying done. Other methods for shaping plastics processing are suitable. For reasons process economics however, it is preferred that the water-soluble wrapping the portion packaging according to the invention is formed from a film material whose thickness is 10 to 1000 microns, preferably 20 to 750 μm and in particular 30 to 500 μm, is.

Included as another ingredient the portion packaging according to the invention a "grain", i.e. a solid, which become clear in its size of particulate Compositions stand out. Preferred cores have, for example Minimum diameter above 2 mm, with cores being preferred, the masses above 200 mg, particularly preferably above 500 mg and especially above 1 g.

The cores can be made using the usual manufacturing processes made for solids be, preferably by tableting. Here are portion packs according to the invention preferred, in which the core is a tablet. For tablets Cores can all common Tablet shapes and types are used, so that, for example, two-layered Cores with different layer compositions can be produced.

Alternatively, cores can also be poured and subsequent solidification can be produced. Here are portion packs according to the invention preferred, in which the core is a solidified melt. Of course of creativity the product designer has no limits, so that cores, what combinations from tableted components and, if necessary, poured in Share usable according to the invention are.

If from material, manufacturing technology or for reasons of aesthetics required will, liquids to process cores are also used, which contain liquid in an envelope. In addition to injection molding or blow molded parts come here in particular gelatin capsules Consideration.

According to the invention, the portion packaging contains at least a core. The description below is not always explicit noted that the Packaging can also contain several cores. The use of the Singulars in the illustration below is therefore not restrictive understand.

The core is according to the water-soluble wrapping fixed. additionally the core can be fixed by walls or compartmentalization devices be surrounded so that he is delimited from at least one area of the water-soluble casing. This The procedure creates several compartments in which each other incompatible Ingredients can be present, without reacting to each other. Corresponding portion packaging according to the invention, where the core by an internal web or a weir spatial delimited are preferred.

The core or cores can be fixed in different ways. For example, it is possible to form a positive or clamping connection between the water-soluble casing and the core. One possibility for this is that the core is attached to the water-soluble coating by positi onation of the core is fixed in a shaped cavity of the cladding.

For reasons of process economy it may be preferable to drop the core into a recess in the casing to allow, penetrating through its own weight in the recess. Liability in such a depression can then be advantageous can be achieved in that the wrapping material is shrunk around the core and thus tightly encloses it. This The type of fixation is due to the mechanically less complex core dosing across from the former preferred. Portion packaging according to the invention is corresponding preferred, in which the core shrinks to the water-soluble coating wrapping material is fixed.

As an alternative to form locking or clamping, or in complement for this purpose, the core can also be fastened to the casing by means of adhesive closure become. Here are portion packs according to the invention preferred, in which the core is attached to the water-soluble coating by an adhesive connection is fixed.

The adhesive connection can, for example can be achieved in that the Place of water-soluble packaging, where the core is inserted, is moistened. This will the water soluble Wrapping in places partially dissolved, whereby a highly concentrated polymer solution is generated "in situ", which acts as an adhesion promoter can serve. Of course can but other adhesion promoters can also be used.

Preferred materials for the adhesive bond are adhesives or so-called adhesion promoters. Here are in the frame the present invention as an adhesion promoter solutions, dispersions, emulsions or melts preferred, which have a viscosity below 3000 mPas.

Within the scope of the present invention refer to the viscosity values on viscosity measurements a sample temperature which corresponds to the processing temperature of the Adhesion promoter) (see below), with a Carrimed-plate-plate rheometer, at a shear force of 50 N per square meter, a plate diameter of 5 cm and a measuring system gap of 250 μm, the value being read after 10 seconds of measurement.

Preferred adhesion promoters have a viscosity below 2500 mPas during processing, preferably below 2000 mPas and in particular below from 1000 mPas.

The processing temperature of the Adhesion promoter) depends on the material nature of the used Adhesion promoter and the desired one Time within which the adhesion promoter develops his liability should. Here are temperatures of room temperature (those in winter months sometimes 10 to 15 ° C can be up to high temperatures above the boiling point realizable by water. In the context of the present invention The preferred types of production of adhesive bonds are the adhesion promoters at a temperature between 10 and 130 ° C, preferably between 20 and 110 ° C and in particular metered into the cavity between 20 and 90 ° C.

The adhesion promoter (s) can as Melt are dosed, which is usually Temperatures above 30 ° C, preferably above 40 ° C and especially above 50 ° C may require.

Within the scope of the present invention Particularly preferred fusible adhesion promoters are substances from the group of polyethylene and polypropylene glycols. Also mixtures of substances, containing these substances are preferred. Adhesion promoter from the Groups of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are used, are therefore preferred embodiments of the present invention.

Polyethylene glycols (abbreviation PEG) which can be used according to the invention are polymers of ethylene glycol which have the general formula H- (O-CH ₂ -CH ₂ ) _n -OH are sufficient, where n can have values between 1 (ethylene glycol) and over 100,000. The decisive factor in evaluating whether a polyethylene glycol can be used according to the invention is the viscosity of the PEG at the processing temperature. Since the preferred processes work above 20 ° C and below 90 ° C, the polyethylene glycols of the above formula are particularly suitable, in which n assumes values between approximately 15 and approximately 150. The polyethylene glycols with higher molecular weights are polymolecular, ie they consist of groups of macromolecules with different molecular weights. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. According to this nomenclature, the technically customary polyethylene glycols PEG 1550, PEG 3000, PEG 4000 and PEG 6000 can preferably be used in the context of the present invention.

A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the above formula. 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) according to the invention, for example, PEG-32, PEG-40, PEG-55, PEG 60, PEG-75 and PEG-100 can preferably be used according to the invention.

Commercially available polyethylene glycols are 540 (Union Carbide), Emkapol ^® 2000 (ICI Americas), Lipoxol ^® 2000 MED (Huls America), polyglycol example, under the trade name Carbowax ^® PEG ^® E-1550 (Dow Chemical), Lutrol ^® E2000 (BASF) and the corresponding trade names with higher numbers.

genügen, wobei n Werte zwischen 1 (Propylenglycol) und ca. 1000 annehmen kann. Ähnlich wie bei den vorstehend beschriebenen PEG kommt es bei der Bewertung, ob ein Polypropylenglycol efindungsgemäß einsetzbar ist, auf die Viskosität des PPG bei der Verarbeitungstemperatur an. Im Rahmen der vorliegenden Erfindung sind die technisch gebräuchlichen Polypropylenglycole PPG 1550, PPG 3000, PPG 4000 und PPG 6000 bevorzugt einsetzbar.Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula

are sufficient, where n values can be between 1 (propylene glycol) and approx. 1000. Similar to the PEGs described above, the assessment of whether a polypropylene glycol can be used according to the invention depends on the viscosity of the PPG at the processing temperature. In the context of the present invention, the technically customary polypropylene glycols PPG 1550, PPG 3000, PPG 4000 and PPG 6000 can preferably be used.

Because the temperature control at dosing of melts can be critical, it is preferred solutions or dispersions of adhesion promoters solid at room temperature or emulsions of adhesion promoters liquid at room temperature according to the invention. Here, the emulsions have problems that may arise later in the liability of the core only of minor importance. Also the Dispersions are due to the settling problem during processing less suitable compared to the particularly preferred solutions.

Particularly preferred adhesion promoters are solutions certain non-ionic substances. Here are solutions from polyvalent alcohols and / or sugars solid at room temperature preferred, with solutions preferred are those which, based on the solution, are at least 30% by weight, preferably at least 40% by weight and in particular at least 50 % By weight of solids).

Polyvalent alcohols in the sense of The present invention are compounds which have at least two Have hydroxyl groups. The state of aggregation of these compounds at room temperature (20 ° C) is particularly suitable include polyhydric alcohols Trimethylolpropane, pentaerythritol and the "sugar alcohols", i.e. those from monosaccharides polyhydroxy compounds formed by reduction of the carbonyl group. One differentiates between these according to the number of those contained in the molecule Hydroxy groups tetrite, pentite, hexite etc. In the context of the present Particularly suitable sugar alcohols according to the invention are e.g. B. Threit u. Erythritol, adonite (ribitol), arabitol (formerly: lyxitol) and xylitol, dulcitol (Galactite), mannitol and sorbitol (glucite), the latter also known as Sorbitol is called.

The term "sugar" in the context of the present Invention single and multiple sugars, i.e. monosaccharides and oligosaccharides, in which 2 to 6 monosaccharides are linked together like acetals are. "Sugar" are part of the present invention thus monosaccharides, disaccharides, trisaccharides, Tetra-, penta- and hexasaccharides.

Monosaccharides are linear polyhydroxy aldehydes (Aldosen) or Polyhydroxyketone (Ketosen). They usually have one chain length of five (Pentoses) or six (hexoses) carbon atoms. Monosaccharides with more (heptoses, Octoses etc.) or fewer (tetroses) carbon atoms are relatively rare. Have monosaccharides partially over a big Number of asymmetric carbon atoms. For this results in a hexose with four asymmetric carbon atoms a number of 24 stereoisomers. The orientation of the OH group on highest numbered asymmetr. C atom in the Fischer projection divides the monosaccharides in D- u. L-configured rows. With the naturally occurring monosaccharides the D configuration is much more common. Form monosaccharides, if possible is intramolecular hemiacetals, so that there are ring-shaped structures of the pyran (pyranoses) and furan type (furanoses). smaller Rings are unstable, larger rings only stable in aqueous solutions. By the cyclization creates another asymmetric carbon atom (the so-called anomeric carbon atom), the number of possible stereoisomers again doubled. This is indicated by the prefixes α- u. expressed in β. The formation of hemiacetates is a dynamic process that depends on various factors such as Temperature, solvent, pH value, etc. Mostly there are mixtures of both anomeric forms, some also as mixtures of the furanose and pyranose forms.

Within the scope of the present invention Monosaccharides that can be used as sugar are, for example, tetroses D (-) - erythrose and D (-) - threose and D (-) - erythrulose, the pentoses D (-) - ribose, D (-) - ribulose, D (-) - arabinose, D (+) - xylose, D (-) - xylulose and D (-) - lyxosis and the hexoses D (+) - allose, D (+) - old rose, D (+) - glucose, D (+) - mannose, D (-) - gulose, D (-) - Idose, D (+) - GalaCtose, D (+) - Talose, D (+) - Psicose, D (-) - Fructose, D (+) - Sorbose and D (-) - tagatose. The main and most common monosaccharides are: D-glucose, D-galactose, D-mannose, D-fructose, L-arabinose, D-xylose, D-ribose u. 2-deoxy-D-ribose.

Disaccharides are made up of two simple monosaccharide molecules linked by glycosidic bonds (D-glucose, D-fructose, etc.). The glycosidic bond lies between the acetal ones Carbon atoms (1 for aldoses or 2 for ketoses) of both monosaccharides, so that the ring form is fixed in the two, the sugars show no mutarotation, do not react with ketone reagents and no longer have a reducing effect (Fehling negative: trehalose or sucrose type). If, on the other hand, the glycosidic bond connects the acetal carbon atom of one monosaccharide with any of the second, this can still take the open-chain form, and the sugar has a reducing effect (Fehling positive: maltose type).

The main disaccharides are Sucrose (cane sugar, sucrose), trehalose, lactose (milk sugar), Lactulose, maltose (malt sugar), cellobiose (breakdown product of cellulose), Gentobiose, Melibiosis, Turanose and others.

Trisaccharides are carbohydrates, built up from 3 glycosidically linked monosaccharides are and for which one occasionally encounters with the incorrect term trios. Trisaccharides are relatively rare in nature, examples are gentianose, kestose, maltotriose, melecitose, raffinose, as well as an example of Trisaccharides streptomycin and validamycin containing amino sugar.

Tetrasaccharides are oligosaccharides with 4 monosaccharide units. Examples of this connection class are Stachyose, Lychnose (Galadtose-Glucose-Fructose-Galactose) and Secalose (from 4-fructose units).

Within the scope of the present invention saccharides from the group glucose, fructose, Sucrose, cellubiosis, maltose, lactose, lactulose, ribose and their mixtures used. Washing and washing are particularly preferred Cleaning tablets, which contain glucose and / or sucrose.

A preferred one can be used in the form of a solution Adhesion promoter is sorbitol. Here are methods according to the invention preferred, in which solutions of sorbitol are used as adhesion promoters which are based on the solution at least 50% by weight, preferably at least 60% by weight and in particular contain at least 70% by weight of sorbitol.

und R¹ sowie R² unabhängig voneinander für einen substituierten oder unsubstituierten, geradkettigen oder verzweigten Alkyl-, Aryl- oder Alkylarylrest mit 1 bis 24 Kohlstenstoffatomen und n jeweils für Zahlen von 5 bis 200 stehen.Another preferred class of substances that can be used as an adhesion promoter in the form of their solution are water-soluble polyurethanes. Among them, certain representatives are particularly preferred. Processes according to the invention are preferred here in which solutions or suspensions of polyurethanes composed of diisocyanates (A) and diols (B) act as adhesion promoters. O = C = NR ¹ -N = C = O (A), HOR ² -OH (B), are used, the diols being selected at least in part from polyethylene glycols (a) and / or polypropylene glycols (b) H- (O-CH ₂ -CH ₂ ) ₂ OH (a),

and R ¹ and R ² independently of one another represent a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical having 1 to 24 carbon atoms and n each number from 5 to 200.

These are preferred polymers below in more detail described.

• – einem Di- oder Polyisocyanat (A) und
• – einer Verbindung (B) mit mindestens 2 aktiven Wasserstoffatomen pro Molekül

Polyurethanes are polyadducts of at least two different types of monomers,

• - A di- or polyisocyanate (A) and
• - A compound (B) with at least 2 active hydrogen atoms per molecule

The solution or suspension or dispersion The polyurethanes used are obtained from reaction mixtures, in which at least one diisocyanate of the formula (A) and at least a polyethylene glycol of formula (a) and / or at least one polypropylene glycol of formula (b) are included.

In addition, the reaction mixtures contain further polyisocyanates. Also a content of the reaction mixtures - and therefore the polyurethane - on other diols, triplets, diamines, triamines, polyetherols and Polyesterols are possible. The compounds with more than 2 active hydrogen atoms are usually used only in small amounts in combination with a large excess of compounds used with 2 active hydrogen atoms.

If additional diols etc. are added, certain quantitative ratios to those according to the invention are mandatory Polyethylene and / or polypropylene glycol units present in the polyurethane must be observed. It is preferred here that at least 10% by weight, preferably at least 25% by weight, particularly preferably at least 50% by weight and in particular at least 75% by weight, of the diols reacted in the polyurethane are selected from polyethylene glycols (a) and / or polypropylene glycols (b).

The solution or dispersion or suspension the adhesion promoter can do other than the special polyurethanes Ingredients such as ingredients of detergents and cleaning agents, in particular dyes and / or fragrances.

The polyurethanes contain diisocyanates of the formula (AA) as a monomer unit. The diisocyanates used are predominantly hexamethylene diisocyanate, 2,4- and 2,6-toluenediisocyanate, 4,4'-methylene di (phenyl isocyanate) and in particular isophorone diisocyanate. These compounds can be described by the formula (A) above, in which stands for a preventive grouping of carbon atoms, for example a methylene-ethylene-propylene, butylene, pentylene, hexylene, etc. group. In the above-mentioned, most widely used hexamethylene diisocyanate (HMDI), R ¹ = (CH ₂ ) ₆ , in 2,4- or 2,6-toluenediisocyanate (TDI) R ¹ stands for C ₆ H ₃ -CH ₃ ) , in 4,4'-methylenedi (phenyl isocyanate) (MDI) for C ₆ H ₄ -CH ₂ -C ₆ H ₄ ), and in isophorone diisocyanate R ^{1 is} the isophorone residue (3,5,5-trimethyl-2-cyclohexenone ).

The polyurethanes also contain diols of the formula (B) as a monomer unit, at least some of these diols originating from the group of polyethylene glycols (a) and / or polypropylene glycols (b). Polyethylene glycols are polymers of ethylene glycol which have the general formula (a) H- (O-CH ₂ -CH ₂ ) _n -OH (a) are sufficient (see above).

genügen, wobei n Werte zwischen 5 und 2000 annehmen kann.Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula b

are sufficient, where n can have values between 5 and 2000.

Both in the case of connections Formula (a) and compounds of formula (b) are such Representatives preferred monomer units in which the number n is for a number between 6 and 1500, preferably between 7 and 1200, especially preferably between 8 and 1000, more preferably between 9 and 500 and especially between 10 and 200. For certain applications, polyethylene and polypropylene glycols of the formulas (II a) and / or (II b) are preferred be in which n for a number between 15 and 150, preferably between 20 and 100, particularly preferably between 25 and 75 and in particular between 30 and 60 stands.

Examples of optional further in the reaction mixtures Compounds contained in the production of the polyurethanes are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycols, ethylenediamine, propylenediamine, 1,4-diaminobutane, Hexamethylenediamine and α, ω-diamines based on long-term alkanes or polyalkylene oxides. Washing according to the invention or detergent tablets, where the polyurethanes in the coating additional Diamines, preferably hexamethylenediamine and / or hydroxycarboxylic acids, preferably dimethylolpropionic are preferred.

Depending on which reactants are reacted with each other to form the polyurethanes, polymers with different structural units are obtained. Processes according to the invention are preferred here in which solutions or suspensions of polyurethanes are used which have structural units of the formula (C) - [OC (O) -NH-R ¹ -NH-C (O) -OR ² ] _k - (C), in which R ^{1 stands} for - (CH ₂ ) ₆ - or for 2,4- or 2,6-C ₆ H ₃ -CH ₃ , or for C ₆ H ₄ -CH ₂ -C ₆ H ₄ and is selected from -CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n - or -CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n -, where n is a number from 5 to 199 and k is a number from 1 to 2000.

The diisocyanates described as preferred can be reacted with all the diols described as preferred to give polyurethanes, so that in preferred processes according to the invention polyurethanes are used as adhesion promoters which have one or more of the structural units (C a) to (C h): - [OC (O) -NH- (CH ₂ ) ₆ -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ )] _k - (C a), - [OC (O) -NH- (2,4-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - (C b), - [OC (O) -NH- (2,6-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - (C c), - [OC (O) -NH- (C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - (C d), - [OC (O) -NH- (CH ₂ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n ] _k - (C e) - [OC (O) -NH- (2,4-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) - CH ₂ ) _n ] _k - (C f), - [OC (O) -NH- (2,6-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) - CH ₂ ) _n ] _k - (C g), - [OC (O) -NH- (C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n ] _k - (C h), where n is a number from 5 to 199 and k is a number from 1 to 2000.

As already mentioned above, the Reaction mixtures in addition to diisocyanates (A) and diols (B) also other compounds from the group of Polyisocyanates (especially triisocyanates and tetraisocyanates) and from the group of polyols and / or di- or polymains included. In particular triols, tetrols, pentoles and hexols as well as di- and triamines can be contained in the reaction mixtures. A content of compounds with more than two "active" H atoms (all above with the exception of diamines) leads to a partial crosslinking of the polyurethane reaction products and can be beneficial Properties such as control of the dissolution behavior, stability or flexibility the adhesive bond, process advantages when dispensing etc. Usually is the content of such compounds with more than two "active" N atoms on the Reaction mixture less than 20% by weight of the total used Reaction partner for the diisocyanates, preferably less than 15% by weight and in particular less than 5% by weight.

In preferred embodiments of the present invention, the polyurethanes have molar masses from 5000 to 150,000 gmol ^-1 , preferably from 10,000 to 100,000 gmol ^-1 and in particular from 20,000 to 50,000 gmol ^-1 .

As a third component, the Portion packaging according to the invention a matrix of flowable material on that in the wrapper is contained and at least partially surrounds the core or cores. "Flowable" means in the context of the present Registration that the Matrix can be introduced into the casing by simple dosing processes. The term flowable thus closes expressly include the term "pourable" or "free-flowing" on.

In preferred embodiments In the present invention, the flowable material is a liquid or a flowable gel. Here are portion packs according to the invention preferred where the flowable material a liquid is whose viscosity (Brookfield viscometer LVT-II at 20 rpm and 20 ° C, spindle 3) preferably in the range of 500 to 50,000 mPas, more preferred from 1000 to 10,000 mPas, particularly preferably from 1200 to 5000 mPas and in particular from 1300 to 3000 mPas.

"Flowable" in the sense of the present invention are also matrices, which are fluent are processable, but later the state of fluidity lose, for example harden or freeze.

The hardening of the flowable matrices can be done by different mechanisms, the temporal delayed Water retention, cooling below the melting point, the evaporation of solvents, the crystallization, by chemical reaction (s), in particular polymerization and the change of rheological properties e.g. by changing the shear mass (s) as the most important hardening mechanism in addition to radiation curing by UV, alpha beta or gamma rays or microwaves are.

The delayed water binding in the Matrices can be realized in different ways become. There are, for example, masses that can be hydrated, anhydrous raw materials or raw materials with low hydration levels, the in stable higher Skip hydrates can, as well as water. The formation of hydrates that are not spontaneous takes place, leads then to bind free water, which in turn cures the Leads masses.

The staggered water retention can also be done, for example, by containing hydrate water Salts that dissolve in their own crystal water when the temperature rises incorporates the matrices. If the temperature drops later, so the water of crystallization is bound again, resulting in a loss of shape Processability with simple means and to a solidification of the Matrices leads.

The swelling of natural or synthetic polymers as a time-delayed water binding mechanism can also be used according to the invention. Here mixtures of unswollen polymer and suitable tem swelling agents, such as water, diols, glycerol, etc., are incorporated into the matrices, swelling and curing after metering.

The main mechanism of curing through delayed Water binding is the use of a combination of water and anhydrous or low-raw materials that hydrate slowly. To do this especially substances that contribute to cleaning performance in the washing or cleaning process contribute. Preferred according to the invention Ingredients of the matrices are, for example, phosphates, Carbonates, silicates and zeolites.

It is particularly preferred if the resulting hydrate forms have low melting points because in this way a combination of the hardening mechanisms by internal Drying and cooling achieved becomes. It is preferred that the Matrices 10 to 95 wt .-%, preferably 15 to 90 wt .-%, particularly preferred 20 to 85 wt .-% and in particular 25 to 80 wt .-% anhydrous Contain substances which are hydrated into a hydrate form with a melting point below 120 ° C, preferably below 100 ° C and in particular pass below 80 ° C.

Another mechanism for curing the processed according to the invention Matrices lies in the cooling when processing the matrices above their softening point. Procedures in which the curing the deformable matrices by cooling below the melting point are preferred.

Softenable under the influence of temperature Masses can be easily assembled by the desired other ingredients with a meltable or softenable substance mixed and the mixture to temperatures in the softening range warmed of this substance and is dosed at these temperatures. Be particularly preferred waxes, paraffins, as meltable or softenable substances Polyalkylene glycols etc. used. These are described below.

The meltable or softenable substances should have a melting range (solidification range) in such a range Have temperature range at which the other ingredients of the processing masses not exposed to excessive thermal stress become. In preferred according to the invention Matrices have a meltable or softenable substance Melting point above 30 ° C.

It has proven to be beneficial if the meltable or softenable substances did not define a sharply Melting point shows, as usual occurs with pure, crystalline substances, but, one under circumstances have a melting range spanning several degrees Celsius. The meltable or softenable Substances preferably have a melting range that is between about 45 ° C and is about 75 ° C. This means in the present case that the Melting range occurs within the specified temperature interval and does not denote the width of the melting range. Preferably is the width of the melting range is at least 1 ° C, preferably about 2 to about 3 ° C.

The above properties are usually fulfilled by so-called waxes. "Growing" is a series of natural or artificial understood substances that usually melt above 40 ° C without decomposition and a little above the melting point, relatively low viscosity and not are stringy. They have a strongly temperature-dependent consistency and solubility on.

They are divided according to their origin Wax in three groups, the natural waxes, chemically modified Waxes and synthetic waxes.

Natural waxes include, for example vegetable waxes such as candelilla wax, camamauba wax, Japanese wax, Esparto grass wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or uropygial fat, Mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

To the chemically modified waxes counting for example hard waxes such as Montanester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the above-mentioned requirements with regard to the softening point can also be used as meltable or softenable substances for the masses which harden by cooling. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, for example Dimynstyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or semi-synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin ^® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances. Shellac, for example shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used according to the invention as meltable or softenable substances.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are high molecular weight, water-insoluble fatty alcohols with usually about 22 to carbon atoms. The wax alcohols come, for example, in the form of wax sesters of higher molecular weight fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ^® (Pamentier & Co). In the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides can also be used, at least in part, as part of the meltable or softenable substances, but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.

Particularly preferred melting or softenable substances in the masses to be processed are such from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) contains where polyethylene glycols with molecular weights between 1500 and 36,000 preferred, those with molecular weights from 2000 to 6000 are particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred are. Appropriate processes, which are characterized by that the the plastically deformable mass (es) consists of at least one substance the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) contains / contain are preferred. Masses to be processed according to the invention are special here preferred as the only meltable or softenable substances Contain propylene glycols (PPG) and / or polyethylene glycols (PEG). These substances have been described in detail above.

In a further preferred embodiment contain the matrices to be processed according to the invention predominantly Share of paraffin wax. This means, that at least 50% by weight of the total meltable or softenable substances contained, preferably more, consist of paraffin wax. Particularly suitable are paraffin wax contents (based on the total amount of melt or softenable substances) of about 60% by weight, about 70% by weight or about 80% by weight, being even higher Fractions of, for example, more than 90% by weight are particularly preferred are.

Paraffin waxes point towards the other named, natural Grow in the context of the present invention, the advantage that in a alkaline detergent environment no hydrolysis of the waxes takes place (as expected for example with the wax star is), since paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of Alkanes, as well as low proportions of iso- and cycloalkanes. The to be used according to the invention Paraffin preferably has essentially no constituents a melting point of more than 70 ° C, particularly preferably of more than 60 ° C on. Shares of high-melting alkanes in the paraffin can Do not drop below this melting point in the detergent fleet desirable Wax residue on the surfaces to be cleaned or leave the goods to be cleaned. Such wax residues result in usually to an unsightly Appearance of the cleaned surface and should therefore be avoided.

Preferred matrices to be processed contain at least one as meltable or softenable substances Paraffin wax with a melting range of 50 ° C to 60 ° C, preferred methods are characterized in that the deformable mass (es) a paraffin wax with a melting range from 50 ° C to 55 ° C contains.

The content of the used is preferably Paraffin wax at ambient temperature (usually about 10 up to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax components are present in a wax at room temperature, the more useful it is within the scope of the present invention. With increasing proportion solid wax components increase the resilience of the process end products across from Bumps or Friction on other surfaces at what becomes a longer lasting Protection leads. High proportions of oils or liquid Wax components can to a weakening the molded body or shaped body areas to lead, which opens pores and the active substances are exposed to the environmental influences mentioned at the beginning become.

The meltable or softenable substances can in addition to paraffin as the main ingredient, one or more of the above mentioned waxes or wax-like substances. In a another preferred embodiment the present invention should be the meltable or softenable Substance-forming mixture should be such that the mass and the molded body formed from it or molded part at least largely insoluble in water are. The solubility in water at a temperature of about 30 ° C about 10 do not exceed mg / l and are preferably below 5 mg / l.

In such cases, the melting or softenable substances, however, the lowest possible solubility in water, even in water with increased Temperature, have a temperature-independent release of the active substances preferably largely avoided.

The principle described above serves the delayed Release of ingredients at a certain point in time Cleaning cycle and can Use particularly advantageously if the main wash cycle is at a lower temperature (e.g. 55 ° C) rinsed is so that the Active substance from the rinse aid particles only in the rinse cycle at higher Temperatures (approx. 70 ° C) is released.

Preferred matrices to be used according to the invention are characterized in that they are used as meltable or softenable substances one or more substances with a melting range of 40 ° C to 75 ° C in amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt. -%, each based on the weight of the mass.

Another mechanism by which the curing the matrices that can be used is the evaporation of solvents. You can do this solutions or dispersions of the desired Ingredients in one or more suitable, volatile solvent are produced after dosing this (s) solvent give and harden. As a solvent there are, for example, lower alkanols, aldehydes, ethers, esters etc., their selection depending on the further composition of the processed Matrices is made. Particularly suitable solvents for such Procedures in which the curing of the deformable mass (s) by evaporation of solvents, are Ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol as well as the acetic acid esters the abovementioned alcohols, in particular ethyl acetate.

Evaporation of the solvents mentioned can by warming, or accelerated by air movement. Combinations too of the measures mentioned are suitable for this, for example blowing with warm or Hot air.

Another mechanism that the corroboration can be based on crystallization.

Crystallization as the basis of curing Mechanism can be used, for example, by melting crystalline substances as the basis of one or more matrices serve. After processing, such systems go into a higher order state, the again for curing of the entire molded body formed leads. However, crystallization can also be carried out by crystallization from supersaturated solution respectively. supersaturation is the term for a within the scope of the present invention metastable state in which in a closed system more of a substance is present than is necessary for saturation. A for example by hypothermia obtained supersaturated solution accordingly contains more solved Substance than it is likely to contain in thermal equilibrium. The excess of dissolved substance can be caused by vaccination with germs or dust particles or by vibration of the system are brought to instantaneous crystallization. In the context of the present invention, the term “oversaturated” always refers to a temperature of 20 ° C. Dissolve in a certain solvent at a temperature of 20 ° C of a substance × grams in liters, that's the solution to be referred to as "oversaturated" in the context of the present invention if it contains (x + y) grams of the substance in liters, where y> 0 applies. So are in Within the scope of the present invention, solutions are also referred to as "oversaturated" with an increased Temperature serve as the basis of a matrix to be processed and be processed at this temperature, at which there is more of solute in the solution is at 20 ° C in same amount of solvent would solve.

The term solubility means the present Invention the maximum amount of a substance that the solvent can absorb at a certain temperature, i.e. the share of the solved Substance in a saturated at the temperature in question Solution. contains a solution more solved Substance than they are at a given temperature in the thermodynamic Should contain balance (e.g. with hypothermia), that's how they are called saturated. By Vaccinate with germs cause the excess as the bottom body of the now only saturated solution fails. However, a solution saturated with one substance can do another Dissolve substances (e.g. you can in a saturated Saline solution still dissolve sugar).

The state of supersaturation can, as described above, by slow cooling or by hypothermia a solution reach as long as the solved Substance in the solvent at higher Temperatures more soluble is. Other options, too saturated solutions to get there are, for example, combining two solutions, whose ingredients react to another substance that does not fails immediately (prevented or delayed Precipitation reactions). The latter mechanism is the basis of the formation of to be processed according to the invention Matrices particularly suitable.

In principle, the state is supersaturation with any kind of solution achievable, although the application of the in the present application The principle described, as already mentioned, is preferred during production of detergents and cleaning agents is used. As a result some systems, which in principle tend to form supersaturated solutions, are less good according to the invention can be used because the underlying material systems are ecological, toxicologically or from economic establish cannot be used. In addition to non-ionic surfactants or common non-aqueous solvents are therefore curing mechanisms according to the invention particularly preferred in which at least one is based processing matrix used a supersaturated aqueous solution becomes.

As already mentioned above, the state of supersaturation in the context of the present invention relates to the saturated solution at 20.degree. By using solutions that have a temperature above 20 ° C, the state of supersaturation can easily be reached. invention Crystallization-hardening masses have a temperature during processing preferably between 35 and 120 ° C, preferably between 40 and 110 ° C, particularly preferably between 45 and 90 ° C and in particular between 50 and 80 ° C, are within the scope of the present Invention preferred.

Because the detergent and cleaning agent portions produced usually neither with elevated Temperatures stored even later at these heightened Temperatures are applied leads the cooling the mixture for precipitation the share of dissolved Substance from the supersaturated Solution, the over the saturation limit at 20 ° C away in the solution was included. The supersaturated solution can so when cooling down into a saturated solution and a bottom body split. But it is also possible that by Recrystallization and hydration phenomena to the supersaturated solution when cooling solidified into a solid. For example, this is the case if certain hydrated salts when heated in their Dissolve crystal water. When cooling down often oversaturated solutions form here, by mechanical action or the addition of germs to a solid - the water of crystallization Salt as the thermodynamically stable state at room temperature - solidify. This phenomenon is well known for example sodium thiosulfate pentahydrate and sodium acetate trihydrate, in particular the latter salt containing hydrate water in Form of supersaturated solution in the method according to the invention can be used advantageously. Also special detergent and cleaning agent ingredients, such as phosphonates show this phenomenon and are suitable in form of solutions excellent as a granulation aid. For this, the corresponding phosphonic (see below) neutralized with concentrated alkali solution, whereby yourself the solution through the heat of neutralization heating up. When cooling down form from these solutions Solids of the corresponding alkali phosphonates. By incorporating further detergent and cleaning agent ingredients in the still warm solutions can be processed according to the invention Prepare matrices of different compositions. Especially it is preferred that you as the basis of the curing Matrix serving supersaturated solution Solidified at room temperature a solid. It is preferred here that the previously supersaturated solution after Solidify to a solid by heating to temperature, where the supersaturated solution was formed cannot be converted back into a supersaturated solution can. This is the case, for example, with the phosphonates mentioned.

The as the basis of the curing Matrix serving supersaturated solution can - as above mentioned - on several Because received and then after optional addition of other ingredients are processed. For example, one easy way is that the as the basis of the curing Matrix serving supersaturated solution Dissolve of the solved Substance in heated solvent will be produced. Do this in the heated solvent higher Amounts of the solved Loosened than at 20 ° C would solve so is a supersaturated solution in the sense of the present invention, which is either hot (see above) or cooled and can be added to the mixer in the metastable state.

It is also possible to contain hydrate water To drain salts by "dry" heating and dissolve in your own crystal water (see above). This is also a method within the present To produce usable supersaturated solutions.

Another way is one unsaturated solution with a gas or another liquid or solution to move so that the dissolved Substance in the solution to a poorly soluble substance reacts or dissolves poorly in the mixture of solvents. The Combine two solutions that each contain two substances, which together lead to a worse soluble Reacting substance is also a method for producing supersaturated Solutions, as long as the less soluble Fabric does not fail immediately. In the context of the present invention it is also preferred that the as Basis of the curing Matrix serving supersaturated solution Merging two or more solutions will be produced. examples for such ways to create supersaturated solutions are discussed below.

It is preferred that the supersaturated aqueous solution by combining one aqueous solution of one or several acidic ingredients of detergents and cleaning agents, preferably from the group of surfactant acids, builder acids and complexing acids, and an aqueous alkali solution, preferably one aqueous alkali hydroxide solution, in particular an aqueous sodium hydroxide solution becomes.

Among the representatives already mentioned above of the classes of compounds mentioned take in particular the phosphonates an outstanding position in the context of the present invention on. In preferred processes according to the invention, therefore, the supersaturated aqueous solution is passed through Combine an aqueous phosphonic acid solution with Concentrations above 45 wt .-%, preferably above 50 wt .-% and in particular above 55% by weight, based in each case on the phosphonic acid solution and with an aqueous sodium hydroxide solution Concentrations above 35% by weight, preferably above 40% by weight and in particular above 45% by weight, based in each case on the sodium hydroxide solution.

According to the invention, the matrix can also be cured by chemical reaction (s), in particular polymerization. In principle, all chemical reactions are suitable which, starting from one or more liquid to pasty substances, lead to solids by reaction with (one) other substances. Chemical reactions that do not suddenly lead to the state change mentioned are particularly suitable. From the variety of chemical reactions that lead to the solidification phenomenon, ins particularly suitable reactions in which larger molecules are made up of smaller molecules. Again, this preferably includes reactions in which many small molecules react to (one) larger molecules. These are so-called polyreactions (polymerization, polyaddition, polycondensation) and polymer-analogous reactions. The corresponding polymers, polyadducts (polyaddition products) or polycondensates (polycondensation products) then give the shaped body which has been cut to length its strength.

With regard to the purpose the manufactured according to the invention Products, it is preferred as the curing mechanism, the formation of such solid substances from liquid or pasty starting materials to use the ingredients in the detergent and cleaning agent anyway, for example cobuilders, soil repellents or should-release polymers should be used. Such cobuilders can, for example, from the Groups of polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, etc. These classes of substances continue to grow described below.

Another mechanism by which the curing the deformable mass (s) take place within the scope of the present invention can, is by change hardening of the rheological properties.

You make the property expected that certain Substances under the influence of shear forces have their rheological properties change drastically in some cases. examples for such systems that are known to the person skilled in the art are, for example Layered silicates that are strong under shear in suitable matrices can thicken and lead to cut-resistant masses.

In summary, for the sake of technical feasibility particularly preferred portion packaging according to the invention characterized in that the flowable material is a solidified melt.

The flowable material can be one (if necessary solidifying or hardening) liquid can also be particulate. Here are portion packs according to the invention preferred, which are characterized in that the flowable material is a partial aggregate whose average particle size is less than 1200 μm, preferably below 300 μm, particularly preferably below 250 μm and in particular below of 200 μm lies.

Depending on the desired application, the Portions according to the invention different ingredients of washing or cleaning agents contain. You can the different areas such as core, individual core region (at multiphase cores), matrix or individual matrix region for separating incompatible Ingredients are used.

The main ingredients that in the portions according to the invention may be included are described below.

The detergent or cleaning agent portions according to the invention preferably contain surfactant (s), anionic, nonionic, cationic and / or amphoteric surfactants can be used. Prefers are mixtures from a technical point of view for textile detergents from anionic and nonionic surfactants, the proportion of anionic surfactants may be larger should be considered the proportion of nonionic surfactants. The total surfactant content the detergent or cleaning agent portions are preferably below 30 wt .-%, based on the total agent. Nonionic surfactants have already been described above as optional plasticizers for the wrapper. The same substances can also be used in the portions as wash-active Use substances., So that on the above statements can be referred.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferred nonionic surfactants, either as the sole nonionic Surfactant or used in combination with other nonionic surfactants become. are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl ester.

Also non-ionic surfactants of the type the amine oxides, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half from that.

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.Other suitable surfactants are polyhydroxy fatty acid amides of the formula VIII below,

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

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.The group of polyhydroxy fatty acid amides also includes compounds of the formula IX below,

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, 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 propylated Derivatives of this remainder.

[Z] is preferably by reductive Obtaining amination of a sugar, for example glucose, fructose, Maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds can then be reacted with fatty acid methyl ester in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

The content more preferred for textile washing washing machine according to the invention or detergent portions of nonionic surfactants is 5 to 20% by weight, preferably 7 to 15% by weight and in particular 9 to 14 % By weight, based in each case on the total composition.

In automatic dishwashing detergents are preferably low-foaming non-ionic surfactants used.

In conjunction with the surfactants mentioned can anionic, cationic and / or amphoteric surfactants are also used be, because of their foam behavior in machine Dishwashing detergents only are of secondary importance and mostly only in quantities below of 10% by weight, mostly even below 5% by weight, for example from 0.01 to 2.5% by weight, based in each case on the agent. In contrast, these surfactants are of significantly greater importance in detergents. The washing according to the invention or portions of detergent thus also anionic, cationic and / or as a surfactant component contain amphoteric surfactants.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_{1 –6}-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8–28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.The agents according to the invention can contain, for example, cationic compounds of the formulas X, XI or XII as cationic active substances:

wherein each R ¹ group is independently selected from C _{1 -6} alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C thereby _{9- 3} alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example _{1 2} _ ₈ monoolefins with terminal or internal double bond by sulfonation with gaseous from C Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates, which are for example derived from C _{1 2} _ ₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of ☐-sulfofatty acids (ester sulfonates), for example the O-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters are the mono-, di- and triesters and their mixtures to understand how they in the manufacture by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycene ends with 0.3 to 2 mol of glycerol be preserved. Preferred sulfonated fatty acid glycerol esters are included the sulfonation products of saturated fatty acids with 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) yl sulfates are the alkali and especially the sodium salts of the Schwefelsäurehalbester C ₁ -C ₂ are _C18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C ₁₀ -C ₂₀ - Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. The C _{1 2} -C _{1 6} alkyl sulfates and C _{1 2} -C _{1 5} alkyl sulfates and C _{1 4} -C _{1 5} alkyl sulfates are preferred from the point of view of washing technology. 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.

Also, the Schwefelsäuremonoester with 1 to 5 moles of ethylene oxide chain or branched C ₁ _ ₂ alcohols, such as 2-methyl-branched _C9-11 alcohols containing on average 3.5 mol ethylene oxide (EO) or C _{1 2} _ ₁₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contained C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Other anionic surfactants especially soaps. Saturated and unsaturated Fatty acid soaps, like the salts of lauric acid, myristic, palmitic acid, Stearic acid, (hydrogenated) erucic and behenic acid and especially from natural ones fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the Can soaps in the form of their sodium, potassium or ammonium salts and as soluble salts organic bases, such as mono-, di- or triethanolamine, are present. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

The content of preferred textile detergents according to the invention of anionic surfactants 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 up to 20 wt .-%, each based on the total agent. Cleaning agents according to the invention for the machine dishwashing are preferably free of anionic surfactants.

Within the scope of the present invention also contain preferred agents one or more substances from the group of builders, bleaching agents, bleach activators, Enzymes, electrolytes, non-aqueous solvents, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, Dyes, hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, Color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating, Swelling and sliding resistant agents as well as UV absorbers.

As builders in the agents according to the invention may be included are in particular phosphates, silicates, aluminum silicates (in particular Zeolites), carbonates, salts of organic di- and polycarboxylic acids as well To name mixtures of these substances.

The use of the well-known Phosphates as builder substances are possible according to the invention, provided that such use is not avoided for ecological reasons should be. Among the variety of commercially available The alkali metal phosphates have particular preference for phosphates of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) of greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the relationship for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid HP ₃ O _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaHP ₂ O ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders that are very easily soluble in water, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O) at 200 ° C, and at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). + NaH ₂ PO _{4 is} acidic; it arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), NaHP ₂ O ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^{- 3} , melting point 35 ° with the loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to the diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), KHP ₂ O ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, NaP ₃ O ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C. and, in anhydrous form (corresponding to 39-40% P ₂ O ₅ ), a density of 2.536 gcm ^{- 3} . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tartan or tri-base potassium phosphate), KP ₃ O ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when Thomas slag is heated with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O, exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with water loss). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, with the pH of the 1% solution at 25 ° is 10.4.

Condensation of the NaHP ₂ O ₄ or the KHP ₂ O ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium phosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these are exact such as sodium tripolyphosphate, potassium tripolyphosphate or mixtures usable from these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and are potassium tripolyphosphate and sodium potassium tripolyphosphate usable according to the invention.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M represents 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.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed in release and have secondary rapid properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide the sharp X-ray reflections that are typical of crystalline substances, but at most one or more maxima of the scattered X-rays which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula n Na 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. The zeolite can be used as a spray-dried powder or as an undried kneaded suspension that is still moist from its manufacture. In the case that the zeolite is used as a suspension, small additions of nonionic surfactants can contain as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁ -C _{2 1 8} fatty alcohols containing 2 to 5 ethylene oxide groups, C _{1 2} -C _{1 4} fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Other important ceramics are especially the carbonates, cirates and silicates. Trisodium citrate is preferred and / or pentasodium tripolyphosphate and / or sodium carbonate and / or Sodium bicarbonate and / or gluconate and / or silicate builders used from the class of disilicates and / or metasilicates.

Alkali carriers can be present as further constituents his. As an alkali carrier apply alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, Alkali metal sesquicarbonate, alkali silicates, alkali metal silicates, and mixtures of the aforementioned substances, wherein for the purposes of this invention preferably the alkali carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate can be used.

A builder system is particularly preferred containing a mixture of tripolyphosphate and sodium carbonate.

It is also particularly preferred a builder system containing a mixture of tripolyphosphate and Sodium carbonate and sodium disilicate.

In addition, other ingredients be present, washing, rinsing or cleaning agents according to the invention are preferred, the additional one or more substances from the group of acidifying agents, Contain chelating agents or the deposit-inhibiting polymers.

Both acidic acids and organic acids are suitable as acidifying agents, provided they are compatible with the other ingredients. The solid mono-, oligo- and polycarboxylic acids can be used in particular for reasons of consumer protection and handling safety. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. The anhydrides of these acids can also be used as acidifying agents, maleic anhydride and succinic anhydride in particular being commercially available. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt.%), Glutaric acid (max. 50 wt.%) And adipic acid (max 33% by weight).

Another possible group of ingredients represent the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, a single Ligand occupies more than one coordination point on a central atom, d. H. is at least "bidentate". In this case are usually elongated connections by complex formation over a Ion closed to rings. The number of ligands bound depends on the coordination number of the central ion.

Common and in the context of Preferred chelate complex images are present invention polyoxycarboxylic, Polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Also complex-forming polymers, i.e. polymers that are either in the Main chain (self or side to this functional groups wear that can act as ligands and with suitable metal atoms in generally react to form chelate complexes can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can come from only one macromolecule or belong to different polymer chains. The latter leads to Cross-linking of the material, unless the complex-forming polymers already before covalent bonds were cross-linked.

Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, Hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cycl.) Polyamino, mercapto, 1,3-dicarbonyl and crown ether residues with z. T. very specific Activities against ions of different metals. The base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.

• (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• (iii) geminalen Diphosphonsäuren,
• (iv) Aminophosphonsäuren,
• (v) Phosphonopolycarbonsäuren,
• (vi) Cyclodextrine

In the context of the present invention, particular preference is given to detergent or cleaning agent portions which contain one or more chelate complexing agents from the groups of

• (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• (ii) nitrogen-containing mono- or polycarboxylic acids,
• (iii) geminal diphosphonic acids,
• (iv) aminophosphonic acids,
• (v) phosphonopolycarboxylic acids,
• (vi) cyclodextrins

in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above of 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the agent.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
• b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsöure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyn-asparaginsäure oder Nitrilotriessigsäure (NTA),
• c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,
• d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäue),
• e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie
• f) Cyclodextrine.

All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups. The following are preferably used individually or in a mixture:

• a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,
• b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di- (β-hydroxyethyl) glycine Dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyne aspartic acid or nitrilotriacetic acid (NTA),
• c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues with up to 8 carbon atoms, and derivatives thereof containing hydroxyl or amino groups, and 1-aminoethane-1,1-diphosphonic acid, their higher homologues with up to 8 carbon atoms as well as derivatives thereof containing hydroxyl or amino groups,
• d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid),
• e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and
• f) cyclodextrins.

As polycarboxylic acids a) in the context of this Patent application for carboxylic acids -also monocarboxylic acids- understood, in which the sum of carboxyl and those contained in the molecule Hydroxyl groups is at least 5. Complexing agent from the Group of nitrogen-containing polycarboxylic acids, especially EDTA prefers. With those required according to the invention These complex bilgeers lie in the alkaline pH values of the treatment solutions at least partially as anions. It is immaterial whether it is in the form of acids or introduced in the form of salts. In case of use as salts are alkali, ammonium or alkylammonium salts, in particular Sodium salts, preferred.

Deposit-inhibiting polymers can also in the agents according to the invention be included. These substances that are chemically different could be come, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, with polymers with Molar masses below 15,000 daltons are preferred.

Deposit-inhibiting polymers can also Have cobuilder properties. As organic cobuilders, in the machine according to the invention dishwashing detergents in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are as follows described.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures from 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 of these.

The acids themselves can also be used become. The acids In addition to their builder effect, they typically also have the property an acidifying component and thus also serve to set a lower and milder one pH value of detergents or cleaning agents. In particular, here are citric acid, Succinic acid, glutaric, adipic acid, gluconic and to name any mixtures of these.

As a builder or base inhibitor polymeric polycarboxylates are also suitable, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight from 500 to 70000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights 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 to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular Polyacrylates, which preferably have a molecular weight of 500 to 20,000 g / mol exhibit. Because of their superior solubility can from this group, in turn, the short-chain polyacrylates, the molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1000 to 4000 g / mol, have, be preferred.

Are particularly preferred in the agents according to the invention both polyacrylates and copolymers of unsaturated Carboxylic acids, Containing sulfonic acid Monomers and optionally other ionic or nonionic Monomers used. The copolymers containing sulfonic acid groups are detailed below described.

Copolymers are also suitable Polycarboxylates, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been particularly suitable maleic proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative molecular mass, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

Are also particularly preferred biodegradable polymers from more than two different monomer units, for example those which are salts of acrylic acid and monomers the maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Acrylic acid salts and 2-alkylallylsulfonic acid as well as sugar derivatives. Other preferred copolymers are those that preferably contain acrolein and acrylic acid / acrylic acid salts as monomers or acrolein and vinyl acetate.

Are also preferred as others Builder substances polymeric aminodicarboxylic acids, their salts or their precursors to call. Polyaspartic acids or theirs are particularly preferred Salts and derivatives which, in addition to cobuilder properties, also have a have a bleach-stabilizing effect.

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

Other 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 according to the usual for example acid or enzyme-catalyzed processes. Preferably acts are hydrolysis products with average molecular weights in the range from 400 to 500000 g / mol. There is a polysaccharide with one Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, are preferred, where DE is a common one Measure of the reducing Effect of a polysaccharide compared to dextrose, which a DE of 100 has. Both maltodextrins can be used with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher Molar masses in the range from 2000 to 30000 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. A product oxidized at C _{8 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccianate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferred in the form of its Sodium or magnesium salts used. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which optionally also in lactone form and which at least 4 carbon atoms and at least one hydroxyl group and maximum two acid groups contain.

Another class of substances with cobuilder properties represent the phosphonates. These are in particular around hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9) reacts. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), Diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reactions Sodium salts, r. B. as the hexasodium salt of EDTMP or as hepta- and octa sodium salt the DTPMP. As a builder, the class becomes the Phosphonates preferably used HEDP. The aminoalkane phosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the agent also bleach contain, be preferred, aminoalkanephosphonates, in particular DTPMP, enter, or to use mixtures of the phosphonates mentioned.

In addition to the fabrics from the mentioned substance classes the agents according to the invention more usual Ingredients of washing, rinsing or detergents, in particular bleach, Bleach activators, enzymes, silver preservatives, colors and fragrances are important. These substances are described below.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaches which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

To when washing at temperatures of 60 ° C and among them to achieve an improved bleaching effect, bleach activators can be incorporated into the detergent tablets. Can be used as bleach activators Compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result can be used. Suitable substances are the O- and / or N-acyl groups of the above Number of carbon atoms and / or optionally substituted benzoyl groups wear. Multiple acylietre alkylondiemines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional Bleach activators or in their place can also be so-called bleach catalysts into the moldings be incorporated. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with tripod ligands containing nitrogen and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or inhibit the transfer of color. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Examples of such lipolytic enzymes are known cutinases. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed on carriers or in coating substances be embedded in order to protect them against shown decomposition. The Proportion of the enzymes, enzyme mixtures or enzyme granules can, for example about 0.1 to 5% by weight, preferably 0.12 to about 2% by weight.

Servings of detergent according to the invention for the machine dishwashing can to protect the dishes or the machine contain corrosion inhibitors, especially Silver protective agents in the field of automatic dishwashing have special meaning. The known substances can be used the state of the art. In general, silver protection agents in particular selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. To be particularly preferred are benzotriazole and / or alkylaminotriazole. One finds in cleaner formulations about that out often Active chlorine-containing agents that clearly corrode the silver surface can reduce. Chlorine-free cleaners contain oxygen and nitrogen in particular organic redox-active compounds, such as di- and trihydric phenols, z. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Prefers here are the transition metal salts, the selected are from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Likewise can Zinc compounds are used to prevent corrosion on the wash ware become.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl ₂ in the agents according to the invention is preferred. The proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.

The pH of the agents according to the invention in the desired Bringing range, the use of pH adjusting agents can be indicated his. All of them can be used here known acids or lyes, provided that their use does not result from application technology or ecological establish or for reasons of consumer protection. Usually exceeds the amount of these adjusting agents is not 5% by weight of the total formulation.

To the aesthetic impression of the agent according to the invention can improve they are dyed with suitable dyes. Preferred dyes, the selection of which is of no difficulty for the person skilled in the art high storage stability and insensitivity to the rest Ingredients of the agents and against light and no pronounced substantivity towards textile fibers, so as not to stain them.

As foam inhibitors used in the agents according to the invention can be used For example, soaps, paraffins or silicone oils can be used which if necessary on carrier materials may be upset. For inventive as a textile detergent Assembled suitable anti-redeposition agents, which are also available as should be called repellents, for example, are nonionic Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30 wt .-% and of hydroxypropyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether and the polymers of phthalic acid and / or known from the prior art terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and Terephthalic acid polymers.

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention made up as textile detergents in order to eliminate graying and yellowing of the treated textiles. These substances absorb onto the fiber and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible converting long-wave light, the ultraviolet light absorbed from the sunlight being emitted as a slightly bluish fluorescence and resulting in pure white with the yellow tone of the grayed or yellowed laundry. Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2 '-stilbene disulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-dianlpyrazolines, naphthalic acid imides, benzoxazole, benzisoxazole and benzimidazole systems as well as the pyrene derivatives optically substituted by heterocycles Usually they become brighter in amounts between 0.05 and 0.3 wt .-%, based on the finished agent used.

Graying inhibitors have that Task, the detached from the fiber Keep dirt suspended in the fleet and keep it moving to prevent the dirt. For this purpose, water-soluble colloids are usually more organic Suitable in nature, for example glue, gelatin, salts of ether sulfonic acids Strength or the cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water soluble, polyamides containing acidic groups are suitable for this purpose. Farther can be soluble Starch preparations and other than the above starch products use, e.g. degraded starch, aldehyde starches, etc. Polyvinyl pyrrolidone is also useful. However, are preferred Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures in amounts of 0.1 to 5% by weight, based on the composition, used The agents according to the invention can - even with further additional benefits. Here are for example for made up according to the invention as a textile detergent Color transfer inhibiting agent Compositions, agents with "anti-gray formula", agents with ironing relief, Agents with special fragrance release, agents with improved dirt release or prevention from re-soiling, antibacterial agents, UV protection agents, color refreshing agents, etc. can be formulated. Some examples will be explained below

Because textile fabrics, especially from Rayon, rayon, cotton and their blends, for wrinkling can, because the individual fibers prevent bending, kinking. Pressing and squeezing The agents according to the invention can be sensitive across the grain contain synthetic anti-crease agents. These include, for example synthetic products based on fatty acids, fatty acid esters. fatty acid amides, -alkyl esters, -alkylolamides or fatty alcohols, mostly with Ethylene oxide are implemented, or products based on lecithin or modified phosphoric acid ester.

To fight microorganisms can the agents according to the invention contain antimicrobial agents. A distinction is made here depending on the antimicrobial spectrum and mechanism of action between Bacteriostatics and bactericides, fungistats and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, Alkylarlyl sulfonates, halophenols and phenol mercuric acetate, wherein in the inventive means also entirely these connections can be dispensed with.

Suitable antimicrobial agents are preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines , Phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propyl-butyl-carbamate, iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of the above. The antimicrobial active ingredient can be selected from ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerin, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (dichlosan), 2,4 , 4'-trichloro-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N (3,4-dichlorophenyl) urea, N, N '- (1,10-decane-diyldi-1 -pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3,12-diimino-2,4,11,13-tetraaza-tetradecanediimidamide, glucoprotamines , antimicrobial surface-active quaternary compounds, guanidines including the bi- and polyguanidines, such as, for example, 1,6-bis (2-ethylhexyl-biguanido-hexane) dihydrochloride, 1,6-di- (N ₁ , N ₁ '-phenyldiguanido -N ₅ , N ₅ ') -hexane-tetrahydochloride, 1,6-di- (N ₁ , N ₁ ' -phenyl-N ₁ , N ₁ methyldiguanido-N ₅ , N ₅ ') -hexane-dihydrochloride, 1,6-di- (N ₁ , N ₁ ' -o-chlorophenyldiguanido-N ₅ , N ₅ ') -hexane dihydrochloride, 1,6-di- (N ₁ , N ₁ ' -2 , 6-dichlorophenyldiguanido-N ₅ , N ₅ ') hexane dihydrochloride, 1,6-di- [N ₁ , N ₁ ' -beta- (p-methoxyphenyl) diguanido-N ₅ , N ₅ '] hexane dihydrochloride , 1,6-di- (N ₁ , N ₁ '-alpha-methyl-.beta.-phenyldiguanido-N ₅ , N ₅ ') -hexane-dihydrochloride, 1,6-di- (N ₁ , N ₁ ' -p-nitrophenyldiguanido-N ₅ , N ₅ ') hexanedihydrochloride, omega: omega-di- (N ₁ , N ₁ ' -phenyldiguanido-N ₅ , N ₅ ') -di-n-propylether-dihydrochloride, omega: omega' -Di- (N ₁ , N ₁ '-p-chlorophenyldiguanido-N ₅ , N ₅ ') -di-n-propylether-tetrahydrochloride, 1,6-Di (N ₁ , N ₁ '-2,4-dichlorophenyldiguanido- N ₅ , N ₅ ') hexane-tetrahydrochloride, 1,6-di- (N ₁ , N ₁ ' -pmethylphenyldiguanido-N ₅ , N ₅ ') hexane-dihydrochloride, 1,6-di- (N ₁ , N ₁ '-2,4,5-trichlorophenyldiguanido-N ₅ , N ₅ ') hexane-tetrahydrochloride, 1,6-di- [N ₁ , N ₁ '-alpha- (p-chlorophenyl) ethyldiguanido-N ₅ , N ₅ ' ] hexanedihydrochloride, omega: omega-di- (N ₁ , N ₁ '-p-chlorophenyldiguan ido-N ₅ , N ₅ ') m-xylene-dihydrochloride, 1,12-di- (N ₁ , N ₁ ' -p-chlorophenyldiguanido-N ₅ , N ₅ ') dodecane-dihydrochloride, 1,10-di- (N ₁ , N ₁ '-phenyldiguanido-N ₅ , N ₅ ') decane tetrahydrochloride, 1,12-di- (N ₁ , N ₁ '-phenyldiguanido-N ₅ , N ₅ ') dodecane tetrahydrochloride, 1.6 -Di- (N ₁ , N ₁ '-o-chlorophenyldiguanido-N ₅ , N ₅ ) hexane-dihydrochloride, 1,6-di- (N ₁ , N ₁ ' -o-chlorophenyldiguanino-N ₅ , N ₅ ') hexane tetrahydrochloride, ethylene bis (1-tolyl biguanide), ethylene bis (p-tolyl biguanide), ethylene bis (3,5-dimethylphenyl biguanide), ethylene bis (p-tert-amylphenyl biguanide), Ethylene bis (nonylphenyl biguanide), ethylene bis (phenyl biguanide), ethylene bis (N-butylphenyl biguanide), ethylene bis (2,5-diethoxyphenyl biguanide), ethylene bis (2,4-dimethylphenyl biguanide), ethylene -bis (o-diphenylbiguanide), ethylene-bis (mixed amyl naphthylbiguanide), N-butylethylene-bis- (phenylbiguanide), trimethylene bis (o-tolylbiguanide), N-butyltrimethyl-bis- (phenylbiguanide) and the corresponding salts such as acetates, gluconates, hydrochlorides, hydrobromides, citrates, bisulfites, fluorides, polymaleates, N-coconut alkyl sarcosinates, phosphites, hypophosphites, perfluorooooctanoates, silicates, sorbates, salicylates, maleates, tartrates, fumarates, ethylenediamine tetraacetate, arylate diamineate, arateateate, arateateate, arateateate, arateateate, , Pyromellitates, tetracarboxybutyrates, benzoates, glutarates, monofluorophosphates, perfluoropropionates and any mixtures thereof. Halogenated xylene and cresol derivatives, such as p-chlorometacresol or p-chloro-meta-xylene, and natural antimicrobial active ingredients of vegetable origin (for example from spices or herbs), animal and microbial origin are also suitable. Preferably, antimicrobial surface-active quaternary compounds, a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline, and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial active ingredient of animal origin from the group comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound with an ammonium, sulfonium, phosphonium, iodonium - Or arsonium group, peroxo compounds and chlorine compounds are used. Substances of microbial origin, so-called bacteriocins, can also be used.

The quaternary ammonium compounds (QAV) suitable as antimicrobial active ingredients have the general formula (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) N ⁺ X ^- , in which R ¹ to R ^{4 are} identical or different C ₁ -C ⁴ ₂₂ -alkyl radicals, C ₁ -C ₂₈ -aralkyl radicals or heterocyclic radicals, two or, in the case of an aromatic integration, such as in pyridine, even three radicals together with the nitrogen atom forming the heterocycle, for example a pyridinium or imidazolinium compound, and X-halide ions , Sulfate ions, hydroxide ions or similar anions. For an optimal antimicrobial effect, at least one of the residues preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QAV are due to the implementation of tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, Dimethyl sulfate, dodecyl bromide, but also ethylene oxide can be produced. The alkylation of tertiary Amines with a long alkyl radical and two methyl groups succeed particularly easy, also the quaternization of tertiary amines with two long residues and a methyl group can be created using Methyl chloride can be carried out under mild conditions. Amines over three have long alkyl radicals or hydroxy-substituted alkyl radicals not very reactive and are preferably quaternized with dimethyl sulfate.

Suitable QAC are, for example, benzalkonium chloride (N-alkyl-N, N-dimethyl-benzyl-ammonium chloride, CAS No. 8001-54-5), benzalkon B (m, p-dichlorobenzyl-dimethyl-C12-alkylammonium chloride, CAS No. 58390- 78-6), benzoxonium chloride (benzyl-dodecyl-bis- (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No. 57-09-0), benzetonium chloride ( N, N-Dimethyl-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0), Dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammoniumchloric, 1-cetylpyridinium chloride (CAS No . 123-03-5) and thiazoline iodide (CAS No. 15764-48-1) and their mixtures. Particularly preferred QUATS are the benzalkonium chlorides with C ₈ -C _{1 8} alkyl radicals, in particular C ₁₂ -C _{1 4} -Aklyl-benryl-dimethyl-ammonium chloride.

Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ^® ex Lonza, Marquat® ^® ex Mason, Variquat ^® ex Witco / Sherex and Hyamine ^® ex Lonza and as Bardac ^® ex Lonza. Other commercially obtainable antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide and Dowicil ^{® ®} ex Dow, benzethonium chloride such as Hyamine ^® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ^® 10X ex Rohm & Haas, cetylpyridinium chloride such as Cepacol ex Merrell Labs , The antimicrobial active ingredients are preferably used in amounts of from 0.0001% by weight to 1% by weight, preferably from 0.001% by weight to 0.8% by weight, particularly preferably from 0.005% by weight to 0.3 % By weight and in particular from 0.01 to 0.2% by weight.

To unwanted, due to exposure to oxygen and other oxidative processes caused changes in the agents and / or To prevent the treated textiles, the agents can have antioxidants contain. This class of compounds includes, for example, substituted ones Phenols, hydroquinones, pyrocatechols and aromatic amines as well organic sulfides, polysulfides, dithiocarbamates, phosphites and Phosphonates.

An increased wearing comfort can result from the additional use of antstatics, which are additionally added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for textiles or as an additive to detergents, with an Aviva effect is achieved.

To improve water absorption, the Rewettability of the treated textiles and for relief of ironing of the treated textiles can in the agents according to the invention, for example Silicone derivatives are used. These also improve that rinse behavior of the agents according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups one to five Have carbon atoms and are partially or completely fluorinated. preferred Silicones are polydimethylsiloxanes, which may be derivatized could be and then are amino-functional or quaternized or Si-OH-, Si-H- and / or have Si-Cl bonds. The viscosities of the preferred silicones are at 25 ° C in the range between 100 and 100,000 centistokes, with the silicones in amounts between 0.2 and 5% by weight, based on the total agent can be used.

Finally, the agents according to the invention also contain UV absorbers that attach to the treated textiles and lightfastness of the fibers improve. Connections that you want Have properties are, for example, those due to non-radiation Deactivating active compounds and derivatives of benzophenone with substituents in 2- and / or 4-position. Substituted benzotriazoles are also in 3-position phenyl-substituted acrylates (cinnamic acid derivatives), if appropriate with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanoic acid.

• a) Herstellung einer einseitig offenen Portionsverpackung aus wasserlöslichem Material;
• b) Befüllen der Portionsverpackung mit einem oder mehreren Kernen) sowie Fixierung des Kerns bzw. der Kerne;
• c) Befüllen der Portionsverpackung mit der fließfähigen Matrix;
• d) Verschließen der Portionsverpackung

gekennzeichnet ist.The present invention further relates to a method for producing water-soluble portion packs with at least one core therein and a matrix of flowable material which at least partially surrounds the core (s) and which comprises the steps

• a) Production of a portion packaging open on one side from water-soluble material;
• b) filling the portion packaging with one or more cores) and fixing the core or cores;
• c) filling the portion packaging with the flowable matrix;
• d) Close the portion packaging

is marked.

The portion packaging that is open on one side can according to common Processes of thermoforming of polymers are produced, deep drawing, so-called rotary die process, blow molding (Blow extrusion) and injection molding are of particular importance. The following explanations raise to the particularly preferred production by injection molding ab, but also apply mutatis mutandis to others from a standing start thermoforming processes known in the art.

The one-sided to be produced according to the invention open portion packaging can blow molded, injection molded, thermoformed or be calendered. Suitable blow molding methods include extrusion blow molding, Coextrusion blow molding, injection stretch blow molding and immersion blowing. The injection molding takes place according to known procedures at high pressures and Temperatures with the steps of closing the to the extruder injection molding connected mold, injection of the polymer at high temperature and high pressure, cooling of the injection molded molding, opening the Shape and remove the molded blank. Other optional steps such as the application of release agents, demolding etc. Known in the art and can be carried out according to technology known per se.

Preferred methods according to the invention are characterized in that the Portion packaging open on one side by injection molding or Thermoforming process, preferably deep drawing, is produced.

The core can, for example, as explained in detail above by tableting or pouring process can be produced, but it can also be a gelatin capsule or similar. his. Preferred methods according to the invention are characterized in that the Core is made by tableting.

Regarding the fixation of the core can on the executions be referred to above. Here are methods according to the invention preferred, in which the fixation of the core to the water-soluble Wrapping by The core is positioned in a shaped cavity of the cladding. Also preferred are procedures in which the core is fixed on the water soluble wrapping by positioning the core in one of the cladding and then shrinking back of the wrapping material is carried out and procedures in which the core is fixed to the water-soluble wrapping done by an adhesive connection.

The closing in step d) takes place, for example by sealing with a thin, water-soluble Foil, through an opening sealing "stopper" or other common Wise. Preferred method according to the invention are characterized in that the close the filled Packaging is carried out by sealing a film, the thickness of which is preferred 10 to 100 μm, particularly preferably 20 to 75 μm and in particular 30 to 50 μm, is.

Claims (19)

Portion packaging, comprising a water-soluble envelope and at least one core therein and a matrix of flowable material at least partially surrounding the core (s), the core (s) being fixed to the water-soluble envelope / are characterized in that the flowable material a ) a solidified melt or b) a particle population with an average particle size of less than 1200 μm. Portion packaging according to claim 1, characterized in that that the water-soluble wrapping one or more materials from the group polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinyl pyrrolidone, polyethylene oxide, Polyethylene glycol, gelatin, cellulose and their derivatives, in particular MC, HEC, HPC, HPMC and / or CMC, and / or copolymers and their Mixtures. Portion packaging according to one of claims 1 or 2, characterized in that polyvinyl alcohols and / or PVAL copolymers, whose degree of hydrolysis is 70 to 100 mol%. Portion packaging according to one of claims 1 to 3, characterized in that the water-soluble wrapping Hydroxypropylmethylcellulose (HPMC) which has a degree of substitution (average number of methoxy groups per anhydroglucose unit of the cellulose) from 1.0 to 2.0 and a molar substitution (average Number of hydroxypropoxyl groups per anhydroglucose unit Cellulose) from 0.1 to 0.3. Portion packaging according to one of claims 1 to 4, characterized in that the water-soluble wrapping is formed from a film material whose thickness is 10 to 1000 microns. Portion packaging according to one of claims 1 to 5, characterized in that the Core is a tablet. Portion packaging according to one of claims 1 to 6, characterized in that the Core is a solidified melt. Portion packaging according to one of claims 1 to 7, characterized in that the Core delimited spatially by an internal web or weir is. Portion packaging according to one of claims 1 to 8, characterized in that the Core to the water-soluble wrapping by positioning the core in a molded. Cavity of the envelope is fixed. Portion packaging according to one of claims 1 to 9, characterized in that the Core to the water-soluble wrapping by shrinking wrapping material is fixed. Portion packaging according to one of claims 1 to 9, characterized in that the Core to the water-soluble wrapping is fixed by an adhesive connection. Portion packaging according to one of claims 1 to 11, characterized in that the flowable material a liquid is whose viscosity (Brookfield viscometer LVT-II at 20 rpm and 20 ° C, spindle 3) is in the range of 500 to 50,000 mPas. Process for the production of water-soluble Portion packaging with at least one core inside and a matrix at least partially surrounding the core (s) made of flowable material, characterized by the steps a) Making one sided open portion packaging made of water-soluble material; b) filling the Portion packaging with one or more cores) and fixation the core or cores; c) Filling the portion packaging with the flowable matrix; d) close the portion packaging. Method according to claim 13, characterized in that the portion packaging is open on one side is produced by injection molding or thermoforming, preferably deep drawing. Method according to one of claims 13 or 14, characterized in that that the Core is made by tableting. Method according to one of claims 13 to 15, characterized in that that the Fixation of the core to the water-soluble coating by positioning of the core takes place in a shaped cavity of the cladding. Method according to one of claims 13 to 15, characterized in that that the Fixation of the core to the water-soluble coating by positioning of the core in one of the wrapping and subsequent shrinking of the wrapping material he follows. Method according to one of claims 13 to 15, characterized in that that the Fixation of the core to the water-soluble covering by an adhesive connection he follows. Method according to one of claims 13 to 15, characterized in that that this close the filled Packaging is carried out by sealing a film whose thickness is 10 up to 100 μm is.