DE10243819A1 - Detergent portions, especially for automatic dishwasher, contain cationic, quaternized aminoacetonitrile in deep-drawn, cast or injection molded, water-soluble or water-dispersible container, - Google Patents

Abstract

Detergent portions, in a deep-drawn, cast or injection molded, water-soluble or water-dispersible container, contain cationic, quaternized aminoacetonitrile(s) (I). Detergent portions, in a deep-drawn, cast or injection molded, water-soluble or water-dispersible container, contain cationic, quaternized aminoacetonitrile(s) of formula (I): R1 = H, CH3, 2-24 C alk(en)yl (optionally mono- or poly-substituted by Cl, Br, OH, NH2, CN), 1-24 C alk(en)yl-aryl (optionally with substituent(s) on the aromatic ring); R2, R3 = -CH2-CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, -(CH2CH2-O)nH; n = 1-6; X = anion. An Independent claim is also included for production of the detergent portions.

Description

The present invention relates to portioned detergent or cleaning agent compositions, which as Bleach activators contain so-called nitrile quats. In particular The invention relates to machine dishwashing detergents with the bleach activators mentioned.

Detergent compositions for the machine dishwashing are described in various forms of offer and represented in the market. Of particular importance are powder or granular cleaners, liquids, Gels etc. or individually in containers from water soluble Film packaged compositions. Have the greatest importance in the market Detergent tablets for machine dishwashing, because they are compact and easy to use.

A disadvantage of the "tablet" offer form is that the ingredients naturally in very are in close contact with each other, which is incompatible with each other Ingredients to undesirable Reactions and loss of active substance can result. Furthermore can Degradation products colored or smelly be so that Product by the consumer as defective perceived and not bought again.

One approach to solving this problem lies in the spatial separation of incompatible ingredients, for example in different shaped body areas such as layers. Detergent tablets, in which individual ingredients are separated from others, are for example in the EP-A-0 481 793 (Unilever). The detergent tablets disclosed in this document contain sodium percarbonate, which is spatially separated from all other components that could influence its stability (for example bleach activators). Information on the particle size of the bleach activator cannot be found in this document, nor are bleach activators of the nitrile quat type mentioned.

The problem can be solved this way minimize, but not completely to solve, there at the phase interface direct and close contacts still exist. Furthermore migrates crystal water and / or constitutional water in the molded body and can also about Phase interfaces away to unwanted Lead reactions. This problem is with the sensitive nitrile quats compared to more robust bleach activators such as the TAED more clearly.

Bleaching compositions containing nitrile quat type bleach activators are described in the prior art. So the European patent application reveals EP 303 520 (Kao Corp.) Bleaching compositions containing a peroxide and a peracid precursor containing at least one group N ⁺ -CH ₂ -CN or one N ⁺ (CH ₂ CN) ₂ .

Cationic nitriles of the general formula R ¹ R ¹¹ R ¹¹¹ N ⁺ CR ¹ R ² -CN and their use as bleach activators are described in the European patent application EP 464 880 (Unilever).

The European patent application EP 458 396 (Unilever) also describes bleaching compositions which contain a peroxy bleach and a persure precursor with at least one group N ⁺ -CH ₂ -CN or N ⁺ (CH ₂ CN) ₂ .

The present invention was now based on the task of offering forms for nitrile quat-containing washing or cleaning agents, especially machine dishwashing detergents, to provide which the stability problems mentioned above do not have.

It has now been found that the long-term storage Incorporation of nitrile quats into washing or cleaning agents, in particular Detergent for machine dishwashing succeeds when the nitrile quats - preferably in particle form with a certain particle size distribution and / or with a certain coating - in injection molded containers from water soluble or water-dispersible material. The injection molded container enable the separate dosing of nitrile quats as a supplement to washing or Detergents while avoiding the stability problems described, these funds exclusively Can contain nitrile quats, optionally in combination with assembly aids, like carrier or coating materials. In a preferred embodiment contain the injection molded containers next to the nitrile quats however, also other active substances, which are then compartmentalized of the injection molded container of those of stability of the nitrile quats detrimental Active substances can be separated.

in der R¹ für -H, -CH₃, einen C_2–24-Alkyl- oder -Alkenylrest, einen substituierten C₂_₂₄-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1–24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1–4-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, – CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist, enthält.The present invention relates in a first to a portioned detergent or cleaning agent composition in an injection molded water-soluble or water-dispersible container, characterized in that the detergent or cleaning agent composition comprises at least one cationic nitrile of the formula (1)

in which R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C ₂ _ ₂₄ alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a C _1-24 alkyl group, or for a substituted alkyl or alkenylaryl radical with a C _1-4 alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , - CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

The portioned washing or Detergent compositions can contain the cationic nitriles of the general formula (I) in varying amounts, wherein the amount of the intended use of the detergent or cleaning agent compositions depends. Detergents and cleaning agents for machine dishwashing usually contain less bleach activator than bleach, for example huge Parts consist of bleach and bleach activator. As part of portioned detergent or cleaning compositions preferred by the present invention are characterized in that they the cationic nitrile of the formula (I) in amounts of 0.1 to 20% by weight, preferably from 0.25 to 15% by weight and in particular from 0.5 to 10 wt .-%, each based on the weight of the detergent or cleaning agent composition including of water soluble or water-dispersible container, contain.

It is particularly preferred if portioned according to the invention Detergent or cleaning compositions the cationic nitrile of the formula (I) in coarser Form included. In preferred detergent and cleaning agent compositions have at least 90% by weight of the particles of the cationic nitrile of formula (I) a particle size above 0.2 mm.

It is within the scope of the present Invention preferred if the particles of the cationic nitrile are not only have more than 90% by weight of particles with sizes above 0.2 mm, but to a large extent contain coarser particles. preferred This includes detergent and cleaning agent compositions characterized that at least 40% by weight, preferably at least 50% by weight and in particular at least 60% by weight of the particles of the cationic nitrile of the formula (I) a particle size above 0.4 mm.

The proportion of particles with sizes above 200 μm should preferably more than 90 wt .-%, based on the total of Particles of the cationic nitrile. To be advantageous homogeneous particle size distribution to own, the bleach activators used should in particular be free of too fine or dust components, so particularly preferred contain no particles under 0.2 mm in diameter. Especially preferred portioned detergent and cleaning agent compositions the cationic nitriles are substantially free of particles with Sizes below 0.2 mm. Under "substantial become free in Contents of the present invention Contents below 2 wt .-%, preferably below 1% by weight and in particular below 0.5% by weight, in each case based to the entirety of the particles.

In particularly preferred portioned Detergent or cleaning agent compositions have the cationic Nitrile of formula (I) an average particle size above 400 microns, preferably above 500 μm, particularly preferably above 600 μm and in particular above of 700 μm on.

In summary, portioned according to the invention Preferred detergent or cleaning compositions in which the one or more contained in the injection molded water soluble or water dispersible container cationic nitrile (s) of the formula (I) are particulate, preferably at least 90% by weight of the particles of the cationic Nitriles of the formula (I) have a particle size above 0.2 mm, particularly preferably at least 40% by weight, preferably at least 50% by weight and in particular at least 60% by weight of the particles of the cationic nitrile of the formula (I) a particle size above Have 0.4 mm and the cationic nitrile of formula (I) in particular preferably an average particle size above 400 μm, preferably above 500 μm, particularly preferably above 600 μm and in particular above of 700 μm having.

General formula (I) includes a large number of cationic nitriles which can be used in the context of the present invention. The portioned detergent or cleaning agent compositions according to the invention particularly advantageously contain cationic nitriles in which R ^{1 is} methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n -Tetradecyl, n-Hexadecyl or n-octadecyl radical. R ² and R ³ are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, where one or both radicals can advantageously also be a cyanomethylene radical. In the table below, preferred cationic nitriles of the formula (I) are characterized by their radicals R ¹ , R ² and R ³ :

enthalten, in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R^S = R⁶ = -CH₃ gilt, und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^- , (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^-, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^- besonders bevorzugt sind.For reasons of easier synthesis, compounds in which the radicals R ¹ to R ^{3 are} identical are preferred, for example (CH3) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , or (HO- CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- . Portioned washing or cleaning agents compositions which, as the cationic nitrile of the formula (I), are a cationic nitrile of the formula (Ia)

contain, in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , where R ^{4 can} additionally be -H and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ^S = R ⁶ = -CH ₃ , and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{- are} particularly preferred.

Portioned detergent or cleaning agent compositions which contain a cationic nitrile of the formula (I), preferably of the formula (Ia), particularly preferably of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , where X ^- for an anion is selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate or xylene sulfonate or mixtures thereof, are particularly preferred.

The aforementioned cationic nitriles can before incorporation into the agents according to the invention in various Be assembled in a way. Examples of such assemblies are the use of solid substrates, on which the cationic nitriles are "grown", or the Coating the nitriles or certain nitrile compounds.

In a preferred embodiment The present invention uses the cationic nitriles in combination with an inorganic carrier material used. The application to the carrier material can take place in such a way that in an aqueous solution of the cationic nitrile, as is obtained in the course of their production, the support material is stirred and the aqueous solvent deducted in vacuo, if appropriate at elevated temperature becomes. Alternatively, the solved kafionic nitrile can also be sprayed onto the carrier material. The resulting product is then optionally dried.

If inorganic carrier materials containing silicon are used, they preferably have an inner surface in the range from 10 m ² / g to 500 m ² / g, in particular 100 m ² / g to 450 m ² / g.

For example, silicates are suitable, silicas, Silica gels and clays and their mixtures. However, the carrier material is preferred free of zeolites.

As carrier materials, silicas which have been produced by a thermal process (flame hydrolysis of SiCl ₄ ) (so-called pyrogenic silicas) are just as useful as silicas produced by wet processes. Silica gels are colloidal silicas with elastic to firm consistency and a largely loose pore structure, which results in a high fluid absorption capacity. They can be produced by the action of mineral acids on water glass. Clays are naturally occurring crystalline or amorphous silicates of aluminum, iron, magnesium, calcium, potassium and sodium, for example kaolin, talc, pyrophyllite, attapulgite, sepiolite, montmorillionite and bauxite. The use of aluminum silicate as a carrier material or as a component of a carrier material mixture is also possible. The carrier material preferably has particle sizes in the range from 100 μm to 1.5 mm.

The cationic packaged in this way Nitriles preferably have a carrier material content of 10 to 50% by weight. % on.

That containing with the help of silicon support material particulate Assembled cationic nitrile can also be an organic material with a melting point above 40 ° C, in particular contain and / or be coated with a nonionic surfactant. This can affect the decay properties of the corresponding particle in aqueous systems and / or its storage stability influence positively.

In summary, portioned detergent or cleaning agent compositions are preferred in which the cationic nitrile (s) of the formula (I) is / are particulate, the cationic nitrile (s) containing an inorganic carrier material, preferably having a Carrier material from the group of silicon-containing substances, particularly preferably the alkali silicates, the silicas, the silica gels or the clays, and / or the phosphates, particularly preferably the alkali phosphates, is present, the carrier material preferably having an inner surface of 12 m ² / g to 480 m ² / g, in particular from 80 m ² / g to 440 m ² / g.

The cationic nitriles described above can, if appropriate in combination with a carrier material, have a coating, water-soluble or water-dispersible coatings being preferred. A coating of the cationic nitriles serves in particular to increase the stability of these compounds against moisture, which is caused, for example, by prolonged storage by the water soluble or water-dispersible materials can diffuse into the interior of the injection-molded container.

A preferred method of coating of the cationic nitriles or nitrile compounds with is the fluidized bed coating process, in which bleach activators are present in solid, in particular powder form of formula (I), optionally in admixture with binder and / or solid filler or as prefabricated granules, with simultaneous drying in a fluidized bed apparatus sprayed with an acidic aqueous coating solution.

To apply the coating on that are suitable for the cationic nitriles or nitrile compounds still a matter of course all Devices with which coatings from an aqueous solution can be produced. So can larger objects for example directly with spray nozzles, preferably two-substance nozzles, under can be sprayed simultaneously or subsequently drying. Smaller objects can in drum coaters, such as those commonly used in pharmacy are sprayed or coating pans become.

The weight percentage of water soluble or water-dispersible coating on the total weight of the particulate coated cationic nitriles / nitriles in the portioned according to the invention Detergent or cleaning agent compositions is preferably 0.8 to 24% by weight, particularly preferably 1.2 to 19% by weight and in particular 1.6 to 14% by weight.

• a) wasserlöslichen nichtionischen Polymeren aus der Gruppe der a1) Polyvinylpynolidone, a2) Vinylpyrrolidon/Vinylester-Copolymere, a3) Celluloseether a4) Polyvinylalkohol a5) Polyatkylenglycol, insbesondere Polyethylenglycol und/oder Polypropylenglycol
• b) wasserlöslichen amphoteren Polymeren aus der Gruppe der b1) Alkylacrylamid/Acrylsäure-Copolymere b2) Alkylacrylamid/Methacrylsäure-Copolymere b3) Alkylacrylamid/Methylmethacrylsäure-Copolymere b4) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymere b5) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure – Copolymere b6) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere b7) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymere b8) Copolymere aus b8i) ungesättigten Carbonsäuren b8ii) kationisch derivatisierten ungesättigten Carbonsäuren b8iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
• c) wasserlöslichen zwitterionischen Polymeren aus der Gruppe der c1) Acrylamidoalkyltnalkylammoniumchlond/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze c2) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze c3) Methacroylethylbetain/Methacrylat-Copolymere
• d) wasserlöslichen anionischen Polymeren aus der Gruppe der d1) Vinylacetat/Crotonsäure-Copolymere d2) Vinylpyrrolidon/Vinylacrylat-Copolymere d3) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere d4) Pfropfpolymere aus Vinylestem, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen d5) gepropften und vernetzten Copolymere aus der Copolymerisation von d5i) mindesten einem Monomeren vom nicht-ionischen Typ, d5ii) mindestens einem Monomeren vom ionischen Typ, d5iii) von Polyethylenglycol und d5iv) einem Vernetzter d6) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere: d6i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesätigter Alkohole und ungesättigter Carbonsäuren, d6ii) ungesättigte Carbonsäuren, d6iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols d7) Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester d8) Tetra- und Pentapolymere aus d8i) Crotonsäure oder Allyloxyessigsäure d8ii) Vinylacetat oder Vinylpropionat d8iii) verzweigten Allyl- oder Methallylestem d8iv) Vinylethern, Vinylestenn oder geradkettigen Allyl- oder Methallylestern d9) Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinymethylether, Acrylamid und deren wasserlöslicher Salze d10) Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in α-Stellung verzweigten Monocarbonsäure
• e) wasserlöslichen kationischen Polymeren aus der Gruppe der e1) quaternierten Cellulose-Derivate e2) Polysiloxane mit quatemären Gruppen e3) kationischen Guar-Derivate e4) polymeren Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure e5) Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats e6) Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere e7) quaternierter Polyvinylalkohol e8) unter den INCI-Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 angegeben Polymere.

Regardless of the choice of coating method, in preferred portioned washing or cleaning agent compositions according to the invention the coating material is at least partially selected from a polymer or polymer mixture, the polymer or at least 50% by weight of the polymer mixture being selected from

• a) water-soluble nonionic polymers from the group of a1) polyvinylpynolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers a4) polyvinyl alcohol a5) polyatkylene glycol, in particular polyethylene glycol and / or polypropylene glycol
• b) water-soluble amphoteric polymers from the group of b1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamylamino / methacrylic amide (meth) acrylic acid - copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers from b8i) unsaturated carboxylic acids b8ii) cationically derivatized further unsaturated ionic carboxylic acids b8ii) nonionic monomers
• c) water-soluble zwitterionic polymers from the group of c1) acrylamidoalkyltnalkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethyl betaine / methacrylate copolymers
• d) water-soluble anionic polymers from the group of d1) vinyl acetate / crotonic acid copolymers d2) vinyl pyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid alone or Mixture copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polykalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the nonionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinker d6) copolymers obtained by copolymerizing at least one monomer of each of the following three groups: d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain ge saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, d6iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohols d7) terpolymers of crotonic acid, Vinyl acetate and an allyl or methallyl ester d8) tetra- and pentapolymers from d8i) crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate d8iii) branched allyl or methallyl esters d8iv) vinyl ethers, vinyl stars or straight-chain or metalolollyl-allyl acid several monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts d10) terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position
• e) water-soluble cationic polymers from the group of e1) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidated derivatives with of the dialkylaminoacrylate and methacrylate e6) vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol e8) under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

A more detailed description of the above Polymers can be found below in the text in connection with the for the Production of the water-soluble or water-dispersible container suitable materials. On the explanations there is to avoid referred by repetitions at this point.

In addition to the polymers mentioned also inorganic salts for coating the cationic nitriles or nitrile compounds. The coating material is preferred at least in part from the group of water-soluble or water-dispersible inorganic salts, preferably of the group of sulfates, chlorides, phosphates and phosphonates, where especially the alkali and alkaline earth salts and here again the Sodium, potassium and / or magnesium salts are particularly preferred.

A third group of preferred coating materials are finally meltable substances or mixtures of substances, in particular substances or mixtures of substances with a melting point above 40 ° C., such as fats and / or triglycerides and / or fatty acids and / or fatty alcohols and / or waxes and / or parrafins.

Fats) or triglyceride (s) is the Term for Compounds of glycerol in which the three hydroxy groups of Glycerins through carboxylic acids are esterified. Of course Occurring fats are triglycerides, which are usually different fatty acids in the same glycerin molecule contain. By saponification of the fats and subsequent esterification or reaction with acyl chlorides are also synthetic triglycerides, in which only one fatty acid bound, accessible (e.g. tripalmitin, triolein or tristearin). Natural and / or synthetic fats and / or mixtures of the two are used as coating material or part of the coating of cationic nitriles in the frame preferred of the present invention.

As fatty acids are used in the present Sign aliphatic saturated or unsaturated, carboxylic acids labeled with branched or unbranched carbon chain. For the Production of the fatty acids exist a variety of manufacturing methods. While the lower fatty acids mostly on oxidative processes based on alcohols and / or aldehydes as well as aliphatic or acyclic hydrocarbons, are the higher homologues are mostly still easiest today by saponification more natural Fat accessible. Due to advances in transgenic plants are now almost unlimited possibilities to vary the fatty acid spectrum in the Storage fats from oil plants given. Preferred fatty acids have a melting point in the context of the present invention, which allows these fats to be processed as coating material. Preferred coating materials or components are therefore capric acid and / or undecanoic acid and / or lauric acid and / or tridecanoic acid and / or myristic acid and / or pentadecanoic acid and / or palmitic acid and / or margaric acid and / or stearic acid and / or nonadecanoic acid and / or arachidic acid and / or erucic acid and / or Elaeosterarinsäure.

Fatty alcohol is a collective term for the by reducing the triglycerides, fatty acids or fatty acid esters available linear, saturated or unsaturated primary Alcohols with 6 to 22 carbon atoms. The fatty alcohols can be found in dependence saturated by the manufacturing process or unsaturated his. Myristyl alcohol and / or 1-pentadecanol and / or cetyl alcohol and / or 1-heptadecanl and / or stearyl alcohol and / or erucyl alcohol and / or 1-nonadecanol and / or arachidyl alcohol and / or 1-heneicosanol and / or behenyl alcohol and / or erucyl alcohol and / or brassidyl alcohol are preferred Components of the coating of cationic nitriles in the frame of the present invention.

It has also proven to be beneficial proven when in the portioned detergent or cleaning compositions as a coating material or part of the coating waxes contain. Preferred waxes have a melting range, the between about 45 ° C and about 75 ° C lies. 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. Grow with Such a melting range are dimensionally stable at room temperature however melt at for mechanical machine cleaning typical temperatures from 30 ° C to 90 ° C and therefore easier to disperse water at these temperatures.

"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 ear 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 hardening 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, such as dimyristyl tartrate, which is the name Cosmacol ^® efiältlich under 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 a coating material.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular 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).

Other beneficial ingredients the matrix of the above coatings are wax alcohols, so Fatty alcohols with approx. 24-36 carbon atoms in the form of wax esters high molecular weight Fatty acids (wax acids) main ingredient many natural Are waxes. Exemplary for preferred wax alcohols here are lignoceryl alcohol, ceryl alcohol, Myricyl alcohol or melissyl alcohol called.

In summary, preferred are portioned Detergent or cleaning agent composition accordingly characterized, that this Coating material is at least partially selected from the group of fusible substances, preferably from the group Fats and / or triglycerides and / or fatty acids and / or fatty alcohols and / or waxes and / or Parraflne, and / or from the group of anionic Surfactants.

The abovementioned processes for packaging the nitrile quats give bulk weights for the process products, some of which differ significantly from the bulk weights of the pure substances. For the incorporation of the made-up nitrile quats into the detergent or cleaning agent compositions, made-up cationic nitriles with a bulk density in the range between 320 and 960 g / l, preferably in the range from 360 to 880 g / l and in particular in the range from 410 to 790 g / l as special proven to be advantageous, since the comparatively low bulk density facilitates the volumetric metering of the nitrile quats during production, and at the same time improves the visual perception of these active substances by the consumer in the end product (for example: bleach booster).

The nitrile quats described above can in liquid, gel, pasty or solid preparation form (preferably in particulate preparation according to the above Details) in an injection molded water soluble or water dispersible container be introduced.

The injection molded water soluble or water-disposable containers can have any shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five, hexagonal and octagonal prismatic and rhombohedral shapes preferred are. Containers too with totally irregular base areas like arrow or animal shapes, trees, clouds etc. can will be realized. Point the injection molded containers to corners and edges, they are preferably rounded.

Of course, the injection molded containers can also Have compartments. Portioned laundry or detergent compositions in which the injection molded water-soluble or water-dispersible containers has at least two separate compartments particularly preferred in the context of the present invention. Although container with two compartments already separating the nitrile quats from enable additional ingredients, it can still be indicated for optical or recipe reasons, the injection molded container to be divided into more than two compartments. spray Poured water-soluble or water-dispersible containers with three four five, six, seven, eight, nine, ten, eleven, twelve or more compartments are therefore further special within the scope of the present invention preferred embodiments.

Has the water-soluble or water-dispersible container two or more compartments, it is within the scope of the present Invention to avoid the disadvantage described above Interactions between cationic nitrile and one or more Ingredients of the portioned detergent or cleaning agent composition preferred that at least one of the compartments none) cationic / cationic nitrile (s) of formula (I) contains.

In the tables below is the separation of certain ingredients described as an example based on selected Active substances for agents according to the invention described with two (entries 1 to 8) or three compartments.

With the portioned detergents or cleaning agents contained in the compartment (s) or Detergent or cleaning agent components, it can be liquids, dispersions or solids. The following table shows exemplary distributions of such liquids, dispersions and solids to a container according to the invention with two (entries 1 to 6) and three compartments:

The in the agents according to the invention Cationic nitriles contained can both be a component of the solid (s), the dispersions) and / or the solutions) his. However, the cationic nitriles are preferred of the solids) and / or the dispersion (s).

As liquids are in Such single-phase substances within the scope of the present applications or mixtures of substances that have a viscosity (Brookfield viscometer LVT-11 at 20 rpm and 20 ° C, Spindle 3) from 500 to 100,000 mPas, preferably from 1000 to 50,000 mPas, particularly preferably from 1200 to 10000 mPas and in particular from 1300 to 5000 mPas.

Such liquids can be used as liquid Matrix except Water, as one of the most common Solvent, also other non-aqueous solvents contain. These non-aqueous solvents are, for example from the groups of mono-alcohols, diols, triols or polyols, the Ethers, esters and / or amides. Non-aqueous solvents are particularly preferred, the water soluble are, "water-soluble" solvents in the sense of the present application are solvents which are at room temperature with water completely, i.e. without miscibility gap, are miscible.

Non-aqueous solvents in the agents according to the invention can be used preferably come from the group of mono- or polyhydric alcohols, Alkanolamines or glycol ethers, provided they are in the specified concentration range are miscible with water. The solvents are preferred selected from ethanol, n- or i-propanol, butanols, glycol, propane or Butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, Etheylenglykolmono-n-butyl ether, Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, Methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, Propylene glycol t-butyl ether and mixtures of these solvents.

A portioned liquid detergent or cleaning agent composition which is particularly preferred in the context of the present invention is characterized in that it particularly contains non-aqueous solvents in amounts of 0.1 to 70% by weight, preferably 0.5 to 60% by weight preferably from 1 to 50% by weight, very particularly preferably from 2 to 40% by weight and in particular from 2.5 to 30% by weight, in each case based on the entire composition, with preferred) non-aqueous solvent (s) being selected from the group of the nonionic surfactants which are liquid at room temperature, the polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, triacetin, ethylene glycol, propylene glycol, propylene carbonate, hexylene glycol, ethanol and n-propanol and / or iso-propanol.

As a dispersion in the context of This application designates multi-phase systems, which in addition a continuous phase (dispersant) at least. a have further finely divided phase (dispersed phase, dispersant). The dispersions include thus, for example, the emulsions, aerosols and suspensions. In preferred embodiments of the present invention is the cationic nitrile (s) in solid, particulate Form, preferably in combination with a carrier material or a coating suspended in a continuous liquid phase before taking it yourself at the liquid phases for example also the aforementioned non-aqueous solvents, as well as water or mixtures of these non-aqueous solvents with water can.

Are preferred as dispersions however fluid, anhydrous formulations with coated or suspended therein uncoated nitrile quats. Being "water free" in the frame of the present application designates formulations which have a water content below 5% by weight, preferably below 3% by weight and in particular have below 1.5 wt .-%. Such suspensions can in addition to mentioned nitrile quats and the dispersant further wash or contain cleaning-active substances. Descriptions for some preferred washing or cleaning active in the context of the present invention Substances such as surfactants, builders etc. can be found below in this description.

in der R³ für H oder einen verzweigten oder unverzweigten C_1-4-Alk(en)ylrest, X für N-R⁵ oder O, R⁴ für einen gegebenenfalls alkoxylierten verzweigten oder unverzweigten, evtl. substituierten C_8-22-Alk(en)ylrest, R⁵ für N oder R⁴ und n für eine natürliche Zahl steht, bevorzugt sind.Both the liquids described above and the suspensions described can additionally contain one or more thickeners. Detergents or cleaning agents preferred in the context of the present invention are characterized in that they additionally contain 0.01 to 5% by weight, preferably 0.02 to 4% by weight, particularly preferably 0.05 to 3% by weight and in particular 0.1 to 1.5% by weight, of a thickener, preferably a polymeric thickener, wherein the thickener is hydroxyethyl cellulose and / or hydroxypropyl cellulose and / or thickener from the group of the polysaccharides, preferably xanthan, the polyurethanes or the modified polyacrylates with particular preference for thickeners of the formula

in which R ^{3 represents} H or a branched or unbranched C _1-4 alk (en) yl radical, X represents NR ⁵ or O, R ^{4 represents} an optionally alkoxylated branched or unbranched, possibly substituted C _8-22 alk (en ) yl radical, R ^{5 is} N or R ⁴ and n is a natural number, are preferred.

As solids are used in the present Application referred in particular to powders, agglomerates, compactates and castings. Portioned according to the invention Detergent or cleaning agent compositions, which as a solid a powder and / or an agglomerate and / or a compactate and / or contain a casting, are particularly preferred.

Powder is a general term for one Form of division of solid substances and / or mixtures of substances that one by crushing, that is Grate or crush in the grinding bowl (pulverization), grinding in mills or as a result of atomization or freeze drying. A particularly fine division is often called atomization or micronization; the corresponding powders are called micro powders designated.

There is a rough classification according to the grain size the powder in coarse, fine and Very fine powder common; a more precise classification powdery Bulk goods are made via their bulk density and through sieve analysis. Preferred in the context of the present application However, powders have lower particle sizes of 500 μm, preferably of 600 μm and in particular of 800 μm on. Methods for determining the lower particle size are supported usually on the aforementioned sieve analysis and are described in detail in the prior art.

Powders can be compacted and agglomerated by extrusion, pressing, rolling, briquetting, pelleting and related processes. In principle, any of the methods known in the prior art for agglomeration of particulate mixtures is suitable which are contained in the agents according to the invention To produce solids. In the context of the present invention, agglomerates which are preferably used as solid e) are, in addition to the granules, the compactates and extrudates.

Accumulations become granules of granules designated. A granulate is an asymmetrical aggregate from powder particles. Granulation processes are state of the art broadly described. Granules can by wet granulation, by dry granulation or compacting and produced by melt solidification granulation.

The most common pelletizing technology is wet granulation since this technique has the fewest restrictions is subjected and most safely to granules with cheap Properties leads. Moist granulation is carried out by moistening the powder mixtures with solvents and / or solvent mixtures and / or solutions of binders and / or solutions of adhesives and is preferably used in mixers, fluidized beds or spray towers, where said mixer equipped for example with stirring and kneading tools could be. For the However, granulation are also combinations of fluidized beds) and Mixer (s) or combinations of different mixers can be used. The granulation is dependent of the starting material and the desired product properties under the influence of low to high shear forces.

The granulation takes place in one spray tower so can as starting materials, for example, melting (melt solidification) or, preferably aqueous, slurries (Spray drying) solid substances are used, which are at the top of a Sprayed tower in a defined droplet size, solidify or dry in free fall and as at the bottom of the tower Granules accumulate. Melt solidification is generally suitable especially for shaping low-melting materials in the area the melting temperature are stable (e.g. urea, ammonium nitrate u. various formulations such as enzyme concentrates, pharmaceuticals etc.), the corresponding granules are also referred to as prills. Spray drying will especially for the production of detergents or detergent components used.

Others described in the prior art Agglomeration techniques are extruder or perforated roll granulation, in which powder mixtures optionally mixed with granulating liquid when pressing through perforated disks (extrusion) or on perforated rollers be plastically deformed. The extruder granulation products are also called extrudates.

Compactas can be, for example through dry granulation techniques such as tableting or roller compaction produce. By compacting in tablet presses, single or multi-phase Tablets or briquettes are made. To the multi-phase Count tablets in addition to the multi-layer or sandwich tablets, for example the coated tablets and the point tablets (bull-eye tablets). The briquettes can just like the slugs produced in compacting rollers after the compacting through opposing Spiked rollers are crushed or struck by sieves. The Size of by Compaction particles obtained may vary.

As castings are within the scope of the present Registration refers to solid substance particles caused by solidification and / or crystallization from melts or solutions. The solidification and / or crystallization preferably takes place in prefabricated ones Matrices. The castings released from the matrices after solidification can be in the Connection each according to the size of the die and intended use of the casting in their original Size or optionally after comminution as solids in the water-soluble according to the invention containers be used.

As a matrix material for castings, which produced by melt solidification are particularly suitable fusible substances from the group of fats and / or triglycerides and / or fatty acids and / or Fatty alcohols and / or waxes and / or parrafins. A detailed one A description of these substances can be found below in this Document in connection with the description in the context of this application preferred coating materials for cationic nitriles. to Avoiding repetitions is at this point on those there versions directed.

In summary, such portioned according to the invention Detergent or cleaning agent compositions are particularly preferred, in which the detergent or cleaning agent composition at least a liquid and / or at least one dispersion and / or at least one solid includes. In a particularly preferred embodiment of the present Invention has the portioned washing or Detergent composition at least one compartment, which is a liquid contains and at least one further compartment, which is a solid contains.

The shapes of the compartments can also be freely selected within wide limits. For the shape of the compartments, what has already been said about the shape of the injection-molded container above in the text applies in special embodiments, to which reference is made here to avoid repetitions. The shape of the compartments must on the one hand adapt to the technical requirements, for example the size of the compartments should be adapted to the volume fraction of the liquid or solid agents contained in these compartments in order to avoid empty volumes. On the other hand, the compartmentalization of the water-soluble or water-dispersible containers naturally still offers a possibility for the optical upgrading of the overall product. In this context, such compartments in particular are divided Injection-molded water-soluble or water-dispersible containers which have a cuboid shape and in which the compartmentalization takes place symmetrically are preferred. Those containers are particularly preferred whose compartments have a C ₂ symmetry, in particular in the direction of view of the top or bottom.

The above geometric Realization forms can be combined with one another as desired. So can container with a rectangular or square base and circular compartments as well as round containers with octagonal compartments, with no limit to the variety of possible combinations are. For reasons process economics and the aesthetic Consumer sensibility, as well as in terms of preferred use means according to the invention in dishwashers are cuboid container prefers.

The size of the compartment (s) compared to the entire container depends on the desired Purpose of the means according to the invention. It depends on the compartment (s) are infested with further active substance should and whether a smaller or larger amount of active substance may contain the size of the compartments vary. Independently portioned washing and inventive portions of use Detergent compositions with two or more compartments preferred where the volume of each compartment present at least 2% by volume, preferably at least 5% by volume and in particular at least 10% by volume, particularly preferably between 15 to 90% by volume and is particularly between 20 and 80 vol .-%. The Volume is calculated from the volume of the closed, compartmented container.

Preferred containers according to the invention have as a locking unit a film which, for example, by gluing, partial Melt or firmly bonded to the container by chemical reaction is. It is possible, apply the film to all container surfaces and bond firmly to them so that the film has a coating, constitutes a "coating" of the entire container. Preferred portioned detergent and cleaning agent compositions are, however, characterized in that the film does not cover the entire container encloses.

For reasons of process economy and the aesthetic It is impressively preferred that the Foil only applied to the container surfaces where it fulfills a function i.e. closing of compartments. agents according to the invention in which the film only the areas of the container covered in which there are openings of the compartment (s) are therefore preferred.

The compartment-closing film can of course also a laminate of several different compositions Slides be about different compositions of individual film layers can the opening different compartments at certain times in the washing and cleaning cycle are released. In particular, the film material or the film thickness, however, is preferably chosen so that the closure unit of the injection molded water soluble or water-dispersible container a dissolution behavior which differs from the dissolution behavior of water soluble or water-dispersible container different.

As "dissolution behavior" in the context of the present application especially the time at which water after the introduction of a container according to the invention in an aqueous fleet the film or the container wall penetrates. In particular, such embodiments are preferred in which the used foils from surrounding water faster is penetrated as the container.

Preferred water soluble or Water-dispersible materials are known from the prior art Polymers. Portioned detergent or cleaning composition preferred, in which the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible sealing unit made of a polymer with a molecular weight between 5000 and 500,000 daltons, preferably between 7,500 and 250,000 daltons and especially between 10,000 and 100,000 daltons.

Such preferred polymers can be synthetic or natural Be of origin. Are polymers on a native or part-native basis portioned detergent or cleaning agent compositions are used as film material preferred, in which the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible closure unit one or more Substances from the group carrageenan, guar, pectin, xanthan, cellulose and their derivatives, starch and their derivatives as well as gelatin comprises or consists entirely of these substances.

Carrageenan is an educated and named after the Irish coastal town of Carragheen and constructed similar to agar. Extract from North Atlantic red algae, which is one of the florids. The carrageenan precipitated from the hot water extract of the algae is a colorless to sand-colored powder with molar masses of 100000-800000 and a sulfate content of approx. 25%, which is very easily soluble in warm water. There are three main components in carrageenan: The yellow-forming f fraction consists of D-galactose-4-sulfate and 3,6-anhydro-α-D-galactose, which are alternately glycosidically linked in the 1,3- and 1,4-positions (In contrast, agar contains 3,6-anhydro-α-L-galactose). The non-gelling I fraction is composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues set and easily soluble in cold water. The i-carrageenan composed of D-galactose-4-sulfate in 1,3-bond and 3,6-anhydro-α-D-galactose-2-sulfate in 1,4-bond is both water-soluble and gel-forming. Other types of carrageenan are also designated with Greek letters: α, β, γ, μ, ν, ξ, π, ω, χ. The type of cations present (K, NH ₄ , Na, Mg, Ca) also influences the solubility of the carrageenans. Semi-synthetic products that contain only one type of ion and can also be used as film and / or container materials in the context of the present invention are also called Carrag (h) eenate.

That in the context of the present invention as foil and / or container material usable guar, also called guar flour, is an off-white powder, that by grinding the endosperm originally in Indian and Pakistani Endemic space, now also in other countries, e.g. in the southern United States, cultivated guar beans (Cyamopsis tetragonobolus) is obtained. The main component of the guar is with up to approx. 85% by weight of the dry substance guaran (guar gum, cyamopsis gum); Minor components are proteins, lipids and cellulose. Guaran himself is a polygalactomannan, i.e. a polysaccharide whose linear Chain of unsubstituted (see Formula II) and in the C6 position substituted with a galactose residue (see formula (III)) mannose units built in β-D (1 → 4) linkage is.

The ratio of II: III is approximately 2: 1; Contrary to original assumptions, the II units are not strictly alternating, but are arranged in pairs or triplets in the polygalactomannan molecule. Information on the molar mass of guaran varies significantly with values of approx. 2.2⋅10 ⁵ -2.2⋅10 ⁶ g / mol depending on the degree of purity of the polysaccharide - the high value was determined on a highly purified product - and corresponds to approx. 1350 -13500 sugar units / macromolecule. Guaran is insoluble in most organic solvents.

The also as foil and / or container material usable pectins are high molecular weight glycosidic plant substances, those in fruits, Roots and leaves are very common. The pectins consist essentially of chains of 1,4-α-glycoside. connected galacturonic acid units, whose acid groups too 20-80% are esterified with methanol, being between highly esterified (> 50%) and low ester pectins (<50%) differs. The pectins have a sheet structure and are therefore in the Middle strength and Cellulose molecules. Your macromolecules contain some glucose, galactose, xylose and arabinose and have weakly acidic properties.

Fruit pectin contains 95%, beet pectin up to 85% galacturonic acid. The Molar masses of the different pectins vary between 10,000 and 500000. The structural properties are also strongly dependent on the degree of polymerization dependent; so form e.g. the fruit pectins are asbestos-like when dry Fasem, the flax pectins, on the other hand, fine, granular powder.

The pectins are mainly extracted from the inner parts of by extraction with dilute acids Citrus peel, leftovers or sugar beet chives are made.

Xanthan can also be used according to the invention as a film and / or container material. Xanthan is a microbial anionic heteropolysaccharide that is produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular weight of 2 to 15 million Daltons. Xanthan is formed from a chain with α-1,4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan. Xanthan can be described by the following formula:

The celluloses and their derivatives are also suitable as film materials. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, viewed formally, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used as film material based on cellulose in the context of the present invention. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

In addition to cellulose and cellulose derivatives can also (modified) dextrins, starch and starch derivatives as foil and / or container materials be used.

As a non-ionic organic film and / or container materials dextrins, for example oligomers or polymers of Carbohydrates obtained by partial hydrolysis of starches can be. 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 have a DE of 100 owns. Both maltodextrins with one can be used 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 at least one alcohol function of the saccharide ring to form carbon to oxidize acid function.

Starch can also be used as a film and / or container material for the inventive washing and detergent compositions are used. Strength is a homoglycan, the glucose units being linked α-glycosidically. Strength is made up of two components of different molecular weights: From approx. 20-30% straight-chain amylose (MG. Approx. 50,000-150,000) and 70-80% branched chain amylopectin (MW. Approx. 300,000-2,000,000), there are also small amounts of lipids, phosphoric acid and cations contain. While the amylose due to the binding in the 1,4-position long, helical, intertwined Forms chains with about 300-1200 glucose molecules, branches the chain for amylopectin after an average of 25 glucose units through 1,6-binding to a knot-like Formation with about 1500-12000 molecules of glucose. In addition to pure starch as film materials in the context of the present invention also Starch derivatives, which are obtainable from starch by polymer-analogous reactions. Such chemically modified starches include, for example, products from esterifications or etherifications, in which hydroxy hydrogen atoms have been substituted. But also Strengthen, in which the hydroxy groups against functional groups that do not have a Oxygen atoms are replaced, can be used as starch derivatives deploy. In the group of starch derivatives fall, for example, alkali starches, carboxymethyl starch (CMS), Stärkeester and ether and amino starches.

Among the proteins and modified Proteins have gelatin as an outstanding film and / or container material Importance. Gelatin is a polypeptide (molecular weight: approx.15,000 → 250,000 g / mol), mainly by hydrolysis of the skin and bones collagen from animals under acidic or alkaline conditions is won. The amino acid composition The gelatin largely corresponds to that of the collagen from which it is made and varies depending on its provenance. The The use of gelatin as a water-soluble coating material is particularly important extremely wide in pharmacy in the form of hard or soft gelatin capsules common.

More than foil and / or container materials usable polymers are synthetic polymers, which are preferred water swellable and / or water soluble are. Such synthetic polymers can provide the desired permeability in storage and dissolution of the film can be tailored ". Especially preferred portioned according to the invention Detergent or cleaning agent compositions are characterized by this from that the injection molded water soluble or water-dispersible containers and / or the water soluble or water-dispersible closure unit a polymer or polymer mixture comprises wherein the polymer or at least 50 wt .-% of the polymer mixture selected is over

• a) water soluble nonionic polymers from the group of a1) polyvinylpynolidones, a2) Vinylpyrrolidone / Vinylester copolymers, a3) Cellulose ether a4) polyvinyl alcohol a5) Polyalkylene glycol, especially polyethylene glycol and / or polypropylene glycol
• b) water soluble amphoteric polymers from the group of b1) Alkyl acrylamide / acrylic acid copolymers b2) Alkylacrylamide / methacrylic acid copolymers b3) Alkyl acrylamide / methyl methacrylic acid copolymers b4) Alkylacrylamide / acrylic acid / Alkylaminoafkyl (meth) acrylic acid copolymers b5) Alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b6) Alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b7) Alkylacrylamide / Alkymethacrylat / Alkylaminoethylmethacrylat / alkyl methacrylate copolymers b8) Copolymers b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids b8iii) optionally further ionic or nonionic monomers
• c) water soluble zwitterionic polymers from the group of c1) Acrylamidoalkyltnalkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts c2) Acrylamidoalkyl trialkylammonium chloride / methacrylic acid copolymers as well as their alkali and ammonium salts c3) methacroylethylbetaine / methacrylate copolymers
• d) water-soluble anionic polymers from the group of d1) vinyl acetate / crotonic acid copolymers d2) vinyl pyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid alone Mixture copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polycal kylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the nonionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinker d6) by copolymerizing at least one monomer of each of the three copolymers obtained in the following groups: d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, d6iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ü) saturated or unsaturated, straight-chain or branched C _8-18 alcohol d7) terpolymers from crotonic acid, vinyl acetate and an allyl or methallyl ester d8) tetra- and pentapolymers from d8i) crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate Al8lyl or branched d8lyl) stem d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters d9) crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts d10) terpolymers of vinyl acetate, crotonic acid and vinyl esters in a saturated aliphatic Position branched monocarboxylic acid
• e) water soluble cationic polymers from the group of e1) quaternized Cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) Copolymers of vinyl pyrrolidone with quaternized derivatives of Dialkylaminoacrylate and methacrylate e6) vinyl pyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol e8) under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 specified polymers.

Water-soluble polymers in the sense of Invention are those polymers that are at room temperature in water more than 2.5% by weight soluble are.

The films and / or containers of the portioned according to the invention Detergent and cleaning agent compositions can be made from individual ones polymers mentioned above, but it can also mixtures or multilayered layers made of the polymers be used. The polymers are described in more detail below.

Water-soluble polymers preferred according to the invention are nonionic. Suitable non-ionogenic polymers are, for example:
- polyvinylpyrrolidones, as, for example, sold under the name Luviskol ^® (BASF). Polyvinylpyrrolidones are preferred nonionic polymers in the context of the invention.

die durch radikalische Polymerisation von 1-Vinylpyrrolidon nach Verfahren der Lösungs- oder Suspensionspolymerisation unter Einsatz von Radikalbildnern (Peroxide, Azo-Verbindungen) als Initiatoren hergestellt werden. Die ionische Polymerisation des Monomeren liefert nur Produkte mit niedrigen Molmassen. Handelsübliche Polyvinylpyrrolidone haben Molmassen im Bereich von ca. 2500-750000 g/mol, die über die Angabe der K-Werte charakterisiert werden und – K-Wert-abhängig – Glasübergangstemperaturen von 130-175° besitzen. Sie werden als weiße, hygroskopische Pulver oder als wäßrige. Lösungen angeboten. Polyvinylpynolidone sind gut löslich in Wasser und einer Vielzahl von organischen Lösungsmitteln (Alkohole, Ketone, Eisessig, Chlorkohlenwasserstoffe, Phenole u.a.).
– VinylpyrrolidonNinylester-Copolymere, wie sie beispielsweise unter dem Warenzeichen Luviskol^® (BASF) vertrieben werden. Luviskol^® VA 64 und Luviskol^® VA 73, jeweils Vinylpyrrolidon/Vinylacetat-Copolymere, sind besonders bevorzugte nichtionische Polymere.Polyvinylpynolidone [poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (IV)

which are produced by radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using radical formers (peroxides, azo compounds) as initiators the. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol, which are characterized by the specification of 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. Polyvinylpynolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).
- VinylpyrrolidonNinylester copolymers, such as those sold 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 (V)

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 various processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization.). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (IV) and M.
- 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 N oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in Formel 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 following general formula

R represents N or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in the formula 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.

Polyvinyl alcohols, abbreviated as PVAL, are polymers of the general structure [-CH ₂ -CH (OH) -] _n which in small proportions also structural units of the type [-CH ₂ -CH (OH) -CH (OH) -CH ₂ ] contain. Since the corresponding monomer, the vinyl alcohol, is not stable in free form, polyvinyl alcohols are prepared in solution via polymer-analogous reactions by hydrolysis, but technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol). These technical processes also make PVAL accessible which contain a predeterminable residual proportion of acetate groups.

Commercial PVAL (eg Mowiol ^® types from Hoechst) are commercially available as white-yellowish powders or granules with degrees of polymerization in the range of approx. 500-2500 (corresponding to molar masses of approx. 20,000-100,000 g / mol) and have different degrees of hydrolysis from 98-99 and 87-89 mole%, respectively. They are therefore partially saponified polyvinyl acetates with a residual acetyl group content of approx. 1-2 or 11-13 mol%.

The water solubility of PVAL can be due to Aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, borax decrease and thus adjust to the desired values.

Other polymers suitable according to the invention are water-soluble amphopolymers. The term amphopolymers includes amphoteric polymers, ie polymers which contain both free amino groups and free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers which contain quaternary ammonium groups and -COO ^- - or -SO ₃ ^- contain groups, and summarize 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. Also preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyl-trimethyl-ammonium chloride) and optionally other ionic or non-ionic monomers, such as in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be seen. Terpolymers of acrylic acid, methyl acrylate and 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.

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

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

Anionic polymers suitable according to the invention include:

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

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

In addition to monomer units of the aforementioned formula (V), these polymers also have monomer units of the general formula (VI): [-CH (CH ₃ ) -CH (COOH) -] _n (VI)

• - vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF). A preferred polymer is 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 by heat polymerization obtained in a homogeneous phase by the polyalkylene glycols in the monomers of vinyl esters, esters of acrylic acid or methacrylic acid, stirred in the presence of radical formers.

Have been found to be suitable vinyl esters for example vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as an ester of acrylic acid or methacrylic acid those with low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-l-butanol, 1-hexanol available are proven.

Polyethylene glycols and polypropylene glycols are particularly suitable as polyethylene glycols costume. Polymers of ethylene glycol which have the general formula VII H- (O-CH ₂ -CH ₂ ) _n -OH (VII) are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. 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. 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 formula VII mentioned above. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-8, PEG-9 , PEG-10, PEG-12, PEG-14 and PEG-16 can be used. Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone -Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers.

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

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 VIII.

In particular, those based on polyethylene glycols grafted vinyl acetate copolymers and those on polyethylene glycols grafted polymers of vinyl acetate and crotonic acid become.

• - grafted and crosslinked copolymers from the copolymerization of i) at least a non-ionic type monomer, ii) at least one Ionic type monomers, iii) of polyethylene glycol and iv) a networked

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

The non-ionic monomers can be from be of very different types and among these the following are preferred: Vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, Allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, Stearyl vinyl ether and 1-hexene.

The non-ionic monomers can equally from be of very different types, among them especially preferably crotonic acid, allyloxyacetic, Vinyl acetic acid, maleic acid, Acrylic acid and methacrylic acid are contained in the graft polamers.

Are preferred as a network Ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, Tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule Saccharin.

• 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 Vernetzters, 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 Grup- pen erhaltene Copolymere: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 wt .-%, preferably 5 to 30 wt .-% 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).

- Copolymers obtained by copolymerization of at least one monomer from 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 to be understood as meaning those with 1 to 8 carbon atoms, the carbon chains of these compounds optionally being interrupted by double-bonded hetero groups such as -O-, -NH-, -S-.
- Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester

worin R³ für -N oder -CH₃, R² für -CH₃ oder -CN(CN₃)₂ und R¹ für -CH₃ oder einen gesättigten geradkettigen oder verzweigten C_1-6-Alkylrest steht und die Summe der Kohlenstoffatome in den Resten R¹ und R² vorzugsweise 7, 6, 5, 4, 3 oder 2 ist.These terpolymers contain monomer units of the general formulas (V) and (V1) (see above) and monomer units of one or more allyl or methallyesters of the formula IX:

wherein R ^{3 is} -N or -CH ₃ , R ^{2 is} -CH ₃ or -CN (CN 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.

• – Tetra- und Pentapolymere aus i) Crotonsäure oder Allyloxyessigsäure ii) Vinylacetat oder Vinylpropionat iii) verzweigten Allyl- oder Methallylestern 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 aliphati- schen in α-Stellung verzweigten Monocarbonsäure.

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 Methallylester of formula IX.

• - Tetra- and penta-polymers 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 α-position.

As foil and / or container materials In the case of anionic polymers, polycarboxylates / polycarboxylic acids and polymers are particularly suitable Polycarboxylates, polyaspartic acid, Polyacetals and dextrins, which are described below.

Usable organic film and / or container materials are for example those in the form of their sodium salts but also in Free form usable polycarboxylic acids. Polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

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 made against an external polyacrylic acid standard, due to its structural relationship with the examined Polymer provides realistic molecular weight values. This information gives way clearly on the molecular weight data, in which polystyrene sulfonic acids as Standard are used. The measured against polystyrene sulfonic acids Molar masses are usually significantly higher than those in this document specified molecular weights.

Suitable polymers are in particular Polyacrylates, which preferably have a molecular weight of 2,000 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 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, have, be preferred.

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.

To improve water solubility, the polymers can also allylsulfonic acids, such as as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

In particular as a film and / or container materials biodegradable polymers of more than two are also preferred various monomer units, for example those used as monomers Acrylic acid salts and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Acrylic acid salts and 2-alkylallylsulfonic acid as well as sugar derivatives.

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

Are also preferred as others Foil and / or container materials polymeric aminodicarboxylic acids, their salts or their precursors to call. Polyaspartic acids or their salts and derivatives.

Other suitable film and / or container materials 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 made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and of polyol carboxylic acids such as gluconic acid and / or glucoheptonic receive.

More, preferably as film and / or Behälermaterialien Polymers that can be used are cationic polymers. Among the cationic Polymers are preferred over the permanently cationic polymers. As "permanent become cationic " according to the invention such Polymers referred to independently the pH of the agent (i.e. both the film and the other washing and detergent composition) have a cationic group. These are usually polymers that have a quaternary nitrogen atom, for example in the form of an ammonium group.

• – quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind. Die Verbindungen Celquat^® H 100, Celquat^® L 200 und Polymer JR^®400 sind bevorzugte quaternierte Cellulose-Derivate.
• – Polysiloxane mit quaternären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning^® 929 Emulsion (enthaltend ein hydroxyl-amino-modiflziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil^®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt; diquaternäre Polydimethylsiloxane, Quaternium-80),
• – Kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia^®Guar und Jaguar^® vertriebenen 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 Dictionary and Handbook, 5^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, finden, auf die hier ausdrücklich Bezug genommen wird.Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives.
• Polysiloxanes with quaternary groups, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (containing a hydroxylamino-modified silicone, which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80),
• Cationic guar derivatives, 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

as well as those under the designations

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

known polymers with quaternary nitrogen atoms in the main polymer chain. The polymers mentioned are named according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionary 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.

In preferred detergent or cleaning agent compositions according to the invention, the film and / or container material is selected from the group (optionally acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose and their derivatives, in particular MC, NEC, HPC, HPMC and / or CMC, and / or copolymers and mixtures thereof. Optionally, plasticizers known to those skilled in the art can be added to the coverings to increase the flexibility of the material.

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, the as white-yellowish Powder or granules with degrees of polymerization in the range of approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol) are offered are, have degrees of hydrolysis of 98-99 and 87-89 mol% so there is still a residual content of acetyl groups. Be characterized the polyvinyl alcohols from the manufacturer by specifying the Degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or 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 portioned detergent or cleaning agent composition are characterized in that the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible closure unit 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 portioned washing or cleaning agent compositions according to the invention being preferred, in which the water-soluble or water-dispersible container and / or the water-soluble or water-dispersible closure unit comprises polyvinyl alcohols and / or PVAL copolymers, the molecular weight of which ranges 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

Portioned washing detergents preferred according to the invention or detergent composition are characterized that the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible closure unit polyvinyl alcohols and / or PVAL copolymers comprises 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 is 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 material for the water-soluble or water-dispersible film and / or containers can be found in the table below:

Other polyvinyl alcohols suitable as material for the water-soluble or water-dispersible films and / or containers 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.

Preferred portioned according to the invention Detergent or cleaning agent compositions are characterized in that that the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible closure unit hydroxypropylmethyl cellulose (HPMC) comprises which have a degree of substitution (average number of methoxy groups per anhydroglucose unit of 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 Cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25.

Regardless of the chemical composition the film are washing according to the invention and detergent compositions preferred, which are characterized are that the Foil (s) which close the compartment (s), a Thickness from 1 to 150 μm, preferably from 2 to 100 μm, particularly preferably from 5 to 75 μm and in particular from 10 to 50 μm, having.

Within the scope of the present invention preferred portioned detergent and cleaning agent compositions are characterized in that these Compositions builders in amounts of 1 to 100% by weight, preferably 5 to 95% by weight, particularly preferably from 10 to 90% by weight and in particular from 20 to 85 wt .-%, each based on the weight of the washing or Detergent composition without the water-soluble or water-dispersible Container, contains.

In the portioned according to the invention Detergent and cleaning agent compositions can all typically be found in detergents and Builders used detergents may be included, in particular Zeolites, silicates, carbonates, organic cobuilders and - wherever - no ecological ones There are prejudices against their use - also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 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 dissolving and have secondary washing 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 sharp X-ray reflections, as are typical for 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 provide 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.

In the context of the present invention, preferred portioned washing and cleaning agents together Compositions are characterized in that these silicate (s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in amounts of 10 to 60% by weight, preferably 15 to 50% by weight and in particular 20 to 40% by weight. -%, each based on the weight of the detergent or cleaning composition without the water-soluble or water-dispersible container.

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 (approx. 80% by weight 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 both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix. 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.

Of course, there is also a stake of the well-known phosphates possible as builder substances, provided that such use is not avoided for ecological reasons should be. Among the variety of commercially available The alkali metal phosphates have a particular preference for phosphates Pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) of greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the general term 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 H ₃ PO _{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, water-soluble powders that lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), 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), Na ₂ HPO 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 loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. 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), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO 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 ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have 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 (tertiary or triphase potassium phosphate), K ₃ PO 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 ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also stated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , 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 adding phosphoric acid Soda is converted in a stoichiometric ratio and the solution is dewatered 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 ₇ , 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, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO 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 triphosphate, 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 within the scope of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these are accurate such as sodium tripolyphosphate, potassium tripolyphosphate or mixtures separable 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 according to the invention.

Within the scope of the present invention preferred portioned detergent and cleaning agent compositions are characterized in that these Phosphate (s), preferably alkali metal phosphate (s), particularly preferred Pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 20 to 80% by weight, preferably 25 to 75% by weight us in particular from 30 to 70 wt .-%, each based on the weight the detergent or cleaning agent composition without the water-soluble or water-dispersible container, contain.

Alkali carriers can be present as further constituents his. As an alkali carrier apply, for example, alkali metal hydroxides, alkali metal carbonates, Alkali metal bicarbonates, alkali metal sesquicarbonates, the aforementioned Alkali silicates, alkali metasilicates, and mixtures of the aforementioned Substances, in the sense of this invention preferably the alkali carbonates, especially sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate be used. A builder system is particularly preferred a mixture of tripolyphosphate and sodium carbonate. Likewise a builder system containing a mixture is particularly preferred from tripolyphosphate and sodium carbonate and sodium disilicate.

Particularly preferred ported Detergent and cleaning agent compositions contain carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably from 7.5 to 40% by weight and in particular from 10 to 30% by weight, in each case based on the weight of the portioned detergent or cleaning agent composition.

As organic cobuilders, in portioned according to the invention Detergent and cleaning agent compositions, in particular polycarboxylates / Polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates can be used. These classes of substances are described below.

Usable organic builders are, for example, those that can be used in the form of their sodium salts polycarboxylic being under polycarboxylic acids such carboxylic acids can be understood that 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 an engagement is not for ecological reasons objectionable, and mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mixtures of these.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. In particular, Cit ronic acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these.

Polymers are also used as builders Suitable polycarboxylates, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

For the purposes 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), using a UV detector. 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 2,000 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 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, have, be preferred.

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 2000 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.

To improve water solubility can the polymers also allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

Are also particularly preferred biodegradable polymers from more than two different monomer units, for example those which are salts of acrylic acid and monomers 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 their salts and.

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.

Such in the oxidized derivatives Dextrins are their reaction products with oxidizing agents, which are capable of at least one alcohol function of the saccharide ring for carboxylic acid function to oxidize.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are others suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates are also preferred in this context and glycerol trisuccinates. Suitable amounts are those containing zeolite and / or silicate-containing formulations at 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, e.g. 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, to use, or to use mixtures of the phosphonates mentioned.

In addition, everyone can Compounds capable of complexes with alkaline earth ions train as cobuilders.

The amount of builders is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50 wt .-%, each based on the washing or Detergent composition without the water-soluble or water-dispersible Container. Again, the amount of builders used depends on Intended use so that bleaching compositions higher Amounts of builders can have (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight), as for example detergent compositions (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight).

In addition to builder (s), the agents according to the invention preferably also in the base tablet as a surfactant component anionic, nonionic, cationic and / or amphoteric surfactants contain, with non-ionic surfactants preferred due to their foaming power are.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-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 triglycerides with 0.3 to 2 moles of glycerin 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.

The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C _12-18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half esters secondary alcohols of these chain lengths 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 analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - 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 especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain 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). Here are 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 fatty acid soaps are suitable, like the salts of lauric acid, myristic, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and especially from natural ones fatty acids, e.g. Coconut, palm kernel or tallow 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 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. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 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.

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 are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

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 (X),

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for 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 Arytrest mit 2 bis 8 Kohlenstoffatomen und R^Z 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 (XI)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} egg NEN is a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ^{Z stands} for a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical with 1 to 8 carbon atoms, where C _1-4 alkyl or Phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives of this radical.

[Z] is preferably by reductive Obtained amination of a reduced sugar, for example glucose, Fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy substituted Connections can by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are stirred.

Low-foaming nonionic surfactants are used as preferred surfactants. The cleaning agents according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. 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. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 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.

Dishwashing agents according to the invention are particularly preferred, which contain a nonionic surfactant that has a melting point above room temperature. Accordingly, preferred dishwashing detergents characterized in that they nonionic surfactants) with a melting point above 20 ° C., preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, contain.

Suitable nonionic surfactants, the melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants, which can be solid or highly viscous at room temperature. Become used at room temperature highly viscous nonionic surfactants, 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 (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants stand out beyond that through good foam control.

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 nonionic surfactant which is solid at room temperature is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide , Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred dishwashing agents according to the invention contain ethoxylated nonionic surfactant (s) consisting 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 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part such nonionic surfactant molecules preferably make up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Make up 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 trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

A further preferred dishwashing detergent according to the invention contains nonionic surfactants of 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 hydrocarbon 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 ] _k CH (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 R ² 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. N, -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 R ³ in the above formula can be different if x is Z 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.

If the last statements are summarized, dishwashing detergents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x (CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² contain, 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, with surfactants of the type R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² in which x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃; -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present invention, weakly foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants. Among these, surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Here, automatic dishwashing agents according to the invention are preferred which contain surfactants of the general formula XII as nonionic (s) surfactants

in which R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently represent integers from 1 to 6.

The preferred nonionic surfactants of the formula XII can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula X can vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is generally not shown, the linear radicals being from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol are preferred. Alcohols accessible from synthetic sources are, for example, Guerbet alcohols or residues which are methyl-branched in the 2-position or linear and methyl-branched residues in a mixture, as are usually present in oxo alcohol residues. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, preferred dishwasher detergents according to the invention are those in which R ¹ in formula I for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 is up to 11 carbon atoms.

In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. However, other alkylene oxides in which R ² or R ³ are selected independently of one another from -CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are also suitable. Preferred automatic dishwashing agents are characterized in that R ² or R ³ for a radical -CH ₃ , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

In summary, nonionic surfactants which have a C _9-15 alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, are particularly preferred for use in the agents according to the invention. These surfactants have the required low viscosity in aqueous solution and can be used with particular preference according to the invention.

The specified C chain lengths as well Degrees of ethoxylation or degrees of alkoxylation are statistical Mean values for a special product can be an integer or a fractional number can. Due to the manufacturing process, there are commercial products for the above Formulas are usually not from an individual representative, but rather from mixtures, which affects both the C chain lengths and the degrees of ethoxylation or degrees of alkoxylation and consequently fractional values Numbers can result.

Instead of the surfactants mentioned or in connection with them cationic and / or amphoteric surfactants can also be used.

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 XIII, XIV or XV 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.

In summary, portioned according to the invention Detergent or cleaning agent compositions preferred, the surfactant (s), preferably nonionic) surfactants) and especially nonionic) surfactants) from the group of alkoxylated alcohols, in amounts from 0.1 to 60% by weight, preferably from 0.5 to 50% by weight, particularly preferably from 1 to 40% by weight, and in particular from 2 to 30% by weight, in each case based on the entire average. Particularly preferred machine according to the invention Detergent or cleaning agent compositions are characterized in that that she 5 to 25% by weight, preferably 6 to 22.5% by weight, particularly preferably 7.5 to 20% by weight and in particular 8 to 17.5% by weight of nonionic (s) Surfactants).

In addition to the builders are in particular Bleach, bleach activators, enzymes, silver preservatives, color and fragrances etc. preferred ingredients of portioned according to the invention Detergent or cleaning agent compositions. In addition, other Ingredients be present, portioned detergent or cleaning agent compositions according to the invention preferred, which are additional one or more substances from the group of acidifying agents or contain the chelating agent.

Both inorganic acids and organic acids are suitable as acidifiers, provided that these 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. Commercially available and also preferred as an acidifying agent in the context of the present invention Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight) can be used.

Another possible group of ingredients represent the chelating agents. Chelating agents are Substances that form cyclic compounds with metal ions, where a single ligand has more than one coordination site at one Central atom occupied, d. H. is at least "bidentate". In this case, normally elongated connections are closed to form rings by complex formation via an ion. 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 itself or sideways contribute to this functional groups that can act as ligands and with suitable metal atoms, usually with the formation of chelate complexes react, 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) more common 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 towards ions different metals. Many base polymers are also commercially available important complex-forming polymers are polystyrene, polyacrylates, Polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethylene imines. Even natural Polymers such as cellulose, starch or chitin are complex-forming polymers. In addition, this provided with further ligand functionalities by polymer-analogous conversions become.

• (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 Mengen oberhalb von 0,1 Gew.-%, vorzugsweise oberhalb von 0,5 Gew.-%, besonders bevorzugt oberhalb von 1 Gew.-% und insbesondere oberhalb von 2,5 Gew.-%, jeweils bezogen auf das Gewicht des Geschirrspülmittels ohne den spritzgegossenen Behälter, enthalten.Portioned detergent or cleaning agent compositions, in particular detergents for machine dishwashing, 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 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the Dishwashing detergent without the injection molded container.

• 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, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-asparaginsäure oder Nitrilotriessigsäure (NTA),
• c) geminate 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(methylenphosphonsäure),
• 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) 1,2-glycine Dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA),
• c) geminate 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.

In the context of this patent application, polycarboxylic acids a) are understood to mean carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the alkaline pH values of the treatment required according to the invention At least some of these complex bilgeers are solutions as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

The mechanical cleaning of dishes in household dishwashers usually includes a pre-wash, a main wash and a rinse aid, which are interrupted by intermediate rinse cycles. Most machines have a pre-wash for heavily soiled dishes switchable, but is only selected by the consumer in exceptional cases, so that in Most machines have a main wash, an intermediate wash pure water and a rinse aid carried out become. The temperature of the main wash cycle varies depending on Machine type and program level selection between 40 and 65 ° C. Be in the rinse aid Rinse aid added from a dosing tank in the machine, which is usually contain non-ionic surfactants as the main ingredient. Such rinse aids lie in liquid Form before and are widely described in the prior art. Your task consists primarily of lime stains and deposits on the cleaned dishes to prevent. In addition to water and low-foaming nonionic surfactants this rinse aid often also hydrotopes, pH regulators such as citric acid or scale inhibitors Polymers.

The storage tank in the dishwasher must in at regular intervals rinse aid filled be a filling depending on the machine type for 10 to 50 rinse cycles are sufficient. Will filling up the Forget tanks, especially glasses become unsightly due to limescale stains and deposits. In the prior art, there are therefore some proposed solutions, one rinse aid in the detergent for machine dishwashing to integrate. "2in1" products which Detergent and rinse aid unite, are now also established in the market.

Another development is going also filling up of the regenerating salt container the dishwasher to make it unnecessary. Also called "3in1" cleaners, which have the three functions of cleaning, rinsing and water softening combine in a single detergent formulation, so that for the consumer also refilling of salt in water hardness from 1 to 3 becomes superfluous, are now in the market. For water softening, these cleaners usually contain Sodium tripolyphosphate and / or polymers effective as softeners.

Portioned washing or Detergent compositions for automatic dishwashing can therefore additionally as a softener contain effective polymers. With particular preference Containing sulfonic acid Polymers used, which are described below.

Particularly preferred as containing sulphonic acid groups Copolymers of unsaturated carboxylic acids containing sulfonic acid groups can be used as polymers Monomers and optionally other ionic or nonionic Monomers.

In the context of the present invention, unsaturated carboxylic acids of the formula XVI are preferred as the monomer, R ¹ (R ² ) C = C (R ³ ) COOH (XVI), in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ ; -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids that can be described by formula XVI are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H; R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) preferred.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula XVII R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XVII), in which R ⁵ to R ¹ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas XVIIa, XVIIb and / or XVIIc, H ₂ C = CH-X-SO ₃ H (XVIIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (XVIIb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XVIIc), in which R ⁶ and R ^{7 are} independently selected from -N, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , - CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula XVIIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula XVIIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula XVIIa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula XVIIb), 3-methacrylamido-2-hydroxy-propanesulfonic acid (X = -C (O) NH-CH ₂ CH (OH) CH ₂ - in formula XVIIb), allylsulfonic acid (X = CH ₂ in formula XVIIa), methallylsulfonic acid (X = CH ₂ in formula XVIIb), allyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula XVIIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula XVIIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid (X = CH ₂ in formula XVIIb), styrene sulfonic acid (X = C ₆ H ₄ in formula XVIIa), vinyl sulfonic acid (X not present in formula XVIIa), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula XVIIa), 3-sulfopropyl methacrylate (X = - C (O) NH-CH ₂ CH ₂ CH ₂ - in formula XVIIb), sulfomethacrylamide (X = -C (O) NH- in formula XVIIb), sulfomethyl methacrylamide (X = -C (O) NH-CH ₂ - in formula XVIIb) and water-soluble salts of the acids mentioned.

As another ionic or non-ionic Monomers are particularly suitable ethylenically unsaturated compounds. Preferably is the content of those used according to the invention Polymers to monomers of group iii) less than 20 wt .-%, based on the polymer. Polymers to be used with particular preference only from monomers of groups i) and ii).

In summary, copolymers are made of
i) unsaturated carboxylic acids of the formula XVI. R ¹ (R ² ) C = C (R ³ ) COOH (XVI), in which R ¹ to R ³ independently of one another are -N -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
ii) Monomers of the formula XVII containing sulfonic acid groups R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XVII), in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) - ^I
iii) optionally further ionic or nonionic monomers, particularly preferred ingredients of the portioned detergent or cleaning agent compositions according to the invention.

Particularly preferred copolymers consist of
i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid
ii) one or more monomers of the formulas XVIIa, XVIIb and / or XVIIc containing sulfonic acid groups: H ₂ C = CH-X-SO ₃ H (XVIIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (XVIIb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XVIIc), in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , - CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ )
iii) optionally further ionic or nonionic monomers.

The copolymers can be the monomers from the groups i) and ii) and optionally iii) in varying amounts, where all Representatives from group i) with all representatives from the Group ii) and all Representatives from group iii) can be combined. Especially preferred polymers have certain structural units that are described below.

For example, portioned detergent or cleaning agent compositions according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula XVIII - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XVIII), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the portioned detergent or cleaning agent compositions according to the invention is also preferred and characterized in that the preferred portioned detergent or cleaning agent compositions contain one or more copolymers which have structural units of the formula XIX - [CH2-C (CH3) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIX), contain, in which m and p each represent an integer between 1 and 2COO and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Completely analogously, acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Portioned detergent or cleaning agent compositions according to the invention which contain one or more copolymers which have structural units of the formula XX - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XX), contain, in which m and p each represent an integer between 1 and 2COO and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -O- (CH ₂ ) with n = 0 to 4, represents -O- (C ₆ H ₄ ) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are preferred, also a preferred embodiment of the present invention, just as portioned detergent or cleaning agent compositions are preferred, which are characterized in that they contain one or more copolymers which have structural units of the formula XXI - (CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XXI), contain, in which m and p each represent an integer between 1 and 2COO and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, washing or cleaning agent compositions which are preferred according to the invention and are characterized in that they contain one or more copolymers, the structural units of the formula XXII - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XXII), contain, in which m and p each represent an integer between 1 and 2COO and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are preferred and for portioned detergent or cleaning agent compositions, which are characterized in that they contain one or more copolymers, the structural units of the formula XXIII - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XXIII), contain, in which m and p each represent an integer between 1 and 2COO and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

enthalten, in denen m und, p jeweils für eine ganze natürliche Zahl zwischen 1 und 2COO sowie Y für eine Spacergruppe steht, die ausgewählt ist aus substituierten oder unsubstituierten aliphatischen, aromatischen oder araliphatischen Kohlenwasserstoffresten mit 1 bis 24 Kohlenstoffatomen, wobei Spacergruppen, in denen Y für -O-(CH₂)_n- mit n = 0 bis 4, für -O-(C₆H₄)-, für -NH-C(CH₃)₂- oder -NH-CH(CH₂CH₃)- steht, bevorzugt sind.In summary, portioned detergent or cleaning agent compositions according to the invention are preferred which contain one or more copolymers which have structural units of the formulas XVIII and / or XIX and / or XX and / or XXI and / or XXII and / or XXIII

contain, in which m and, p each represent an integer between 1 and 2COO and Y for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is preferred.

In the polymers, the sulfonic acid are wholly or partly in neutralized form, i.e. that the acid Hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular can be exchanged for sodium ions. Appropriate portioned Detergent or cleaning agent compositions, characterized in that are that the sulfonic acid Partially or fully neutralized in the copolymer are preferred according to the invention.

The monomer distribution of the in the portioned according to the invention Copolymers used in detergent or cleaning agent compositions is in the case of copolymers which only contain monomers from groups i) and ii), preferably in each case 5 to 95% by weight i) or ii), particularly preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight Monomer from group ii), in each case based on the polymer.

Such are special with terpolymers preferred, the 20 to 85 wt .-% monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) included.

The molar mass of the sulfo copolymers described above used in the portioned washing or cleaning agent compositions according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred detergent or cleaning agent compositions are characterized in that the copolymers have molecular weights from 2COO to 200.COO gmol ^-1 , preferably from 4COO to 25.COO gmol ^-1 and in particular from 5COO to 15.COO gmol ^-1 .

In addition to the fabrics from the mentioned substance classes the agents according to the invention more usual Contain ingredients of cleaning agents, in particular Bleach, enzymes, silver protectors, colors and fragrances from Meaning. 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 bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or Diperdodecanedioic. Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidthanoic acid paproacidaproacidoxyhexanoic acid , o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic acid, diperoxyphthalic acids, the 2-decyldiperoxybutane-1,4- diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

As a bleaching agent in the portioned portions according to the invention Detergent or cleaning agent compositions can also release chlorine or bromine Substances are used. Among the appropriate chlorine or bromine release materials come, for example, heterocyclic N-bromo and N-chloramides, for example trichloroisocyanuric acid, tbromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Preferred portioned according to the invention Detergent or cleaning agent compositions additionally contain bleach in amounts of 1 to 40% by weight, preferably 2.5 to 30% by weight and in particular from 5 to 20% by weight, in each case based on the total Means without the water-soluble or water-dispersible container.

As a bleach activator that has the effect that supports bleach, is / are according to the invention in the portioned detergent or cleaning agent compositions cationic Contain nitrile (s). It is possible that the means contain further bleach activator (s). Possible other bleach activators, which have not already been described as nitrile quats, are, for example, compounds that contain one or more N or Contain O-acyl groups, such as substances from the anhydride class, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylene diamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

As bleach activators can continue 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 C number of carbon atoms and / or optionally substituted benzoyl groups. Multi-acylated alkylene diamines, in particular tetraacetylethylene diamine, are preferred (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, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl morpholinium acetonitrile methyl sulfate (MMA) and acetylated sorbitol and mannitol or their Mixtures (SORMAN), acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. hydrophilic Substituted acylacetals and acyl lactams are also preferred used. Combinations of conventional bleach activators can also be used become. The bleach activators are commonly used in automatic dishwashing detergents in amounts from 0.1 to 20% by weight, preferably from 0.25 to 15% by weight and in particular from 1 to 10% by weight, in each case based on the composition, used. In the context of the present invention, the mentioned proportions on the weight of the agent without the water-soluble or water-dispersible container.

In addition to the conventional Bleach activators or in their place can also be so-called bleach catalysts be incorporated into the active substance particles. With these fabrics are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also with Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes Tripod ligands containing N as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

If further bleach activators are to be used in addition to the nitrile quats, bleach activators from the group of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonananoylonoyl or (isonoloyloxy) or (isonoloyloxy) or (isonoloyloxy) or (isonoloyloxy) or isonolonoxy n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts up to 10% by weight, in particular 0.1% by weight to 8% by weight, be particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, based on the portioned detergent or cleaning agent compositions, without the water-soluble or water-dispersible container.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferred selected 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, of manganese sulfate in usual Amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01 % By weight to 0.25% by weight, in each case based on the total agent without the container, used. But in special cases more bleach activator can also be used.

To decay solid washing or To facilitate detergent compositions, it is possible to use disintegration aids, so-called tablet disintegrants to be incorporated into these agents, to shorten the decay times. Under tablet disintegrants or disintegrators according to Römpp (9. Edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, P. 182-184) understood auxiliary substances necessary for the rapid disintegration of tablets in water or gastric juice and for ensure the release of the pharmaceuticals in an absorbable form.

These substances, also because of their Effect called "explosive" medium increase with water ingress their volume, on the one hand increasing their own volume (swelling), on the other hand also about the Release of gases creates a pressure on the tablet can disintegrate into smaller particles. Well-known Disintegration aids include carbonate / citric acid systems, taking other organic acids can be used. Swelling disintegration aids are, for example, synthetic Polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or modified Natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred portioned washing and Detergent compositions contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more Disintegration aids, each based on the weight of the Compositions without the water-soluble or water-dispersible Container. contains refer only to the composition of disintegration aids the information given relates only to the weight of this composition.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred portioned detergent and cleaning agent compositions contain such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular Contain 4 to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, from a formal point of view, is a (3-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of about 500 to 5COO glucose units and consequently have average molar masses of 50.COO to 500.COO. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions, such as chemically modified celluloses For example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted, but also celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound by an oxygen atom can be entered as cellulose derivatives the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention.

Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine Cel produced by the hydrolysis Lulosen supplies the microcrystalline celluloses, which have primary particle sizes of approx. 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

Within the scope of the present invention preferred portioned detergent and cleaning agent compositions included in addition a disintegration aid, preferably a disintegration aid Cellulose based, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the composition without the water-soluble or water-dispersible Container.

The portioned washing and Detergent compositions can also be gas-evolving Shower system included. The gas-developing shower system can consist of a single substance that comes into contact with water Releases gas. Among these compounds is magnesium peroxide in particular to be mentioned, which releases oxygen on contact with water. Usually However, the gas-free bubble system consists of itself at least two components that form gas together react. While a variety of systems is conceivable and executable here, for example Nitrogen, oxygen or hydrogen will be released in the washing machine according to the invention and bubble system used detergent compositions both based on economic as also based on ecological Select points of view to let. Preferred shower systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent that is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

In the case of the alkali metal carbonates or -hydrogen carbonates are the sodium and potassium salts for reasons of cost compared to other salts clearly preferred. Of course, they don't have to pure alkali metal carbonates or bicarbonates used become; rather can Mixtures of different carbonates and hydrogen carbonates are preferred his.

In preferred portioned washing and detergent compositions are used as a shower system 2 to 20 wt .-%, preferably 3 to 15 wt .-% and in particular 5 to 10 wt .-% of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight an acidifying agent, each based on the washing or Detergent composition used.

Acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred from this group. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

Are preferred within the scope of the present Invention detergent compositions in which as an acidifying agent in the shower system, a substance from the group the organic di-, tri- and oligocarboxylic acids or mixtures thereof be used.

The portioned cleaning agents according to the invention can to protect the dishes or the machine contain corrosion inhibitors, wherein. 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 used particularly preferably 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 especially contain oxygen and nitrogen 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-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred 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.

Instead of or in addition to the silver protective agents described above, for example the benzotriazoles, redox-active substances can be used in the portioned washing or cleaning agent compositions according to the invention. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and contains cerium salts and / or complexes, the metals preferably being in one of the oxidation states II, III, IV, V or VI.

The metal salts used or Metal complexes are said to be at least partially soluble in water. The counterions suitable for salt formation include all customary ones one, two or three times negatively charged inorganic anions, z. B. oxide, sulfate, nitrate, fluoride, but also organic anions such as B. stearate.

Metal complexes in the sense of the invention are compounds consisting of a central atom and one or more Ligands and optionally one or more the above Anions exist. The central atom is one of the above metals in one of the above Oxidation states. The ligands are neutral molecules or Anions that are monodentate or multidentate are; the term "ligand" in the sense of the invention is e.g. in "RÖmpp Chemie Lexicon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, Page 2507 "explained in more detail. Complement each other the charge of the central atom and the charge in a metal complex of the ligand (s) is not zero, depending on whether a or there is an anionic excess charge, either one or more of the above Anions or one or more Cations, r. B. sodium, potassium, ammonium ions for charge balance. Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The definition common in chemistry for "oxidation level" is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3168 "reproduced.

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ and mixtures thereof. So that preferred portioned automatic dishwashing agents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II ) - [1-hydroxyethane-1,1-diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ . These metal salts or metal complexes are generally commercially available substances which can be used in the agents according to the invention for the purpose of protecting against silver corrosion without prior cleaning. For example, the mixture of pentavalent and tetravalent vanadium (V ₂ O ₅ , VO ₂ , V ₂ O ₄ ) known from SO ₃ production (contact process) is suitable, as is that by diluting a Ti (SO ₄ ) ₂ - Solution of titanyl sulfate, TiOSO ₄ .

The inorganic redox active substances, in particular metal salts or metal complexes are preferably coated, i.e. Completely with a waterproof, but easily soluble at cleaning temperatures Material covered, to prevent their premature decomposition or oxidation during storage prevent. Preferred coating materials, which are produced by known processes, such as Sandwik melt coating processes from the food industry, are applied, paraffins, micro waxes, waxes are natural Origin such as carnauba wax, candella wax, beeswax, higher melting Alcohols such as hexadecanol, soaps or fatty acids. there the coating material, which is solid at room temperature, is melted State applied to the material to be coated, e.g. by fine-grained material to be coated in a continuous stream through a likewise continuously generated spray zone of the molten coating material is thrown. The melting point must be like this chosen be that yourself the coating material during the Silver treatment easily dissolves or melts quickly. The melting point should ideally be in Range between 45 ° C and 65 ° C and preferably in the range of 50 ° C up to 60 ° C lie.

The metal salts mentioned and / or Metal complexes are in the portioned washing or Detergent compositions, especially machine dishwashing detergents, preferably in an amount of 0.05 to 6% by weight, preferably 0.2 to 2.5 wt .-%, based on the agent without the water-soluble or water-dispersible container, included Another important criterion for assessing a automatic dishwashing detergent is, in addition to its cleaning performance, the visual appearance dry dishes after cleaning. Possibly occurring Calcium carbonate deposits on dishes or inside the machine can For example, affect customer satisfaction and thus have causal Influence on the economic success of such a cleaning agent. Another longstanding problem with machine dishwashing is the corrosion of glassware, which is usually characterized by the appearance of cloudiness, streaks and scratches but can also manifest by iridescence of the glass surface. They watched Effects are essentially based on two processes, the Leaks of alkali and alkaline earths from the glass in connection with hydrolysis of the silicate network, on the other hand in one Deposition of silicate compounds on the glass surface.

The problems mentioned can with portioned according to the invention Means solved be if additional to the above mandatory and optionally oprional Ingredients certain glass corrosion inhibitors in the agents be incorporated. Preferred agents according to the invention therefore additionally contain a or several magnesium and / or zinc salts and / or magnesium and / or zinc complexes.

A preferred class of compounds which can be added to the agents according to the invention to prevent glass corrosion are insoluble zinc salts. These can change during the dishes attach the rinsing process to the glass surface and prevent the metal ions from the glass network from dissolving and the hydrolysis of the silicates. In addition, these insoluble zinc salts also prevent silicate from being deposited on the glass surface, so that the glass is protected from the consequences described above.

Insoluble zinc salts in the sense of this preferred embodiment are zinc salts which have a solubility of at most 10 grams of zinc salt per liter of water at 20 ° C. Examples of particularly insoluble zinc salts preferred according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn ₂ (OH) ₂ CO ₃ ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (PO ₄ ) ₂ ), and zinc pyrophosphate (Zn ₂ (P ₂ O ₇ )).

The zinc compounds mentioned are in the means according to the invention used in amounts that contain zinc ions between the agents 0.02 and 10 wt .-%, preferably between 0.1 and 5.0 wt .-% and in particular between 0.2 and 1.0 wt .-%, each based on the Agent without the injection molded container. The exact one The content of the agent in the zinc salt or zinc salts is of course dependent on the type of zinc salts - each less soluble the zinc salt used, the higher its concentration should be in the agents according to the invention his.

Since the insoluble zinc salts during the Dishwashing process for the most part unchanged remain is the particle size of the salts a criterion to be observed so that the salts are not on glassware or machine parts stick. Here are liquid aqueous machine according to the invention Dishwashing liquid preferred where the insoluble Zinc salts one particle size below Have 1.7 millimeters.

If the maximum particle size is the insoluble Zinc salts below 1.7 mm are insoluble residues in the dishwasher not to fear. Preferably has the insoluble Zinc salt has an average particle size that is well below this value is in order to further minimize the risk of insoluble residues, for example an average particle size smaller 250 μm. This, in turn, is all the more the less the zinc salt is soluble. In addition, the glass corrosion-inhibiting effectiveness increases with decreasing Particle size. at very poorly soluble zinc salts the average particle size is preferably below 100 μm. For yet less soluble Salts can be even lower; for example, are very for that poorly soluble Zinc oxide mean particle sizes below of 100 μm prefers.

Another preferred class of Compounds are magnesium and / or zinc salts) at least one monomeric and / or polymeric organic acid. These also cause repeated use does not change the surfaces of glassware, especially no cloudiness, Streaks or scratches but also no iridescence on the glass surfaces become.

Although according to the invention all magnesium and / or zinc salts) of monomeric and / or polymeric organic acids in the claimed agents may be included, as above described, the magnesium and / or zinc salts monomeric and / or polymeric organic acids from the groups of unbranched saturated or unsaturated Monocarboxylic acids, the branched saturated or unsaturated Monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, of oxo acids, of amino acids and / or of polymeric carboxylic acids prefers. Within these groups, within the scope of the present According to the invention, the acids mentioned below are preferred: from the group the unbranched saturated or unsaturated Monocarboxylic acids: Methansäure (Formic acid), Ethansäure (Acetic acid), propanoic acid (propionic acid), pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid (tetranoic acid) Myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotinic acid), meliacid acid (9) ), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaid) 9c, 12c, 15c-Octadecatreinsäure (Linolenic acid).

From the group of branched saturated or unsaturated Monocarboxylic acids: 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, 2-butyloctanoic acid, 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-octyldodecanoic acid, 2-nonyltridecanoic acid, 2-decyltetradecanoic acid, 2- Undecylpentadecansäure, 2-Dodecylhexadecansäure, 2-Tridecylheptadecansäure, Contains 2-tetradecyloctadecanoic acid, 2-pentadecylnonadecanoic acid, 2-hexadecyleicosanoic acid, 2-heptadecylheneicosanoic acid.

From the group of unbranched saturated or unsaturated Di- or tricarboxylic acids: propanedioic (Malonic acid), Butandisäure (Succinic acid), pentanedioic (Glutaric acid), hexanedioic (Adipic acid), heptanedioic (Pimelic acid), octanedioic (Suberic acid), Nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), 2c-butenedioic acid (maleic acid), 2t-butenedioic acid (fumaric acid), 2-butynedicarboxylic acid (acetylenedicarboxylic acid).

From the group of aromatic mono-, di- and tricarboxylic acids: benzoic acid, 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3,5-dicarboxybenzoic acid (trimesionic acid).

From the group of the sugar acids: galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid, alginic acid. - From the Group of hydroxy acids: hydroxyphenylacetic (Mandelic acid), 2-hydroxypropanoic (Lactic acid), H.ydroxybernsteinsäure (Malic acid), 2,3-dihydroxy-butanedioic acid (tartaric acid), 2-hydroxy-1,2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2-hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).

From the group of oxo acids: 2-oxopropionic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).

From the group of amino acids: alanine, Valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, Glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, Lysine, arginine, histidine.

From the group of polymeric carboxylic acids: polyacrylic acid, polymethacrylic acid, alkyl acrylamide / acrylic acid copolymers, Alkylacrylamide / methacrylic acid copolymers, Alkyl acrylamide / methyl methacrylic acid copolymers, Copolymers of unsaturated Carboxylic acids, Vinyl acetate / crotonic acid copolymers, Vinylpyrrolidone / vinyl acrylate copolymers.

The spectrum of the zinc salts of organic acids, preferably organic carboxylic acids preferred according to the invention, extends from salts which are sparingly or not soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility, up to such salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, particularly preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C. water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate; the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate:
In a further preferred embodiment of the present invention, the portioned detergent or cleaning agent compositions according to the invention contain at least one zinc salt, but no magnesium salt of an organic acid, which is preferably at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group of zinc stearate, zinc oleate , Zinc gluconate, zinc acetate, zinc lactate andi or zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

A preferred agent in the context of the present invention contains zinc salt in amounts of 0.1 to 5% by weight, preferably 0.2 to 4% by weight and in particular 0.4 to 3% by weight, or zinc in oxidized form (calculated as Zn ²⁺ ) in amounts from 0.01 to 1% by weight, preferably from 0.02 to 0.5% by weight and in particular from 0.04 to 0.2% by weight , each based on the total weight of the automatic dishwashing detergent without the water-soluble or water-dispersible container.

In addition to the components mentioned Builder, surfactant, disintegration aid, bleach and bleach activator can the washing according to the invention and detergent compositions further ingredients common in detergents and cleaning agents from the group of dyes, fragrances, optical brighteners, Enzymes, foam inhibitors, silicone oils, anti-redeposition agents, Graying inhibitors, color transfer inhibitors and contain corrosion inhibitors.

Agents according to the invention can contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all the enzymes established in the prior art for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Invention. Agents preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5 percent by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and that which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. The variants listed under the name BLAP ^{® are} derived from the protease from Bacillus lentus DSM 5483.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, which is sold under the trade name Protosol ^® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ^® by Wuxi Snyder Bioproducts Ltd., China, which is sold under the trade names Proleather ^® and Protease P ^® by from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus and their further developments which are improved for use in detergents and cleaning agents. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

Furthermore are for this Purpose of the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae. Another commercial product is the Amylase-LT ^® .

Agents according to the invention can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^® , Lipolase ^® Ultra, LipoPrime ^® , Lipozyme ^® and Lipex ^® . Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. Lipase ^® , Lipase AP ^® , Lipase M-AP ^® and Lipase AML ^® available. The Genencor company can use, for example, the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanü. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention, also the product Lumafast ^® from Genencor.

Agents according to the invention can contain further enzymes, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, United States. The obtained from B. subtilis β-glucanase is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, portioned washing and cleaning agent compositions according to the invention can use oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) ) contain. Suitable commercial products are Denilite ^® 1 and 2 from Novozymes. Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of greatly different redox potentials between the oxidizing enzymes and the soiling.

The agents according to the invention the enzymes used are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or according to known biotechnological processes produced by suitable microorganisms, such as transgenic Expression hosts of the genera Bacillus or filamentous fungi.

Purification of the concerned Enzymes are conveniently made by themselves established processes, for example via precipitation, sedimentation, concentration, Filtration of the liquid Phases, microfiltration, ultrafiltration, exposure to chemicals, Deodorization or suitable combinations of these steps.

Agents according to the invention can Enzymes are added in any form established according to the prior art become. This includes for example by granulation, extrusion or lyophilization obtained solid preparations or, especially with liquid or gel-shaped Means, solutions the enzymes, advantageously if possible concentrated, low in water and / or mixed with stabilizers.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with one preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed in a solidified gel or in those of the core-shell type in which an enzyme-containing core with a water, air and / or chemical impermeable protective layer. is. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.

It is also possible to have two or assemble several enzymes so that a single Granulate multiple enzyme activities having.

One in an agent according to the invention contained protein and / or enzyme can be particularly during the Storage against damage such as inactivation, denaturation or decay, for example through physical influences, Oxidation or proteolytic cleavage are protected. With microbial Obtaining the proteins and / or enzymes is an inhibition of Proteolysis is particularly preferred, especially if the agents Proteases included. Agents according to the invention can stabilizers for this purpose contain; the provision of such means is preferred embodiment of the present invention.

A group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, especially derivatives with aromatic groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their Salts or esters. As peptide protease inhibitors are among mention other ovomucoid and leupeptin; an additional Option is the formation of fusion proteins from proteases and peptide inhibitors.

Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders can additionally stabilize an enzyme contained.

Lower aliphatic alcohols but above all polyols, such as glycerol, ethylene glycol, Propylene glycol or sorbitol are other frequently used enzyme stabilizers. Calcium salts, such as calcium acetate, are also used or calcium formate, and magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, among other things, against physical influences or pH fluctuations. Polymers containing polyamine-N-oxide act as enzyme stabilizers. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkyl polyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance. Cross-linked N-containing compounds also act as enzyme stabilizers.

Reducing agents and antioxidants increase the stability of the enzymes oxidative decay. A sulfur-containing reducing agent is, for example Sodium sulphate.

Combinations of are preferred Stabilizers used, for example from polyols, boric acid and / or Borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing Salt. The effect of peptide-aldehyde stabilizers is due to the combination with boric acid and / or boric acid derivatives and polyols increased and by the additional use of divalent Cations, such as calcium ions further enhanced.

Preferred machine according to the invention Dishwashing liquid are characterized in that they also have a or more enzymes and / or enzyme preparations, preferably solid and / or liquid protease preparations and / or amylase preparations, in amounts of 1 to 5% by weight, preferably from 1.5 to 4.5 and in particular from 2 to 4% by weight, in each case based on the entire average.

Dyes and fragrances can be added to the agents according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a product that is visually and sensorially "typical and unmistakable". Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylpropionate, stally. The ethers include, for example, benzyl ethyl ether, the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, α-isomethylionone and methylcedryl ketone the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. Be however, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be portioned directly into the portions according to the invention Detergent or cleaning agent compositions are incorporated, but it can also be advantageous to apply the fragrances to carriers, which ensure a long-lasting fragrance due to a slower fragrance release. As such carrier materials Cyclodextrins have proven themselves, for example, the cyclodextrin-particle complexes in addition can be coated with other auxiliaries.

To the aesthetic impression of the agent according to the invention To improve it (or parts of it) with suitable dyes colored become. Preferred dyes, the selection of which no expert Difficulty, high storage stability and insensitivity across from the other ingredients of the means and against light as well as no pronounced substantivity towards the with substrates to be treated such as glass, ceramic or Plastic dishes so as not to stain them.

The portioned washing or Detergent compositions dissolve in the washing or cleaning cycle Completely on, where it - like mentioned above - advantages can have if the different regions are different dissolution rates exhibit. Due to the different release speeds, besides the release of certain ingredients at certain times also target the properties of the washing or cleaning liquor changed become. For example, detergent and cleaning agent compositions preferred, in which the pH of a 1% by weight solution of the Detergent or cleaning agent composition in water in the area from 8 to 12, preferably from 9 to 11 and in particular from 9.5 to 10.

In addition to this, are portioned Preferred detergent and cleaning compositions in which the pH of a 1 wt .-% solution of the total washing or Detergent composition in water in the range of 7 to 11, preferably from 7.5 to 10 and in particular from 8 to 9.5, lies.

In the water-soluble for the production of the invention or water-dispersible container used The process is injection molding. Injection molding thereby shaping a molding compound in such a way that the in a mass cylinder for more as an injection molding process contained mass under the influence of heat plastically softened and under pressure through a nozzle into the cavity of a previously flows into the closed tool. The process is mainly at non-curable Molding compounds applied that solidify in the mold by cooling. The injection molding is a very economical modern process for the production without cutting shaped objects and is particularly suitable for automated mass production. One heats up in practical operation the thermoplastic molding compounds (powder, granules, cubes, pastes, etc.) up to liquefaction (up to 180 ° C) and then injects them under high pressure (up to 140 MPa) into closed, two-part, that is from die (formerly Matrix) and core (formerly Patrix) existing, preferably water-cooled molds, where they cool and solidify. Piston and screw injection molding machines can be used. As molding compounds (injection molding compounds) are water-soluble Polymers such as the cellulose ethers, pectins, Polyethylene glycols, polyvinyl alcohols, polyvinyl pyrrolidones, alginates, Gelatin or starch.

• a) Spritzgießen eines wasserlöslichen oder wasserdispergierbaren Behälters mit n Kompartimenten,
• b) Einfüllen mindestens eines kationische Nitrils der Formel (I)
  
  in der R¹ für -N, -CH₃, einen C_{2– 24}-Alkyl- oder -Alkenylrest, einen substituierten C_{2– 24}-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -ON, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CN₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CN₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, – CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist, in flüssiger, gelförmiger, pastöser oder fester Form in mindestens 1, jedoch maximal n-1 Kompartiment(e)
• c) optionales Aufbringen eines oder mehrerer Haftvermittler auf ein oder mehrere Flächen des Behälterss
• d) Verschließen mindestens einer der Öffnungen mit einer wasserlöslichen oder wasserdispergierbaren Verschlußeinheit
• e) optionale Nachbehandlung einzelner Folien- und/oder Behälteroberflächen oder des gesamten Behälters.

Another object of the present application is a method for producing portioned detergent or cleaning agent compositions according to the invention, characterized by the steps

• a) injection molding of a water-soluble or water-dispersible container with n compartments,
• b) filling in of at least one cationic nitrile of the formula (I)
  
  in which R ¹ is -N, -CH _3, a C _{2- 24} alkyl or alkenyl group, a substituted C _{2- 24} alkyl or alkenyl group having at least one substituent from the group -Cl, -Br, - ON, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a C _1-24 alkyl group, or for a substituted alkyl or alkenylaryl radical with a C _1-24 alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CN ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CN ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, - CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion, in liquid, gel-like, pasty or solid form in at least 1, but at most n-1 compartment (s)
• c) optional application of one or more adhesion promoters to one or more surfaces of the container
• d) closing at least one of the openings with a water-soluble or water-dispersible closure unit
• e) optional post-treatment of individual film and / or container surfaces or the entire container.

A cleaning process for cleaning of dishes in a dishwasher, which is characterized in that one or more portion (s) according to the invention are portioned Detergent and detergent compositions in the dosing chamber the dishwasher and a washing program runs out in its The metering chamber opens and the means or means dissolved are another object of the present invention.

Also in the cleaning process according to the invention you can do without the metering chamber and portioned or the portion of the invention Place the compositions in the cutlery basket, for example. It goes without saying but also here the use of a dosing aid, for example one the basket, that in the washroom attached, easily possible. Accordingly, there is a cleaning method for cleaning dishes in a dishwasher, in which one or more portioned washing and washing according to the invention Detergent compositions with or without dosing aid in the Wash cabinet the dishwasher and a washing program runs out in its Course of the portioned detergent or cleaning agent compositions disbanded are another object of the present invention.

Claims (24)

Portioned detergent or cleaning agent composition in an injection-molded water-soluble or water-dispersible container, characterized in that the washing or cleaning agent composition comprises at least one cationic nitrile of the formula (I)

in which R ^{1 is} -H, -CH ₃ , a C ₂ _ ₂₄ alkyl or alkenyl radical, a substituted C ₂ _ ₂₄ alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a C _2-24 alkyl group, or for a substituted alkyl or alkenylaryl radical with a C _2-24 alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion. Portioned detergent or cleaning agent composition according to Claim 1, characterized in that it is a cationic nitrile of the formula (Ia) as the cationic nitrile of the formula (I)

contain, in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , where R ^{4 can} additionally be -H and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ^{( +)} CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH (CH ₃ )) ₃ N ^{( +)} CH ₂ -CN X ^- , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{- are} particularly preferred. Portioned detergent or cleaning agent composition according to one of claims 1 or 2, characterized in that X ^{- represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate) and cumene sulfonate or xylene sulfonate or mixtures thereof. Portioned detergent or cleaning agent composition according to one of the claims 1 to 3, characterized in that the cationic nitrile (s) of the formula (I) in particulate form is / are, preferably at least 90% by weight of the particles of the cationic nitrile of the formula (I) has a particle size above 0.2 mm, particularly preferably at least 40% by weight, preferably at least 50% by weight and in particular at least 60% by weight of the particles of the cationic nitrile of the formula (I) has a particle size above Have 0.4 mm and the cationic nitrile of formula (I) in particular preferably an average particle size above 400 μm, preferably above 500 μm, particularly preferably above 600 μm and in particular above of 700 μm having. Portioned detergent or cleaning agent composition according to one of claims 1 to 4, characterized in that the cationic nitrile (s) of the formula (I) is / are particulate, the cationic nitrile (s) is made up with an inorganic carrier material, preferably with a carrier material from the group of silicon-containing substances, particularly preferably the alkali silicates, the silicas, the silica gels or the clays, and / or the phosphates, particularly preferably the alkali phosphates, the carrier material preferably has an inner surface area of 12 m ² / g to 480 m ² / g, in particular 80 m ² / g to 440 m ² / g. Portioned detergent or cleaning agent composition according to one of the claims 1 to 5, characterized in that the cationic nitrile (s) of the formula (I) in particulate form is / are and these particles are water-soluble or water-dispersible Have coating, the weight proportion of this coating on the total weight of the coated cationic nitrile / nitriles preferably 0.8 to 24% by weight, particularly preferably 1.2 to 19% by weight and in particular is 1.6 to 14% by weight. Portioned detergent or cleaning agent composition according to claim 6, characterized in that the coating material is at least partially selected from a polymer or polymer mixture, the polymer or at least 50% by weight of the polymer mixture being selected from a) water-soluble nonionic polymers from the group of a1) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers a4) polyvinyl alcohol a5) polyalkylene glycol, in particular polyethylene glycol and / or polypropylene glycol b) water-soluble amphoteric polymers from the group of b1) alkyl acrylamide / acrylic acid copolymers amide b2) Copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers lamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers from b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids b8iii) optionally further ionic or nonionic monomers c) water-soluble zwitterionic polymers from the group of c1) acrylamidoalonium chlorides and their acrylamidoalonium chloride - and ammonium salts c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethylbetaine / methacrylate copolymers d) water-soluble anionic polymers from the group of d1) vinyl acetate / crotonic acid copolymers d2) vinyl pyrrolidone / vinyl copolymer d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers d4) graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the Copolymerization of d5i) at least one monomer of the non-ionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinker d6) by copolymerization of at least one monomer of each of the following three groups: d6i) unsaturated esters Alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, d6iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol d7) terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester d8) tetra and pentapolymers of d8i) crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate d8iii) branched allyl or vinyl ester, d8) or straight-chain allyl or methallyl esters d9) crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts d10) terpolymers from vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position e) water-soluble cationic polymers from the group of e1) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone with quaternary Derivatives of dialkylaminoacrylate and methacrylate e6) vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol e8) polymers given the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27. Portioned detergent or cleaning agent composition according to one of the claims 6 or 7, characterized in that the coating material at least partially selected is from the group of water-soluble or water-dispersible inorganic salts, preferably of the group of sulfates, chlorides, phosphates and phosphonates, where especially the alkali and alkaline earth salts and here again the Sodium, potassium and / or magnesium salts are particularly preferred. Portioned detergent or cleaning agent composition according to one of the claims 6 to 8, characterized in that the coating material at least partially selected is from the group of meltable substances, preferably from the group of fats and / or triglycerides and / or fatty acids and / or Fatty alcohols and / or waxes and / or parrafins, and / or from the Group of anionic surfactants. Portioned detergent or cleaning agent composition according to one of the claims 5 to 9, characterized in that the bulk density of the assembled cationic nitriles / nitriles in the range between 320 and 960 g / l, preferably in the range from 360 to 880 g / l and in particular in Range is from 410 to 790 g / l. Portioned detergent or cleaning agent composition according to one of the claims 1 to 10, characterized in that the detergent or cleaning agent composition at least one liquid and / or comprises at least one dispersion and / or at least one solid. Portioned detergent or cleaning composition according to one of claims 1 to 11, because characterized in that the injection molded water-soluble or water-dispersible container has at least two separate compartments. Portioned detergent or cleaning agent composition according to claim 12, characterized in that at least one of the compartments contains) cationic / cationic nitrile (s) of the formula (I). Portioned detergent or cleaning agent composition according to one of the claims 12 or 13, characterized in that at least one compartment a liquid contains and at least one further compartment contains a solid. Portioned detergent or cleaning agent composition according to one of the claims 11 or 14, characterized in that the solid in the form of a Powder and / or an agglomerate and / or a compactate and / or a casting is present. Portioned detergent or cleaning agent composition according to one of the claims 1 to 15, characterized in that the closure unit of the injection molded water soluble or water-dispersible container one on dissolution behavior of water soluble or water-dispersible container different dissolution behavior shows. Portioned detergent or cleaning agent composition according to one of the claims 1 to 16, characterized in that the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible sealing unit made of a polymer with a molecular weight between 5COO and 500.COO daltons, preferably between 7500 and 250.COO daltons and especially between 10.COO and 100th COO Dalton. Portioned detergent or cleaning agent composition according to one of the claims 1 to 17, characterized in that the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible closure unit one or more Substances from the group carrageenan, guar, pectin, xanthan, cellulose and their derivatives, starch and their derivatives and gelatin. Portioned detergent or cleaning agent composition according to one of Claims 1 to 18, characterized in that the injection-molded water-soluble or water-dispersible container and / or the water-soluble or water-dispersible closure unit comprises a polymer or polymer mixture, the polymer or at least 50% by weight of the polymer mixture is selected from a) water-soluble nonionic polymers from the group of a1) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ether b) water-soluble amphoteric polymers from the group of b1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid / methacrylic acid b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b7) id / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers from b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids b8iii) optionally further ionic or nonionic monomers c) water-soluble zwitterionic polymers from the group of the c1k acrylamido ammonium chloride trials and ammonium salts c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethylbetaine / methacrylate copolymers d) water-soluble anionic polymers from the group consisting of d1) vinyl acetate / crotonic acid copolymers d2) vinylpyrryl acrylate / vinyloloyl acid / copolymers ethyl acrylate / N-tert-butylacrylamide terpolymers d4) 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 d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the nonionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinker d6) copolymers obtained by copolymerizing at least one monomer of each of the following three groups: d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, d6iii) esters of long chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group d6ii) with saturated or unsaturated, linear or branched C _8-18 alcohol d7) terpolymers of crotonic ure, vinyl acetate and an allyl or methallyl ester d8) tetra- and pentapolymers from d8i) crotonic acid or altyloxyacetic acid d8ii) vinyl acetate or vinyl propionate d8iii) branched allyl or methallyl esters d8iv) vinyl ethers, vinyl esters or straight-chain allyl copolyhallylyl) allyl one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts d10) terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position e) water-soluble cationic polymers from the group of e1) quaternized cellulose Derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate e6) inylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol e8) polymers given the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27. Portioned detergent or cleaning agent composition according to one of the claims 1 to 19, characterized in that the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible closure unit polyvinyl alcohols and / or PVAL copolymers comprises 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. Portioned detergent or cleaning agent composition according to one of Claims 1 to 20, characterized in that the water-soluble or water-dispersible container and / or the water-soluble or water-dispersible closure unit comprises polyvinyl alcohols and / or PVAL copolymers, the molecular weight of which is in the range from 3,500 to 100.COO gmol ^-1 , preferably from 10.COO to 90.COO gmol ^-1 , particularly preferably from 12.COO to 80.COO gmol ^-1 and in particular from 13.COO to 70.COO gmol ^-1 . Portioned detergent or cleaning agent composition according to one of the claims 1 to 21, characterized in that the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible closure unit polyvinyl alcohols and / or PVAL copolymers comprises 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 is between 0.45 and 0.6. Portioned detergent or cleaning agent composition according to one of claims 1 to 22, characterized in that the water-soluble or water-dispersible container and / or the water-soluble or water-dispersible closure unit comprises hydroxypropylmethyl cellulose (HPMC), which has a degree of substitution (average number of methoxy groups per anhydroglucose unit of the 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 the cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25. Process for the production of portioned detergent or cleaning agent compositions characterized by the steps a) injection molding of a water-soluble or water-dispersible container with n compartments, b) filling in of at least one cationic nitrile of the formula (I)

in which R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical with at least one substituent from the group -CI, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a C _1-24 alkyl group, or for a substituted alkyl or alkenylaryl radical with a C _1-24 alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, - CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion, in liquid, gel-like, pasty or solid form in at least 1, however, a maximum of n-1 compartment (e) c) optional application of one or more adhesion promoters to one or more surfaces of the container d) closing at least one of the openings s with a water-soluble or water-dispersible closure unit e) optional aftertreatment of individual film and / or container surfaces or the entire container.